CN1392890A - Curable composition and uses thereof - Google Patents

Abstract

A curable composition comprising (A1) a silyl-bearing ethylene/a-olefin/nonconjugated polyene random copolymer rubber which contains constituent units derived from a specific vinyl-terminated norbornene compound and bears specific hydrolyzable silyl groups in the molecule and (B) a compound other than the rubber (A1) which contains a hydroxyl group and/or a hydrolyzable group, for example, (B1) a compound bearing one silanol group in the molecule and/or a compound which reacts with water to form a compound bearing one silanol group in the molecule. This composition can be cured at a high rate to give products of curing which are improved in elongation and residual surface tack and excellent in weather resistance. The composition is suitable for adhesives, pressure-sensitive adhesives, coating materials, sealants (sealing materials), waterproof materials, spraying compounds, templating materials, casting rubber materials and so on.

Description

Curable composition and use thereof

Technical Field

The present invention relates to a curable composition containing a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber having a structural unit derived from a norbornene compound having a specific vinyl terminal group as a nonconjugated polyene and containing a specific hydrolyzable silyl group in the molecule, and its use.

Background

(1) Many methods have been proposed for preparing propylene oxide-based polymers having at least one reactive silicon functional group in the molecule (as described below), some of which have been produced industrially. An organic polymer is polyoxypropyleneHaving methoxysilyl functional groups attached to the terminal end, e.g.Kaneka corporation (MS Polymer)^TM) Polymers made and sold. Depending on the purpose of use, the polymer has insufficient elongation of the cured product and remains tacky on the surface due to the influence of the composition and the use conditions.

Japanese patent laid-open publication No.34066/1986 discloses a composition for improving tensile properties, characterized in that it comprises a propylene oxide-based polymer having at least one reactive silicon functional group in the molecule, a compound having one silanol group in the molecule, and/or a compound capable of reacting with water to form a compound having one silanol group in the molecule.

Japanese patent laid-open publication No.34067/1986 discloses a curable elastic composition characterized in that it comprises an organic vinyl polymer having at least one reactive silicon functional group in the molecule, a compound having one silanol group in the molecule, and/or a compound capable of reacting with water to form a compound having one silanol group in the molecule.

Therefore, there is a need for improving the elongation and residual tackiness of the cured product of a curable elastic composition (curable rubber composition) while obtaining a cured product of high curing speed and high weather resistance.

(2) Saturated hydrocarbon-based polymers having at least one reactive silicon group in the molecule (substantially free of unsaturated C-C bonds except for aromatic rings) are known to have interesting properties of being able to crosslink even at room temperature: the reactive silicon group is hydrolyzed by moisture or the like to form a siloxane bond, which is a silicon-containing group having a hydrolyzable group bonded to a silicon atom and capable of forming a siloxane bond, to form a rubber-like cured product.

These saturated hydrocarbon-based polymers have a main chain composed of a saturated hydrocarbon, are resistant to thermal or light-induced deterioration, and give cured products excellent in heat resistance, weather resistance and gas barrier properties. Therefore, the saturated hydrocarbon-based polymer can be used, for example, as a sealing material for laminated glass and an elastic sealing material for buildings.

Silanol condensation catalysts are useful for crosslinking/curing polymers having reactive silicon groups. The use of such catalysts can reduce the curing time. In particular, a sealant for laminated glass, which is a product that must be delivered in a very short order period, needs to be cured very quickly. Thus, a strong silanol condensation catalyst is required for this purpose.

Japanese patent laid-open publication No.41360/1996 discloses a curable composition represented by the formula Q₂Sn(OZ)₂Or [ Q₂Sn(OZ)]₂A compound represented by O, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms, is used as a silanol condensing catalyst to accelerate the curing of a saturated hydrocarbon-based polymer having a reactive silicon group; z is an organic group having a functional group capable of forming a coordinate bond with Sn in its structure, or a monovalent hydrocarbon group of 1 to 20 carbon atoms. These curing catalysts tend to accelerate the cure of saturated hydrocarbon-based polymers faster than divalent tin-based curing catalysts (e.g., tin octoate) or tin carboxylate catalysts (e.g., dibutyltin dilaurate). However, for a product which must be delivered in a very short order period, such as a sealant for laminated glass, the curing time is also required to be shorter.

Some additives have been proposed to accelerate the silanol condensation reaction of saturated hydrocarbon-based polymers having reactive silicon groups. For example, Japanese patent laid-open publication No.97562/1990 discloses a curable composition using "a polyhydroxymonosilane having two or more silicon-bonded hydroxyl groups in the molecule". Japanese patent laid-open publication No.196842/1990 discloses a curable composition using "a silicon compound other than polysiloxane having two or more silicon-bonded hydroxyl groups and two or more silicon atoms in its molecule". The addition of one of the above additives, the curability of silanol compounds is indeed improved, however, still insufficient, and more effective additives are needed.

The sealant for laminated glass is required to have non-primer adhesion, i.e., to be quickly adhered to various objects without a primer. In recent years, the above properties have been required not only for sealants for laminated glass but also for sealants for other uses such as elastic sealants for buildings, in order to improve the application efficiency of the primer applied. However, the sealing material using the above-mentioned saturated hydrocarbon-based polymer having a reactive silicon group is insufficient in adhesion without an undercoat layer.

Japanese patent laid-open publication No.116832/1999 describes that the inventors, after extensive studies to solve the above problems, found that when a specific compound is incorporated into a composition, the composition can have improved curing speed and adhesion without causing problems such as deterioration of the properties of the cured product, and thus made the invention.

The invention disclosed by the above publication relates to a curable composition having improved curing speed and adhesion, characterized in that the composition comprises (A) a saturated hydrocarbon-based polymer having at least one reactive silicon group, (B) a tetravalent tin compound, and (C) a compound represented by the general formula R¹ _aSi(OR²)_4-aA silicon compound represented by the formula (wherein R¹AndR²Each is a hydrocarbyl group of 1 to 20 carbon atoms, which may be substituted or unsubstituted; "a" is an integer of 0 to 3). More specifically, the composition comprises (A)100 parts by weight of a saturated hydrocarbon-based polymer inHaving at least one reactive silicon group in the molecule and having a molecular weight of 500-50,000, (B)0.1 to 20 parts by weight of a tetravalent tin alcoholate, and/or (C)0.01 to 20 parts by weight of a compound of the formula R¹ _aSi(OR²)_4-aA silicon compound represented by the formula (wherein R¹Is an aryl group of 1 to 20 carbon atoms; r²Is a hydrocarbon group of 1 to 20 carbon atoms, which may be substituted or unsubstituted; "a" is an integer of 0 to 3).

The inventors of the present invention have re-examined the curable composition described in the above publication and confirmed that the curing speed is certainly improved, but it is still insufficient.

Therefore, the curable rubber composition is required to have higher curing speed, more excellent adhesion to various objects and weather resistance.

(3) An example of a reactive silicon group is represented by the formula-Si (OCH)₃)₃Indicates that it can be hydrolyzed into-Si (OH) by moisture in the air₃Which is reacted with another by silanol condensationA reactive silicon group reacts to form a siloxane bond (Si-O-Si). Therefore, the polymer containing the reactive silicon compound can be crosslinked/cured in the presence of moisture even at room temperature. Among these polymers, an oxyalkylene polymer having, for example, polyoxypropylene in the main chain skeleton has been widely used as a building sealant and other industrial applications because of its properties (e.g., being liquid at room temperature and being curable into a rubber elastomer). However, when the polymer is used to fill joints (i.e., gaps between building materials such as wall coverings) and the like, it leaves residual tackiness on the surface of the cured product even after curing, so that the surface is easily stained with dust or the like to deteriorate the appearance. A coating may be applied to the surface of the cured product. In this case, the coating material is not always sufficiently adhered to the surface of the sealing material, especially when a solvent-based coating material is used.

Japanese patent laid-open publication No.302213/1997 discloses a curable composition comprising (a) an oxyalkylene polymer having at least one reactive silicon group in the molecule and (b) a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule. The composition is said to retain only a very limited degree of residual tack and to have high adhesion to the coating after curing.

Nevertheless, improvement of these characteristics is still insufficient, and further improvement is demanded in curing speed and weather resistance of the cured product.

Therefore, the curable composition is required to have a high curing speed, to have little residual tackiness on the surface of the cured product, to have high weather resistance after curing, to have strong adhesion between a coating material and the surface of a sealing material when the coating material is applied, and to be useful as a sealing material, a primer, or the like.

(4) RTV (room temperature vulcanizable) silicone rubber is well known as a polymer which cures to form a rubber-like material even at low temperatures (room temperature), and has been used as a sealing material for buildings and various molding materials. However, RTV silicone rubbers containing polysiloxanes in the main chain are expensive and have some inadequate properties.

Thus, for example, Japanese patent laid-open publication No.156599/1975 proposes a rubber-based organic polymer curable at room temperature, such as RTV silicone rubber, which contains a rubber-based organic polymer in its main chain in place of a polysiloxane.

The polymer has a functional reactive silicon group curable by forming a siloxane bond, and is likeRTV silicone rubbers, like these, cure to form rubber-like materials even at room temperature by the following reaction. The polymer is less expensive than polysiloxane and has properties lacking in polysiloxane.Wherein X' is a hydrolyzable group.

The rubber is generally required to have tensile properties of low modulus and high elongation, and thus rubber-based organic polymers having a reactive silicon group are also required to have these tensile properties.

Japanese patent laid-open publication Nos. 34066/1986 and 34067/1986 propose to improve the modulus and elongation of a cured rubber-based organic polymer having a reactive silicon group by adding a monovalent silanol compound or a derivative thereof.

The compounds disclosed in the above two documents do not always sufficiently improve modulus and elongation, and even when modulus and elongation are improved, problems occur such as insufficient curing of the cured product to cause residual tackiness on the surface, insufficient performance as a molding material or a sealing material, and poor storage stability of the composition. In other words, in the conventional curable compositions containing a rubber-based organic polymer having a reactive silicon group, almost none of them can satisfy all the requirements, i.e., the cured product is excellent in modulus and elongation, no residual tackiness on the surface of the cured product, and the composition is excellent in storage stability.

Japanese patent laid-open publication No. 96648/1995 discloses a mixture of a rubber-based organic polymer having a functional reactive silicon group cross-cured by siloxane bonds and an organosiloxane compound. However, the curing speed and weather resistance of the mixture are still insufficient.

Therefore, there is a need for a curable composition comprising a rubber-based organic polymer having a reactive functional silicon group, which is rapidly cured with moisture, is excellent in tensile-related properties, can give a rubbery elastomer having no residual tackiness on the surface, and is improved in weather resistance and storage stability.

(5) It is known that vinyl resins containing hydrolyzable silyl groups are hydrolyzed with moisture in the air at ordinary temperature to form resins having a dense network structure, which are excellent in properties such as gloss, weather resistance, discoloration resistance and solvent resistance, hardness, adhesion to inorganic substrates.

Vinyl resins containing hydrolyzable silyl groups have a wide range of uses such as paints, adhesives, coatings, sealants and adhesives due to the above-mentioned excellent properties.

However, the adhesion of vinyl resins containing hydrolyzable silyl groups to organic substrates is not always satisfactory. For example, refinish automotive paints are required to adhere to the coating films of various conventional paints, especially melamine acrylic paints and melamine alkyd paints.

One known method of improving adhesion to melamine acrylic paints and melamine alkyd paints is the addition of amine-based silane coupling agents or variants thereof. However, this also causes problems such as a decrease in storage stability of the vinyl copolymer containing a hydrolyzable silyl group and easy discoloration.

Japanese patent laid-open publication No. 75567/1989 discloses a resin composition curable at room temperature, which comprises (A)100 parts by weight of a vinyl polymer containing silyl groups, the main chain of which mainly consists of a vinyl polymer chain, at least one silicon atom in the molecule being bonded to a hydrolyzable group at a terminal or in a side chain, (B)0.1 to 100 parts by weight of a specific silane compound, and (C)0 to 20 parts by weight of a curing catalyst. It is said that the adhesion of a vinyl copolymer containing hydrolyzable silyl groups to melamine alkyd paints or melamine acrylic paints is greatly improved when a specific silane compound is added. It has also been found that the resin composition curable at room temperature has improved properties such as hardness, solvent resistance and stain resistance of the cured coating film.

However, the weather resistance of the composition is not always satisfactory, and the document makes no mention of an ethylene/α -olefin/nonconjugated polyene random copolymer rubber at all.

Therefore, there is a need for a room temperature-curable rubber composition having a high curing speed, excellent weather resistance, and capable of obtaining a cured product of high adhesion.

(6) Compounds having reactive silyl groups are used in various applications such as paints, coatings, silane coupling agents, adhesives for rubbers and sealants due to the reactivity of the silyl groups thereof. Especially compounds having condensed silyl groups curable at room temperature (having reactive groups such as hydroxyl, acetoxy, oxime or alkoxy groups) are found to have wide use.

The compound having a condensed silyl group curable at room temperature is usually hydrolyzed in the presence of a curing catalyst, although the hydrolysis may be carried out without a catalyst by using moisture in the air. Well-known curing catalysts include organotin compounds such as dibutyltin dilaurate and dibutyltin dimaleate. However, when these curing catalysts are used, the curing speed is slow, and the curing acceleration effect is hardly exhibited at low-temperature heating around 60-80 ℃ and the curing speed is still low even at the baking temperature of 120-300 ℃. Therefore, a catalyst having a curing speed higher than that of the conventional organotin compound is required. There are problems to be solved when using catalysts for repairing automobiles and coating bridges (requiring fast-drying coatings), when using catalysts in applications requiring simple coating systems, such as new car production lines, curtain walls and precoated metals.

Japanese patent laid-open publication No.660/1990 discloses a curable composition comprising the following effective components:

(A) at least one compound having a silyl group selected from the group consisting of a polyester having at least one specific silyl group, a vinyl copolymer with acrylic acid or methacrylic acid, a diallyl phthalate-based compound and a diallyl phthalate-based copolymer;

(B) an amine compound selected from the group consisting of aliphatic amines, cycloaliphatic amines, modified cycloaliphatic polyamines, and ethanolamines,

(C) silane coupling agent of the formula Y₃-Si-Z, wherein Y is alkoxy; z is an alkyl group containing a functional group selected from amino groups which may be substituted by aminoalkyl groups or mercapto groups,

(D) a lacquer-based paint, an acryl varnish-based paint, an acrylic resin-based paint, a thermosetting acrylic-based paint, an alkyd paint, a melamine paint, an epoxy-based paint, or an organopolysiloxane.

This document also describes that a silyl group-containing compound having a hydrolyzable group can be cured more rapidly (particularly under heating) without any adverse effect on the properties of the cured product of a binder, an acrylic resin-based, a thermosetting acrylic-based coating, an alkyd coating, a melamine coating, an epoxy-based coating or an organopolysiloxane when a catalytic amount of a specific amine compound and a silane coupling agent are added and further a binder, an acrylic resin-based, a thermosetting acrylic-based coating, a melamine coating, an epoxy-based coating or an organopolysiloxane is added.

However, the present inventors have re-examined the composition, confirming that the curing speed is not sufficient and the weather resistance is not satisfactory, the above-mentioned document also describes a silyl group-containing compound having a hydrolyzable group, but does not mention an ethylene/α -olefin/nonconjugated polyene random copolymer rubber.

Therefore, there is a need for a curable rubber composition which can be easily cured at room temperature or under heating with moisture in the air, has a high curing speed, and is excellent in the weather resistance of the cured product.

(7) For example, Japanese patent laid-open publication No. 73998/1977 discloses an oxyalkylene-based polymer having a silicon-containing group to which a hydroxyl group and/or a hydrolyzable group are bonded to the silicon atom, and which can be crosslinked by forming a siloxane bond (such a silicon-containing group is hereinafter referred to as a reactive silicon group). The oxyalkylene-based polymer is generally represented by the following general formula:

wherein X' is a hydrolyzable group such as methoxy.

The oxyalkylene-based polymer having a reactive silicon group is cured at room temperature after forming siloxane bonds (Si-O-Si) between polymer molecules by the action of moisture in the air, and like the room-temperature curable silicone rubber, a rubber-likecured product is formed. The cured product has been used for, for example, sealants and adhesives because it has excellent properties such as elongation, strength and adhesion.

The rubber-like cured product must have various properties when used as a sealing material or the like, among which more important are the properties relating to stretching and adhesion to an object. The properties relating to the tensile include modulus, elongation and breaking strength, and as the properties of rubber, low modulus and high elongation are generally required. The adhesion includes the adhesive strength to an object and its weather resistance, and high adhesive strength and high weather resistance are required. Particularly, it is generally used as a sealing material for transparent building materials such as glass, which requires high weather resistance in terms of adhesive strength, particularly when exposed to sunlight.

Japanese patent laid-open publication No.34066/1986 proposes a composition comprising an oxyalkylene-based polymer having a reactive silicon group and a compound having a silanol group in the molecule and/or a compound having a hydrolyzable silicon group in the molecule (this compound is hereinafter referred to as monovalent silanol-based compound, and reacts with moisture to form a compound having a silanol group in the molecule), which gives a cured product of low modulus.

Japanese patent laid-open publication No. 182350/1982 discloses the use of a compound having an amino group and a silicon atom having a hydrolyzable group, such as gamma-aminopropyltrimethoxysilane (H)₂NCH₂CH₂CH₂Si(OCH₃)₃) Or gamma-aminopropylmethyldimethoxysilane (H)₂NCH₂CH₂CH₂Si(CH₃)(OCH₃)₂) Bonded to silicon atoms.

However, the composition comprising a compound having a silicon atom bonded to 3 hydrolyzable groups (e.g., γ -aminopropyltrimethoxysilane) has a disadvantage of deteriorating effect of a monovalent silanol-based compound due to increase in modulus of its cured product. On the other hand, the composition comprising a compound having a silicon atom bonded to two hydrolyzable groups (e.g., γ -aminopropylmethyldimethoxysilane) has a disadvantage that the weather resistance of the adhesive strength is insufficient although the modulus of the cured product thereof is hardly increased.

Japanese patent laid-open publication No. 117955/1990 proposes a composition comprising an oxyalkylene-based polymer having a reactive silicon group and a monovalent silanol-based compound, and incorporating a compound having an amino group and a silicon atom to which 2 hydrolyzable groups are bonded, and a small amount of a compound having an amino group and a silicon atom to which 3 hydrolyzable groups are bonded. The composition is curable and has improved properties with respect to modulus, adhesive strength to an object, and weatherability of adhesive strength. However, the curable product of the composition is still insufficient in weather resistance, and there is a room for further improvement.

Therefore, there is a need for a curable composition which is high in curing speed, gives a weather-resistant cured product, and is suitable for use as an adhesive, a sealant, or the like.

(8) For example, Japanese patent laid-open publication No. 73998/1977 discloses an oxyalkylene-based polymer having a silicon-containing group to which a hydroxyl group and/or a hydrolyzable group are bonded to the silicon atom, and which can be crosslinked by forming a siloxane bond (such a silicon-containing group is hereinafter referred to as a reactive silicon group). The oxyalkylene-based polymer is generally represented by the following general formula:wherein X' is a hydrolyzable group such as methoxy.

The oxyalkylene-based polymer having a reactive silicon group is cured at room temperature after forming siloxane bonds (Si-O-Si) between polymer molecules by the action of moisture in the air, and like the room-temperature curable silicone rubber, a rubber-like cured product is formed. The cured product has been used for, for example, sealants and adhesives because it has excellent properties such as elongation, strength and adhesion.

The polymer is typically used as a composition in admixture with a filler, for example to reduce costs. However, the addition of fillers greatly increases the viscosity of the composition, and thus it is technically necessary to use plasticizers to reduce the viscosity sufficiently to obtain a composition that can be processed by conventional methods.

The use of fillers or plasticizers generally causes a number of problems, the more serious of which is the deterioration of the storage stability, in particular leading to a reduction in the curing speed of the stored compositions.

Therefore, there is a need for a curable composition which is high in curing speed and storage stability (in particular, rapidly cured when used even after being stored for a long period of time) and can give a weather-resistant cured product.

(9) The vinyl-based resin containing silyl groups is characterized by the ability to be cured at room temperature with moisture, in particular in the air, which opens up a wide range of applications for the composition. However, the disadvantages of short storage time and insufficient weather resistance sometimes limit the applications.

Japanese patent laid-open publication No. 47747/1988 proposes an invention relating to a vinyl resin composition. The silyl group functionalized vinyl resin (A) used in the composition has at least one silyl group in the molecule and has a molecular weight of 1,000-20,000. The silyl group is represented by the formula:(in the formula, R₁And R₂Each is hydrogen or a monovalent hydrocarbon group selected from alkyl, aryl and aralkyl groups of 1 to 10 carbon atoms; x is halogen or a group selected from alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy and amino, at least one being alkoxy or phenoxy; "a" is an integer of 0 to 2).

This document describes that the curable composition is stable and comprises (A) the above-mentioned vinyl resin, (B) an alcohol and/or an alkyl orthoformate, and (C) an alkoxysilane compound. The document also mentions that the invention relates to a composition comprising a compound having a silyl group at a terminal or side chain. The composition can be cured at room temperature with moisture, especially in air, which is characteristic of silyl group-containing vinyl resins, and at the same time has long-term storage stability. Therefore, it is very suitable as a resin for solventless coating materials or high solid content coating materials, and these coating materials are attracting attention as non-polluting, energy-saving coating materials. It is specifically mentioned in this document that the resins of the invention have a lower molecular weight than conventional vinyl resins, which brings about an advantage: the resin can be more easily applied to non-fouling or high-solids type coatings. The silyl group containing vinyl resin used in the composition of the present invention can be easily obtained by, for example, reacting a vinyl resin having a C-C double bond with a hydrosilane compound in the presence of a group VIII transition metal catalyst.

However, the inventors of the present invention have newly examined the curable compositionand confirmed that, although the composition does have the above-mentioned characteristics, curability and weather resistance at room temperature are still insufficient.

Therefore, there is a need for a curable rubber composition which is high in storage stability and curing speed and gives a cured product of high resistance to weather.

(10) The silicon-containing group having a hydrolyzable group bonded to a silicon atom and crosslinkable by forming a siloxane bond (hereinafter referred to as a reactive silicon group) may be replaced with-Si (OCH)₃)₃Which represents a well-known functional group.

Hydrolyzing the functional group to-Si (OH) with moisture (e.g., moisture in air)₃Etc., which react with another reactive silicon group to form a siloxane bond (Si-O-Si) by silanol condensation.

Therefore, the polymer having a reactive silicon group can be crosslinked/cured even at room temperature in the presence of moisture. Among these polymers, a polymer having a rubber-based main chain skeleton is characterized by being a highly viscous liquid at room temperature and cured into a rubber elastomer, and is widely used as a sealing material for buildings and other industries. The sealing material is used for gaps (joints) of building materials, and is used for filling and maintaining waterproofness and airtightness after being cured.

Among these rubber-based polymers, a saturated hydrocarbon-based polymer (e.g., polyisobutylene) can give a cured product excellent in weather resistance, heat resistance and gas barrier properties. The high gas barrier property means high moisture barrier property, which is a disadvantage of curing polymers with moisture in the air because it takes a considerable time (one week or more) to completelycure the inside although it is cured on the surface quickly. Japanese patent laid-open publication No. 185565/1990 proposes a dispersion composition using a hydrate of a metal salt for rapidly allowing solidification deep into the interior thereof at room temperature.

The polymer having a reactive silicon group is usually used after mixing a silanol condensing catalyst (curing catalyst), a filler, a plasticizer, etc. to form a curable composition. There are two broad classes of curable compositions: single liquid component (one-liquid) and double liquid component types (two-liquid types). The one-liquid type curable composition is a liquid containing all of the above additives. It is convenient, does not require mixing prior to use, but must remain completely dehydrated to prevent curing prior to use. On the other hand, two-liquid type curable compositions are not convenient and require mixing before use, but do not have to be kept dehydrated as completely as a one-liquid type curable composition because polymers having reactive silicon groups are not easily cured in the absence of a silanol condensing catalyst even in the presence of a certain degree of moisture.

The hydrate of the metallic salt as described above cannot be used as a moisture source for curing a polymer used for producing a one-liquid type curable composition because the polymer starts to cure once mixed with the silanol condensing catalyst and the hydrate.

Titanium and tin compounds are commonly used as silanol condensation catalysts. Many of them decompose in the presence of moisture, and the silanol condensing catalyst is considered to be decomposed by the hydrate of the metallic salt. Therefore, when the metal salt hydrate is used as a moisture source, it is added to the curable composition immediately before the composition is used (cured), or to the main component (i.e., the component containing the polymer component) of the two-liquid type composition.

However, it is inconvenient to add the hydrate of the metallic salt immediately before the composition is used (cured). Moreover, the addition of the hydrate of the metallic salt to the main component causes another problem in that the viscosity of the main component increases, although to a limited extent, due to the curing of the polymer having a reactive silicon group.

A silane coupling agent is usually mixed in the sealing material as a tackifier. However, the silane coupling agent is easily reacted with moisture and cannot be added as an additive to the main component nor to the hardener. For example, silane coupling agents (e.g., gamma-isocyanatopropyltrimethoxysilane (ONCCH)₂CH₂CH₂Si(OCH₃)₃) When added to the main component) reacts with the hydrate of the metallic salt and is decomposed by the silanol condensing catalyst when added to the hardener, with the result that it can no longer function as a silane coupling agent, for example, to increase the tackiness.

Japanese patent laid-open publication No. 182992/1998 discloses a curable composition. The object of the invention is to provide a curable composition of a saturated hydrocarbon-based polymer having silicon-containing groups, for example, silicon-bonded hydrolyzable groups of moisture-curable polyisobutylene, crosslinkable by forming siloxane bonds, and a metal salt hydrate as a moisture source. The composition does not increase in viscosity upon storage. It is another object of the invention to provide a curable composition to which a compound having a reactive silicon group which can easily react with moisture, such as a compound like a silane coupling agent, can be added. The invention provides a two-liquid or multi-liquid type curable composition in which a hydrate of a metallic salt is mixed into a hardener containing a silanol condensing catalyst. Briefly, this invention provides a two-liquid component and multi-liquid component type curable composition comprising at least two liquids: (A) a main component of a saturated hydrocarbon-based polymer having a hydrolyzable group bonded to a silicon atom and also having a silicon-containing group crosslinkable by forming a siloxane bond, (B) a hardener containing a silanol condensing catalyst and a hydrate of a metallic salt.

However, the isobutylene-based polymer of this invention as a saturated hydrocarbon-based polymer still has an improvement because of insufficient curing speed and weather resistance.

This document does not mention a multi-liquid type curable rubber composition comprising at least two liquids, which contains a silyl group-containing ethylene/α -olefin/non-conjugated polyene random copolymer rubber having a structural unit derived from a norbornene compound having a specific vinyl terminal group as a non-conjugated polyene, and containing a specific hydrolyzable silyl group in the molecule.

Therefore, there is a need for a curable rubber composition which contains a metal salt hydrate as a moisture source, does not increase in viscosity upon storage, is high in curing speed and weather resistance, and can contain a compound having a reactive silicon group capable of reacting easily with moisture (e.g., a silane coupling agent).

(11) Japanese patent laid-open publication No. 6041/1988 discloses an isobutylene-based polymer having a silicon-containing group at the molecular terminal, which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and can be crosslinked by forming a siloxane bond (such a group is hereinafter referred to as a reactive silicon group). The isobutylene-based polymer is cured by moisture to give a rubber-like cured product even at ordinary temperature, which has excellent properties such as heat resistance, water resistance and weather resistance.

However, the cured product must have long molecular chains to obtain good rubber elasticity, which always increases the viscosity of the cured product, making it difficult to process. This disadvantage can limit its use due to the difficulty of application. Lowering the viscosity of the polymer in order to avoid the above problems always results in insufficient elongation-related properties of the polymer. The cured isobutylene-based polymer is strong in moisture barrier property, which deteriorates curability thereof because of insufficient supply of moisture necessary for curing.

In order to solve the above-mentioned problems, Japanese patent laid-open publication No. 252670/1989 proposes a curable resin composition comprising a saturated hydrocarbon-based polymer having at least one silicon-containing group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond, and an organosilicon polymer. However, the composition does not always sufficiently solve the above problems, and the cured product thereof is insufficient in weather resistance and curing speed.

Therefore, there is a need for a composition which is low in viscosity, good in workability, sufficient in curing speed, and excellent in weather resistance, heat resistance and water resistance, and which is capable of giving a rubber-like cured product having high strength and high elongation (low elastic modulus).

(12) As a result, the random copolymer rubber is used as a vulcanizable elastomer, which gives a vulcanized product having heat resistance and weather resistance much higher than those of diene-based elastomers (such as natural rubber, polyisoprene or polybutadiene).

From the viewpoint of vulcanization speed, the vulcanization speed is slow due to insufficient unsaturated C-C bond content, thereby limiting the line speed of vulcanization, which becomes a cause of cost increase.

Therefore, there is a need for a rubber composition having a high vulcanization speed, improved weather resistance and excellent mechanical strength while maintaining various advantageous properties of the ethylene/α -olefin/nonconjugated polyene random copolymer rubber, such as excellent heat resistance and chemical resistance of the vulcanized product.

(13) The polymer having a hydrolyzable silyl group having a hydroxyl group and a hydrolyzable group bonded to a silicon atom and capable of forming a siloxane bond is crosslinked/cured in the presence of moisture, and thus is useful as a curable composition. Among these polymers, a polymer in which a polyether is used as a main chain skeleton is generally called a modified siloxane, and is widely used as a sealing material or the like.

A mixture of a polymer having a hydrolyzable silyl group and a curable resin which is compatible with the polymer and curable with a different curing reaction shows phase separation upon curing, and can form cured products of various layered structures. The properties of the cured product obtained from the composition consisting of the hydrolyzable silyl group containing polymer and the epoxy resin compatible therewith greatly depend on the cohesion of the matrix. Japanese patent laid-open publication No. 292616/1992 proposes a method for incorporating a silane coupling agent to control the production of the cured product and for changing the content thereof.

The above-mentioned curable composition can be controlled to obtain a cured product of a layered structure. The modulus of elasticity and tensile shear strength of the curable resin composition can be improved because the size of the dispersed epoxy resin particles and the matrix strength can be varied over a wide range. However, the curing speed and weather resistance of the resin composition are still insufficient.

Therefore, there is a need for a rubber composition which is high in adhesiveness and curing speed, and which can give various types of cured products high in weather resistance and good in other properties, such as a cured product in which the layer structure is greatly changed, another cured product of low elastic modulus and high elongation, or another cured product of high elastic modulus and tensile shear strength achieved by reducing the size of dispersed epoxy resin particles and increasing the epoxy resin content of the matrix.

(14) A rubber-based organic polymer having a hydrolyzable silyl group, which, although having such an interesting property that it can be cured into a rubber elastomer even at room temperature, generally has a disadvantage of insufficient strength of the cured product, which limits its application fields.

Japanese patent laid-open publication No. 280217/1987 discloses a curable composition comprising a rubber-based organic polymer having a hydrolyzable silyl group and an epoxy resin, and incorporating two silicon compounds (one silicon compound having a functional group reactive with an epoxy group and a hydrolyzable silicon group in the molecule and the other silicon compound having at least two hydroxyl groups bonded to the silicon atom in the molecule) to overcome the disadvantages of the conventional cured rubber-based organic polymer having a hydrolyzable silyl group.

Incorporation of these silicon compounds into the curable composition can improve insufficient strength of the rubber-based organic polymer containing a hydrolyzable silicon group and give a high-strength cured product irrespective of the amount of moisture. However, the composition has drawbacks of insufficient curing speed and weather resistance of the cured product.

Therefore, there is a need for a curable rubber composition which has improved toughness and strength, can give a high-strength cured product irrespective of the amount of moisture, is high in curing speed, and gives a cured product having high weather resistance.

(15) A saturated hydrocarbon-based polymer containing a reactive silicon group which is crosslinked by hydrolysis with moisture and subsequent formation of siloxane bonds even at room temperature to obtain a rubber-like cured product. Therefore, it is used as a sealant for laminated glass and an elastic sealant for buildings.

The elastic sealing materials for construction are usually mixed with calcium carbonate fillers such as gelled calcium carbonate or limestone powder. The gelled calcium carbonate-containing composition used as a sealing material has high thixotropy, less filaments, and hence high operability. The cured product is suitable for use as a sealing material for buildings because of its tensile-related properties of low modulus and high elongation.

On the other hand, limestone powder is used as the filler.

Sealants for laminated glass are required to have sufficiently high modulus and strength to support glass, unlike sealants for buildings, which are required to have low modulus and high elongation. Therefore, it is essential that the sealant for laminated glass has mechanical properties (such as strength and hardness) and at the same time has good workability. However, a composition comprising a saturated hydrocarbon-based polymer containing a reactive silicon group does not satisfy these properties at the same time.

Japanese patent laid-open publication No. 316804/1998 discloses a curable composition comprising a saturated hydrocarbon-based polymer containing a reactive silicon group, in combination with calcium carbonate and talc, which can solve the problems of satisfying these properties. However, the proposed composition does not always sufficiently satisfy the workability and mechanical properties. And the curing speed and the weather resistance of the cured product are not satisfactory.

Thus, there is a need for a rubber composition having the following combination of properties: the cured product is sufficient in handling and mechanical properties, curing speed and weather resistance of the cured product, and is suitable as a sealant for laminated glass.

(16) Curable polymers are liquid or similarly moldable before curing, and when cured give a high strength solid, such as a rubbery solid. The curable polymers are widely used in adhesives and sealants. Adhesives and sealants for glass and plastics are also required to have the additional property of light resistance because surfaces using them are exposed to light unlike the case for opaque materials. When deteriorated by light, these materials may completely lose their function as an adhesive or a sealant due to peeling of the adhesive layer. As an important property for transparent materials, light resistance is required for adhesion, and adhesion at this time is called weather-resistant adhesion. In particular, the additional property of the adhesive or sealant for construction that maintains weather-resistant adhesion for a long period of time is required. When the adhesive layer is made of a material having insufficient weather resistance to any extent, the adhesive layer is thin and loses weather-resistant adhesion. There are not many materials that exhibit excellent weather-resistant adhesion.

The saturated hydrocarbon-based polymer containing a crosslinkable silicon group in the curable polymer is cured by, for example, the action of moisture in the air. It exhibits advantageous properties such as high weather resistance and heat resistance, adhesion in the presence of water, non-staining properties and low moisture permeability when cured. Moreover, the polymer shows good workability and can be sprayed smoothly because it can be a liquid at room temperature and has suitable viscosity and structural viscosity (thixotropy). Further, the polymer is not malodorous, hardly emits odor at the time of handling, and is particularly suitable for use as a sealing material (Japanese patent laid-open publication No. 6041/1988). Japanese patent laid-open publication No. 198673/1989 describes that the above-mentioned polymer can also be used as a sealing material for transparent materials such as laminated glass. When used for laminated glass, the above polymers bring advantages in that the production line production speed can be increased and the conventionally required double seal is replaced with a single seal because the above polymers can be rapidly cured upon heating. Needless to say, the polymer can be used for double sealing of laminated glass by a conventional method.

However, it has been found that when a curable composition comprising a saturated hydrocarbon-based polymer containing a crosslinkable silicon group is used for some transparent materials, particularly surface-treated glass (e.g., heat ray reflective type glass), the cured composition does not always exhibit sufficient weather-resistant adhesion.

Japanese patent laid-open publication No. 286895/1997 proposes a curable composition comprising a saturated hydrocarbon-based polymer having a crosslinkable silicon group, in admixture with a specific light stabilizer and a silane coupling agent, which composition has improved weather-resistant adhesion to surface-treated glass. However, the cured product still has insufficient weather resistance, and there is also room for improvement in curing speed.

Therefore, there is a demand for a curable composition which is high in curing speed, gives a cured product of high weather resistance, and is suitable for use as an adhesive and a sealant.

(17) There is known a polyalkylene oxide-based polymer (e.g., polypropylene oxide-based polymer) having a reactive silicon group at the molecular terminal thereof. The polymer is characterized by being capable of curing with moisture to a rubbery solid even at room temperature. However, the polymer has disadvantages of insufficient heat resistance, water resistance and weather resistance.

Therefore, there is a demand for a curable rubber composition containing a silyl group-containing rubber having a specific hydrolyzable silyl group in its molecule as a main component, which can give a cured product excellent in weather resistance and heat resistance.

(18) A saturated hydrocarbon-based polymer having at least one reactive silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and crosslinkable by forming a siloxane bond is known to have such an interesting property: even at room temperature, crosslinking can be achieved by formation of siloxane bonds accompanied by hydrolysis of reactive silicon groups or the like with moisture or the like, thereby forming a rubber-like cured product. Therefore, the polymer is useful as a sealant for laminated glass and an elastic sealant for construction, for example.

The sealant for laminated glass is required to have primer-free adhesion, i.e., to be quickly adhered to various objects without a primer. In recent years, the above properties have been required not only for sealants for laminated glass but also for sealants for other uses such as elastic sealants for buildings in order to improve the application efficiency of applying a primer. However, the sealing material using the above-mentioned saturated hydrocarbon-based polymer having a reactive silicon group is insufficient in adhesion without an undercoat layer.

Furthermore, the sealant for laminated glass (particularly, a material for glass edging) is particularly required to have excellent weather-resistant adhesion. The weather-resistant adhesion of the above-mentioned saturated hydrocarbon-based polymer having a reactive silicon group is insufficient for some reason, and particularly, the weather-resistant adhesion to highly insulating heat ray reflective glass which has been widely used in recent years is insufficient.

Japanese patent laid-open publication No. 152584/1998 discloses a curable composition comprising (A) a saturated hydrocarbon-based polymer containing at least one reactive silicon group, (B) a silane coupling agent, (C) a compound containing an unsaturated group in the molecule, which initiates polymerization by reacting with oxygen in the air, and/or a photopolymerizable compound. However, the curable composition still has a place to improve curing speed and weather resistance.

Therefore, a curable composition comprising a saturated hydrocarbon-based polymer having a reactive silicon group as a main component, which has high adhesion to various materials, improved weather-resistant adhesion to various glasses (particularly heat ray reflective glasses), and excellent weather resistance and curing speed, is demanded.

(19) A silicone-based adhesion promoter (a dimethylpolysiloxane rubber-based silicone resin) is known as a heat-resistant adhesion promoter.

However, it is generally known that the silicone-based tackifier has several disadvantages such as strong adhesiveness to a nonpolar compound (e.g., polytetrafluoroethylene) and strong compatibility with a so-called silicone release paper coated with a silicone release agent (since both contain silicone), which makes it difficult to release itself from the release paper, impairing the release effect thereof.

On the otherhand, tackifiers having good release properties include those composed of components having only one organic skeleton, such as rubber-based tackifiers, e.g., natural or synthetic rubbers blended with tackifier resins, and acrylic tackifiers obtained by copolymerization with acrylates. These tackifiers also have their own disadvantages, for example the former are of the non-crosslinked type and would not be expected to have high heat resistance, while the latter, although crosslinkable by the action of a crosslinking agent (such as isocyanate incorporated therein), may not give a crosslinked product having sufficient heat resistance per se. Therefore, they do not have sufficient heat resistance to be used as a tackifier.

In recent years, it has been proposed to use hydrolyzable silicon-containing groups capable of causing condensation reactions in organic backbone polymers to which the groups are added to form thermally stable siloxane crosslinks to obtain adhesion promoters with high heat resistance.

Such a tackifier composition is disclosed in, for example, Japanese patent laid-open publication No. 71377/1984. One disadvantage of this silicone crosslinking type tackifier is poor releasability, as with the silicone-based tackifiers described above, despite the fact that the polymeric backbone is essentially an organic backbone. More specifically, when the tackifier composition is adhered to a release paper or a release film coated with a silicone-based release agent, or when a laminate having the tackifier on one side of a substrate and the silicone-based release agent on the other side is wound, the peel resistance between the tackifier and the release paper or the release film increases with time, and the release paper may be torn when the worst case is, making it impossible to peel the paper.

As is generally known, a silicone-based release paper is generally used as an essential component of an adhesive tape, andthe above-mentioned so-called silicone-based tackifier is not well separated from the silicone-based release paper. Although it is considered to develop a release paper coated with a non-silicone-based (e.g., fluorine-based) release agent, the use of the tackifier on the release paper is very limited because it is not smoothly separated from the release paper.

Japanese patent laid-open publication No. 60771/1986 discloses an adhesion promoter composition comprising (A) an organic polymer containing at least one hydrolyzable silicon group in the molecule, (B) an adhesion promoter resin and (C) a specific organozirconium or aluminum as a curing catalyst. In view of the fact that there is no tackifier composition which has high heat resistance and can be well released from a release paper coated with a silicone-based release agent, the composition has been advanced. The composition is said to peel well from silicone-based paper or film.

However, further improvements in releasability and heat resistance are also required. Furthermore, improvements in weather resistance and curing speed are also major technical problems to be solved.

Therefore, there is a need for an adhesion promoter composition which has high heat resistance, is well releasable from a release paper or the like coated with a silicone-based release agent, and has high curing speed and weather resistance.

(20) Japanese patent laid-open publication No. 36395/1979 describes a vinyl resin containing a hydrolyzable silyl group in the terminal or side chain, which is not only excellent in gloss, weather resistance and discoloration resistance but also improved in adhesion to inorganic materials by the action of a hydrolyzable silicon group, and which is crosslinked with moisture (especially moisture in the air) at room temperature to form a resin of a dense network structure, thereby having high hardness, solvent resistance, water resistance, heat resistance and weather resistance.

However, according to Japanese patent laid-open publication No. 63351/1982, the vinyl-based resin having a hydrolyzable silicon group, although giving an excellent resin when cured in the presence of a curing catalyst, has a disadvantage of a short pot life in an open atmosphere, particularly when the vinyl-based resin having 3 hydrolyzable silyl groups contains a curing catalyst.

The above publication also illustrates the following problems.

Inventions aimed at improving shelf life in open atmospheres have been patented. For example, the invention disclosed in USP 4,043,953Is to improve the pot life of a polymeric organosilane in the presence of a curing catalyst, said polymer being prepared by copolymerizing: containing CH₂(ii) a monomer having a ═ C<group (excluding active hydrogen group-containing monomers such as hydroxyl, carboxyl and amido groups) and an acrylate alkoxysilane, methacrylate alkoxysilane or vinyl alkoxysilane in admixture with 0.5 to 15% by weight (based on the weight of the polymeric organosilane) of a compound of formula X_nSi(OR)_4-nA hydrolyzable reactive silane monomer of formula (I) wherein X is an organic group of 1 to 12 carbon atoms; r is methyl, ethyl, 2-methoxymethyl, 2-ethoxyethyl or an alkyl group having 5 or less carbon atoms; "n" is an integer of 0 to 2).

The curing catalyst used in the above invention comprises 0.1 to 5% by weight, preferably 0.2 to 1% by weight, of an organic acid such as p-toluenesulfonate and n-butylphosphate; metal salts of organic acids such as tin naphthenate, dibutyltin dilaurate, iron stearate, and lead octenate; organic amines such as boron isodiamine (borone isodiamine), methylene diamine and imidazole. However, the pot life in the examples was measured after storage of the polymeric organosilane, hydrolyzable reactive silane monomer and curing catalyst under closed conditions. This document does not mention the pot life in an open atmosphere, which is important in practice. In fact, the pot life of the polymeric organosilanes, hydrolysable reactive silane monomers and curing catalysts described in this us patent document in an open atmosphere is satisfactory only when organic amines are used, and in other cases short. However, resins cured in the presence of organic amines have the disadvantage of being stained by the amine, and there is also a need to develop further catalysts.

Japanese patent laid-open publication No. 63351/1982 discloses a composition showing an improved pot life in the above-mentioned case. This document discloses a composition having an improved pot life comprising

100 parts by weight of a vinyl resin containing a silyl group, the main chain of which consists essentially of a vinyl polymer having at least one silicon group bonded to a hydrolyzable group at a terminal or side chain in the molecule,

0.01 to 10 parts by weight of a curing catalyst selected from the group consisting of a mercaptide-type organotin compound having Sn-S bond, a sulfide-type organotin compound having Sn ═ S bond, a mixture of a carboxylate-type organotin compound and a mercaptide-type organotin compound having Sn — S bond, a mixture of a carboxylate-type organotin compound and a sulfide-type organotin compound having Sn ═ S bond, a mixture of a carboxylate-type organotin compound and an organic carboxylic acid anhydride, and a mixture of an organic carboxylate compound and an organic carboxylic acid anhydride.

The above silyl group containing vinyl resin may be prepared by reacting a hydrosilane compound with a vinyl resin having a C-C double bond in the presence of a group VIII transition metal catalyst, which describes that the vinyl resin used in the present invention is not limited, except that it contains a hydroxyl group, and suitable resins include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid, acid anhydrides such as maleic anhydride, epoxides such as glycidyl (meth) acrylate, amino compounds such as diethylaminoethyl acrylate and aminoethyl vinyl ether, amide compounds such as (meth) acrylamide, itaconic amide, α -ethyl acrylamide, crotonamide, fumaric amide, maleic amide and N-butoxymethyl (meth) acrylamide, and resins containing a copolymer as a main component selected from acrylonitrile, styrene, α -methyl styrene, propionic acid, and the like.

However, Japanese patent laid-open publication No. 63351/1982 does not mention the use of a mixture of ethylene, a α -olefin of 3 to 20 carbon atoms and a vinyl group (═ C ═ CH) at the terminal₂) An ethylene/α -olefin/nonconjugated polyene random copolymer rubber obtained by copolymerizing the norbornene compound of (a) in place of the vinyl resin.

Therefore, there is a need for a curable rubber composition comprising an ethylene/α -olefin/nonconjugated polyene random copolymer rubber containing a hydrolyzable silyl group in a terminal or side chain and a curing catalyst, which has an improved pot life in an open atmosphere, a high curing speed and excellent weather resistance.

(21) A curable composition containing an organotin compound is known, wherein the organotin compound is in the form of a saturated hydrocarbon-based polymer having at least one silicon-containing group which has a hydroxyl group or a hydrolyzable group attached to a silicon atom and can be crosslinked by forming a siloxane bond (the silicon-containing group is hereinafter referred to as a reactive silicon group). However, the curable composition has many problems such as low curing speed and residual tackiness, and insufficient curing of the film.

Japanese patent laid-open publication No.41360/1996 describes the use of a specific organotin compound to solve the above-mentioned problems. However, the composition is strongly required to further improve the curing speed. Meanwhile, improvement of weather resistance is a major problem to be solved.

Therefore, there is a need for a curable composition which can form a three-dimensional network structure with moisture in the air, rapidly cures into a solid having rubber-like elasticity, and is excellent in weather resistance.

(22) Saturated hydrocarbon-based polymers having at least one reactive silicon group in the molecule are known to have the following interesting properties: even at room temperature, crosslinking can be achieved by formation of siloxane bonds accompanied by hydrolysis of reactive silicon groups or the like with moisture or the like, thereby forming a rubber-like cured product. The polymer has excellent heat resistance, water resistance and weather resistance, and can be used as a sealing material for laminated glass and an elastic sealing material for buildings.

The sealant for laminated glass is required to have excellent primer-free adhesion, i.e., to be quickly adhered to various objects without a primer. In recent years, the above properties have been required not only for sealants for laminated glass but also for sealants for other uses (e.g., elastic sealants for buildings) in order to improve the application efficiency of applying the primer. However, the sealing material using the above-mentioned saturated hydrocarbon-based polymer having a reactive silicon group is insufficient in adhesion without an undercoat layer. Moreover, the curing speed and weather resistance of the polymer are not always satisfactory.

Therefore, there is a demand for a curable rubber composition comprising a rubber containing a hydrolyzable silyl group as a main component, which has a high curing speed, is excellent in adhesion to various objects and is excellent in weather resistance.

(23) Underbody coatings have been applied to the underside or other surfaces of the underbody of a vehicle body for a variety of purposes such as preventing damage from debris such as sand bouncing on the moving vehicle, rust prevention, and damping to reduce vibration and noise. The vehicle body also has a body seal material for preventing corrosion by rainwater, moisture, etc. at a position structurally difficult to be subjected to rust-proofing treatment, such as a joint between an inner panel and an outer panel. Vinyl chloride sol has been used as a material suitable for the above-mentioned use.

In recent years, there has been a strong demand for better properties of automotive coatings, such as better rust prevention and damping effects with thinner films (for weight reduction), and reduction of the baking temperature of automobiles or even implementation of a baking step from the viewpoint of resource and energy saving.

Vinyl chloride sols, while inexpensive and meeting minimum requirements, have one disadvantage: a sufficient rust prevention effect or chipping resistance (i.e., a breakage prevention effect) cannot be achieved at a low baking temperature because the vinyl chloride sol is slowly gelled. Moreover, the damping effect of the vinyl chloride sol itself is not very high, and tends to be further deteriorated when a thinner coating film is required.

Japanese patent laid-open publication No. 41349/1996 discloses a coating material for vehicles comprising a saturated hydrocarbon-based polymer having a reactive silicon group as a crosslinking group. Various properties of the coating are improved as compared with vinyl chloride sol, such as low-temperature baking-related properties, rust-preventing properties, chipping resistance and damping properties. However, these properties are still insufficient, and particularly the damping properties are yet to be further improved. Curing speed and weather resistance of the coating film are also desired to be improved.

Therefore, there is a demand for a curable composition (e.g., a coating material for vehicles) which has a high curing speed even at a low baking temperature, is rapidly cured, forms a uniform and stable coating film, and has excellent rust prevention, chipping resistance, damping properties and weather resistance even when the coating film is thin.

(24) Many industries, such as the construction, automotive and electrical industries, have used a variety of sealant materials for joining similar or dissimilar materials in assembly/production lines, as well as for other uses, such as reinforcement, repair and replacement. Various curing modes or backbone structures of the sealing material have been proposed for specific purposes. However, there is hardly any one of the sealing materials generally used for laminated glass which satisfies all of weather resistance, heat resistance, non-polluting property, low moisture permeability and weather-resistant adhesion. In addition, there are fewer sealing materials with less odor.

For example, a polysulfide-based sealant that is currently used, although having excellent weather resistance, heat resistance and non-polluting properties, is insufficient in low moisture permeability and cannot be independently used for single sealing.

The sealant is also insufficient in weather-resistant adhesion, which is one of the most important properties for sealing laminated glass for heat ray reflective glass that has been used in large quantities in recent years to save energy. In the production of laminated glass, an additional step of removing the heat ray-reflecting metal coating before filling the glass with a sealing material may be required. In addition, the sealant is still insufficient in terms of adhesion to hot water and low odor, and there are environmental problems in the process of producing laminated glass.

As another sealant for laminated glass, a condensation-curable silicone-based sealant which, although satisfying weather resistance, heat resistance, weather-resistant adhesion and low odor, does not have sufficient non-staining properties and low moisture permeability and cannot be used independently for single sealing.

Therefore, there is a need for a sealant for laminated glass which satisfies weather resistance, heat resistance, non-staining property, low moisture permeability, weather-resistant adhesion and less odor, and which is excellent in mechanical properties and can be produced at low cost.

(25) The sealing materials for laminated glass can be classified into two categories: a sealing material for primary sealing and a sealing material for secondary sealing. Depending on the specific application, the laminated glass may be sealed at its edges with one sealant (single sealing) or may be sealed with two sealants for primary sealing and secondary sealing (double sealing).

Butyl rubber-based hot-melt resin (hereinafter sometimes referred to as hot-melt butyl) is often used as a sealing material for primary sealing materials of single sealing and double sealing. It has the following characteristics.

Hot melt butyl is a solid or waxy polymer at room temperature and becomes fluid when heated at temperatures around 100 ℃ and 250 ℃. When used as an adhesive, it can adhere to a variety of bottom surfaces after melting by wetting these bottom surfaces. In the actual manufacturing of laminated glass, hot meltbutyl is discharged from a special applicator in which the hot melt butyl is heated to melt, and after application, cures as the sealant temperature rapidly decreases. Therefore, the hot melt butyl can be cured in a much shorter time than other reaction curing type sealing materials, so that the curing time can be greatly shortened, and the control and the treatment of the sealing material are facilitated. The hot melt butyl can simultaneously achieve a short procurement time and an improvement in productivity due to its good processability, and thus will play a more important role in the future laminated glass market.

However, the single-sealed laminated glass mainly using a hot-melt butyl group has low structural strength, and it is difficult to ensure the vapor barrier property inside the laminated glass for a long period of time. It has limited industrial use, for example, as a sealing material for showcase units which are to be replaced in a short period of time.

The secondary sealing in the double-sealed laminated glass is poor in vapor barrier property although mechanical properties (such as adhesion to glass) are high, and thus primary sealing is required. Thus structurally blocking the passage of vapor through the secondary seal with a hot melt butyl. The double-sealed laminated glass requires 2 kinds of sealing materials in the manufacturing process, and although the double-sealed laminated glass has longer durability than the single-sealed laminated glass, the double-sealed laminated glass has higher cost. Even the double-sealed laminated glass cannot maintain the primary seal, and when the secondary seal is aged, it is deteriorated to the level of the single-sealed glass.

The adhesiveness of hot melt butyl depends on the tackiness of butyl rubber and may be deteriorated by low temperature embrittlement. Furthermore, the sealing material is thermoplastic at high temperatures, may soften to cause the laminate components to deviate from each other, and therefore creep resistance at high temperatures is required to prevent the above problems.

The main drawback of the current thermoplastic hot melt butyl and reactive curing type sealants (e.g. polysulfide-based or silicone-based sealants) is that the properties (e.g. mechanical properties) fluctuate significantly with temperature, although the former are much better to handle. Thus, thermoplastic hot melt butyl tends to have narrower applications in terms of glass size and weight than reaction curable sealants.

Therefore, there is a demand for a sealant for laminated glass, which has improved temperature dependence of structural strength and adhesion to a substrate while maintaining the vapor barrier property of a hot melt butyl group, and is suitable as a sealant for laminated glass for primary sealing of double sealing or single sealing.

The present invention has the following objects.

(1) The present invention is intended to solve the problems encountered in the conventional technology (1) described above. Accordingly, it is an object of the present invention to provide a curable elastic composition (curable rubber composition) which is improved in elongation and surface residual tackiness of the cured product, is high in curing speed, and can give a cured product of high weather resistance. Also provides the use of the composition.

(2) Accordingly, the present invention has been made keeping in mind the above problems occurring in the conventional technology (2), and an object of the present invention is to provide a curable rubber composition which comprises, as a main component, a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber having a structural unit derived from a norbornene compound having a specific vinyl terminal group as a nonconjugated polyene and containing a specific hydrolyzable silyl group in the molecule, which has a high curing speed and is excellent in adhesion to various objects and weather resistance, and use of the composition.

(3) The present invention is intended to solve the problems encountered in the conventional technology (3) described above. Accordingly, another object of the present invention is to provide a curable composition which is high in curing speed, hardly leaves tackiness on the surface of the cured product, has high weather resistance after curing, is strong in adhesion between a coating material and the surface of a sealing material when the coating material is applied, and is useful as a sealing material, a primer and the like.

(4) The present invention is intended to solve the problems encountered in the conventional technologies (4) described above. Therefore, it is another object of the present invention to provide a curable composition comprising a rubber-based organic polymer having a reactive functional silicon group, which is rapidly curable with moisture, is excellent in tensile-related properties, can give a rubbery elastomer having no residual tackiness on the surface, and is improved in weather resistance and storage stability.

(5) The present invention is intended to solve the problems encountered in the conventional technology (5) described above. Therefore, another object of the present invention is to provide a rubber composition curable at room temperature, which has a high curing speed, is excellent in weather resistance, and can give a cured product of high adhesion. Also provided is the use of the composition.

(6) The present invention is intended to solve the problems encountered in the conventional technologies (6) described above. Therefore, another object of the present invention is to provide a curable rubber composition which can be easily cured at room temperature or under heating with moisture in the air, has a high curing speed, and is excellent in weather resistance.

(7) The present invention is intended to solve the problems encountered in the conventional technologies (7) described above. Accordingly, it is another object of the present invention to provide a curable composition which is high in curing speed, gives a weather-resistant cured product, and is suitable for use as an adhesive, a sealant or the like.

(8) The present invention is intended to solve the problems encountered in the conventional technology (8) described above. Therefore, another object of the present invention is to provide a curable composition which can be cured rapidly even when used after being stored for a long period of time and can give a weather-resistant cured product.

(9) The present invention is intended to solve the problems encountered in the conventional technologies (9) described above. Therefore, another object of the present invention is to provide a curable rubber composition which is high in storage stability and curing speed and can give a cured product of high weather resistance. Also provided is the use of the composition.

(10) The present invention is intended to solve the problems encountered in the conventional technologies (10) described above. Accordingly, it is another object of the present invention to provide a novel curable rubber composition comprising a hydrate of a metal salt as a moisture source. Also provided is the use of the composition.

It is still another object of the present invention to provide a curable rubber composition which does not increase in viscosity upon storage and is high in curing speed and weather resistance. Also provided is the use of the composition.

It is still another object of the present invention toprovide a curable rubber composition comprising a compound having a reactive silicon group which can easily react with moisture (e.g., a silane coupling agent), and use of the composition.

(11) The present invention is intended to solve the problems encountered in the conventional technologies (11) described above. Therefore, another object of the present invention is to provide a composition which is low in viscosity, good in workability, sufficient in curing speed, and excellent in weather resistance, heat resistance and water resistance, and which is capable of giving a rubber-like cured product having high strength and high elongation (low elastic modulus).

(12) Accordingly, it is another object of the present invention to provide a rubber composition which has a high vulcanization speed, improved weather resistance and excellent mechanical strength while maintaining various advantageous properties of an ethylene/α -olefin/nonconjugated polyene random copolymer rubber, such as excellent heat resistance and chemical resistance of the vulcanized product.

(13) The present invention is intended to solve the problems encountered in the conventional technologies (13) described above. Therefore, another object of the present invention is to provide a rubber composition having high adhesion; obtaining a cured product with a widely varying layered structure, low elasticity and high elongation; obtaining a cured product having dispersed epoxy resin (the content of epoxy resin in the matrix increases as its particle size decreases), high modulus of elasticity, and tensile shear strength; the curing speed of the rubber composition is sufficiently high to obtain a cured product of high weather resistance. Also provided is the use of the composition.

(14) The present invention is intended to solve the problems encountered in the conventional technologies (14) describedabove. Therefore, it is another object of the present invention to provide a curable rubber composition which has improved toughness and strength, can give a cured product of high strength irrespective of the amount of moisture, is high in curing speed, and gives a cured product of high weather resistance.

(15) The present invention is intended to solve the problems encountered in the conventional technologies (15) described above. It is therefore another object of the present invention to provide a rubber composition having a good balance of properties: workability and mechanical properties of the cured product, sufficient curing speed and weather resistance of the cured product, and is suitable as a sealant for laminated glass.

(16) The present invention is intended to solve the problems encountered in the conventional technologies (16) described above. Accordingly, it is another object of the present invention to provide a curable composition which is high in curing speed, gives a cured product of high weather resistance, and is suitable for use as an adhesive and a sealant.

(17) Accordingly, it is another object of the present invention to provide a curable rubber composition comprising, as a main component, a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber having a structural unit derived from a norbornene compound having a specific vinyl terminal group as a nonconjugated polyene and containing a hydrolyzable silyl group in the molecule, and a cured product thereof which is excellent in weather resistance and heat resistance, and use thereof.

(18) The present invention is intended to solve the problems encountered in the conventional technologies (18) described above. Therefore, it is another object of the present invention to provide a curable rubber composition comprising a saturated hydrocarbon-based polymer having a reactive silicongroup as a main component, which has high adhesion to various materials, improved weather-resistant adhesion to various glasses (especially heat ray reflective glasses), and excellent weather resistance and curing speed.

(19) The present invention is intended to solve the problems encountered in the conventional technologies (19) described above. Therefore, another object of the present invention is to provide an adhesion promoter composition which has high heat resistance, is well releasable from a release paper or the like coated with a silicone-based release agent, and is high in curing speed and weather resistance. Also provided is the use of the composition.

(20) Accordingly, it is another object of the present invention to provide a rubber composition comprising an ethylene/α -olefin/nonconjugated polyene random copolymer rubber having a hydrolyzable silyl group in a terminal or side chain and a curing catalyst, which has an improved pot life in an open atmosphere.

It is still another object of the present invention to provide a curable rubber composition which is high in curing speed and excellent in weather resistance. Also provides the application of the composition.

(21) The present invention is intended to solve the problems encountered in the conventional technologies (21) described above. Therefore, another object of the present invention is to provide a novel curable composition which can form a three-dimensional network structure with moisture in the air, is rapidly cured into a solid having rubber-like elasticity, and is excellent in weather resistance.

(22) Accordingly, it is another object of the present invention to provide a curable rubber composition comprising, as the main component, a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, which has a high curing speed and is excellent in adhesion to various objects and weather resistance.

(23) The present invention is intended to solve the problems encountered in the conventional technologies (23) described above. Therefore, another object of the present invention is to provide a curable composition (e.g., automotive coating) which has a high curing speed even at a low baking temperature, is rapidly cured, forms a uniform and stable coating film, and has excellent rust prevention, chipping resistance, damping properties and weather resistance even when the coating film is thin.

(24) The present invention is intended to solve the problems encountered in the conventional technologies (24) described above. Therefore, another object of the present invention is to provide a sealant for laminated glass which satisfies weather resistance, heat resistance, non-staining property, low moisture permeability, weather-resistant adhesion and little odor, and which is excellent in mechanical properties and can be produced at low cost.

(25) The present invention is intended to solve the problems encountered in the conventional technologies (25) described above. Therefore, another object of the present invention is to provide a sealant for laminated glass, which has improved temperature dependence of structural strength and adhesion to a substrate while maintaining the vapor barrier property of a hot melt butyl group, and is suitable as a sealant for laminated glass for primary sealing of double sealing or single sealing.

Summary of The Invention

The curable composition of the invention is characterized in that it comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structural unit derived from a norbornene compound having at least one specific vinyl terminal group (represented by the following formula (I) or (II)) as a nonconjugated polyene and containing a hydrolyzable silyl group (represented by the following formula (III)) in the molecule, and

a compound (B) having a hydroxyl group and/or a hydrolyzable group other than the rubber (A1).

Wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms.In the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms.Wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoximate, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy, and amino; "a" is an integer of 0 to 2.

The compound (B) having a hydroxyl group and/or a hydrolyzable group is preferably a silicon-containing compound.

The curable composition of the present invention includes the following compositions.

(1) A curable elastomeric composition characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

a compound having a silanol group and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule (B1).

(2) A vulcanizable rubber composition characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

a tetravalent tin compound (C), and

a silicon compound (B2) represented by the following general formula [ V]:

R⁴ _aSi(OR⁵)_4-a[V]in the formula, R⁴And R⁵Each is a substituted or unsubstituted hydrocarbyl group of 1 to 20 carbon atoms, "a" is 0, 1, 2, or 3.

(3) Curable composition, characterized in that it comprises:

(a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

(b) a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule (B3).

(4) Curable composition, characterized in that it comprises:

(a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

(b) an organosilicon compound (B4) represented by the following general formula [ VI]:

(R²(CH₃)₂SiO)_nR¹[VI]in the formula, R¹Is an alcohol residue or a weak acid residue, R²Is methyl or vinyl and "n" isA positive integer.

(5) A room temperature vulcanizable rubber composition characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

a silane compound (B5) represented by the following general formula [ VII-1]To [ VII-6]One of them represents: in the formula, R⁴Is a monovalent hydrocarbon group of 1 to 10 carbon atoms selected from the group consisting of alkyl, aralkyl and aryl groups;

x is a group selected from the group consisting of halogen, hydroxy, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoximoyloxy (ketoximate), mercapto and alkenyloxy;

R⁵is alkylene or arylene of 8 to 200 carbon atoms; r⁶Is a monovalent alkyl group of 8 to 200 carbon atoms; "n" is an integer of 0 to 2.

(6) Curable rubber composition, characterized in that it comprises as active component

A silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1),

an amine (D) selected from the group consisting of aliphatic amines, cycloaliphatic amines, modified cycloaliphatic polyamines and ethanolamine,

silane coupling agent (B6) represented by the general formula Y₃(Si) Z, wherein Y is alkoxy; z is an alkyl group containing a functional group selected from the group consisting of an amino group (which may be substituted or unsubstituted with an aminoalkyl group) and a mercapto group, and

a resin (E) composed of a clear coat base paint, an acrylic resin base paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy paint or organopolysiloxane.

(7) Curable composition, characterized in that it comprises:

(a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

(b) a silyl compound substituted with an amino group (B7).

(8) Curable composition, characterized in that it comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

a filler (F), a plasticizer (G), a curing catalyst (H), and an organic carboxylate compound (B8).

(9) A vulcanizable rubber composition characterized in that the composition comprises:

a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1),

an alcohol (B9), and/or a hydrolyzable ester compound (I) (other than the hydrolyzable organosilicon compound (B10)), and

a hydrolyzable organosilicon compound (B10).

(10) A two-liquid or multi-liquid type vulcanizable rubber composition comprising at least two liquid components characterized in that it comprises:

a main component (I) containing a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and a curing agent (II) comprising:

a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11).

Each of the curable compositions (1) to (10) may contain, in place of the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a1), a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a2) as described below.

Other curable compositions of the present invention are characterized in that they comprise a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) having a hydrolyzable silyl group (represented by the following general formula (1)) in the molecule, and a high molecular compound (K) other than the rubber (A2) and/or an inorganic filler (L):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime, amide, acid amide, aminoxy, thioAlkoxy, amino, mercapto and alkenyloxy; "a" is an integer of 0 to 2.

These curable compositions include the following compositions.

(11) A rubber composition characterized by comprising a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) and a silicone polymer (K1).

(12) A rubber composition characterized by comprising a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), an organic rubber (K2) and a crosslinking agent (M) for the organic rubber.

(13) A rubber composition characterized by containing a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), an epoxy resin (K3), a silane coupling agent (N), a silanol condensing catalyst (O) and a curing agent (P) for the epoxy resin.

(14) A rubber composition characterized by comprising a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), an epoxy resin (K3), a silicon compound (Q) having a hydrolyzable silyl group and a functional group capable of reacting with the epoxy group in the molecule, and a silicon compound (R) having at least two hydroxyl groups bonded to the silicon atom in the molecule.

(15) A rubber composition characterized by containing a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), calcium carbonate (L1) and talc (L2).

In the compositions (11) to (15), the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) generally has at least one silyl group represented by the following general formula (2) or (3):wherein R is a monovalent hydrocarbon groupof 1 to 12 carbon atoms; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; r³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, ammoniaA group, a mercapto group and an alkenyloxy group; "m" is an integer of 0 to 2 and "n" is an integer of 0 to 10.

It is particularly preferable to obtain a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) by reacting an ethylene/α -olefin/nonconjugated polyene random copolymer rubber with a silicon compound, and adding the SiH group in the silicon compound to the double bond of the copolymer rubber, said rubber comprising a norbornene compound having at least one vinyl terminal group as a nonconjugated polyene, represented by the following general formulae (4) and/or (5): in the formula, R¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; r³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; "n" is an integer of 0 to 10,

the silicon compound is represented by the following general formula (6):

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2.

Each of the curable compositions (11) to (15) may contain a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a1) in place of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a 2).

Other curable compositions of the present invention are characterized in that they contain a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a stabilizer.

(16) A curable composition, characterized in that the composition comprises (a) a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), (b) a nickel-containing light stabilizer (S), and (c) a silane coupling agent (T).

(17) A vulcanizable rubber composition characterized in that the composition comprises:

a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a sulfur-based aging inhibitor (U).

(18) A curable composition characterized by comprising a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a compound (V) having an unsaturated group capable of causing polymerization by reacting with oxygen in the air and/or a photopolymerizable material in the molecule.

Each of the curable compositions (16) to (18) may contain a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a2) in place of the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a 1).

Other curable compositions of the present invention are characterized in that they contain a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a silanol catalyst.

(19) Tackifier composition, characterized in that the composition comprises a silyl group-containing ethylene/α -olefin/nonconjugated polyene randomcopolymer rubber (A1),

a tackifier resin (W), and

a curing catalyst (H) comprising the following general formula [ VIII]An organozirconium compound represented by the formula (H1) or the following general formula [ IX []]Organoaluminum compound (H2) represented:

wherein "n" is an integer of 0 to 4.

R is a monovalent hydrocarbon group of 1 to 20 carbon atoms,

y is a group selected from the group consisting of a hydrocarbon group of 1 to 8 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, a cyanoalkoxy group and an amino group, which may be the same or different, andwherein "p" is an integer of 0 to 3.

R is a monovalent hydrocarbon group of 1 to 20 carbon atoms,

y is a group selected from the group consisting of a hydrocarbon group of 1 to 8 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, a cyanoalkoxy group and an amino group, which may be the same or different.

(20) A rubber composition having improved pot life, characterized in that the composition comprises:

a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1),

the curing catalyst (H) includes a mercaptide-type organotin compound having Sn — S bond (H3), a sulfide-type organotin compound having Sn ═ S bond (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds and a carboxylic acid-type organotin compound (H7).

(21) Curable composition, characterized in that it comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

the compound (H8) as the curing catalyst (H) is represented by the general formula Q₂Sn(OZ)₂Or [ Q]₂Sn(OZ)]₂O represents, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn therein.

(22) A vulcanizable rubber composition characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and

titanate (Y).

Each of the curable compositions (19) to (22) may contain a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a2) in place of the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a 1).

Other curable compositions of the invention include the following.

They are crosslinkable rubber compositions comprising an organic polymer (Z) containing the following formula [ III]A hydrolyzable silyl group represented by (a) and having substantially no unsaturated double bond in its main chain, a compound (B), preferably a silicon-containing compound having a hydroxyl group and/or a hydrolyzable group; these crosslinkable rubber compositions are useful for electric/electronic parts, transportation machinesAnd civil engineering/construction, medical and leisure areas:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2.

More specifically, these compositions include the following respective compositions.

(1) A curable elastomer composition which is a crosslinkable rubber composition, characterized in that it comprises:

an organic polymer (Z), and

a compound having a silanol group in the molecule and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule (B1),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(2) A vulcanizable rubber composition, crosslinkable, characterized by comprising:

an organic polymer (Z) which is a polymer of,

a tetravalent tin compound (C), and

a silicon compound (B2),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(3) Curable composition, characterized in that it comprises:

(a) an organic polymer (Z), and

(b) a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule (B3),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(4) Curable composition, characterized in that it comprises:

(a) an organic polymer (Z), and

(b) an organosilicon compound (B4) represented by the following general formula [ VI]:

(R²(CH₃)₂SiO)_nR¹[VI]in the formula, R¹Is an alcohol residue or a weak acid residue, R²Is methyl or vinyl, "n" is a positive integer,

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(5) A rubber composition which is crosslinkable and curable at room temperature, characterized in that it comprises:

an organic polymer (Z), and

a silane compound (B5),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(6) Curable rubber composition which is crosslinkable, characterized in that it comprises as active component

An organic polymer (Z) which is a polymer of,

an amine (D) selected from the group consisting of aliphatic amines, cycloaliphatic amines, modified cycloaliphatic polyamines and ethanolamine,

silane coupling agent (B6) represented by the general formula Y₃(Si) Z, wherein Y is alkoxy; z is an alkyl group containing a functional group selected from the group consisting of an amino group (which may be substituted or unsubstituted with an aminoalkyl group) and a mercapto group, and

a resin (E) composed of a varnish-based paint, an acrylic resin-based paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy paint or organopolysiloxane,

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(7) Curable composition, characterized in that it comprises:

(a) an organic polymer (Z), and

(b) a silyl compound substituted with an amino group (B7),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(8) A curable composition, characterized in that the composition comprises an organic polymer (Z), a filler (F), a plasticizer (G), a curing catalyst (H) and an organic carboxylate compound (B8), and is useful for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(9) A vulcanizable rubber composition characterized in that the composition is crosslinkable and comprises:

an organic polymer (Z) which is a polymer of,

an alcohol (B9), and/or a hydrolyzable ester compound (I) (other than the hydrolyzable organosilicon compound (B10)), and

a hydrolyzable organosilicon compound (B10),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(10) A curable, crosslinkable rubber composition of the two-liquid or multi-liquid type, consisting of at least two liquids, characterized in that it comprises:

a main component (I) containing an organic polymer (Z),

a curing agent (II) comprising:

a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

The rubber composition of the present invention is crosslinkable and comprises an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain, a high-molecular compound (K) other than the polymer (Z1) and/or an inorganic filler (L),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.Wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoximoyloxy, amide, acid amide, aminooxy, thioalkoxy, thioloxy, and mixtures thereof,Amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2.

These rubber compositions include the following compositions.

(11) A rubber composition which is crosslinkable, characterized in that it comprises an organic polymer (Z1) and a silicone polymer (K1),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(12) A rubber composition which is crosslinkable, characterized in that the composition comprises an organic polymer (Z1), an organic rubber (K2) and a crosslinking agent (M) for the organic rubber (K2),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(13) A rubber composition which is crosslinkable, characterized in that the composition comprises an organic polymer (Z1), an epoxy resin (K3), a silane coupling agent (N), a silanol condensing catalyst (O) and a curing agent (P) for the epoxy resin,

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(14) A rubber composition which is crosslinkable, characterized in that it comprises:

an organic polymer (Z1),

epoxy resin (K3),

A silicon compound (Q) having a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group in the molecule,

a silicon compound (R) having at least two hydroxyl groups bonded to a silicon atom in the molecule,

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(15) A rubber composition which is crosslinkable and is characterized in that it comprises an organic polymer (Z1), calcium carbonate (L1) and talc (L2),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(16) A curable composition, characterized in that the composition comprises (a) an organic polymer (Z), (b) a nickel-containing light stabilizer (S) and a silane coupling agent (T), and is useful for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(17) A rubber composition which is crosslinkable and characterized in that it comprises an organic polymer (Z) and a sulfur-based aging inhibitor (U),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(18) Curable composition, characterized in that the composition comprises an organic polymer (Z) and a compound (V) containing in the molecule an unsaturated group capable of causing polymerization by reacting with oxygen in the air and/or a photopolymerizable material,

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(19) A tackifier composition which is a crosslinkable rubber composition, characterized in that the composition comprises:

an organic polymer (Z) which is a polymer of,

a tackifier resin (W), and

a curing catalyst (H) comprising an organozirconium compound (H1) or an organoaluminum compound (H2), which is useful for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(20) A rubber composition which is crosslinkable, characterized in that it comprises:

an organic polymer (Z), and

curing catalysts (H) including a mercaptide-type organotin compound having Sn — S bond (H3), a sulfide-type organotin compound having Sn ═ S bond (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds with a carboxylic acid-type organotin compound (H7) are used in electric/electronic devices, transportation machines, and civil engineering/construction, medical and leisure areas.

(21) Curable composition, characterized in that the composition comprises

An organic polymer (Z), and

the compound (H8) as the curing catalyst (H) is represented by the general formula Q₂Sn(OZ)₂Or [ Q]₂Sn(OZ)]₂O represents a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn therein, which is useful for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(22) A vulcanizable rubber composition characterized in that the composition comprises:

an organic polymer (Z) and a titanate (Y),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

(23) A curable composition characterized in that it comprises a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

In the above-mentioned curable composition (23), a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) may be used in place of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The electric/electronic parts to which the composition of the present invention can be applied include compositions for heavy electric parts, electronic parts, sealing materials for electric/electronic device circuits and substrates, encapsulating materials, coating materials and adhesives, repairingmaterials for covering electric wires, insulating sealing materials for electric wire connecting parts, rollers for office automation equipment, vibration damping materials, and sealing materials for gels and capacitors.

The sealing material can be used in refrigerators, freezers, washing machines, gas meters, microwave ovens, steam irons and earth leakage circuit breakers.

The encapsulating material can be used for high-voltage transformer circuits, printed wiring boards, high-voltage transformers equipped with variable resistors, electrical insulating devices, semiconductor devices, conductive devices, solar cells, and flyback transformers for televisions.

The coating material can be used for coating thick film resistors of high voltage devices and circuit elements for hybrid integrated circuits; HIC; an electrically insulating member; a semiconductor component, a conductive member; a module; printing a circuit; a ceramic substrate; a buffer material for a diode, a transistor, and a connection line; a semiconductor device; and an optical fiber for optical communication.

The adhesive may be used to bond Cathode Ray Tube (CRT) high voltage wedges or necks, electrically insulating components, semiconductor components, and conductive components.

Transport aircraft in which the compositions of the present invention may be used include automobiles, ships, aircraft, and railway vehicles.

More specifically, the composition of the present invention can be used in the following fields. They are useful in automobiles as sealing materials for engine gaskets, electrical components, and fuel filters; packaging materials for igniter HIC and hybrid integrated circuits; coating materials for vehicle bodies, window glasses, and engine control substrates; and adhesives for oil pan gaskets, timing belt covers, braids (braids), headlamplenses, sunroof seals, and rearview mirrors.

The compositions of the present invention are also useful in ships as wire connection/distribution boxes, electrical system components, and wire sealing materials; and adhesives for electrical wires and glass.

The composition of the invention can also be used in the civil engineering/construction field, as a sealant for construction materials, for the following joints: butt joints in commercial architectural glass curtain wall methods, glass edge joints with window frames, interior joints in sanitary fixtures, toilets and showcases, joints around bath tubs, joints in exterior flexible joints and siding for prefabricated houses; a sealing material for laminated glass; sealing materials for civil engineering (for example for road repair); coatings/adhesives for metals, glass, stone, slate, concrete and tile; an adhesive sheet, a waterproof sheet, and a vibration-proof sheet.

The composition of the present invention can be used in the medical field, for example, a sealing material for rubber stoppers for medical use, syringe gaskets, and rubber stoppers for hypotensive tubes.

The compositions of the invention may also be used in leisure areas, such as swimming caps, diving masks and earplugs for swimming; gel cushioning materials for athletic shoes and baseball gloves.

The main fields of curable compositions of the invention may relate to sealants, potting agents, coating materials and adhesives.

Curable compositions for sealants, potting agents, coating materials and adhesives include crosslinkable rubber compositions comprising an organic polymer (Z) and a compound (B), preferably a silicon-containing compound having hydroxyl and/or hydrolyzable groups.

More specifically, these compositions include the followingrespective compositions.

(1) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition containing

An organic polymer (Z), and

a compound having a silanol group in the molecule and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule (B1).

(2) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition containing

An organic polymer (Z) which is a polymer of,

a tetravalent tin compound (C), and

a silicon compound (B2).

(3) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable composition containing

(a) An organic polymer (Z), and

(b) a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule (B3).

(4) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable composition containing

(a) An organic polymer (Z), and

(b) an organosilicon compound (B4) represented by the following general formula [ VI]:

(R²(CH₃)₂SiO)_nR¹[VI]in the formula, R¹Is an alcohol residue or a weak acid residue, R²Is methyl or vinyl and "n" is a positive integer.

(5) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is a crosslinkable rubber composition comprising

An organic polymer (Z), and

a silane compound (B5).

(6) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition containing, as an active ingredient

An organic polymer (Z) which is a polymer of,

an amine (D) selected from the group consisting of aliphatic amines, cycloaliphatic amines, modified cycloaliphatic polyamines and ethanolamine,

silane coupling agent (B6) represented by the general formula Y₃(Si) Z, wherein Y is alkoxy; z is an alkyl group containing a functional group selected from the group consisting of an amino group (which may be substituted or unsubstituted with an aminoalkyl group) and a mercapto group,

a resin (E) composed of a clear coat base paint, an acrylic resin base paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy paint or organopolysiloxane.

(7) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition containing

(a) An organic polymer (Z), and (B) a silane-based compound (B7) substituted with an amino group.

(8) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable composition comprising

An organic polymer (Z), a filler (F), a plasticizer (G), a curing catalyst (H), and an organic carboxylate compound (B8).

(9) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable rubber composition containing

Anorganic polymer (Z) which is a polymer of,

an alcohol (B9), and/or a hydrolyzable ester compound (I) (other than the hydrolyzable organosilicon compound (B10)), and

a hydrolyzable organosilicon compound (B10).

(10) ' A sealant, a potting agent, a coating material or an adhesive, characterized by being composed of a two-liquid component or multi-liquid component type crosslinkable rubber composition comprising at least two liquids, characterized by comprising:

a main component (I) containing an organic polymer (Z),

a curing agent (II) comprising:

a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11).

The composition of the present invention is also useful as a sealant, a potting agent, a coating material or an adhesive, and is characterized by being composed of a crosslinkable rubber composition comprising an organic polymer (Z1), a high-molecular compound (K) other than the polymer (Z1) and/or an inorganic filler (L). More specifically, these compositions include the following respective compositions.

(11) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition containing an organic polymer (Z1) and a silicone polymer (K1).

(12) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition comprising an organic polymer (Z1), an organic rubber (K2) and a crosslinking agent (M) for the organic rubber (K2).

(13) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition comprising an organic polymer (Z1), an epoxy resin (K3), a silane coupling agent (N), a silanol condensing catalyst (O) and a curing agent (P) for the epoxy resin.

(14) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition comprising an organic polymer (Z1), an epoxy resin (K3), a silicon compound (Q) having a functional group reactive with an epoxy group and a hydrolyzable silyl group in the molecule, and a silicon compound (R) having at least two hydroxyl groups bonded to a silicon atom in the molecule.

(15) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition comprising an organic polymer (Z1), calcium carbonate (L1) and talc (L2).

(16) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable composition comprising (a) the organic polymer (Z), (b) the nickel-containing light stabilizer (S) and (c) the silane coupling agent (T).

(17) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a crosslinkable rubber composition comprising an organic polymer (Z) and a sulfur-based aging inhibitor (U).

(18) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable composition comprising an organic polymer (Z) and a compound (V) containing in the molecule an unsaturated group capable of causing polymerization by reacting with oxygen in the air and/or a photopolymerizable material.

(20) ' A sealant, a potting agent, a coating material or an adhesive, characterized by being composed of a crosslinkable rubber composition comprising:

an organic polymer (Z), and

the curing catalyst (H) includes a mercaptide-type organotin compound having Sn — S bond (H3), a sulfide-type organotin compound having Sn ═ S bond (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds and a carboxylic acid-type organotin compound (H7).

(21) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable composition comprising

An organic polymer (Z), and

the compound (H8) as the curing catalyst (H) is represented by the general formula Q₂Sn(OZ)₂Or [ Q]₂Sn(OZ)]₂O represents, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn therein.

(22) ' A sealant, a potting agent, a coating material or an adhesive, characterized in that it is composed of a curable rubber composition comprising an organic polymer (Z) and a titanate (Y).

(23) ' A coating material for vehicles, characterized in that it comprises a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

(24) ' A sealant, a potting agent, a coating material for vehicles or an adhesive, characterized in that it is composed of a curable composition containing a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

(25) ' A sealant for laminated glass, characterized in that the material contains

A silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), a curing catalyst (H), and water or a metal salt hydrate (B11).

(26) ' A sealant for laminated glass, characterized in that the material contains

A silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), a hot-melt resin (X), a curing catalyst (H) and water or a metal salt hydrate (B11).

The silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) usually contains at least one silyl group-containing unit represented by the general formula (2) or (3).

It is particularly preferable that the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) is obtained by reacting an ethylene/α -olefin/nonconjugated polyene random copolymer rubber with a silicon compound represented by the general formula (6) such that the SiH group in the silicon compound is added to the double bond of the copolymer rubber, said copolymer rubber containing a norbornene compound having at least one vinyl terminal as a nonconjugated polyene, as represented by the general formulae (4) and/or (5).

In the sealants, potting agents, coating materials or adhesives (23) 'to (26)', the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) may also be used in place of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and vice versa.

Best mode for carrying out the invention

More specifically, the curable composition of the present invention and its use are described.

Curable elastomer composition (1)

The curable elastomer composition (1) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a compound having a silanol group and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule (B1) [ silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1)]

The silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) of the present invention comprises the following general formula [ III]The hydrolyzable silyl group represented can be represented by, for example, a specific ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) Reaction with specific silicon compounds (hydrosilylation reaction) to give:

in the formula [ III], R is a monovalent hydrocarbon group of 1 to 12 carbon atoms, which may be substituted or unsubstituted, and is preferably a monovalent hydrocarbon group free of aliphatic unsaturated bonds, including alkyl groups such as methyl, ethyl, propyl, butyl, hexyl or cyclohexyl; aryl groups such as phenyl or tolyl; or the above groups in which hydrogen atoms bonded to carbon atoms are substituted in whole or in part with halogen such as fluorine.

X is a hydrolyzable group selected from hydride (-H), halogen, alkoxy (-OR), acyloxy (-ORO), ketoxime salt, amide (-OR), acid amide (-OR), aminoxy (-AMO), mercapto (-SH), alkenyloxy (-OR, thioalkoxy (-OR), and amino (-OR).

Specific examples of the halogen, alkoxy, acyloxy, ketoxime salt, acid amide and thioalkoxy group as X in the formula [ IV]will be explained below.

"a" is an integer of 0 to 2, preferably 0 or 1.

Ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀)

Ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A) used in the invention₀) Is a random copolymer of ethylene, an α -olefin of3 to 20 carbon atoms and a nonconjugated polyene.

Specific examples of the α -olefin of 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene.

Among them, α -olefins of 3 to 10 carbon atoms are more preferable, particularly propylene, 1-butene, 1-hexene and 1-octene.

These α -olefins may be used alone or in combination of two or more.

The nonconjugated polyene used in the present invention is a norbornene compound having a vinyl group at the terminal represented by the following general formula (I) or (II).

"n" is an integer of 0 to 10,

R¹is a hydrogen atom, or

Alkyl groups of 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, nonyl and decyl;

R²is a hydrogen atom, or

R¹Examples of the alkyl group include alkyl groups of 1 to 5 carbon atoms.

In the formula, R³Is a hydrogen atom, or

1 to 10 carbon atomsWith R as specific examples¹The same applies to the example of (1).

Specific examples of the norbornene compound represented by the general formula (I) or (II) include: 5-methylene-2-norbornene, 5-vinyl-2-norbornene,5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2, 3-dimethyl-3-butenyl) -2-norbornene, alpha-hydroxy-methyl-ethyl-methyl-2-norbornene, alpha-hydroxy-methyl-ethyl-2-norbornene, alpha-methyl-2, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3, 4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1, 2-dimethyl-5-hexenyl) -2-norbornene, alpha-hydroxy-methyl-ethyl-2-norbornene, alpha-methyl-ethyl-5-hexenyl-2-norbornene, alpha-methyl-2-norbornene, 5- (5-Ethyl-5-hexenyl) -2-norbornene and 5- (1, 2, 3-trimethyl-4-pentenyl) -2-norbornene. Of these, more preferable are 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene. These norbornene compounds may be used alone or in combination.

In addition to the use of the above norbornene compound (e.g., 5-vinyl-2-norbornene), a non-conjugated polyene shown below may be used as long as it does not adversely affect the object of the present invention.

More specifically, these non-conjugated polyenes include straight-chain type non-conjugated polyenes such as 1, 4-hexadiene, 3-methyl-1, 4-hexadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1, 4-hexadiene, 4, 5-dimethyl-1, 4-hexadiene and 7-methyl-1, 6-octadiene; cyclic nonconjugated polyenes such as methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; and trienes such as 2, 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2, 2-norbornadiene.

Ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A) comprising the above-mentioned components₀) Has the following properties.

(i) Molar ratio of ethylene to α -olefin of 3 to 20 carbon atoms (ethylene/α -olefin)

In the case of an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) Wherein the molar ratio of the component unit (a) derived from ethylene to the component unit (b) derived from α -olefin having 3 to 20 carbon atoms (hereinafter sometimes abbreviated as "α -olefin") [ (a)/(b) molar ratio]40/60 to 95/5, preferably 50/50 to 90/10, more preferably 55/45 to 85/15, particularly preferably 60/40 to 80/20.

When the molar ratio (a)/(b) is within the above range, the rubber composition obtained from the random copolymer rubber can form a crosslinked rubber molded article excellent in aging resistance upon heating, strength characteristics and rubber elasticity, and also excellent in low-temperature resistance and moldability.

(ii) Iodine number

Ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) The iodine value of (A) is from 0.5 to 50 (g/100 g), preferably from 0.8 to 40 (g/100 g), more preferably from 1 to 30 (g/100 g), still more preferably from 1.5 to 25 (g/100 g).

When the iodine value is within the above range, the random copolymer rubber can obtain a desired content of hydrolyzable silyl groups, and the resulting rubber composition can form a crosslinked rubber molded article having excellent compression set resistance and aging resistance under the use conditions (i.e., under heating). An iodine value exceeding 50 is disadvantageous in terms of cost and is therefore undesirable.

(iii) Intrinsic viscosity

Ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) The intrinsic viscosity (η) measured in decalin at 135 ℃ is in the range of 0.001 to 2dl/g, preferably 0.01 to 2dl/g, more preferably 0.05 to 1.0dl/g, still more preferably 0.05 to 0.7dl/g, most preferably 0.1 to 0.5 dl/g.

When the intrinsic viscosity (η) is within the above range, the random copolymer rubber can give a rubber composition excellent in flowability, which can provide a crosslinked rubber molded article excellent in strength characteristics and compression set resistance.

(iv) Molecular weight distribution (Mw/Mn)

Ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) The molecular weight distribution (Mw/Mn), as measured by Gel Permeation Chromatography (GPC), is in the range of 3 to 100, preferably 3.3 to 75, more preferably 3.5 to 50.

When the molecular weight distribution (Mw/Mn) is within the above range, the resulting rubber composition of the random copolymer rubber can form a crosslinked rubber molded article having excellent processability and strength characteristics.

Ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) Is obtained by random copolymerization of ethylene, α -olefin having 3 to 20 carbon atoms and a norbornene compound having a vinyl terminal group represented by the above formula (I) or (II) in the presence of a catalyst under such conditions that the polymerization temperature is 30 to 60 deg.C (preferably 30 to 59 deg.C) and the polymerization pressure is 4 to 12 kg-f/cm²(preferably 5-8 kg/cm)²) The feed molar ratio of the nonconjugated polyene to ethylene (nonconjugated polyene/ethylene) is from 0.01 to 0.2, and the catalyst used contains the following compounds (h) and (i) as the main components. The random copolymerization is preferably carried out in a hydrocarbon solvent.

(h) From the general formula VO (OR)_nX_3-nA soluble vanadium compound represented by (wherein R is a hydrocarbon group, X is a halogen atom, and "n" is an integer of 0 to 3), or VX₄The vanadium compound (X is a halogen atom).

The above soluble vanadium compound (h) is a component soluble in a hydrocarbon solvent of the polymerization reaction system. More specifically, representative examples are those of the formula VO (OR)_aX_bOr V (OR)_cX_dVanadium compounds represented by the formula (wherein R is a hydrocarbon group, 0. ltoreq. a.ltoreq.3, 0. ltoreq. b.ltoreq.3, 2. ltoreq. a + b. ltoreq.3, 0. ltoreq. c.ltoreq.4, 0. ltoreq. d.ltoreq.4 and 3. ltoreq. c + d. ltoreq.4) and electron donor adducts of these compounds.

More specifically, examples of these compounds include VOCl₃、VO(OC₂H₅)Cl₂、VO(OC₂H₅)₂Cl、VO(O-iso-C₃H₇)Cl₂、VO(O-n-C₄H₉)Cl₂、VO(OC₂H₅)₃、VOBr₃、VCl₄、VOCl₃、VO(O-n-C₄H₉)₃And VCl₃·2OC₆H₁₂OH。

(i) From the general formula R'_mAlX′_3-mAn organoaluminum compound of (wherein R 'is a hydrocarbon group, X' is a halogen atom, and "m" is an integer of 1 to 3) is represented.

Specific examples of the organoaluminum compound (i) include:

trialkylaluminums such as triethylaluminum, tributylaluminum, and triisopropylaluminum;

dialkylaluminum alkoxides, diethylaluminum ethoxide and dibutylaluminum butoxide;

alkylaluminum sesquialkoxides, such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;

partially alkoxylated alkylaluminums having an average composition of the formula R¹ _0.5Al(OR¹)_0.5Etc.;

dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide;

partially halogenated alkylaluminums, such as alkylaluminum sesquihalides (e.g., ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide) and alkylaluminum dihalides (e.g., ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide);

partially hydrogenated alkylaluminums such as dialkylaluminum hydride (e.g., diethylaluminum hydride, dibutylaluminum hydride) and alkylaluminum dihydrides (e.g., ethylaluminum dihydride, propylaluminum dihydride); and

partially alkoxylated and halogenated alkylaluminums such as ethoxyethylaluminum chloride, butoxybutylaluminum chloride and ethoxyethylaluminum bromide.

Preferably, the catalyst is prepared by using a catalyst comprising VOCl₃Soluble vanadium compounds as compound (h) and Al (OC)₂H₅)₂Cl/Al₂(OC₂H₅)₃Cl₃A mixture (mixing ratio: 1/5 or more) was used as a catalyst for the compound (i), since the ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A) thus obtained₀) Extraction in a soxhlet extractor (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) the content of insoluble matter thereafter is 1% or less.

A metallocene catalyst may be used for the copolymerization, for example, a metallocene catalyst described in Japanese patent laid-open publication No. 40586/1997.

Silicon compounds

The silicon compound used in the present invention is represented by the following general formula [ IV]Represents:

in the formula [ IV], R is a monovalent hydrocarbon group of 1 to 12 carbon atoms, which may be substituted or unsubstituted, preferably is free of unsaturated aliphatic bonds, and includes alkyl groups such as methyl, ethyl, propyl, butyl, hexyl or cyclohexyl; aryl groups such as phenyl or tolyl; or the above groups in which hydrogen atoms bonded to carbon atoms are substituted in whole or in part with halogen such as fluorine.

X is hydride (-H), halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy or amino.

Halogen groups include chlorine, fluorine, bromine and iodine atoms.

Alkoxy groups include methoxy, ethoxy, propoxy, propoxybutoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, and phenoxy.

The acyloxy group includes acetoxy and benzoyloxy.

Ketoxime salt groups include acetoxime salt, dimethylketoxime salt, diethylketoxime salt and cyclohexanone oxime salt (cyclohexxylmate).

Amide groups include dimethylamide, diethylamide, dipropylamide, dibutylamide and diphenylamide.

Acid amide groups include carboxylic acid amides, maleic acid amides, acrylic acid amides, and itaconic acid amides.

Thioalkoxy includes thiomethoxy, thioethoxy, thiopropoxy, thioisopropoxy, thioisobutoxy, secondary thiobutoxy, tertiary thiobutoxy, thiopentoxy, thiohexoxy and thiophenoxy.

The amino group includes dimethylamino,diethylamino, dipropylamino, dibutylamino and diphenylamino.

Among these groups, more preferable are alkoxy groups, particularly alkoxy groups of 1 to 4 carbon atoms.

"a" in the formula [ IV]is an integer of 0 to 2, preferably 0 or 1.

Specific examples of the silicon compound represented by the general formula [ IV]include:

halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, diethylchlorosilane, phenyldichlorosilane, and diphenylchlorosilane;

alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, butyldimethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, butylethoxysilane and phenyldimethoxysilane;

acyloxysilanes such as triacetoxysilane, methyldiacetoxysilane, and phenyldiacetoxysilane;

ketoxime salt silanes, such as tris (acetoxime salt) silane, tris (dimethylketoxime salt) methylsilane, bis (methylethylketoxime salt) methylsilane, bis (cyclohexanone oxime salt) methylsilane;

aminoxysilanes such as aminoxysilane and triaminoxysilane;

aminosilanes, such as methyldiaminosilane and triaminosilane.

Among these compounds, alkoxysilanes are preferred.

It is preferably an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) In which 0.01 to 5 mol of [ IV]are incorporated per mol of double bonds]The silicon compound is preferably 0.05 to 3 mol.

The hydrosilylation reaction is carried out in the presence of a transition metal complex catalyst.

An effective catalyst for the hydrosilylation reaction includes a complex of a group VIII transition metal selected from platinum, rhodium, cobalt, palladium and nickel, of which chloroplatinic acid and a platinum/olefin complex are particularly preferable, and in this case, the catalyst is used in an amount of ethylene/α -olefin/unconjugated polyene random copolymer rubber (A)₀) The amount of the reactant is 0.1 to 10,000ppm in terms of metal unit, 1 to 1000ppm, preferably 20 to 200 ppm.

The hydrosilylation reaction is carried out at 30 to 180 c (preferably 60 to 150 c) under high pressure, and the reaction is carried out for about 10 seconds to 10 hours as needed.

A solvent may be used, but is not required. When a solvent is used, an inert solvent such as an ether or a hydrocarbon is preferred.

In the present invention, the hydrosilylation reaction produces an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a hydrolyzable silyl group, which is represented by one of the following general formulas₀) Has the general formula [ IV]The SiH groups of the silicon compounds shown are attached to a double bond.

In addition to the general formula [ IV]In addition to the compound having a hydrolyzable silyl group shown, a siloxane modified at one end with hydrogen represented by the following general formula may be added to the copolymer rubber (a1) for imparting weather resistance, slip property and gas permeability of the siloxane to the copolymer rubber:in the formula, R¹Is a monovalent hydrocarbon group of 1 to 12 carbon atoms which may be substituted or unsubstituted, as in the formula [ IV]]The R group in (1) is the same, particularly preferably an alkyl group; "m" is an integer of 5 to 200, particularly preferably 10 to 150. [ Compound having silanol group and/or Compound capable of reacting with moisture to form Compound having silanol group in molecule (B1)]

The compound having a silanol group in the molecule of the present invention is not limited as long as the compound has one ≡ SiOH group in the molecule. Specific examples of such compounds for use in the present invention include:

general formula R₃SiOH compound (wherein R is₃Is alkyl or aryl, which may or may not be substituted, and the various R groups may be the same or different), for example (CH)₃)₃SiOH，(CH₃CH₂)₃SiOH，(CH₃CH₂CH₂)₃SiOH，(n-C₄H₉)₃SiOH，(sec-C₄H₉)₃SiOH，

(t-C₄H₉)₃SiOH，(C₅H₁₁)₃SiOH，(C₆H₁₃)₃SiOH，(C₆H₅)₃SiOH，

(C₆H₅)₂Si(CH₃)(OH)，(C₆H₅)Si(CH₃)₂(OH)，(C₆H₅)₂Si(C₂H₅)(OH)，

(C₆H₅)Si(C₂H₅)₂(OH)，(C₆H₅)-CH₂Si(C₂H₅)₂(OH)，

And cyclic polysiloxane compounds having silanol groups, such as:

linear polysiloxane compounds having silanol groups, for example:

compounds having silanol groups attached to the ends of polymers whose backbone comprises silicon and carbon, such as:

compounds having silanol groups attached to the ends of the polysilane backbone, for example:

compounds having silanol groups attached to the ends of polymers whose backbone comprises silicon, carbon and oxygen, such as:

compounds with a higher content of ≡ SiOH groups show higher effects at the same amounts. In this respect, (CH) is more preferable₃)₃SiOH and (CH)₃CH₂)₃SiOH, more preferable from the viewpoint of easy processability and stability in air, is (C)₆H₅)₃SiOH，(C₆H₅)₂Si(CH₃) OH and (C)₆H₅)Si(CH₃)₂OH。

The compounds capable of reacting with moisture to form a compound having a silanol group in the molecule according to the present invention include the following compounds, each of which is referred to as a silylation agent:(CH₃)₃Si-NH-Si(CH₃)₃，(CH₃)₃SiN(CH₃)₂，(CH₃)₃SiO-C(CH₃)(NSi(CH₃)₃)，

(CH₃)₃Si-NH-CO-NH-Si(CH₃)₃，

andCF₃-SO₂-OSi(CH₃)₃. These compounds are suitable for the present invention, and particularly preferred is (CH)₃)₃Si-NH-Si(CH₃)₃Because of the high content of ≡ SiOH groups in the hydrolysable products.

The effect of the compound (B1) is to improve the tensile properties of the cured product (i.e., to lower the modulus and to increase the elongation) and to improve the residual tackiness, the improved tensile properties are considered to be caused by the phenomenon that a silicon compound or a silanol compound as a hydrolysate thereof reacts with the hydrolyzable silyl group in the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) to cap the group, the number of crosslinking points in the copolymer rubber (A1) is reduced, thereby increasing the molecular weight between the crosslinking points, resulting in a cured product of low modulus and high elongation.

The addition amount of the compound (B1) is changed depending on the intended properties of the cured product.the addition ratio of the compound (B1) is determined by the silanol (. ident.SiOH) equivalent ratio per mole of the hydrolyzable silyl group in the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). the addition amount of the compound (B1) is usually 0.1 to 0.9 equivalent of silanol groups per mole of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) to obtain a cured product of low modulus and high elongation, however, although the compound (B1) is present, it is necessary to leave unblocked hydrolyzable silyl groups at a ratio of at least 0.1 group in 1 molecule. 1 may be added with silanol groups exceeding 0.9 equivalent, but it is not recommended from the economical point of view.a composition of 0.3 equivalent or more, particularly a composition of the compound (B1) of O.5 equivalent or more, is not sufficiently left to be cured on the surface, however, a composition of which is not so-cured in which a thin layer is sufficiently cured, so-called a sealant composition.

The method of adding the compound (B1) can be classified into three broad categories, the first method is to add only the compound (B1) to the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), in which the compound (B1) is uniformly dispersed and dissolved by carefully setting conditions (such as temperature and stirring conditions) as required in consideration of the properties of the compound (B1). in this case, the composition is not necessarily completely transparent, and can sufficiently achieve the object even when it is opaque, as long as the compound (B1) is sufficiently dispersed therein.

The second method is to mix a given amount of compound (B1) with the final product when it is used. For example, when the composition is used as a two-liquid component type sealant, the compound (B1) may be mixed as a third component with the base material and the curing agent of the composition.

The third method is to react the compound (B1) with the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) in advance, if necessary, in the presence of a tin group, a titanate group, an acidic or basic catalyst, or in the presence of water when the compound (B1) is a compound (B1) capable of reacting with moisture to form a compound having a silanol group in the molecule, followed by heating under vacuum to evaporate.

Specific examples of the catalyst used in the present invention include:

titanates such as tetrabutyl titanate and tetrapropyl titanate;

organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; lead octoate;

amino compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine and 1, 3-diazabicyclo (5, 4, 6) undecene-7 (DBU);

low molecular weight polyamide resins, made by the reaction of excess polyamine and polybasic acid;

a product of the reaction between an excess of polyamine and an epoxy compound; and

silanol condensing catalysts, for example, amino group-containing silane coupling agents such as gamma-aminopropyltrimethoxysilane and N- (β -aminoethyl) aminopropylmethyldimethoxysilane.

The curable elastomer composition (1) of the present invention thus obtained can be incorporated, as required, with various additives such as white carbon, carbon black, calcium carbonate, titanium oxide, talc, asbestos and glass fiber, which are used as materials such as reinforcing or non-reinforcing fillers, plasticizers, antioxidants, ultraviolet absorbers, pigments or flame retardants, for use as adhesives, tackifiers, coating and sealant compositions, waterproofing materials, spray materials, shaping materials or casting rubber materials. Among them, particularly useful are sealing materials and adhesion promoter compositions.

The curable elastomer composition (1) of the present invention, when used as a sealant, may be incorporated with a plasticizer, a filler, a reinforcing agent, a sagging inhibitor (driping inhibitor), a colorant, an anti-aging agent, an adhesion promoter, acuring catalyst or a property adjuster, as required.

Plasticizers useful in the present invention include:

phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;

esters of polyalkylene glycols, such as diethylene glycol dibenzoate and triethylene glycol dibenzoate;

phosphoric acid esters such as tricresyl phosphate and tributyl phosphate;

chlorinated paraffin; and

hydrocarbon-based oils such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomers, α -methylstyrene oligomers, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene.

Of these, hydrocarbon-based compounds free of unsaturated groups, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable because these compounds are well compatible with the respective components of the composition of the present invention, have a limited effect on the curing speed of the rubber composition, and the cured product obtained is high in resistance to weather and inexpensive.

When a hydrolyzable silyl group is introduced into the ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A0), the above-mentioned plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

Fillers and reinforcing agents useful in the present invention include limestone powder and calcium carbonate; calcium carbonate surface-treated with fatty acid, resin acid or cationic or anionic surfactant; magnesium carbonate; talc; titanium oxide; barium sulfate; alumina; metal (e.g., aluminum, zinc, or iron) powder; bentonite; kaolin; fumed silica; quartz powder and carbon black. These are general substances, and one or more of them may be used. Among them, a filler or a reinforcing agent capable of imparting transparency (e.g., fumed silica) can give a sealing material having high transparency.

Sag inhibitors useful in the present invention include hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. The sagging inhibitor is not necessarily required, and depending on the use of the curable composition, a filler or a reinforcing agent may be mixed.

The colorant used in the present invention includes common inorganic and organic pigments and dyes, each of which may be used as needed.

The property-adjusting agent used in the present invention includes various silane coupling agents, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane and N-propyltrimethoxysilane, alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriipropenoxysilane and γ -glycidoxypropylmethyldiisopropenoxysilane, alkoxysilanes containing functional groups such as γ -glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, γ -mercaptopropyltrimethoxysilane and γ -mercaptopropylmethyldimethoxysilane, silicone varnishes and polysiloxanes.

The above-mentioned property adjuster can increase the hardness of the curable elastomer composition (1) of the present invention when it is cured, or decrease the hardness and increase the elongation thereof.

The adhesion promoter is not necessarily used because the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) itself has adhesion to glass, other ceramic materials and metals, and to a wide range of materials in the presence of each primer layer.

The curing catalysts useful in the present invention include titanates such as tetrabutyl titanate and tetrapropyl titanate, organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octoate, tin naphthenate, lead octoate, amino compounds and salts of these compounds and carboxylic acids, such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, and 1, 3-diazabicyclo (5, 4, 6) undecene-7 (DBU), low molecular weight polyamide resin products made by reaction between excess polyamine and polybasic acid, silanol condensation products of reaction between excess polyamine and epoxy compound, and known silanol condensation catalysts, such as amino-containing silane coupling agents (e.g., gamma-aminopropyltrimethoxysilane and N- (β -aminoethyl) aminopropylmethyldimethoxysilane), and such compounds may be used alone or in combination with solvents such as the viscosity-reducing catalysts such as the conjugated methyl acetate, isobutyl acetate, vinyl acetate, and/or the use of such solvents as the aforementioned solventbornene, polyisobutyl acetate, and/or the use of such solvents for the use of the aforementioned non-methyl acetate-based curing process.

The aging inhibitors useful for the presentinvention include common antioxidants such as sulfur-based antioxidants, radical inhibitors and ultraviolet absorbers, although the use of the aging inhibitors is not essential.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

More specifically, the sulfur-based aging inhibitors include:

thiols, such as 2-mercaptobenzothiazole;

mercaptides, such as the zinc salt of 2-mercaptobenzothiazole;

sulfides, such as 4, 4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (2-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, terephthaloyl bis (2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and diethyl 2, 2-thio [ bis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate];

polysulfides, such as 2-benzothiazole disulfide;

dithiocarboxylates such as zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate and zinc dimethylcarbamate;

thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolylthiourea and ethylenethiourea; and

thiophosphates, such as trilauryl trithiophosphate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of the curable rubber composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

The age resistor is added in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The sealant composition may be made into a one-liquid type in which a composition containing all the components is prepared in advance and sealed, and is cured with moisture in the air after application of the composition, or a two-liquid type in which a curing agent composition (e.g., a curing catalyst, a filler, a plasticizer, and water used as a curing agent) and a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber are separately prepared, and the two are mixed before use.

When the sealant composition is of a one-liquid type, it is preferable that the aqueous component is dehydrated/dried in advance, or dehydrated at the time of mixing/kneading under vacuum, because the composition contains all the components before use.

On the other hand, when the two-liquid type is employed, the sealant composition may contain water to some extent, because the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) is not mixed with a curing catalyst in advance and therefore does not gel even if water is present.

The preferred dehydration/drying method is: drying the solid (such as powder and composition) under heating; for liquid compositions, dehydration is carried out under vacuum or in the presence of synthetic zeolite, activated alumina or silica gel. Further, the liquid composition may be dehydrated in the presence of a small amount of an isocyanate compound in which isocyanate groups react with water. The storage stability of the composition is further improved by the above-mentioned dehydration/drying treatment and the incorporation of: lower alcohols such as methanol or ethanol; or alkoxysilane compounds such as n-propyltrimethoxysilane, vinylmethyldimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-glycidoxypropyltrimethoxysilane.

The curable elastomer composition (1) of the present invention, when used as a tackifier, may be incorporated, as required, with a curing catalyst, an age resistor, a plasticizer, a reinforcing agent, a property adjuster or a solvent which can be used for a sealant. Known additives commonly used for tackifiers, such as rosin ester resins, phenol resins, xylene/phenol resins, benzofuran resins, petroleum-based resins (such as aromatic, aliphatic/aromatic copolymers or acrylic-based resins), terpene resins, terpene/phenol resins or low molecular weight polystyrene resins, may also be added depending on the application. The tackifier composition has a wide range of uses, such as tapes, sheets, labels, and foils. For example, the above-mentioned tackifier composition of a solventless liquid, a solventtype, an emulsion type or a hot melt type is applied to a substrate such as a synthetic resin or modified natural film, paper, any type of cloth, a metal foil, a metallized plastic foil, asbestos or a glass fiber cloth, and cured at normal or high temperature after being exposed to moisture or water.

Curable elastomer composition (1) and use thereof

The curable elastomer composition (1) of the present invention contains a curable composition, the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber specified above as the component (A1). more specifically, the composition comprises an organic polymer (Z) containing a hydrolyzable silyl group represented by the general formula [ III]and having substantially no unsaturated double bond in the main chain, and a compound (B1) having a silanol group and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule.

The curable elastomer composition is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, as described in the summary of the invention.

The curable elastomer composition (1) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

The present inventors have made the present invention by seeking a composition capable of replacing a propylene oxide-based polymer described in the background of the invention, which composition gives a cured product having improved elongation and residual surface tackiness, faster curing speed and higher weather resistance, and have extensively studied to develop the curable elastomer composition (1)of the present invention, the present inventors have found that a composition having a faster curing speed gives a cured product having higher weather resistance, improved elongation and residual surface tackiness, and thus have made the present invention, which composition comprises a silyl-containing ethylene/α -olefin/non-conjugated polyene random copolymer rubber having a structural unit derived from a norbornene compound having a specific vinyl terminal group (as a non-conjugated polyene) and having a specific hydrolyzable silyl group in the molecule, a compound having a silanol group and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule.

The above-mentioned Japanese patent laid-open publication Nos. 34066/1986 and 34067/1986 do not mention at all an ethylene/α -olefin/nonconjugated polyene random copolymer rubber which has a structural unit derived from a norbornene compound having a specific vinyl terminal group and contains a specific hydrolyzable silyl group in the molecule.

Curable rubber composition (2)

The curable rubber composition (2) of the present invention comprises a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), a tetravalent tin compound (C), a silicon compound (B2), and if necessary, a silane coupling agent having an isocyanate group.

[ tetravalent tin Compound (C)]

The curable rubber composition (2) of the present invention contains a tetravalent tin compound (C) as a high-activity silanol condensing catalyst.

More specifically, the tetravalent tin compound (C) used in the present invention includes:

a tin salt of a carboxylic acid,

dialkyltin oxides, and

general formula Q_dSn(OZ)_4-dOr [ Q₂Sn(OZ)]₂A tin compound represented by O, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms; z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn within its structure; "d" is an integer of 1 to 3).

Other effective curing catalysts which significantly accelerate the silanol condensation reaction are the reaction products between tetravalent tin compounds (e.g., dialkyltin oxide or dialkyltin diacetate) and low molecular weight silicon compounds having hydrolyzable silicon groups (e.g., tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane or phenyltrimethoxysilane).

Among them, tin compounds represented by the above general formula (i.e., chelate compounds such as dibutyltin diacetylacetate or tin (tinalcolates)) are more preferable because they have high activity as a silanol condensing catalyst and can accelerate curing of the rubber composition. Particularly preferred are tin alkyds because they accelerate curing of the curable rubber composition of the present invention more remarkably and have a long workable time (i.e., working time), for example, blade finishing may be carried out after the main component is kneaded with the curing agent.

Tin carboxylates useful in the present invention include: dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexoxide, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diisooctylmaleate, dibutyltin ditridecyl maleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmaleate and dioctyltin diisooctylmaleate.

The dialkyltin oxides used in the present invention include: dibutyl tin oxide, dioctyltin oxide, and mixtures of dibutyl tin oxide and phthalate esters.

Specific examples of the chelate include:specific examples of tin alkyds include: (C)₄H₉)₃SnOCH₃，(C₄H₉)₂Sn(OCH₃)₂，C₄H₉Sn(OCH₃)₃，Sn(OCH₃)₄，(C₄H₉)₂Sn(OC₃H₇)₂，(C₄H₉)₂Sn(OC₄H₉)₂，(C₄H₉)₂Sn(OC₈H₁₇)₂，(C₄H₉)₂Sn(OC₁₂H₂₅)₂，(C₈H₁₇)₂Sn(OCH₃)₂，

Among them, dialkoxydialkyltin is more preferable. Dimethoxydibutyltin is particularly preferable because of its low cost and high availability.

The tetravalent tin compound (C) used as the silanol condensing catalyst may be used together with another silanol condensing catalyst as long as the object of the present invention is achieved.

Specific examples of these silanol condensing catalysts include:

titanates such as tetrabutyl titanate and tetrapropyl titanate;

organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and aluminum diisopropoxide ethylacetoacetate;

chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate;

lead octoate;

amino compounds such as butylamine, octylamine, dodecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU);

salts of these amino compounds with carboxylic acids;

low molecular weight polyamide resins, made by the reaction of excess polyamine and polybasic acid;

a product of the reaction between an excess of polyamine and an epoxy compound; and

amino group-containing silane coupling agents such as γ -aminopropyltrimethoxysilane and N- (β -aminoethyl) aminopropylmethyldimethoxysilane;

and other known silanol condensing catalysts such as acidic or basic catalysts.

These compounds may be used alone or in combination.

The tetravalent tin compound (C) is added in an amount of usually 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). the tetravalent tin compound (C) as a silanol curing catalyst can sufficiently accelerate the curing reaction at a high speed when used in the above range, and can give a good cured product without causing local overheating or foaming when the rubber composition is cured.

[ silicon Compound (B2)]

The curable rubber composition (2) of the present invention may be incorporated with a silicon compound (B2) having no silanol group, represented by the following general formula [ V], for further enhancing the activity of thetetravalent tin compound (C) as a silanol condensing catalyst:

R⁴ _aSi(OR⁵)_4-a[V]in the formula, R⁴And R⁵Each is a substituted or unsubstituted hydrocarbyl group of 1 to 20 carbon atoms, "a" is 0, 1, 2, or 3.

Specific examples of the silicon compound (C) used in the present invention include:

(CH₃)₃SiOCH₃，(CH₃)₂Si(OCH₃)₂，(CH₃)₃SiOC₂H₅，(CH₃)₂Si(OC₂H₅)₂，

(CH₃)₃SiOC₆H₅，(CH₃)₂Si(OC₆H₅)₂，(C₆H₅)₃SiOCH₃，(C₆H₅)₂Si(OCH₃)₂，

(C₆H₅)₃SiOC₂H₅，(C₆H₅)₂Si(OC₂H₅)₂，(C₆H₅)₃SiOC₆H₅，(C₆H₅)₂Si(OC₆H₅)₂，

CH₃Si(OCH₃)₃，C₆H₅Si(OCH₃)₃，CH₃Si(OC₂H₅)₃，C₆H₅Si(OC₂H₅)₃，

CH₃Si(OC₆H₅)₃，C₆H₅Si(OC₆H₅)₃，C₆H₅Si(CH₃)(OCH₃)₂，

(C₆H₅)₂Si(CH₃)(OC₆H₅)，C₆H₅Si(CH₃)₂(OCH₃)，(C₆H₅)₂Si(CH₃)(OCH₃)，

(C₆H₅)₂Si(OC₄H₉)₂，(C₄H₉)₂Si(OC₆H₅)₂，(C₆H₅)₂Si(OC₈H₁₇)₂，

(C₈H₁₇)₂Si(OC₆H₅)₂，(C₆H₅)₂Si(OC₁₂H₂₅)₂，(C₁₂H₂₅)₂Si(OC₆H₅)₂，

(CH₃)₂Si(OC₄H₉)₂，(C₂H₅)₃SiOCH₃，(CH₃)₂Si(OC₈H₁₇)₂，(C₂H₅)₂Si(OCH₃)₂，(CH₃)₂Si(OC₁₂H₂₅)₂，C₂H₅Si(OCH₃)₃，

among these compounds, more preferred is the compound of the formula [ V]]R of⁴And (c) aryl groups of 6 to 20 carbon atoms, because they are effective in accelerating the curing of the composition. These compounds include: phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethaneOxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and triphenylmethoxysilane. Particularly preferred are diphenyldimethoxysilane and diphenyldiethoxysilane because of their low cost and high availability.

The silicon compound (B2) is used in an amount of usually 0.001 to 50 parts by weight, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weightof the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the silicon compound (B2) is used in the above-mentioned amount range, a remarkable effect of accelerating the curing of the composition can be obtained without deteriorating the hardness and tensile strength of the cured product.

[ other Components]

The curable rubber composition (2) of the present invention may be incorporated with one or more additives as needed within limits not adversely affecting the object of the present invention. These additives for use in the present invention include silane coupling agents containing isocyanate groups, anti-settling agents and leveling agents; cellulose, nitrocellulose and cellulose acetate butyrate; resins such as alkyd resins, acrylic resins, vinyl chloride resins, chloropropene resins, chlorinated rubbers, and polyvinyl butyral resins; an adhesion promoter; a performance modifier; a storage stability improver; plasticizers, fillers; an anti-aging agent; an ultraviolet absorber; a metal deactivator; inhibitors against ozone-induced aging; a light stabilizer; an amine-based free radical chaining inhibitor; a phosphorus-based peroxide decomposer; a lubricant; pigments and blowing agents.

The silane coupling agent containing an isocyanate group can improve the adhesive strength of the cured silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) to an object or substrate.

The silane coupling agent containing an isocyanate group is a compound having a silicon atom-containing group, which has a hydrolyzable group bonded to the silicon atom (hydrolyzable silicon group) and an isocyanate group. Specific examples of the hydrolyzable silicon group are shown by the general formula [ III], and X is a hydrolyzable group, i.e., hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acidamide, aminoxy, thioalkoxy and amino. Among them, the silicon group having an alkoxy group (e.g., methoxy group or ethoxy group) is more preferable in view of the hydrolysis rate. The silane coupling agent preferably has 2 or more hydrolyzable groups, more preferably 3 or more hydrolyzable groups.

Specific examples of the isocyanate group-containing silane coupling agent used in the present invention include: gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-isocyanatopropylmethyldiethoxysilane and gamma-isocyanatopropylmethyldimethoxysilane.

The curable rubber composition (2) of the present invention may further contain a silane coupling agent other than the isocyanate-containing silane coupling agent or a tackifier other than the silane coupling agent.

The isocyanate group-free silane coupling agent used in the present invention includes amino group-containing silanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldiethoxysilane, gamma-ureidopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-benzyl-gamma-aminopropyltrimethoxysilane and N-vinylbenzyl-gamma-aminopropyltriethoxysilane;

mercapto group-containing silanes such as gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane;

epoxy-containing silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and β - (3,4-epoxycyclohexyl) ethyltriethoxysilane;

carboxysilanes, such as β -carboxyethyltriethoxysilane, β -carboxyethylphenylbis (2-methoxyethoxy) silane and N- β - (carboxymethyl) aminoethyl- γ -aminopropyltrimethoxysilane;

vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane and gamma-acryloxypropylmethyltriethoxysilane;

halogen-containing silanes, such as gamma-chloropropyltrimethoxysilane; and

silane isocyanurates, such as tris (trimethoxysilyl) isocyanurate.

Derivatives obtained by modifying some of the above-mentioned compounds may also be used as the silane coupling agent. They include: amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylaminoalkyl (long chain) silanes, aminosilylated siloxanes and silylated polyesters.

The above-mentioned isocyanate-containing silane coupling agents may be used alone or in combination.

The isocyanate-containing silane coupling agent is usually added in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The incorporation of the isocyanate-containing silane coupling agent into the curable rubber composition (2) of the present invention brings about an effect of significantly improving the adhesion of the composition to various objects, either in the presence of a primer layer or in the absence of a primer layer, particularly more significantly in the absence of a primer layer. Such as inorganic substrates of glass, aluminum, stainless steel, zinc, copper and plaster, organic substrates of vinyl chloride, acrylic, polyester, polyethylene, polypropylene and polycarbonate.

Specific examples of the adhesion promoter include phenol resins, epoxy resins, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates, the adhesion promoter is preferably added in an amount of about 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/polyene α -olefin/nonconjugated random copolymer rubber (A1).

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded and esters of organic acids. Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate.

The storage stability improver is incorporated preferably at about 0.5 to 20 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), more preferably 1 to 10 parts by weight.

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. However, a plasticizer compatible with each component in the curable rubber composition (2) of the present invention is preferable.

Specific examples of these plasticizers include:

hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin co-oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene;

chlorinated paraffin;

phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;

esters of polyalkylene glycols, such as diethylene glycol dibenzoate and triethylene glycol dibenzoate;

phosphoric acid esters such as tricresyl phosphate and tributyl phosphate;

among them, the saturated hydrocarbon-based compounds are more preferable. They may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with the various components of the rubber composition of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

When a hydrolyzable silyl group is introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A0), a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

The plasticizer is preferably added in an amount of about 10 to 500 parts by weight, more preferably 20 to 300 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Specific examples of the above filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc.

When the filler is used, it is preferably used in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The aging inhibitors useful for the present invention include commonly known sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylates and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, monothioacids, polythioacids, thioamides, and sulfoxides.

More specifically, the sulfur-based aging inhibitors include:

thiols, such as 2-mercaptobenzothiazole;

mercaptides, such as the zinc salt of 2-mercaptobenzothiazole;

sulfides, such as 4, 4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (2-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, terephthaloyl bis (2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and diethyl 2, 2-thio [ bis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate];

polysulfides, such as 2-benzothiazole disulfide;

dithiocarboxylates such as zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate and zinc dimethylcarbamate;

thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolylthiourea and ethylenethiourea; and

thiophosphates, such as trilauryl trithiophosphate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of the curable rubber composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

The age resistor is added in an amount of about 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

By using the tetravalent tin compound (C) of the present invention and the silicon compound (B2) represented by the general formula [ V]in combination, the effect of improving curability can be also observed irrespective of the presence or absence of an isocyanate-containing silane coupling agent (which can be used in the present invention as desired).

An improvement in curability was also observed when the above-mentioned various additives were incorporated. More specifically, when the curable rubber composition (2) of the present invention is used as an elastomer sealant for construction, a sealant for laminated glass and an electric/electronic part (such as a back surface of a solar cell); electrical insulation for the insulation coating of wires and cables; tackifiers and adhesives; when the above additive is added to the composition (2) in the production of a sealant for rust-proofing and water-proofing edges (cut portions) of mesh-reinforced or laminated glass, it can be cured significantly more quickly.

Curable rubber composition (2) and use thereof

The curable rubber composition (2) of the present invention comprises a curable composition comprising a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, a composition comprising an organic polymer (Z) containing a hydrolyzable silyl group represented by the general formula [ III]and having substantially no unsaturated double bond in the main chain, a tetravalent tin compound (C), a specific silicon compound (B1), and, if necessary, an isocyanate group-containing silane coupling agent.

The curable rubber composition (2) of the present invention can beused as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

Curable composition (3)

The curable composition (3) of the present invention comprises (a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and (B) a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule (B3).

The silyl group containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) as the component (a) has an intrinsic viscosity [ η]of about 0.001 to 2dl/g, preferably 0.01 to 1dl/g, more preferably 0.05 to 1dl/g, still more preferably 0.05 to 0.7dl/g, still more preferably 0.1 to 0.5 dl/g.

[ silicon Compound (B3)]

The silicon compound (B3) having at least one amino group and at least one trialkylsiloxy group in the molecule of the present invention is represented by the following general formula:

in the formula, Y_dIs an alkyl group having an amino group; r¹Is alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, or is represented by R⁵ ₃Triorganosiloxy group represented by SiO- (wherein R is⁵Is a monovalent hydrocarbon radical of 1 to 20 carbon atoms, three R⁵May be the same or different), when 2 or more R's are present¹When they are the same, they may be different; x is hydroxy, identical or different hydrolyzable groups or-O-SiQ₃Wherein Q is a group selected from the group consisting of a hydroxyl group, the same or different hydrolyzable groups, a monovalent organic group of 1 to 20 carbon atoms which may be substituted or unsubstituted, and a triorganosiloxy group; and X contains at least one hydroxyl group or identical or different hydrolyzable groups; r²、R³And R⁴Each is an alkyl group of 1 to 6 carbon atoms or a phenyl group, which may be substituted or unsubstituted; "c" is an integer of 0 to 2, and "d" and "e" are 1 or 2, respectively.

Examples of these compounds include γ -aminopropyltrimethylsiloxydiethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethylsiloxydimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethylsiloxymethylmethoxysilane, diethylenetriaminopropyltrimethylsiloxydimethoxysilane, N-dimethyl- γ -aminopropyltrimethylsilyldimethoxysilane which can be easily synthesized by reacting a silicon compound having at least one amino group and at least one hydrolyzable group in the molecule with a trialkylsilanol compound.

Examples of silicon compounds having at least one amino group and at least one hydrolyzable group in the molecule include, but are not limited to, γ -aminopropyltriethoxysilane (Nippon Unicar Co., Ltd., A-1100), N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane (Nippon Unicar Co., Ltd., A-1120), N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-602), diethylenetriaminopropyltrimethoxysilane (Nippon Unicar Co., Ltd., A-1130), N-dimethyl- γ -aminopropyltrimethoxysilane (Chisso, D0), N' -bis [ γ -trimethoxysilylpropyl]ethylenediamine (Chisso, XS1003), N-benzyl- γ -aminopropyltrimethoxysilane (Shin-Etsu Co., Ltd., X-12-aminopropyl) and N-aminopropyl trimethoxysilane (Shin-gamma-Etsu Co., Lbm, K520512, Shi K-573).

Examples of trialkylsilyl alcohol compounds include, but are not limited to: trimethylsilanol, triethylsilanol, and triphenylsilanol.

[ other Components]

The curable composition (3) of the present invention can be incorporated, as required, with one or more of various types of plasticizers, good effects can be obtained when the total amount of the plasticizer is from 0 to 300 parts by weight per 100 parts by weight of the silyl group containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the total amount of the plasticizer exceeds 300 parts by weight, the effect of improvement is hardly observed due to the excessive content of the liquid component.

Plasticizers useful in the present invention include phthalates such as dioctyl phthalate, diisodecyl phthalate, dibutyl phthalate and butyl benzyl phthalate, epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil and benzyl epoxy stearate, polyester-based plasticizers such as polyesters of dibasic acids and glycols, polyethers such as polypropylene glycol and derivatives thereof, hydrocarbon-based plasticizers such as polybutene, ethylene/α -olefin oligomers, polystyrene, α -methyl styrene oligomers, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene, and polychloroprene, polyisoprene and chlorinated paraffin.

These compounds may be used alone or in combination. Of these, more preferable are hydrocarbon-based compounds having no unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, because these compounds are well compatible with the respective components of the curable composition (3) of the present invention, have a limited effect on the curing speed of the rubber composition, and the resulting cured product is high in resistance to weather and inexpensive. When the reactive silicon group is introduced into the saturated hydrocarbon-based polymer, the above plasticizer may be used instead ofthe solvent to adjust the reaction temperature and the viscosity of the reaction system.

The composition (3) of the present invention may be mixed with a silanol condensing catalyst for accelerating the reaction of the hydrolyzable silyl group.

Specific examples of the silanol condensing catalyst used in the present invention include titanates such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; a reaction product between dibutyltin oxide and phthalic acid ester, and dibutyltin bisacetylacetonate; organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and aluminum diisopropoxide ethylacetoacetate; reaction products between bismuth salts and organic carboxylic acids, such as bismuth tris (2-ethylhexanoate) and bismuth tris (neodecanoate); chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organolead compounds such as lead octoate; organic vanadium compounds, amino compounds, and salts of these compounds with carboxylic acids, such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU); a low molecular weight polyamide resin produced by a reaction between an excess of polyamine and a polybasic acid; a product of the reaction between the excess polyamine and the epoxy compound. The silanol condensing catalyst used in the present invention is not limited to the above-mentioned compounds, and includes a commonly used condensation catalyst. These silanol condensing catalysts may be used alone or in combination. Among these silanol condensing catalysts, preferable are organometallic compounds and mixtures of organometallic compounds and amino compounds from the viewpoint of curability of the composition.

The silanol condensing catalyst is added in an amount of about 0.1 to 50 parts by weight, preferably about 0.2 to 20 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). the content of the catalyst relative to the copolymer rubber (A1) is unfavorable because of insufficient curing speed and insufficient degree of curing reaction, and exceeding of the above range is unfavorable because of local overheating or foaming during curing, resulting in difficulty in obtaining a cured product having good properties.

The composition (3) of the present invention may be appropriately blended with various additives such as a dehydrating agent, a compatibilizing agent, an adhesion promoter, a property adjuster, a storage stability improver, a filler, an aging inhibitor, an ultraviolet absorber, a metal deactivator, an ozone-induced aging inhibitor, a light stabilizer, an amine-based radical chaining inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, a foaming agent, a flame retardant, an antistatic agent and a silane compound, as required.

The adhesion promoter used in the present invention includes a conventional binder, a silane coupling agent such as aminosilane and epoxysilane compound, and other compounds specific examples of these adhesion promoters include phenolic resin, epoxy resin, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, benzofuran/indene resin, rosin ester resin, terpene/phenol resin, α -methylstyrene/vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanate and aromatic polyisocyanate.

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded and esters of organic acids. Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate.

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate, quartz powder, glass beads, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc. These compounds may be used alone or in combination.

The aging inhibitors useful for the present invention include commonly used known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful in the present invention include mercaptans, salts thereof, sulfides including sulfide carboxylates and hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptanes, monothio acids, polythioacids, thioamides, and sulfoxides more specifically, the sulfur-based aging inhibitors include mercaptans, for example, 2-mercaptobenzothiazole, salts thereof, for example, zinc salt of 2-mercaptobenzothiazole, sulfides, for example, 4 '-thiobis (3-methyl-6-t-butylphenol), 4' -thiobis (2-methyl-6-t-butylphenol), 2 '-thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2' -thiobis (4-octylphenol) nickel thiodipropionate, dilauryl thiodipropionate, dioctadecyl thiodipropionate, dipropionate, distearyl dithiodipropionate, zinc dithiodiethoxy dithiocarbamothionate, zinc bis (e), dithiobutyl-3-dithio), dithiodiethoxy-thiodipropionate, e, dithiodiethoxy-bis (e, dithiobutyl-3-butyl-3-dithio), dithiodiethoxy-thiodipropionate, e, dithiodiethoxy-3-dithiodiethoxy-dithiobutyl-3-dithio, e, dithiobutyl-bis (e, dithiobutyl-butyl-3-butyl-dithiobutyl-5-dithiobutyl-thiodipropionate, dithiobutyl-thiodipropionate, dithiobutyl-bis (e, dithiobutyl-dithiodiethoxy-thiodipropionate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than the other type of composition (3) of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

The curable composition (3) of the present invention may be incorporated with a polymer having a reactive silicon group, for example, polydimethylsiloxane, other than the hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) as component (a).

The preparation method of the composition (3) of the present invention comprising (a) the hydrolyzable silyl group containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and (B) the silicon compound (B3) is not limited more specifically, the component (B) is added to and uniformly dispersed in the component (a) while appropriately controlling the conditions (such as stirring conditions) as required.

The composition thus prepared is suitable for a one-liquid type curable composition, not to mention a two-liquid type composition. For the one-liquid type composition, the composition of the present invention is prepared under substantially moisture-free conditions. It can withstand long-term storage maintained under sealed conditions, and rapidly starts to cure from the surface when exposed to an atmospheric atmosphere.

The curable composition (3) of the present invention is useful as an elastomer sealant for building structures, civil engineering and other industrial fields, and also as a coating material, an adhesive, an impregnant and a coating material.

Curable rubber composition (3) and use thereof

The curable rubber composition (3) of the present invention contains a curable composition, as the component (A1), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, more specifically, a composition comprising (a) an organic polymer (Z) and (B) a silicon compound (B3) having at least one amino group and at least one trialkylsiloxy group in the molecule, which is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, as described previously.

The curable composition (3) of the present invention can be used as sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

In other words, the present invention provides a sealant, a potting agent, a coating material or an adhesive composed of a curable composition comprising (a) the organic polymer (Z) and (B) the silicon compound (B3) having at least one amino group and at least one trialkylsiloxy group in the molecule.

Curable composition (4)

The curable composition (4) of the present invention comprises (a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and (B) an organosilicon compound (B4).

[ organosilicon Compound (B4)]

The organosilicon compound (B4) used in the present invention is represented by the following general formula [ VI]:

(R²(CH₃)₂SiO)_nR¹[VI]in the formula, R¹Is an alcohol residue or a weak acid residue; r²Is methyl or vinyl and "n" is a positive integer.

General formula [ VI]]R in (1)¹Preferably monovalent to trivalent alcohol residues or weak acid residues, wherein the term alcohol residue refers to a monohydric or polyhydric alcohol partially or completely deprived of its hydroxyl groups, and weak acid residue refers to a monohydric or polyhydric weak acid partially or completely deprived of its hydroxyl groups. The residue may be a compound having both a hydroxyl group and a weak acid group (e.g., a carboxyl group) while partially or totally losing its hydroxyl group.

R¹Specific examples of the alcohol and weak acid to be represented include aliphatic alcohols of 30 or less carbon atoms (which may be substituted or unsubstituted),such as methanol, ethanol, n-butanol, isobutanol, n-pentanol, isopentanol, 2-chloroethanol, benzyl alcohol, cyclohexanol, 3-chloropropanol, ethylene glycol, propylene glycol, butylene glycol, glycerol, and acetylacetone (tautomers); aromatic hydroxy compounds of 6 to 30 carbon atoms, which may be substituted or unsubstituted, such as phenol, cresol, chlorophenol, bisphenol A, naphthol, hydroquinone and naphthalenediol; aliphatic and aromatic carboxylic acids of 30 or less carbon atoms, which may be substituted or unsubstituted, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, heptacosanoic acid, behenic acid, melissic acid, acrylic acid, undecylenic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearynoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, chlorobenzoic acid, toluic acid, hydroxypropionic acid, hydroxybenzoic acid, and hydroxytoluene acid (oxytoluyl acid); diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, hydroxyl-or carboxyl-containing polybutadiene, hydroxyl-or carboxyl-containing hydrogenated polybutadiene, polyethylene terephthalate and polybutylene terephthalate having hydroxyl groups and/or carboxyl groups; and inorganic acids such as boric acid and carbonic acid.

Of these alcohols and weak acids, the organic compound is preferably free of heteroatoms other than oxygen and halogen.

It is particularly preferable to have a phenyl group as R¹(which may be substituted or unsubstituted) because the compound is widely applicable and gives good effects.

The weak acid in the present specification is defined as an acid having a pKa value of 1 or more, preferably 2 or more, more preferably 3 or more when dissolved in water.

General formula [ VI]]In (1)R²Is methyl or vinyl (CH)₂CH-). Any other group is not suitable as R²Because they do not sufficiently achieve the object of the present invention. Methyl group is more preferable because of wider applicability.

Specific examples of suitable organosilicon compounds (B4) include:

CH₃OSi(CH₃)₃，CH₃CH₂OSi(CH₃)₃，ClCH₂CH₂OSi(CH₃)₃，(CH₃)₃SiOCH₂CH₂OCH₂CH₂OSi(CH₃)₃，(CH₃)₃SiO(CH₂CH(CH₃)O)₂Si(CH₃)₃，(CH₃)₃SiO(CH₂CH₂O)₃Si(CH₃)₃，(CH₃)₃SiO(CH₂CH(CH₃)O)₃Si(CH₃)₃，((CH₃)₃SiO)₃CCH₂CH₃，(CH₃)₃SiOCH₂CH₂OCH₂CH₂CH₃，(CH₃)₃SiO(CH₂)₄OSi(CH₃)₃，p-(CH₃)₃SiOC₆H₄OSi(CH₃)₃，(CH₃)₃SiOCOCH₃，(CH₃)₃SiOCOCH₂CH₂CH₂CH₂COOSi(CH₃)₃，(CH₃)₃SiOC(CH₃)＝CHCOCH₃，

((CH₃)₃SiO)₃B，((CH₃)₃SiO)₂CO，ClCH₂CH₂OSi(CH₃)₂C₂H₃，C₂H₃(CH₃)₂SiO(CH₂)₂OSi(CH₃)₂C₂H₃，

among these compounds, the molecular weight is more preferably 140 from the viewpoint of improving modulus and elongationOr larger, and further preferably a compound having a molecular weight of 150 or larger. It is best to

Because of its wide applicability. The upper limit of the molecular weight of the organosilicon compound (B4) is not particularly limited, but is preferably 5,000 or less, more preferably 2,000 or less.

The amount of the organosilicon compound (B4) added is usually about 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

When the composition is cured to form a silanol compound, the organosilicon compound (B4) is hydrolyzed, reacting with the hydrolyzable silyl group or hydrolyzed hydrolyzable group in the copolymer rubber (a 1).

The method of mixing the silyl group containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and the organosilicon compound (B4) with each other is not limited as long as the conditions (such as temperature and stirring conditions) are carefully set as necessary to dissolve or disperse the component (B4) uniformly in the component (A1). in this case, the composition may not necessarily be completely transparent, and the object can be sufficientlyachieved even when it is opaque, as long as the composition (B4) is dispersed almost uniformly.

[ other Components]

The curable composition (4) of the present invention may be incorporated, as required, with various additives such as white carbon, carbon black, calcium carbonate, titanium oxide, talc, asbestos and glass fiber, which are used as materials such as reinforcing or non-reinforcing fillers, plasticizers, antioxidants, ultraviolet absorbers, pigments or flame retardants, to be used as adhesives, tackifiers, coatings and sealant compositions, waterproofing materials, spray materials, shaping materials or casting rubber materials. Among them, particularly useful is as a sealant composition.

The curable composition (4) of the present invention, when used as a sealant, may be incorporated with a plasticizer, a filler, a reinforcing agent, a sagging inhibitor, a colorant, an aging inhibitor, an adhesion promoter, a curing catalyst or a property adjuster, as required.

Plasticizers useful in the present invention include: phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; esters of polyalkylene glycols, such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffin; and

hydrocarbon-based compounds such as alkylbiphenyls, polybutenes, hydrogenated polybutenes, ethylene/α -olefin oligomers, α -methylstyrene oligomers, biphenyls, terphenyls, triaryldimethanes, alkylene terphenyls, liquid polybutadienes, hydrogenated liquid polybutadienes, paraffin oils, naphthene oils, and atactic polypropylenes.

Of these, hydrocarbon-based compounds free of unsaturated groups, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable because these compounds are well compatible with the respective components of the composition (4) of the present invention, have a limited effect on the curing speed of the rubber composition, and the resulting cured product is high in resistance to weather and inexpensive.

When a reactive silicon group is introduced into the saturated hydrocarbon-based polymer, the above plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

Fillers and reinforcing agents useful in the present invention include limestone powder and calcium carbonate; calcium carbonate surface-treated with fatty acid, resin acid or cationic or anionic surfactant; magnesium carbonate; talc; titanium oxide; barium sulfate; alumina; metal (e.g., aluminum, zinc, or iron) powder; bentonite; kaolin; fumed silica; quartz powder and carbon black. These are general substances, and one or more of them may be used. Among them, a filler or a reinforcing agent capable of imparting transparency (e.g., fumed silica) can give a sealing material having high transparency.

Sag inhibitors useful in the present invention include hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. The sagging inhibitor is not necessarily required, and depending on the use of the curable composition, a filler or a reinforcing agent may be mixed.

The colorant used in the present invention includes common inorganic and organic pigments and dyes, each of which may be used as needed.

The property-adjusting agent used in the present invention includes various silane coupling agents, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane and N-propyltrimethoxysilane, alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriipropenoxysilane and gamma-glycidoxypropylmethyldiisopropenoxysilane, alkoxysilanes containing functional groups such as gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropylmethyldimethoxysilane, silicone varnishes and polysiloxanes.

The above property adjuster can increase the hardness of the curable composition (4) of the present invention when it is cured, or decrease the hardness and increase the elongation.

Adhesion promoters are not necessary because the polymers of the present invention are inherently adhesive to glass, other ceramic materials and metals, and to a wide range of materials in the presence of various primer coatings. However, when one or more epoxy resins, phenol resins, various silane coupling agents, alkyl titanates or aromatic polyisocyanates are mixed in the composition, adhesion to a wider range of materials can be improved.

The curing catalyst used in the present invention includes titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate, organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octoate and tin naphthenate, lead octoate, amino compounds and salts of these compounds and carboxylic acids, such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine and 1, 3-diazabicyclo (5, 4, 6) undecene-7 (DBU), low molecular weight polyamide resin products produced by the reaction between an excess polyamine and a polybasic acid, products of the reaction between an excess polyamine and an epoxy compound, and silanol condensation catalysts such as amino group-containing silane coupling agents (e.g., gamma-aminopropyltrimethoxysilane and N- (β -aminoethyl) aminopropylmethyldimethoxysilane) which may be used alone or in combination.

Solvents may be used, for example, to improve handling and to reduce viscosity. Solvents used for the above purpose include aromatic hydrocarbon-based solvents such as toluene and xylene; ester-based solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate; and ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. Solvents may be used in the process of preparing the polymer.

The aging inhibitors useful for the present invention include common antioxidants such as sulfur-based ones, radical inhibitors and ultraviolet absorbers, although the use of the aging inhibitors is not essential.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

More specifically, the sulfur-based aging inhibitors include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc salt of 2-mercaptobenzothiazole, sulfides such as 4, 4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2 ' -thiobis (4-octylphenol) nickel, dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and 2, 2-thio [ di-3- (3, 5-di-t-butyl-4-hydroxyphenol) diethyl thiodipropionate], diethyl dithiobenzoate, zinc dithiobutyl-dithiobenzoate, zinc dithiobenzoate, e.g., zinc dithiobutyldithiocarbamate, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, and zinc dithiobutyldithiocarbamate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of the curable composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

The sealant composition may be of a one-liquid type or a two-liquid type. The one-liquid type is a type in which a composition containing all components is prepared in advance and sealed, and curing is performed with moisture in the air after applying the composition. The two-liquid type is a type in which a curing agent composition (e.g., a curing catalyst, a filler, a plasticizer, and water used as a curing agent) and a polymer composition are separately prepared and mixed before use.

When the sealant composition is of a one-liquid type, it is preferable that the aqueous component is dehydrated/dried in advance, or dehydrated at the time of mixing/kneading under vacuum, because the composition contains all the components before use.

When the two-liquid type is employed, on the other hand, the sealant composition may contain water to some extent because the main component containing the polymer is not mixed with the curing catalyst in advance and therefore does not gel even if water is present. Nevertheless, when the sealant composition is required to maintain storage stability for a long period of time, it is preferable to dehydrate/dry the composition.

The preferred dehydration/drying method is: drying the solid (such as powder and composition) under heating; for liquid compositions, dehydration is carried out under vacuum or in the presence of synthetic zeolite, activated alumina or silica gel. Further, the liquid composition may be dehydrated in the presence of a small amount of an isocyanate compound in which isocyanate groups react with water.

The storage stability of the composition is further improved by the above-mentioned dehydration/drying treatment and the incorporation of: lower alcohols such as methanol or ethanol; or an alkoxysilane compound such as n-propyltrimethoxysilane, vinylmethyldimethoxysilane, γ -mercaptopropylmethyldimethoxysilane, γ -mercaptopropylmethyldiethoxysilane or γ -glycidoxypropyltrimethoxysilane.

Curable composition (4) and use thereof

The curable composition (4) of the present invention contains a curable composition, as component (A1), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as described previously, more specifically, the composition comprises (a) an organic polymer (Z) and (B) anorganosilicon compound (B4).

The curable composition (4) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

In other words, the present invention provides a sealant, a potting agent, a coating material or an adhesive composed of a curable composition comprising (a) the organic polymer (Z) and (B) the organosilicon compound (B4).

Rubber composition curable at ordinary temperature (5)

The rubber composition (5) curable at ordinary temperature of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), a silane compound (B5), and if necessary, a curing catalyst.

[ silane Compound (B5)]

The silane compound (B5) of the present invention is represented by the following general formula [ VII-1]To [ VII-6]One of them represents:

in the formula, R⁴Is a hydrocarbon group selected from the group consisting of alkyl, aryl and aralkyl groups of 1 to 10 carbon atoms;

x is a group selected from halogen, or from hydroxyl, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoximate and alkenyloxy;

R⁵is alkylene or arylene of 8 to 200 carbon atoms;

R⁶is 8-A monovalent alkyl group of 200 carbon atoms;

"n" is an integer of 0 to 2.

General formula [ VII-1]]Or [ VII-2]]The silane compound represented canbe synthesized by hydrosilylation by reacting a polyolefin compound having a molecular weight of 100-3,000 and an allyl group at one or both ends with a hydrosilane compound represented by the following general formula:

in the formula, R⁴Is a monovalent hydrocarbon group selected from the group consisting of alkyl, aryl and aralkyl groups of 1 to 10 carbon atoms;

x is a group selected from halogen, or from hydroxyl, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoximate and alkenyloxy;

"n" is an integer of 0 to 2.

The silane compound represented by the general formula [ VII-3]or [ VII-4]can be synthesized by first conducting hydrosilylation by Williamson ether synthesis, in which a polyolefin compound having a molecular weight of 100-3,000 and a hydroxyl group at one or both ends is allowed to have an allyl group at one or both ends in a first step, and then conducting hydrosilylation on the product by the above-mentioned hydrosilane compound in a second step.

The silane compound represented by the general formula [ VII-5]or [ VII-6]can be synthesized, for example, by capping a polyolefin compound having a molecular weight of 100-3,000 and having a hydroxyl group at one or both ends with isocyanate silane.

The hydrosilylation reaction between allyl and hydrosilane compound is quantitatively carried out at 50 to 150 ℃ for 1 to 4 hours in the presence of a complex catalyst of a transition metal of group 8 selected from platinum, rhodium, cobalt, palladium and nickel.

The reaction between the hydroxyl groups and the isocyanate silane can be carried out in the presence or absence of a catalystIn the presence of a catalyst. However, a catalyst may be used when it is desired to accelerate the addition reaction.Catalysts which can be used for the above purpose include organotin compounds such as dibutyltin dilaurate and tin octylate, and tertiary amine compounds such as dimethylbenzylamine and triethylamine. The reaction is carried out at 50-150 deg.C, and the far infrared light is absorbedSpectrum at 2270cm^-1The NCO absorption peak at (A) was traced.

Specific examples of the polyolefin compound having an allyl group at one or both terminals thereof include: 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1, 7-octadiene, 1, 9-decadiene, and 1, 13-tetradecadiene.

Specific examples of the polyolefin compound having a hydroxyl group at one or both terminals thereof include: 1-octanol, 1-decanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 1, 8-octanediol, 1, 10-decanediol, 1, 14-tetradecanediol, 1, 16-hexadecanediol, 1, 18-octadecanediol, polyolefin polyols (Polytail-HA,<M-1000>_3, Polytail HA _, Mitubishi Chemical Corporation) and polybutadiene diols and hydrogenated polybutadiene diols (NISSO-PB G-1000_, NISSO-PB G-2000_, NISSO-PB-1000 _ and NISSO-PB-GI-2000 _ Nippon Soda).

Specific examples of the hydrosilane compound include:

halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane;

alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane and phenyldimethoxysilane;

acyloxysilanes such as triacetoxysilane, methyldiacetoxysilane, and phenyldiacetoxysilane;

dimethyl ethyl methyl oxime silane; and

triaminooxysilane, methyldiaminooxysilane and methyldiaminosilane.

Specific examples of the isocyanate silane include gamma-isocyanate propyltrimethoxysilane, gamma-isocyanate propyltriethoxysilane, gamma-isocyanate propylmethyldimethoxysilane.

[ curing catalyst (C)]

Specific examples of the curing catalyst (C) which can be used in the present invention as required include:

organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dioctyltin laurate, dioctyltin maleate and tin octylate;

phosphoric acid and phosphoric acid esters such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecanyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate and didecyl phosphate;

propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidyl, allyl glycidyl ether, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane,

Addition reaction products between Epoxy compounds and phosphoric acid or monoacid-valent phosphoric esters, such as Cardura E (Yuka Shell Epoxy), and Epikote 828 and Epikote 1001 (Yuka Shell Epoxy);

β -hydroxyethyl mono [ methacrylate]acid phosphates (KAYAMER PM-1. ANG., KAYAMERPM-2. ANG., and KAYAMER PM-21. ANG. (NIPPON KAYAKU), and copolymers having a number average molecular weight of 1,000-30,000 and an acid phosphate group, are obtained by copolymerization of a compound having both an acid phosphate group and a polymerizable double bond in the molecule (e.g., a reaction product between glycidyl methacrylate and a phosphate ester) and a vinyl monomer;

an alkyl titanate;

organoaluminum;

acidic compounds such as maleic acid and p-toluenesulfonic acid;

amines such as hexylamine, di-2-ethylhexylamine, N-dimethyldodecylamine, and dodecylamine; and

basic compounds, such as sodium hydroxide and potassium hydroxide.

The reaction can be carried out in the absence of a curing catalyst (C). However, when the curing reaction is to be accelerated, the above-mentioned catalysts may be used alone or in combination.

[ composition ratio]

The mixing ratio (A)/(B)/(C) of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), the silane compound (B5) and the curing catalyst (C) is preferably 100/0.1 to 100/0 to 20 (weight ratio), more preferably 100/0.5 to 20/0.01 to 10.

If the content of the silane compound (B5) is less than 0.1 part by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), the effect of improving adhesion cannot be exhibited, while if it exceeds 100 parts by weight, problems such as deterioration of compatibility with the copolymer rubber (A1) and embrittlement of the coating film are caused.

The mechanism involved in the effect of improving the adhesion by the silane compound having a long polyolefin chain (B5) is not completely understood, but it is thought to be caused by incorporation of a lower molecular weight compound (B5) into the network structure.

The effect of the silane compound (5) is not limited to improvement of adhesion to melamine alkyd resin or melamine acrylic resin, but also to improvement of hardness, solvent resistance and stain resistance of the rubber composition (5) curable at ordinary temperatures of the present invention. The above-mentioned effects are particularly remarkable in terms of improvement in hardness and solvent resistance with the silane compound (5) having 2 hydrolyzable silyl groups in the molecule and improvement in stain resistance with the silane compound (B5) having 1 hydrolyzable silyl group in the molecule.

[ other Components]

The rubber composition (5) curable at ordinary temperature of the present invention may be incorporated with a dehydrating agent, although this is not essential. However, a dehydrating agent may be incorporated for keeping the rubber composition (5) stable for a long period of time, or may be recycled without causing problems.

Specific examples of the dehydrating agents used in the present invention include: hydrolyzable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate and ethyl silicate.

The hydrolyzable ester compound may be added to the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) at the time of its production or after it has been produced.

The rubber composition (5) curable at ordinary temperature of the present invention may further be incorporated with various additives such as: anti-settling agents and leveling agents; cellulose, nitrocellulose and cellulose acetate butyrate; resins such as alkyd resins, acrylic resins, vinyl chloride resins, chlorinated acrylic resins, chlorinated rubbers, and polyvinyl butyral rubbers; an adhesion promoter; a performance modifier; a storage stability improver; plasticizers, fillers; an anti-aging agent; an ultraviolet absorber; a metal deactivator; inhibitors against ozone-induced aging; a light stabilizer; an amine-based free radical chaining inhibitor; a phosphorus-based peroxide decomposer; a lubricant; pigments and foaming agents, within limits not adversely affecting the object of the invention.

Specific examples of the adhesion promoter include phenol resins, epoxy resins, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates, the adhesion promoter is preferably added in an amount of about 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/polyene α -olefin/nonconjugated random copolymer rubber (A1).

The storage stability improver used in the present invention comprises an organic acid ester, and the storage stability improver is preferably added in an amount of about 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. It is preferable that the plasticizer should be compatible with each component of the rubber composition (5) curable at ordinary temperature of the present invention.

Specific examples of these plasticizers include:

hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin co-oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene;

chlorinated paraffin;

phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;

esters of polyalkylene glycols, such as diethylene glycol benzoate and triethylene glycol dibenzoate;

phosphoric acid esters such as tricresyl phosphate and tributyl phosphate;

among them, the saturated hydrocarbon-based compounds are more preferable. They may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with the various components of the rubber composition of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

When a hydrolyzable silyl group is introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A0), a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

The plasticizer is preferably added in an amount of about 10 to 500 parts by weight, more preferably 20 to 300 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Specific examples of the filler include wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder and zinc powder, among which thixotropicfillers such as settling silica, fumed silica and carbon black are more preferable, and calcium carbonate, titanium oxide and talc are preferably used in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the silyl-containing ethylene/α -olefin/nonconjugated random copolymer rubber (A1).

The aging inhibitors useful for the present invention include commonly known sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

More specifically, the sulfur-based aging inhibitors include:

thiols, such as 2-mercaptobenzothiazole;

mercaptides, such as the zinc salt of 2-mercaptobenzothiazole;

sulfides, such as 4, 4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (2-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, terephthaloyl bis (2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and diethyl 2, 2-thio [ bis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate];

polysulfides, such as 2-benzothiazole disulfide;

dithiocarboxylates such as zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate and zinc dimethylcarbamate;

thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolylthiourea and ethylenethiourea; and

thiophosphates, such as trilauryl trithiophosphate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of the curable rubber composition of the present invention, and controls problems such as residual surface tackiness.

Free radical inhibitors useful in the present invention include phenolic free radical inhibitors such as 2, 2-methylenebis- (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino free radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

The age resistor is added in an amount of about 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Rubber composition curable at ordinary temperature (5) and use thereof

The rubber composition (5) curable at ordinary temperature of the present invention comprises a curable composition comprising a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, the composition comprises an organic polymer (Z), a silane compound (B5), and if necessary, a curing catalyst (C). the curable rubber composition is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, as described above.

The rubber composition (5) curable at ordinary temperatures of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

Curable rubber composition (6)

The curable rubber composition (6) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), a specific amine (D), a specific silane coupling agent (B6) and a specific resin (E) as active components.

[ amine (D)]

The amine (D) used in the present invention is selected from aliphatic amines, alicyclic amines, modified cycloaliphatic polyamines and ethanolamine.

Specific examples of the aliphatic amine used in the present invention include triethylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

Specific examples of the alicyclic amine used in the present invention include piperidine and piperazine.

Specific examples of the modified cyclic aliphatic polyamine used in the present invention include materials used as hardeners for epoxy resins.

Specific examples of the ethanolamine used in the present invention include monoethanolamine, diethanolamine and triethanolamine.

These amines may beused alone or in combination.

The amine is usually added in an amount of 30 parts by weight or less but more than 0 part by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ silane coupling agent (B6)]

The silane coupling agent (B6) used in the present invention is represented by the following general formula:

Y₃(Si) Z wherein Y is alkoxy; z is an alkyl group containing a functional group selected from the group consisting of an amino group (which may be substituted or unsubstituted with an aminoalkyl group) and a mercapto group.

Specific examples of the silane coupling agent (B6) represented by the above general formula include gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane.

The silane coupling agent (B6) is added in an amount of usually 10 parts by weight or less but more than 0 part by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ resin (E)]

The resin (E) used in the present invention includes: known as a varnish-based paint, an acrylic resin-based paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy-based paint, or an organopolysiloxane.

For the present invention, a sufficient amount of the resin (E) is mixed with the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), the amine (D) and the silane coupling agent (B6).

The content of the resin (E) is not limited, but it is generally 0.1 to 1,000 parts by weight, preferably 1 to 500 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and the above-mentioned amount also includes a solvent when the resin (E) is dissolved in the solvent.

Curable rubber composition (6)

The curable rubber composition (6) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), an amine (D), a silane coupling agent (B6) and a resin (E) as active components, as described previously.

The curable rubber composition (6) of the present invention may be incorporated, as required, with various additives such as adhesion promoter; a performance modifier; a storage stability improver; plasticizers, fillers; an anti-aging agent; an ultraviolet absorber; a metal deactivator; inhibitors against ozone-induced aging; a light stabilizer; an amine-based free radical chaining inhibitor; a phosphorus-based peroxide decomposer; a lubricant; pigments and blowing agents within limits that do not adversely affect the objects of the invention.

The adhesion promoter used in the present invention includes silane coupling agents such as conventional adhesives and aminosilane compounds, and other compounds, and specific examples of these adhesion promoters include phenol resins, epoxy resins, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanate and aromatic polyisocyanate, and when the adhesion promoter is used, it is preferably added in an amount of about1 to 50 parts by weight, more preferably about 5 to 30 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/non-conjugated polyene random copolymer rubber (A1).

The storage stability improvers useful for the present invention include esters of ortho-organic acids, such as methyl orthoformate.

When the storage stability improver is used, it is preferably added in an amount of about 0.5 to 20 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. It is preferable that the plasticizer should be compatible with each component of the rubber composition (6) of the present invention.

Specific examples of these plasticizers include:

hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin co-oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene;

chlorinated paraffin;

phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;

esters of polyalkylene glycols, such as diethylene glycol benzoate and triethylene glycol dibenzoate;

phosphoric acid esters, such as tricresyl phosphate and tributyl phosphate. Among them, the saturated hydrocarbon-based compounds are more preferable. They may be used alone or in combination.

Of these compounds, hydrocarbon-based compounds free of unsaturated groups, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable because they are well compatible with the respective components of the rubber composition (6) of the present invention, have a limited effect on the curing speed of the rubber composition, are high in the resistance to weather of the cured product, and are inexpensive.

When a hydrolyzable silyl group is introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A0), a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is preferably added in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Specific examples of the filler include wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder and zinc powder, among which thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable, and calcium carbonate, titanium oxide and talc are preferably used in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the silyl-containing ethylene/α -olefin/nonconjugated random copolymer rubber (A1).

The aging inhibitors useful for the present invention include commonly known sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful for the present invention include:

thiols, such as 2-mercaptobenzothiazole;

mercaptides, such as the zinc salt of 2-mercaptobenzothiazole;

sulfides, such as 4, 4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (2-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, terephthaloyl bis (2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and diethyl 2, 2-thio [ bis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate];

polysulfides, such as 2-benzothiazole disulfide;

dithiocarboxylates such as zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate and zinc dimethylcarbamate;

thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolylthiourea and ethylenethiourea; and

thiophosphates, such as trilauryl trithiophosphate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of the curable rubber composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Curable rubber composition (6) and use thereof

The curable rubber composition (6) of the present invention comprises a curable composition, a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, the composition comprises, as active components, an organic polymer (Z), an amine (D), a silane coupling agent (B6), and a resin (E) comprising a varnish-based coating, an acrylic resin-based coating, a thermosetting acrylic coating, an alkyd coating, a melamine coating, an epoxy-based coating, or an organopolysiloxane.

The curable rubber composition (6) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

Curable composition (7)

The curable composition (7) of the present invention comprises (a) a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and (B) a silane group compound substituted with an amino group (B7).

The curable composition (7) of the present invention is preferably a composition comprising (a) a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), (B) a compound having a silanol group and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule (B1), and the above-mentioned silyl group-substituted compound (B7) substituted with an amino group, wherein the compound (B7) comprises:

(c) a compound having a group containing a silicon atom to which two hydrolyzable groups are bonded and an amino group (B7-1), and

(d) a compound having a group containing a silicon atom to which three hydrolyzable groups are bonded and an amino group (B7-2).

The curable composition (7) of the present invention shows excellent properties in curing speed and weather resistance, which are mainly derived from a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The curable composition (7) of the present invention may be incorporated, as required, with a compound having a silanol group and/or a compound (monovalent silanol-based compound) capable of reacting with moisture to form a compound having a silanol group in the molecule (B1).

Component (B1) is expected to lower the modulus of the cured silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) component (B1) is readily available and is excellent in that it can produce the above-mentioned effects as long as it is blended into the hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ amino-containing silyl Compound (B7)]

The curable composition (7) of the present invention is compounded with the amino group-containing silane-based compound (B7) and with the hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). A wide variety of amino group-containing silane-based compounds can be used alone or in combination, however, it is preferable to use both the following compounds (B7-1) and (B7-2), wherein the compound (B7-1) has a group containing a silicon atom to which 2 hydrolyzable groups are bonded and an amino group (bifunctional aminosilane compound), and the compound (B7-2) has a group containing a silicon atom to which 3 hydrolyzable groups are bonded and an amino group (trifunctional aminosilane compound).

[ bifunctional aminosilane Compound (B7-1)]

The group containing silicon to which 2 hydrolyzable groups are bonded in the bifunctional aminosilane compound (B7-1) of the present invention is represented by the following general formula:

in the formula, R²Is a monovalent organic group of 1 to 40 carbon atoms; x' is a hydrolyzable group.

Examples of hydrolyzable groups include halogen and hydrogen atoms, as well as alkoxy, acyloxy, ketoxime, amino, amide, aminoxy, mercapto and alkenyloxy groups. More preferable are alkoxy groups such as methoxy or ethoxy groups because of their mild hydrolyzability.

The amino group may be-NH₂Or substituted amino groups, e.g. -NH, in which a hydrogen atom is substituted by another group₂. Amino groups of the general formula-N (R)⁴)₂Is represented by the formula (I) in which R⁴Are hydrogen atoms or hydrocarbon groups of 1 to 30 carbon atoms, which may be substituted or unsubstituted, and may be the same or different.

Specific examples of the bifunctional aminosilane compound (B7-1) include H₂NCH₂CH₂CH₂Si(CH₃)(OCH₃)₂，H₂NCH₂CH₂NHCH₂CH₂CH₂Si(CH₃)(OCH₃)₂，(CH₃)NHCH₂CH₂CH₂Si(CH₃)(OCH₃)₂，(C₂H₅)NHCH₂CH₂NHCH₂CH₂CH₂Si(CH₃)(OCH₃)₂，H₂NCH₂CH₂CH₂Si(CH₃)(OCOCH₃)₂，H₂NCH₂CH₂CH₂Si(CH₃)(ON＝C(CH₃)(C₂H₅))₂And H₂NCH₂CH₂CH₂Si(CH₃)(OC(CH₃)＝CH₂)₂.

The bifunctional aminosilane compound (B7-1) is preferably added in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). at the same time, the addition of an excess amount of the bifunctional aminosilane compound (B7-1) relative to the monovalent silanol-based compound (B1) is disadvantageous.the weight ratio of the monovalent silanol-based compound (B1)/the bifunctional aminosilane compound (B7-1) is preferably 1/0.01 to 1/5, more preferably 1/0.05 to 1/2.

[ trifunctional aminosilane Compound (B7-2)]

The group containing the silicon atom to which 3 hydrolyzable groups are bonded in the trifunctional aminosilane compound (B7-2) of the invention is represented by the general formula-SiX₃Wherein X is a hydrolyzable group. The amino group is the same as described above.

Specific examples of the trifunctional aminosilane compound (B7-2) include: h₂NCH₂CH₂CH₂Si(OCH₃)₃，H₂NCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃，(CH₃)NHCH₂CH₂CH₂Si(OCH₃)₃，(C₂H₅)NHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃，H₂NCH₂CH₂CH₂Si(OCOCH₃)₃，H₂NCH₂CH₂CH₂Si(ON＝C(CH₃)(C₂H₅))₃And H₂NCH₂CH₂CH₂Si(OC(CH₃)＝CH₂)₃.

The trifunctional aminosilane compound (B7-2) is preferably added in an amount of 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). at the same time, it is disadvantageous to add the trifunctional aminosilane compound (B7-2) in an excess amount relative to the monovalent silanol-based compound (B1) because the modulus of the cured composition increases. the weight ratio of the monovalent silanol-based compound (B1)/trifunctional aminosilane compound (B7-2) is preferably1/0.01 to 1/0.75, more preferably 1/0.02 to 1/0.5.

[ other Components]

The curable composition (7) of the present invention may be incorporated with one or more additives, such as a curing accelerator, a plasticizer or a filler, as required.

The curing accelerators used in the present invention include: organotin compounds, acid phosphates, reaction products between acid phosphates and amines, saturated or unsaturated polyvalent carboxylic acids or anhydrides thereof, and organotitanate compounds.

The organotin compounds used in the present invention include dibutyltin dilaurate, dioctyltin maleate, dibutyltin phthalate, tin octylate and dibutyltin methoxide.

Acid phosphates useful in the present invention include compounds containing a moiety represented by the formula:

for example, compounds represented by the following general formula:

wherein "d" is 1 or 2, R⁵Is an organic group. More specifically, the following compounds are included:

organic titanate compounds include titanates such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.

When the curing accelerator is used, it is preferably added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Plasticizers useful in the present invention include low molecular weight plasticizers (such as dioctyl phthalate), high molecular weight plasticizers, and high viscosity plasticizers.

Specific examples of the plasticizer used in the present invention include: phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; esters of polyalkylene glycols, such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffin; and

hydrocarbon-based oils such as alkylbiphenyls, polybutenes, hydrogenated polybutenes, ethylene/α -olefin oligomers, α -methylstyrene oligomers, biphenyls, terphenyls, triaryldimethanes, alkylene terphenyls, liquid polybutadienes, hydrogenated liquid polybutadienes, paraffin oils, naphthene oils, atactic polypropylenes, and partially hydrogenated terphenyls.

These plasticizers may be used alone or in combination, and may be mixed in when preparing the polymer.

Of these, hydrocarbon-based compounds free of unsaturated groups, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable because these compounds are well compatible with the respective components of the curable composition (7) of the present invention, have a limited effect on the curing speed of the composition, and the resulting cured product is high in resistance to weather and inexpensive.

The above plasticizers can be selected according to the particular use, for example, to adjust characteristics and properties.

When the plasticizer is used, it is incorporated in an amount of about 1 to 400 parts by weight, preferably 1 to 150 parts by weight, further preferably 10 to 120 parts by weight, particularly preferably 20 to 100 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate, quartz powder, glass beads, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc. These fillers may be used alone or in combination.

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

More specifically, the sulfur-based aging inhibitors include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc salt of 2-mercaptobenzothiazole, sulfides such as 4, 4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2 ' -thiobis (4-octylphenol) nickel, dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and 2, 2-thio [ di-3 (3, 5-di-t-butyl-4-hydroxyphenol) diethyl thiodipropionate], diethyl dithiobenzoate, zinc dithiobenzoate, e.g., zinc dibutyldithiocarbamate, zinc dithiobutyl-dithiobenzoate, zinc dithioethylthiodicarbamate, zinc dithiobenzoate, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, and zinc dithioethylthiodicarbamate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than the other types of the curable composition (7) of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

The thus-obtained curable composition (7) of the present invention can be used for adhesives, tackifiers, coatings, water-proofing materials for coating films, sealant compositions, molding materials, casting rubber materials and foaming materials.

For example, when used as a sealant for construction engineering, the composition (7) of the present invention is mixed with an inorganic filler such as calcium carbonate, talc or kaolin, usually in an amount of 10 to 300 parts by weight, and may further have a pigment (e.g., titanium oxide, carbon black), an ultraviolet absorber or an age resister (radical chaining inhibitor) as required, and kneaded uniformly andsufficiently by a kneader or a paint roll. The composition cures into a rubber elastomer with good properties when applied and exposed to moisture in the air.

Curable composition (7) and its use

The curable composition (7) of the present invention comprises a curable composition, a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, the curable composition (7) comprises (a) an organic polymer (Z) and (B) a silane-based compound substituted with an amino group (B7), and is suitable for use in the fields of electric/electronic device members, transportation machines, and civil engineering/construction, medical care, and leisure, as described previously.

As mentioned above, the composition (7) preferably comprises:

(a) an organic polymer (Z) which is a polymer of,

(b) a monovalent silanol-based compound (B1), and

the above silane-based compound substituted with amino group (B7), which comprises:

(c) a bifunctional aminosilane compound (B7-1) and

(d) a trifunctional aminosilane compound (B7-2).

The curable composition (7) of the present invention is suitable as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

In other words, the present invention can provide a sealant, a potting agent, a coating material or an adhesive composed of a curable composition comprising the organic polymer (Z) and the silane-based compound substituted with an amino group (B7).

As described above, it is preferable that each of the sealing material, thepotting agent, the coating material and the adhesive contains:

(a) an organic polymer (Z) which is a polymer of,

(b) a monovalent silanol-based compound (B1), and

the above silane-based compound substituted with amino group (B7), which comprises:

(c) a bifunctional aminosilane compound (B7-1) and

(d) a trifunctional aminosilane compound (B7-2).

Curable composition (8)

The curable composition (8) of the present invention contains a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and filler (F), plasticizer (G), curing catalyst (H) and organic carboxylate compound (B8).

The curable composition (8) of the present invention exhibits excellent properties in curing speed and weather resistance, which are mainly derived from a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ Filler (F)]

The filler (F) used in the present invention is not limited. Specific examples of the filler include reinforcing fillers such as fumed silica, settling silica, silicic anhydride, silicon hydride (silica hydride), and carbon black; inorganic or organic fillers such as calcium carbonate, magnesium carbonate, diatomaceous earth, fireclay, clay, talc, titanium oxide, bentonite, organic bentonite, iron oxide, zinc oxide, activated zinc white, hydrogenated castor oil, PVC and polyolefins; fibrous fillers, such as asbestos and glass fibers or filaments; inorganic or organic spheres such as silas, glass, vinylidene chloride, and phenol.

These fillers may be used alone or in combination.

[ plasticizer (G)]

The plasticizer (G) used in the present invention is not limited and specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, dioctyl phthalate, butylbenzyl phthalate and butylphthaloyl butyl glycolate, non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate, phosphoric acid esters such as tricresyl phosphate and tributyl phosphate, chlorinated paraffins, and hydrocarbon-based oils such as alkylbiphenyl, polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atactic polypropylene and partially hydrogenated terphenyl.

These compounds may be used alone or in combination, and these plasticizers may be incorporated in the preparation of the polymer.

Of these, the hydrocarbon-based compounds are more preferable because they are commonly used, low in cost and excellent in weather resistance.

[ curing catalyst (H)]

Specific examples of the curing catalyst include silanol condensation catalysts such as titanates, e.g., tetrabutyl titanate and tetrapropyl titanate, tin carboxylates, e.g., dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octoate and tin naphthenate, reaction products between dibutyltin oxide and phthalates, dibutyltin bisacetylacetonate, organoaluminum compounds, e.g., aluminum triacetylacetonate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate, chelates, e.g., zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octoate, amino compounds, and salts of these compounds with carboxylic acids, e.g., butylamine, octylamine, dodecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1, 8-diazabicyclo (5, 4, 0) diamine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1, 8-diazabicyclo (5, 7-bis (7-dimethoxysilane) condensation catalysts, gamma-7-epoxypropyl silane, such as a polyamine, a low molecular weight coupling agent, a combination of these compounds, and a polyamine, such as a polyamine, a low molecular weight, a polyamine, a combination of the use of the above, a polyamine, a.

Of these curing catalysts, the more preferable are titanium-based or tin-based compounds from the viewpoint of availability and cost performance.

The curing condensation catalyst is added preferably in an amount of about 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). A catalyst content below the above range is disadvantageous because of insufficient curing speed and insufficient extent of curing reaction, and above the above range is disadvantageous because local overheating or foaming occurs during curing, making it difficult to obtain a cured product having good properties.

[ organic carboxylate Compound (B8)]

The organic carboxylic acid salt compound (B8) used in the present invention includes aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aliphatic polycarboxylic acids and aromatic carboxylic acids. Specific examples of the various carboxylic acids are as follows, but notlimited thereto.

(1) Aliphatic monocarboxylic acids:

(a) saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, acetoacetic acid, ethylmethylacetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethylbutyric acid, ethoxybutyric acid, valeric acid, isovaleric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, undecanoic acid, stearic acid, glyoxylic acid, glycolic acid and gluconic acid;

(b) olefinic monocarboxylic acids, such as acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenic acid, elaidic acid, erucic acid, and oleic acid;

(c) acetylenic monocarboxylic acids, such as propiolic acid;

(d) diolefinic monocarboxylic acids, such as linoleic and elaidic acid;

(e) highly unsaturated monocarboxylic acids such as linolenic acid and arachidonic acid; and

(f) halogen-substituted monocarboxylic acids such as chloroacetic acid, 2-chloroacrylic acid, and chlorobenzoic acid;

(2) aliphatic dicarboxylic acids:

(a) saturated dicarboxylic acids such as adipic acid, azelaic acid, ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, and oxydiacetic acid; and

(b) unsaturated dicarboxylic acids such as maleic acid, fumaric acid, acetylene dicarboxylic acid and itaconic acid;

(3) aliphatic polycarboxylic acids:

(a) tricarboxylic acids, such as aconitic acid, citric acid and isocitric acid,

(4) aromatic carboxylic acids:

(a) aromatic monocarboxylic acids such as benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acidand phenylacetic acid;

(b) aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, carboxyphenylacetic acid and pyromellitic acid;

(5) others

Amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan and histidine.

Any compound can be used as the organic carboxylic acid (8) of the present invention as long as the compound has at least one carboxyl group. These compounds may be used alone or in combination. Of these compounds, aliphatic monocarboxylic acid compounds are more preferable, and monocarboxylic acids having 2 to 30 carbon atoms are still more preferable.

However, from the viewpoint of a balance between the effect improvement and the cost, the organic carboxylic acid (8) is usually added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ other Components]

The curable composition (8) of the present invention may be appropriately blended with various additives such as a dehydrating agent, a tackifier, a property adjuster, a storage stability improver, an aging inhibitor, an ultraviolet absorber, a metal deactivator, an ozone-induced aging inhibitor, a light stabilizer, an amine-based radical chaining inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment and a foaming agent, as required.

The dehydrating solvent used in the present invention includes a compound capable of reacting with water, particularly preferably a hydrolyzable silicon compound. The hydrolyzable silicon compound is a generic term for a low molecular weight silicon compound having a hydrolyzable functional group which is reactive in the presence of moisture, and the molecular weight of such hydrolyzable silicon compound is generally preferably 300 or less. The hydrolyzable silicon compound may contain any other functional group in addition to the hydrolyzable functional group. Hydrolyzable groups include alkoxy, acyloxy, ketoximate, amino, aminoxy, amide, and alkenyloxy groups. Other functional groups include epoxy groups, amino groups, acrylic groups, and thiol-containing groups.

Specific examples of these compounds include:Si(OC₂H₅)₄、CH₂＝CHSi(OAc)₃、

HSCH₂CH₂CH₂Si(OCH₃)₃

in addition to being used as a dehydrating agent, an aminosilane compound may be incorporated as a tackifier and a dehydrating agent.

The aminosilane compound used in the present invention includes alkoxysilane substituted with amino group and its derivative. Specific examples of these compounds include a reaction product between an amino-substituted alkoxysilane or a derivative thereof such as:H₂NCH₂CH₂CH₂Si(OCH₃)₃，H₂NCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃，

(C₂H₅O)₃SiCH₂CH₂CH₂NHCH₂CH₂-

-NHCH₂CH₂CH₂Si(OC₂H₅)₃the epoxy silanes are, for example:the acryl silane is, for example:

the reaction product of the amino group-substituted alkoxysilane with the epoxy silane compound or with the acryl silane compound can be easily prepared by mixing the silane compound and the amino group-substituted alkoxysilane in a molar ratio of 0.2: 5 at room temperature to 180 ℃ with stirring for 1 to 8 hours.

The amino-substituted alkoxysilane or derivative thereof is preferably added in an amount of about 0.01 to 20 parts by weight per 100 parts by weight of the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Specific examples of the adhesion promoters include phenol resins, epoxy resins, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, benzofuran/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates.

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded and esters of organic acids. Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate.

The aging inhibitors useful for the present invention include commonly used known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfoniumcompounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

More specifically, the sulfur-based aging inhibitors include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc salt of 2-mercaptobenzothiazole, sulfides such as 4, 4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2 ' -thiobis (4-octylphenol) nickel, dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and 2, 2-thio [ di-3 (3, 5-di-t-butyl-4-hydroxyphenol) diethyl thiodipropionate], diethyl dithiobenzoate, zinc dithiobenzoate, e.g., zinc dibutyldithiocarbamate, zinc dithiobutyl-dithiobenzoate, zinc dithioethylthiodicarbamate, zinc dithiobenzoate, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, and zinc dithioethylthiodicarbamate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of compositions of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole andbis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

The method for preparing the composition (8) of the present invention is not limited. For example, the composition comprising the above components may be kneaded at normal or high temperature with a mixer, a roller or a kneader, or mixed after dissolving the components in a small amount of a suitable solvent. These components are added in an appropriate ratio to prepare a one-liquid type or two-liquid type curable composition.

The curable composition (8) of the present invention forms a three-dimensional network structure when exposed to moisture in the air, which itself is converted into a solid having rubber-like elasticity.

Curable composition (8) and its use

The curable composition (8) of the present invention contains a curable composition, as component (A1), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber more specifically, the curable composition (8) of the present invention comprises (a) an organic polymer (Z), and a filler (F), a plasticizer (G), a curing catalyst (H) and an organic carboxylate compound (B8), and is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, as described previously.

The curable composition (8) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

In other words, the present invention provides a sealant, a potting agent, a coating material or an adhesive composed of a curable composition comprising (a) the organic polymer (Z), and filler (F), plasticizer (G), curing catalyst (H) and organiccarboxylate compound (B8).

The curable composition (8) of the present invention is particularly suitable for use in elastomer sealants for buildings, ships, vehicles and roads, and also for various sealants and adhesive compositions because it has adhesion to a wide range of substrates such as glass moldings, porcelain, wood, metal and resin with or without a primer. Further, the curable composition (8) can be used as a tackifier, a coating material, a water-repellent material for coating film, a food packaging material, a molding material, a casting rubber material and a foaming material. Curable rubber composition (9)

The curable rubber composition (9) of the present invention contains a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), an alcohol (B9) and/or a hydrolyzable ester compound (I) (except for the hydrolyzable organosilicon compound (B10)).

[ alcohol (B9)]

Specific examples of the alcohol (B9) among the alcohols (B9) and/or hydrolyzable ester compounds (I) used in the present invention (except for the hydrolyzable organosilicon compound (B10)) include methanol, ethanol, 2-methoxyethanol, sec-butanol and tert-butanol. These mentioned alcohols are preferably used in the present invention.

The amount of the alcohol (B9) added is preferably 5 to 40 parts by weight, more preferably 7 to 30 parts by weight, still more preferably 10 to 20 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the amount added is less than 5 parts by weight, the storage stability of the cured composition, which is one of the objects of the present invention, is not sufficiently improved, and when the amount added exceeds 40 parts by weight, a phenomenon called brushing (blushing) occurs, so that not only the composition itself but also the coating film is clouded and whitish.

Hydrolyzable ester Compound (I)

Specific examples of the alkyl orthoformate include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate and orthophenyl, among the alcohol (B9) and/or hydrolyzable ester compound (I) used in the present invention (except for the hydrolyzable organosilicon compound (B10)), of which methyl orthoformate and ethyl orthoformate are more preferable, the hydrolyzable ester compound (I) is added in an amount of 3 to 30 parts by weight, more preferably 5 to 20 parts by weight, still more preferably 10 to 20 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the amount added is less than 3 parts by weight, the storage stability of the cured composition cannot be sufficiently improved, which is one of the objects of the present invention, the upper limit of the content of the hydrolyzable ester compound (I) is not limited, but it is uneconomical to use of the compound in excess of 30 parts by weight.

Hydrolyzable organosilicon Compound (B10)

The hydrolyzable organosilicon compounds (B10) used in the present invention include: an alkoxysilane compound. Specific examples of these compounds include: trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, ethyldiethoxysilane, ethyldimethoxysilane, butyldiethoxysilane, butyldimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, dibutyldiethoxysilane, and diphenyldiethoxysilane.

The hydrolyzable organosilicon compound (B10) is added preferably in an amount of 2 to 20 parts by weight, more preferably 2 to 15 parts by weight, still more preferably 2 to 10 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the amount added is less than 2 parts by weight, the storage stability of the cured composition, which is one of the objects of the present invention, cannot be sufficiently improved, whereas when the amount added exceeds 20 parts by weight, the cured coating film becomes brittle.

[ curing accelerators]

A curing accelerator is not necessary for curing the curable rubber composition of the present invention. The curing accelerators useful in the present invention, when used, include alkyl titanates, metal carboxylates (e.g., tin octoate and dibutyltin laurate), amine salts (e.g., dibutylamine-2-hexanoate), and other acidic or basic catalysts.

The curing accelerator is preferably added in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ other Components]

The curable rubber composition (9) of the present invention may be incorporated, as required, with one or more additives within limits not adversely affecting the object of the present invention. The additives used in the invention comprise adhesion promoters, performance regulators, storage stability improvers, plasticizers, fillers; an anti-aging agent, an ultraviolet absorber, a metal deactivator, an inhibitor against aging caused by ozone, a light stabilizer, an amine-based radical chaining inhibitor, a phosphorus-based peroxide decomposer; a lubricant; pigments and blowing agents.

The adhesion promoter used in the present invention includes conventional adhesives and silane coupling agents such as aminosilane compounds and epoxysilane compounds, and other compounds specific examples of these adhesion promoters include phenol resins, epoxy resins, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, benzofuran/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanate and aromatic polyisocyanate, and when the adhesion promoter is used, it is preferably added in an amount of about 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The storage stability improver used in the present invention comprises an orthoorganic acid ester (excluding an orthoformic acid alkyl ester). when the storage stability improver is used, it is preferably added in an amount of about 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. It is preferable that the plasticizer should be compatible with each component of the rubber composition (9) of the present invention.

Specific examples of these plasticizers include:

hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene;

chlorinated paraffin;

phthalic acid esters,such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;

esters of polyalkylene glycols, such as diethylene glycol benzoate and triethylene glycol dibenzoate;

phosphoric acid esters, such as tricresyl phosphate and tributyl phosphate. Among them, the saturated hydrocarbon-based compounds are more preferable. They may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the rubber composition (9) of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

When a hydrolyzable silyl group is introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A0), a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

The plasticizer is incorporated preferably at about 10 to 500 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), more preferably about 20 to 300 parts by weight.

Specific examples of the filler include wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc,titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder and zinc powder, among which thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable, and calcium carbonate, titanium oxide and talc are preferably used in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the silyl-containing ethylene/α -olefin/nonconjugated random copolymer rubber (A1).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful for the present invention include:

thiols, such as 2-mercaptobenzothiazole;

mercaptides, such as the zinc salt of 2-mercaptobenzothiazole;

sulfides, such as 4, 4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (2-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, terephthaloyl bis (2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and diethyl 2, 2-thio [ bis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate];

polysulfides, such as 2-benzothiazole disulfide;

dithiocarboxylates such as zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate and zinc dimethyldithiocarbamate;

thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolylthiourea and ethylenethiourea; and

thiophosphates, such as trilauryl trithiophosphate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of the curable rubber composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Curable rubber composition (9)

The curable rubber composition (9) of the present invention contains the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), the alcohol (B9) and/or the hydrolyzable ester (I) (preferably, alkyl orthoformate), the hydrolyzable organosilicon compound (B10) (preferably, an alkoxysilane compound) as previously described, and a curing accelerator which may be added as needed.

[ preparation of curable rubber composition (9)]

An example is kneading of a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and an alcohol (B9) and/or a hydrolyzable ester (I), a hydrolyzable organosilicon compound (B10), and one or more additives such as a curing accelerator, an adhesion accelerator, a property adjuster, a storage stability improver, a plasticizer, a filler and a pigment which may be used as needed to uniformly disperse these components in the copolymer rubber, kneading the composition at room temperature to 180 ℃ for 30 seconds to 30 minutes with a planetary mixer, a roller, a kneader or an internal mixer.

The composition thus prepared is suitable for a one-liquid type curable composition, not to mention a two-liquid type composition. For the one-liquid type composition, it is necessary to remove moisture from the composition when the copolymer rubber (A1) is dispersed with other components. It can withstand long-term storage maintained under sealed conditions, and rapidly starts to cure from the surface when exposed to an atmospheric atmosphere. It is preferred to remove moisture from the composition under heating or with a mixer equipped with a pressure reducing device.

Can be fixedRubber composition (9) and use thereof

As described previously, the curable composition (9) of the present invention comprises a curable composition, a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, the curable composition (9) of the present invention comprises a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), an alcohol (B9) and/or a hydrolyzable ester (I), a hydrolyzable organosilicon compound (B10), and a curing accelerator which may be added as required.

The curable rubber composition (9) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

Curable rubber composition (10)

The curable rubber composition (10) of the present invention is a curable rubber composition of two-liquid type or multi-liquid type composed of at least two liquids, i.e., a main component (I) containing a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a curing agent (II) containing a silanol condensing (curing) catalyst (J) and water or a hydrate of metallic salt (B11), the main component (II) may further be incorporated with a silane coupling agent.

The curing agent (II) comprises a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11).

[ silanol condensing (curing) catalyst (J)]

The silanol condensing (curing) catalyst (J) which is one of the components of the hardening agent (II) of the present invention may be a known catalyst.

Specific examples of the silanol condensing (curing) catalyst used in the present invention include:

titanates such as tetrabutyl titanate and tetrapropyl titanate;

tin carboxylates, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diisooctylmaleate, dibutyltin ditridecyl maleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dioctyltin diacetate, tin octylate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmaleate, dioctyltin diisooctylmaleate, dioctyltin a branched alkane carboxylate and tin naphthenate;

alkoxytin such as dibutyltin dimethoxide, dibutyltin diphenoxy and dibutyltin diisopropoxide;

tin oxides such as dibutyltin oxide and dioctyltin oxide;

a reaction product between dibutyltin oxide and a phthalate;

dibutyl tin diacetyl pyruvate;

organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and aluminum diisopropoxide ethylacetoacetate;

chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate;

lead octoate;

amino compounds, and salts of these compounds with carboxylic acids, such as butylamine, octylamine, dodecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU);

a low molecular weight polyamide resin produced by a reaction between an excess of polyamine and a polybasic acid;

a product of the reaction between an excess of polyamine and an epoxy compound;

amino-containing silane coupling agents, such as gamma-aminopropyltrimethoxysilane and N- (β -aminoethyl) aminopropylmethyldimethoxysilane, and

other known acidic or basic silanol condensation catalysts.

Among these catalysts, when rapid curing at room temperature is desired, tetravalent tin compounds are more preferable, particularly dialkoxy tin dialkoxides, and dibutyltin diacetylacetonate, dibutyltin dimethoxide and dibutyltin dipropoxide are more preferable. The effect of the present invention is more remarkable when a tetravalent tin compound (e.g., dialkoxydialkyltin) is used, because the tetravalent tin compound is not substantially deactivated when mixed with water or a metal salt hydrate in a curing agent, and the curing speed does not deteriorate after storage.

These catalysts may be used alone or in combination.

The amount of the silanol condensing catalyst (J) added in the curing agent (II) component is preferably about 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) in the main component (I). the amount of the silanol condensing catalyst (J) used is unfavorably less than the above range because of insufficient curing speed and insufficient curing reaction degree.

[ hydrate of Water or metallic salt (B11)]

In the water or the metal salt hydrate (B11) in the curing agent (II) component of the present invention, the metal salt hydrate serves as a water source necessary for condensation/curing of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) in the main component (I), promoting the formation of a crosslinked structure.

The commonly used commercial metal salt hydrates can be widely usedin the present invention. They include hydrates of alkaline earth metals and other metals. Specific examples of these hydrates include: al (Al)₂O₃·H₂O、Al₂O₃·3H₂O、Al₂(SO₄)₃·18H₂O，Al₂(C₂O₄)₃·4H₂O，AlNa(SO₄)₂·12H₂O，AlK(SO₄)₂·12H₂O，BaCl₂·2H₂O，Ba(OH)₂·8H₂O，CaSO₄·2H₂O，CaS₂O₃·6H₂O，Ca(NO₃)₂·4H₂O，CaHPO₄·2H₂O，Ca(C₂O₄)·H₂O，Co(NO₃)₂·6H₂O，Co(CH₃COO)₂·4H₂O，CuCl₂·2H₂O，CuSO₄·5H₂O，FeCl₂·4H₂O，FeCl₃·6H₂O，FeSO₄·7H₂O，Fe(NH₄)(SO₄)₂·12H₂O，K₂CO₃·1.5H₂O，KNaCO₃·6H₂O，LiBr·2H₂O，Li₂SO₄·H₂O，MgSO₄·H₂O，MgSO₄·7H₂O，MgHPO₄·7H₂O，Mg₃(PO₄)₂·8H₂O，MgCO₃·3H₂O，Mg₄(CO₃)₃(OH)₂·3H₂O，MoO₃·2H₂O，NaBr·2H₂O，Na₂SO₃·7H₂O，Na₂SO₄·10H₂O，Na₂S₂O₃·5H₂O，Na₂S₂O₆·2H₂O，Na₂B₄O₇·10H₂O，NaHPHO₃·2.5H₂O，Na₃PO₄·12H₂O，Na₂CO₃·H₂O，Na₂CO₃·7H₂O，Na₂CO₃·10H₂O，NaCH₃COO·3H₂O，NaHC₂O₄·H₂O，NiSO₄·6H₂O，NiC₂O₄·2H₂O，SnO₂·nH₂O，NiC₂O₄·2H₂O，Sn(SO₄)₂·2H₂O，ZnSO₃·2H₂O，ZnSO₄·7H₂O，Zn₃(PO₄)₂·4H₂O and Zn (CH)₃COO)₂·2H₂Among them, preferable are hydrates of alkali metals and alkaline earth metals. Specific examples of these hydrates include: MgSO (MgSO)₄·7H₂O、Na₂CO₃·10H₂O、Na₂SO₄·10H₂O、Na₂S₂O₃·5H₂O、Na₃PO₄·12H₂O and Na₂B₄O₇·10H₂O。

These metal salt hydrates can be used alone or in combination.

When water is used in the present invention, it is added in an amount of preferably 0.01 to 25 parts by weight, more preferably 0.05 to 15 parts by weight, still more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The hydrate of the metallic salt is incorporated preferably in an amount of 0.01 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, further preferably 1 to 20 parts by weight, most preferably 2 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Water and hydrates of metallic salts may be used alone or in combination.

[ other Components]

The curable rubber composition (10) of the present invention may be mixed with various additives.

Representative of these additives are adhesion promoters, and representative of adhesion promoters is a silane coupling agent, but not limited thereto.

The silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as hydrolyzable group)Silicon group) and one or more other groups. Examples of the hydrolyzable silicon group include groups represented by the following general formula (1), preferably groups represented by the following general formula (2):

in the formula, R¹And R²Each is an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or (R')₃A triorganosiloxy group represented by SiO- (R's are each a hydrocarbon group of 1 to 20 carbon atoms, which may be substituted or unsubstituted);

x is a hydrolyzable group;

"a" is an integer from 0 to 3, "b" is an integer from 0 to 2, wherein "a" and "b" cannot both be zero; "m" is an integer of 0 to 19,

in the formula, R²X and "a" are the same as in the general formula (1).

These hydrolyzable groups include hydrogen atoms, alkoxy groups, acyloxy groups, ketoxime salts, amino groups, amide groups, aminoxy groups, mercapto groups and alkenyloxy groups, which are commonly used. Of these, methoxy and ethoxy groups are more preferable because of their high hydrolysis rate. The silane coupling agent preferably contains 2 or more hydrolyzable groups, more preferably 3 or more hydrolyzable groups.

The functional groups other than the hydrolyzable silicon groups for use in the present invention include primary, secondary and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups and isocyanurate groups, and halogen atoms.

Of these, primary, secondary and tertiary amino groups, epoxy groups, isocyanate groups and isocyanurate groups are more preferable, and isocyanate groups and epoxy groups are particularly preferable.

The silane coupling agent used in the present invention includes:

amino group-containing silanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, gamma-ureidopropyltrimethoxysilane, N- β - (N-vinylbenzylaminoethyl) -gamma-aminopropyltriethoxysilane and gamma-anilinopropyltrimethoxysilane;

mercapto group-containing silanes such as gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane;

epoxy-containing silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane and β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane;

carboxysilanes, such as β -carboxyethyltriethoxysilane, β -carboxyethylphenylbis (2-methoxyethoxy) silane and N- β - (carboxymethylaminoethyl) - γ -aminopropyltrimethoxysilane;

vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane and gamma-acryloxypropylmethyltriethoxysilane;

halogen-containing silanes, such as gamma-chloropropyltrimethoxysilane;

silane isocyanurates, such as tris (trimethoxysilyl) isocyanurate; and

isocyanate-containing silanes such as gamma-isocyanatopropyltrimethoxysilane and gamma-isocyanatopropyltriethoxysilane.

Derivatives obtained by modifying some of the above-mentioned compounds may also be used as the silane coupling agent. They include: amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanate silanes (block isocyanate silanes), phenylamino-long chain-alkyl silanes, aminosilylated siloxanes and silylated polyesters.

These silane coupling agents are easily hydrolyzed in the presence of moisture, but are stable when incorporated into the main component (I) of the curable rubber composition (10) of the present invention.

Needless to say, compounds having an epoxy group and an isocyanate group in the molecule (including isocyanate polymers) other than the silane coupling agent can be used as the tackifier without causing any problem.

These tackifiers may be used alone or in combination.

The tackifier used in the present invention is added in an amount of 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The curable rubber composition (10) may be further modified with one or more different fillers.

The filler used in the present invention comprises:

reinforcing fillers such as fumed silica, settling silica, silicic anhydride, silicon hydride, talc and carbon black;

other fillers such as limestone powder, gelled calcium carbonate, diatomaceous earth, refractory earth, clay, titanium oxide, bentonite, organic bentonite, iron oxide, zinc oxide, and active zinc white; and

fibrous fillers, such as glass fibers or filaments.

When a reinforcing filler, mainly fumed silica, settling silica, silicic anhydride, silicon hydride, talc or carbon black, is used when a curable rubber composition having high strength is to be produced, a cured product having high strength and modulus can be produced when the reinforcing filler is added in an amount of 1 to 100 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) in the main component (I) of the present invention.

On the other hand, when a cured product having a low modulus and a high elongation is to be produced, it is recommended to add other types of fillers such as limestone powder, gelled calcium carbonate, diatomaceous earth, refractory earth, clay, titanium oxide, bentonite, organobentonite, iron oxide, zinc oxide or active zinc white in an amount of 5 to 400 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) in the main component (I) of the present invention.

The fillers may be used alone or in combination.

The filler may be added to the main component (I) component or the curing agent (II) component, or to both.

When a plasticizer and a filler are mixed, the curable rubber composition (10) of the present invention may have one or more additional advantages such as further improvement of elongation of the cured product and mixing of a larger amount of filler.

Itis preferable that these plasticizers should be compatible with the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Specific examples of the plasticizer include process oil, polybutene, hydrogenated polybutene, α -methylstyrene oligomer, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, and among them, hydrocarbon-based compounds free of unsaturated groups, such as process oil, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil and naphthene oil, are more preferable.

When hydrolyzable silyl groups are introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A0), a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

The curable rubber composition (10) of the present invention may be appropriately blended with various additives such as antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, thixotropic enhancers, pigments and surfactants as needed within limits not adversely affecting the object of the present invention.

The curable rubber composition (10) of the present invention can be used for a two-liquid type composition or a liquid composition containing three or more liquids. When used as a two-liquid type composition, for example, the main component (I) mixed with a filler, a plasticizer or the like and the curable agent (II) mixed with a filler, a plasticizer or the like used in the present invention are separately prepared, and the main component (I) and the curable agent (II) are mixed with each other immediately before the two-liquid type composition is used, and even if they have been stored for a long time, the initial properties of the cured product can be stably achieved.

The curable rubber composition (10) of the present invention is mainly used for curable elastomer compositions which are suitable as sealants for electric/electronic device members, civil engineering works (e.g., stopping water), buildings, ships, automobiles and roads. The curable rubber composition (10) of the present invention can also be used for a wide variety of adhesive compositions because it can rapidly adhere to various substrates such as glass, stone, ceramics, wood, synthetic resins and metals without a primer.

The curable rubber composition (10) of the present invention is particularly suitable as a sealant for laminated glass, which stably exhibits long-term adhesion to, for example, float glass and various surface-treated heat-ray reflective glasses. The composition is also suitable for use as a gasket for pure aluminum and anodized aluminum.

Curable rubber composition (10) and its use

As described previously, the curable rubber composition (10) of the present invention comprises a curable composition, a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, the curable composition (10) of the present invention comprises at least a main component (I) containing an organic polymer (Z), and a curing agent (II) containing a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11). As described previously, the curable rubber composition is suitable for use in electric/electronic device members, transportation machines, civil engineering/construction, medical and leisure areas.

The curable rubber composition (10) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

Rubber composition (11)

The rubber composition (11) of the present invention comprises a specific silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) and a silicone polymer (K1).

The silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) (hereinafter sometimes referred to as "silyl-containing copolymer rubber (A2)") contains a hydrolyzable silyl group represented by the following general formula (1)And preferably a norbornene compound having at least one specific vinyl terminal group (represented by the above general formula (4) or (5)) as a structural unit of the non-conjugated polyene, the hydrolyzable silyl group represented by the following general formula (1) being in the side chain or at the terminal of the ethylene/α -olefin/non-conjugated polyene random copolymer rubber:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms, which may be substituted or unsubstituted, preferably a monovalent hydrocarbon group free of aliphatic unsaturated bonds, for example, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl or cyclohexyl; aryl groups such as phenyl or tolyl; or the above groups in which hydrogen atoms bonded to carbon atoms are substituted in whole or in part with halogen (e.g., fluorine); x is a group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy, more preferably alkoxy, especially alkoxy of 1 to 4 carbon atoms; "m" is an integer of 0 to 2, preferably 0 or 1.

The silyl group represented by the general formula (1) is the same as the hydrolyzable silyl group represented by the general formula [ III]in the ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) generally has at least one silyl group represented by the following general formula (2) or (3):

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; r³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2 and "n" is an integer of 0 to 10.

R, X and "m" in the general formulae (2) and (3) are the same as those in the general formula (1), R¹、R²、R³And "n" and throughFormula [ I]And [ II]The same as in (1).

The silyl-containing copolymer rubber (A2) has one or more silyl groups in the molecule, preferably 0.1 to 10 groups on average. When the silyl group content is less than 0.1 per molecule, the copolymer rubber no longer has good rubber elasticity due to insufficient curability.

However, it is particularly preferable to prepare an ethylene/α -olefin/nonconjugated polyene random copolymer rubber containing a norbornene compound having at least one vinyl terminal group (represented by the general formula (4) or (5)) as a nonconjugated polyene by reacting the ethylene/α -olefin/nonconjugated polyene random copolymer rubber with a silicon compound represented by the following general formula (6):

the ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) to be reacted with the silicon compound represented by the general formula (6) is a random copolymer of ethylene, α -olefin of 3 to 20 carbon atoms and a nonconjugated polyene.

The α -olefin of 3 to 20 carbon atoms is the same as the specific example of the α -olefin of 3 to 20 carbon atoms constituting the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). the α -olefin is preferably a α -olefin of 3 to 10 carbon atoms, more preferably propylene, 1-butene, 1-hexene, 1-octene and the like.

These α -olefins may be used alone or in combination.

The non-conjugated polyene suitable for the present invention is a norbornene compound having a vinyl terminal group represented by the general formula (4) or (5):

the general formulae (4) and (5) are the same as the general formulae [ I]and [ II], respectively. Thus, specific examples of the norbornene compounds are the same as those represented by the general formulae [ I]and [ II]. Of these, more preferable ones include 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene.

These norbornene compounds may be used alone or in combination.

In addition to the use of the above norbornene compound (e.g., 5-vinyl-2-norbornene), a non-conjugated polyene shown below may be used as long as it does not adversely affect the object of the present invention.

More specifically, these non-conjugated polyenes include:

straight-chain type non-conjugated polyenes such as 1, 4-hexadiene, 3-methyl-1, 4-hexadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1, 4-hexadiene, 4, 5-dimethyl-1, 4-hexadiene and 7-methyl-1, 6-octadiene;

cyclic nonconjugated polyenes such as methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; and

trienes, such as 2, 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2, 2-norbornadiene.

The ethylene/α -olefin/nonconjugated polyene random copolymer rubber containing the above components had the following properties.

(i) Molar ratio of ethylene to α -olefin of 3 to 20 carbon atoms (ethylene/α -olefin)

In the ethylene/α -olefin/nonconjugated polyene random copolymer rubber, the molar ratio [ (a)/(b) molar ratio]of the component unit (a) derived from ethylene and the component unit (b) derived from a α -olefin of 3 to 20 carbon atoms (hereinafter sometimes simply referred to as "α -olefin") is 40/60 to 95/5, preferably 50/50 to 90/10, more preferably 55/45 to 85/15, particularly preferably 60/40 to 80/20.

When the molar ratio (a)/(b) is within the above range, a rubber composition obtained from the random copolymer rubber can form a vulcanized rubber molded article excellent in aging resistance, strength characteristics and rubber elasticity under heating, and also excellent in moldability and low-temperature resistance.

(ii) Iodine number

The iodine value of the ethylene/α -olefin/nonconjugated polyene random copolymer rubber is from 0.5 to 50 (g/100 g), preferably from 0.8 to 40 (g/100 g), more preferably from 1 to 30 (g/100 g), still more preferably from 1.5 to 25 (g/100 g). the iodine value corresponds to the content of the double bond in the structural unit derived from the norbornene compound having a vinyl terminal group represented by the general formula (4) or (5).

When the iodine value is within the above range, the random copolymer rubber can obtain a desired content of hydrolyzable silyl groups, and the resulting rubber composition can form a vulcanized rubber molded article having excellent compression set resistance and aging resistance under the use conditions (i.e., under heating). An iodine value exceeding 50 is disadvantageous in terms of cost and is therefore undesirable.

(iii) Intrinsic viscosity

The ethylene/α -olefin/nonconjugated polyene random copolymer rubber has an intrinsic viscosity (η) as measured in decalin at 135 ℃ of 0.001 to 2dl/g, preferably 0.01 to 2dl/g, more preferably 0.05 to 1.0dl/g, still more preferably 0.05 to 0.7dl/g, still more preferably 0.1 to 0.5 dl/g.

When the intrinsic viscosity (η) is within the above range, the random copolymer rubber can give a rubber composition excellent in fluidity and capable of providing a crosslinked rubber molded article excellent in strength characteristics and compression set resistance.

(iv) Molecular weight distribution (Mw/Mn)

The ethylene/α -olefin/nonconjugated polyene random copolymer rubber has a molecular weight distribution (Mw/Mn) in the range of 3 to 100, preferably 3.3 to 75, more preferably 3.5 to 50 as measured by Gel Permeation Chromatography (GPC).

When the molecular weight distribution (Mw/Mn) is within the above range, the resulting rubber composition of the random copolymer rubber can form a crosslinked rubber molded article having excellent processability and strength characteristics.

The ethylene/α -olefin/nonconjugated polyene random copolymer rubber is obtained by random copolymerization of ethylene, α -olefin of 3 to 20 carbon atoms and norbornene compound having a terminal vinyl group represented by the general formula (4) or (5) in a similar manner to the preparation of the ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A0).

The process for producing a modified silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber by a hydrosilylation reaction in which ethylene/α -olefin/nonconjugated polyene random copolymer rubber is reacted with a silicon compound represented by the general formula (6) is similar to the production process of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

In the above hydrosilylation reaction, the SiH group in the silicon compound represented by the general formula (6) is added to the double bond derived from the nonconjugated polyene in the ethylene/α -olefin/nonconjugated polyene random copolymer rubber, and when the nonconjugated polyene is represented by the general formula (4) or (5), a silyl group containing structure represented by the general formula (2) or (3) is formed, respectively.

A siloxane modified with hydrogen at one end represented by the following general formula (7) and a silicon compound represented by the general formula (6) may be added to impart the characteristics (weather resistance, slip property and air permeability) of the siloxane to the copolymer rubber:

in the formula, R⁴Is a monovalent hydrocarbon group of 1 to 12 carbon atoms, which may be substituted or unsubstituted, particularly preferably an alkyl group; "p" is an integer of 5 to 200, particularly preferably 10 to 150.

The silyl group functionalized copolymer rubber (A2) is contained in the rubber composition (11) of the present invention preferably in an amount of 10% or more, more preferably 20% or more, still more preferably 30% or more.

The rubber composition (11) of the present invention is compounded with the silicone polymer (K1) for the purpose of reducing its viscosity to make it easier to handle, increasing the curing speed and reducing the tackiness of the surface of the cured product.

The silicone polymer (K1) of the present invention is a polymer having a siloxane bond as a main chain skeleton, in which silicon atoms have organic groups and oxygen atoms occur alternately. One example is a polymer represented by the general formula (8):in the formula, R⁴、R⁵、R⁶And R⁷Each having 1 to 12 carbonsA non-hydrolyzable organic group of atoms or X (the same as X in the general formula (1)), these groups may be the same or different, R⁴To R⁶At least one of which is a non-hydrolyzable organic group, R⁵And R⁶Can be mutually connected to form a ring; "q" is an integer of 1 to 5000, preferably 5 to 100.

Specific examples of the non-hydrolyzable organic group of 1 to 12 carbon atoms include alkyl groups such as methyl and ethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; aralkyl radicals, such as benzyl.

Specific examples of X include X of the general formula (1). A plurality of q-R of the formula (5)⁴Not necessarily identical, a plurality of q-R⁵As well as the same.

There are many kinds of silicone polymers represented by K1 used in the present invention, for example, silicone polymers disclosed in Japanese patent laid-open publication No. 38987/1984, Japanese patent laid-open publication Nos. 60558/1980, 78055/1980, 145147/1982, 190043/1982, 25837/1984 and 23643/1986 and "9586 chemical commercial product" (Kagaku KogyoNippoh published on 1986, 30.1: 721-. More specifically, they include: silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; an organopolysiloxane such as an organopolysiloxane having an organic group (e.g., an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group) as described above. They may be used as such or in the form of copolymers, for example block or graft copolymers with organic polymers, such as alkyd resins, epoxy resins, polyester resins, polyurethane resins, acrylic resins, polyethylene oxide, polypropylene oxide, ethylene oxide/propylene oxide copolymers, polybutylene oxide or polytetrahydrofuran.

The silicone polymer (K1) of the present invention also includes the above-mentioned copolymer, silicone oil and organopolysiloxane into which a reactive silicon group (such as a group represented by the general formula (1)) is introduced, as well as organopolysiloxane having hydrolyzable groups (such as hydrogen atoms bonded to silicon atoms in methylhydrosilicone oil, and hydroxyl groups).

Among the above silicone polymers (K1), more suitable are polymers that are liquid or have fluidity because they can be processed more easily.

Suitable are silicone polymers (K1) having hydroxyl groups or hydrolyzable groups bonded to silicon atoms, because they can react with the silyl group-containing copolymer rubber (a2) during curing, giving various advantages such as prevention of leakage of the silicone polymer (K1), control of decrease in elastic modulus and elongation even after repeated use for many times, and prevention of surface tackiness.

The copolymer of organopolysiloxane and organic polymer can be synthesized by the method disclosed in Japanese patent laid-open publication No. 145147/1982, but is not limited thereto.

Among the silicone polymers (K1), particularly suitable are polysiloxanes having 2 or more silanol groups. These polysiloxanes give rubber compositions which have particularly good curability deep inside (a measure of curing speed inside a thick cured product), and are capable of imparting excellent weather resistance and heat resistance to the cured product.

A wide variety of commercially available general purpose polysiloxanes can be used in the present invention. In particular, the polysiloxane compatible with the (A2) component can give a cured product having higher stability. It is therefore preferable to use a lower molecular weight polysiloxane, for example, a polysiloxane having 50 or less silicon atoms in the molecule. Some specific examples of these polysiloxane structures are as follows:where Me is methyl and Ph is phenyl, as is the case in the examples below).

These silicone polymers (K1) may be used alone or in combination.

The content of the silicone polymer (K1) cannot be summarized in full because it depends on, for example, the desired Mooney viscosity (ML (1+4) at 100 ℃), the resulting rubber composition and the type of the organic polymer (K1) used. However, the recommended amount of silicone polymer (K1) added is generally about 1 to 1000 parts by weight, preferably about 10 to 150 parts by weight, per 100 parts by weight of (A2) component.

When a polysiloxane having 2 or more silanol groups is used as the silicone polymer (K1), the recommended amount of addition of the silicone polymer (K1) is such that about 0.1 to 8, more preferably 0.3 to 4, hydroxyl groups are bonded to silicon atoms in the polysiloxane per 1 hydrolyzable group in the (A2) component.

In the present invention, the polysiloxane is incorporated preferably at about 20 to 120 parts by weight per 100 parts by weight of the (A2) component, more preferably at about 25 to 100 parts by weight. An excessively low content of the polysiloxane is disadvantageous because it may result in insufficient curability of the resin composition deep inside. Too high a content of the polysiloxane is also disadvantageous because the properties of the cured product with respect to stretching may be deteriorated.

The cured product of the rubber composition (11) of the present invention has good resistance such as weather resistance, heat resistance and water resistance, can maintain the excellent properties of high strength and elongation obtained from the cured product of the (A2) component, and also has good effects obtained from the (K1) component such as lowering of viscosity to improve workability and prevention of surface tackiness.

In the present invention, in the introduction of the reactive silicon group into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber, the silicone polymer (K1) may be used in place of the solvent for adjusting the reaction temperature and the viscosity of the reaction system.

The rubber composition (11) of the present invention is preferably incorporated with a curing catalyst capable of promoting silanol condensation.

Specific examples of these catalysts used in the present invention include titanates such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octoate and tin naphthenate, reaction products between dibutyltin oxide and phthalates, dibutyltin bisacetylacetonate, organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate, chelates such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octoate, amino compounds and salts of these compounds with carboxylic acids such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1, 8-diazabicyclo (5, 4, 0) undec-7 (7-dimethoxymethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1, 8-diazabicyclo (5, 4, 0) silane (7-bis (7-epoxypropyl) amine, polyamine, a condensation catalyst alone or a combination of these with known amine, a polyamine, such as an excess of an acidic polyamine, such as a polyamine, and a combination of an acid, a polyamine.

When the curing catalyst is used, it is usually added in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the (A2) component. An excessively low catalyst content is disadvantageous because it results in a slow curing speed of the resin composition product. An excessively high catalyst content is also disadvantageous because it deteriorates the tensile-related properties of the cured product.

The rubber composition (11) of the present invention may be appropriately blended with one or more additives. The additives used in the invention comprise adhesion promoters, performance regulators, storage stability improvers, plasticizers, fillers; an anti-aging agent, an ultraviolet absorber, a metal deactivator, an inhibitor against aging caused by ozone, a light stabilizer, an amine-based radical chaining inhibitor, a phosphorus-based peroxide decomposer; a lubricant; pigments and blowing agents.

The adhesion promoter used in the present invention includesconventional adhesives and silane coupling agents such as aminosilane compounds and epoxysilane compounds; and other compounds.

Specific examples of such adhesion promoters include phenol resins, epoxy resins, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, benzofuran/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates, and when an adhesion promoter is used, it is preferably added in an amount of about 1 to 50 parts by weight, more preferably about 5 to 30 parts by weight, per 100 parts by weight of the total of component (A2) and component (K1).

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded, and esters of ortho-organic acids (except for alkyl orthoformate).

Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate. When the storage stability improver is used, it is incorporated preferably at about 0.5 to 20 parts by weight per 100 parts by weight of the total of component (A2) and component (K1), more preferably about 1 to 10 parts by weight.

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. It is preferable that the plasticizer should be compatible with each component of the rubber composition (11) of the present invention.

Specific examples of such plasticizers include hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl,triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene, chlorinated paraffin, phthalate esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butylphthaloyl butyl glycolate, non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, polyalkylene glycol esters such as diethylene glycol benzoate and triethylene glycol dibenzoate, phosphate esters such as tricresyl phosphate and tributyl phosphate, which may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the rubber composition (11) of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

In the introduction of the reactive silicon group into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber, a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

The plasticizer is incorporated preferably at about 10 to 500 parts by weight per 100 parts by weight of the total of component (A2) and component (K1), more preferably about 20 to 300 parts by weight.

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate,clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc. When the filler is used, it is used in an amount of preferably about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the total of component (A2) and component (K1).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4, 4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, laurylstearyl thiodipropionate and diethyl 2, 2-thio [ di-3 (3, 5-di-t-butyl-4-hydroxy]dipropionate, diethyl thiodipropionate, zinc di-butyl-3-thiodipropionate, zinc dithiobutyl-dithiobenzoate, zinc dithiobenzoate, e, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate,e.g., dithiobutylthiodipropionate, dithiobutyl-bis (3-4-bis-4-butylthiodipropionate, dithiobutyl-dithiobenzoate, dithiobutyl-dithiobenzoate, dithiobenzoate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of the curable rubber composition of the present invention, and controls problems such as residual surface tackiness.

Free radical inhibitors useful in the present invention include phenolic free radical inhibitors such as 2, 2-methylenebis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino free radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the total of component (A2) and component (K1).

The rubber composition (11) of the present invention comprises a rubber composition, as component (A2), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, wherein the organic polymer (Z1) containing a hydrolyzable silyl group represented by the above general formula (1) and substantially no unsaturated double bonds in the main chain can be obtained by uniformly kneading the components with a kneader such as an internal mixer, a planetary mixer, a Banbury mixer, a kneader or a two-roll apparatus.

The rubber composition (11) of the present invention is cured at room temperature to 200 ℃ for several minutes to several days because the composition can be cured rapidly. It is particularly preferred to crosslink the composition with moisture in air at room temperature.

Curable rubber composition (11) and its use

The rubber composition (11) of the present invention comprises a rubber composition, as component (A2), an ethylene/α -olefin/nonconjugated polyene random copolymer rubber containing a hydrolyzable silyl group more specifically, the crosslinkable rubber composition (11) of the present invention comprises an organic polymer (Z1) containing a hydrolyzable silyl group represented by the above general formula (1) and containing substantially no unsaturated double bond in the main chain, and an organosilicon compound (K1). As described above, the composition is suitable for use in the fields of electric/electronic device members, transportation machines, civil engineering/construction, medical care and leisure.

The curable rubber composition (11) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

Rubber composition (12)

The rubber composition (12) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), an organic rubber (K2) and a crosslinking agent (M) for the organic rubber (K2).

The rubber composition (12) of the present invention contains preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

The organic rubber (K2) used in the rubber composition (12) of the present invention comprises: a hydrolyzable silyl group-containing polypropylene glycol-based rubber, a hydrolyzable silyl group-containing polyisobutylene-based rubber, natural rubber, polyisoprene, polybutadiene, styrene/butadiene copolymer rubber, polychloroprene, acrylic rubber, acrylonitrile/butadiene copolymer rubber, ethylene/propylene copolymer rubber (EPM), ethylene/propylene/nonconjugated polyene copolymer rubber (EPDM), butyl rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, ethylene/vinyl acetate copolymer rubber, ethylene/acrylic copolymer rubber, fluororubber, chlorosulfonated polyethylene, and a mixture of the above.

Of these, particularly preferred are a hydrolyzable silyl group-containing polypropylene glycol-based rubber, a hydrolyzable silyl group-containing polyisobutylene-based rubber, a natural rubber, polyisoprene, polybutadiene, a styrene/butadiene copolymer rubber, polychloroprene, an acrylic rubber, an acrylonitrile/butadiene copolymer rubber, an ethylene/propylene copolymer rubber (EPM), an ethylene/propylene/nonconjugated polyene copolymer rubber (EPDM), a butyl rubber, a urethane rubber, an ethylene/acrylic copolymer rubber, a silicone rubber, and a mixture of the above because of their good compatibility with the component (A2).

Other rubbers are suitable for use in the presence of a solubilizer.

From the viewpoint of the balance of formability of a three-dimensional crosslinked structure, moldability and mechanical strength, the ratio of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) to the organic rubber (K2), i.e., (A2)/(K2) is usually from 3/97 to 70/30 (weight ratio), preferably from 5/95 to 50/50 (weight ratio).

The crosslinking agent (M) for the organic rubber (K2) of the present invention isnot limited as long as it is commonly used as a vulcanizing agent for rubber and can be used for EPDM. For example, the crosslinking agents useful in the present invention include: sulfur, a sulfur donor, a low-sulfur high-efficiency vulcanization accelerator, a quinoid resin, a peroxide and a compound containing SiH groups.

Other materials useful as crosslinking agents (M) in the present invention include polyfunctional compounds having two or more functional groups capable of reacting with the crosslinking groups in the organic rubber (K2), including amino, isocyanate, maleimide, epoxide, hydrosilyl and carboxyl groups.

Specific examples of the catalyst used in the present invention include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octoate and tin naphthenate, reaction products between dibutyltin oxide and phthalic acid esters, dibutyltin bisacetylacetonate, organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate, chelates such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octoate, amino compounds, and salts of these compounds with carboxylic acids such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1, 8-diazabicyclo-amino propyl silane (1, 7-bis (7-aminopropyl) silane, and other known condensation catalysts such as a combination of a polyamine containing excess of an amino acid such as N-bis (7-aminopropyl) silane and a polyamine, such as a polyamine, a polymer.

When a curing catalyst is used, it is usually added in an amount of 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of the (A2) component. An excessively low catalyst content is disadvantageous because it results in a slow curing speed of the resin composition product. An excessively high catalyst content is also disadvantageous because it deteriorates the tensile-related properties of the cured product.

The rubber composition (12) of the present invention may be appropriately blended with one or more additives. The additives used in the invention comprise adhesion promoters, performance regulators, storage stability improvers, plasticizers, fillers; an anti-aging agent, an ultraviolet absorber, a metal deactivator, an inhibitor against aging caused by ozone, a light stabilizer, an amine-based radical chaining inhibitor, a phosphorus-based peroxide decomposer; a lubricant; pigments and blowing agents.

The adhesion promoter used in the present invention includes conventional adhesives and other adhesives, except for a silane coupling agent used as a silanol condensation catalyst, specific examples of which include phenolic resins, epoxy resins, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates, and when an adhesion promoter is used, it is preferably added in an amount of about 1 to 50 parts by weight, more preferably about 5 to 30 parts by weight, per 100 parts by weight of the component (A2).

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded, and esters of ortho-organic acids. Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate. When the storage stability improver is used, it is incorporated preferably at about 0.5 to 20 parts by weight per 100 parts by weight of the (A2) component, more preferably about 1 to 10 parts by weight.

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. Preferably, the plasticizer should be compatible with each component of the rubber composition (12) of the present invention.

Specific examples of such plasticizers include hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene, chlorinated paraffin, phthalate esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butylphthaloyl butyl glycolate, non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, polyalkylene glycol esters such as diethylene glycol benzoate and triethylene glycol dibenzoate, phosphate esters such as tricresyl phosphate and tributyl phosphate, which may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the rubber composition (12) of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

In the introduction of the reactive silicon group into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber, a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is preferably added in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the component (A2).

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc. When used, the filler is preferably used in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the component (A2).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

Specific examples of the sulfur-based aging inhibitors used in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4, 4 '-thiobis (3-methyl-6-t-butylphenol), 4' -thiobis (2-methyl-6-t-butylphenol), 2 '-thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2' -thiobis (4-octylphenol) nickel, dilauryl thiodipropionate, distearyl dithiodipropionate, zinc di-butyl-4-t-butyl-3-hydroxybenzyl) sulfide, zinc dithio, polysulphide, polysulphides, dithiocarboxylates such as zinc-dithiobenzoate, dithiodiethoxy-3-butyl-thiodipropionate, dithiodiethoxy-3-thiodipropionate, dithiodiethoxy-bis (e), dithiodiethoxy-butyl-5-thiodipropionate, dithiodiethoxy-3-bis (e), dithiodiethoxy-butyl-3-thiodipropionate, dithiodiethoxy-thiodipropionate, e, dithiodiethoxy-bis (e, dithiodiethoxy-butyl-bis (e, dithiodiethoxy-butyl-bis (e), dithio), and zinc-3-butyl-bis (e), zinc dithio), dithiodiethoxy-butyl-3-butyl-thiodipropionate, e, dithio, e.g., zinc dithiodiethoxy-bis (di-butyl-3-thiodipropionate, dithio, dithiodiethoxy-.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of rubber compositions of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the component (A2).

The rubber composition (12) of the present invention can be obtained by uniformly kneading the components by a kneader (e.g., an internal mixer, a planetarymixer, a Banbury mixer, a kneader or a two-roll apparatus).

The rubber composition (12) of the present invention is cured at room temperature to 200 ℃ for several minutes to several days because the composition can be cured rapidly. It is particularly preferred to crosslink the composition with moisture in air at room temperature.

[ rubber composition (12) and use thereof]

The rubber composition (12) of the present invention comprises a rubber composition, as the component (A2), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, more specifically, the rubber composition (12) of the present invention comprises an organic polymer (Z1), an organic rubber (K2) and a crosslinking agent (M) for the organic rubber (K2). As described above, the composition is suitable for use in the fields of electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure.

The curable rubber composition (12) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

Rubber composition (13)

The rubber composition (13) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), an epoxy resin (K3), a silane coupling agent (N), a silanol condensing catalyst (O) and a curing agent (P) for the epoxy resin.

The rubber composition (13) of the present invention contains preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

The epoxy resin (K3) used for the rubber composition (13) of the present invention includes epichlorohydrin-bisphenol A type epoxy resin; epichlorohydrin-bisphenol F type epoxy resins; epichlorohydrin-bisphenol S type epoxy resins; flame retardant type epoxy resins (e.g., tetrabromophenol type a glycidyl ether); a novolac type epoxy resin; hydrogenated bisphenol a type epoxy resin; glycidyl ether type epoxy resins of bisphenol a type epoxy propane adduct; glycidyl ether type epoxy resins of bisphenol a type ethylene oxide adducts; glycidyl ester type epoxy resins such as diglycidyl p-hydroxybenzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate and diglycidyl adipate; glycidyl amine type epoxy resins, triglycidyl meta-aminophenol, N' -tetraglycidyl aminophenylmethane, N-diglycidylaniline and N, N-diglycidylotoluidine; hydantoin type epoxy resins such as 1, 3-diglycidyl-5-methyl-5-ethylhydantoin; triglycidyl isocyanurate; a polyalkylene glycol diglycidyl ether; polyols (such as glycerol and sorbitol) and glycidyl ethers; alicyclic epoxy resins such as alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate and vinylcyclohexene oxide; epoxidized unsaturated polymers such as polybutadiene and oil derived resins. The epoxy resin (K3) used in the present invention is not limited to the above-mentioned compounds, and a commonly used epoxy resin can be used. Among these epoxy resins, the epoxy resins having two or more epoxy groups are more preferable because they can more easily obtain a network structure. Still more preferable is an epoxy resin having a glycidyl ether, particularly an epichlorohydrin-bisphenol A type epoxy resin, because it has compatibility with the component (A2).

When component (K3) is used, it is incorporated preferably in an amount of 5 to 900 parts by weight, more preferably 10 to 300 parts by weight, per 100 parts by weight of component (A2). If the amount is less than 5 parts by weight, toughness of the epoxy resin may not be achieved and cohesion may be insufficient. On the other hand, if the amount exceeds 900 parts by weight, the polymer having a reactive silicon group as the component (A2) is not contained in the matrix of the cured product, so that the cured product is insufficient in elasticity and becomes brittle. Therefore, the amount outside the above range is disadvantageous.

The silane coupling agent (N) used in the present invention is generally a silane containing a hydrolyzable silicon group and one or more other functional groups in the molecule, and the functional groups used in the present invention include primary, secondary and tertiary amino groups, mercapto, epoxy, ureide, isocyanato, vinyl, methacryloyl and haloalkyl groups, among which more preferable are primary, secondary and tertiary amino groups, mercapto, epoxy or ureide groups, which are capable of reacting with the reactive silicon group-containing polymer (component (A2)) and the epoxy resin (component (K3)), and further preferable are silanes having amido groups (especially primary and secondary amides). the hydrolyzable silicon group used in the present invention includes groups represented by the above general formula (I) wherein X is a hydrolyzable group, more preferable are alkoxy groups because it is easily handled.the silane coupling agent used in the present invention includes amino-containing silanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyl-methyldiethoxysilane, gamma-dimethoxypropyl-aminopropyl-2-dimethoxypropyl) aminopropyl-trimethoxysilane, gamma-aminopropyl-2-aminopropyl-ethoxysilane, gamma-aminopropyl-trimethoxysilane, gamma-aminopropyl-trimethoxysilane, gamma-aminopropyl-ethoxysilane, gamma-aminopropyl-trimethoxysilane, gamma-ethoxysilane, gamma-aminopropyl-ethoxysilane, gamma-aminopropyl-ethoxysilane, gamma-aminopropyl-ethoxysilane, gamma-aminopropyl-ethoxy-ethoxysilane, gamma-aminopropyl-ethoxysilane, gamma.

The component (N) is preferably added in an amount of 0.01 to 50 parts by weight per 100 parts by weight of the component (A2). When the content of the component (N) is outside the above range, the layered structure cannot be effectively controlled, and particularly when the content is less than 0.01 part by weight, the interface adhesion is caused to be insufficient, and thus it is undesirable. More preferably, the amount is 0.1 to 5 parts by weight.

The silanol condensing catalyst (O) used in the present invention includes titanates such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; a reaction product between dibutyltin oxide and a phthalate; dibutyl tin diacetone; organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and aluminum diisopropoxide ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organolead compounds such as lead octoate; amino compounds, and salts of these compounds with carboxylic acids, such as butylamine, octylamine, dodecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU); a low molecular weight polyamide resin produced by a reaction between an excess of polyamine and a polybasic acid; a product of the reaction between the excess polyamine and the epoxy compound. The silanol condensing catalyst (O) used in the present invention is not limited to the above-mentioned compounds, and a commonly used catalyst may be used. These silanol condensing catalysts may be used alone or in combination.

Of these silanol condensing catalysts, more preferable are an organometallic compound, a mixture of an organometallic compound and an amino compound, from the viewpoint of curability of the composition. Still more preferably, organotin compounds, particularly tetravalent organotin compounds, are included. The mixture of the tetravalent organotin compound with the compound having an amino group (primary or secondary) and a hydrolyzable silicon group as the component (N) gives a cured product particularly excellent in elastic modulus and strength.

The component (O) is incorporated preferably in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (A2). When the addition amount is less than 0.1 part by weight, the crosslinking reactivity of the reactive silicon group-containing component (A2) is insufficient. And when the amount exceeds 20 parts by weight, the adhesion and other properties are adversely affected. Therefore, the addition amount outside the above range is disadvantageous.

The epoxy resin curing agent (P) used in the present invention includes primary or secondary amines such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine (piperizine), menthenediamine, isophoronediamine, morpholine, piperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; tertiary amines such as trialkylamine, N-methylmorpholine, N' -dimethylpiperazine, pyridine, picoline, guanidine, diphenylguanidine, 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU), benzyldimethylamine, 2- (dimethylaminomethyl) phenol and 2, 4, 6-tris (dimethylaminomethyl) phenol; organic acid salts of these tertiary amines; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole and 1-benzyl-2-methylimidazole; a polyamide; dicyandiamide; boron trifluoride/complex; carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylene/tetrahydrophthalic anhydride, dodecylsuccinic anhydride, trimellitic anhydride, pyromellitic anhydride, chlorendic anhydride; an alcohol; phenol; a carboxylic acid; lewis acids such as boron trifluoride, phosphorus hexafluoride, aluminum trichloride, and tin tetrachloride; and salts of these lewis acids. The epoxy resin curing agent (P) used in the present invention is not limited to the above-mentioned ones, and a commonly used epoxy resin curing agent can be used. These epoxy resin curing agents may be used alone or in combination. Of these epoxy resin curing agents, tertiary amines, organic salts of tertiary amines and imidazoles are more preferable from the viewpoint of curability of the composition.

The desired content of component (P) varies depending on its type and the type of epoxy resin as component (K3). However, for specific uses, the amount thereof added is in the range of 0.01 to 300 parts by weight per 100 parts by weight of the component (K3).

The method for producing the curable resin composition comprising components (A2), (K3), (N), (O) and (P) is not limited. It can be prepared by a conventional method, for example, kneading these components by a mixer, a roller or a kneader, or mixing after dissolving the components in a suitable solvent. Each component can be mixed well with other components to prepare a one-liquid type or two-liquid type composition.

The rubber composition (13) of the present invention may be appropriately blended with one or more additives. The additives used in the present invention include adhesion promoters, property modifiers, storage stability improvers, plasticizers, fillers, aging inhibitors, ultraviolet absorbers, metal deactivators, ozone-induced aging inhibitors, light stabilizers, amine-based radical chaining inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments and foaming agents.

The adhesion promoter used in the present invention includes the conventional adhesives and others, in addition to the above-mentioned epoxy resin (K3) and silane coupling agent (N). specific examples of these adhesion promoters include phenol resin, coumarone/indene resin, rosin ester resin, terpene/phenol resin, α -methylstyrene/vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanate and aromatic polyisocyanate, and when the adhesion promoter is used, it is preferably added in an amount of about 1 to 50 parts by weight, more preferably about 5 to 30 parts by weight, per 100 parts by weight of component (A2).

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded, and esters of ortho-organic acids. Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate. When the storage stability improver is used, it is incorporated preferably at about 0.5 to 20 parts by weight per 100 parts by weight of the (A2) component, more preferably about 1 to 10 parts by weight.

Specific examples of the plasticizer include hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl-dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkylbiphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene, chlorinated paraffin, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butylphthaloyl butyl glycolate, non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, esters of polyalkylene glycols such as diethylene glycol benzoate and triethylene glycol dibenzoate, and

phosphoric acid esters, such as tricresyl phosphate and tributyl phosphate. They may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the rubber composition (13) of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

In the introduction of the reactive silicon group into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber, a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is preferably added in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the component (A2).

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc. When the filler is used, it is used in an amount of preferably about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the total of the components (A2), (K3), (N), (O) and (P).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

Specific examples of the sulfur-based aging inhibitors used in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4, 4 '-thiobis (3-methyl-6-t-butylphenol), 4' -thiobis (2-methyl-6-t-butylphenol), 2 '-thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2' -thiobis (4-octylphenol) nickel, dilauryl thiodipropionate, distearyl dithiodipropionate, zinc di-butyl-4-t-butyl-3-hydroxybenzyl) sulfide, zinc dithio, polysulphide, polysulphides, dithiocarboxylates such as zinc-dithiobenzoate, dithiodiethoxy-3-butyl-thiodipropionate, dithiodiethoxy-3-thiodipropionate, dithiodiethoxy-bis (e), dithiodiethoxy-butyl-5-thiodipropionate, dithiodiethoxy-3-bis (e), dithiodiethoxy-butyl-3-thiodipropionate, dithiodiethoxy-thiodipropionate, e, dithiodiethoxy-bis (e, dithiodiethoxy-butyl-bis (e, dithiodiethoxy-butyl-bis (e), dithio), and zinc-3-butyl-bis (e), zinc dithio), dithiodiethoxy-butyl-3-butyl-thiodipropionate, e, dithio, e.g., zinc dithiodiethoxy-bis (di-butyl-3-thiodipropionate, dithio, dithiodiethoxy-.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of rubber compositions of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the component (A2).

The rubber composition (13) of the present invention can be obtained by uniformly kneading the components by a kneader (e.g., an internal mixer, a planetary mixer, a Banbury mixer, a kneader or a two-roll apparatus).

The rubber composition (13) of the present invention is cured at room temperature to 200 ℃ for several minutes to several days because the composition can be cured rapidly. It is particularly preferred to crosslink the composition with moisture in air at room temperature.

[ uses of rubber compositions]

The rubber composition (13) of the present invention is suitably used as a sealant, and also as an adhesive, a tackifier, a coating, a molding material, a spray material, a casting rubber material and a foaming material. When it is used as a sealant, it may be a one-liquid type sealant composition which can be rapidly cured when exposed to moisture in the air while being applied to form a good rubber elastomer because the composition can be kept stable for a long period of time when stored under a closed condition after a curing catalyst is kneaded with other components under moisture-free conditions.

The rubber composition (13) of the present invention contains a curable composition, an ethylene/α -olefin/nonconjugated polyene random copolymer rubber containing a hydrolyzable silyl group as the component (A2), wherein the organic polymer (Z1) contains a hydrolyzable silyl group represented by the above general formula (1) and has substantially no unsaturated double bond in the main chain, as described above, the composition is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

The rubber composition (13) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

The curable rubber composition (13) thus obtained has a different matrix cohesion by changing the type and the addition amount of the silane coupling agent, thereby controlling the multilayer structure of the cured product. As a result, a wide variety of cured products can be produced, from cured products having a low modulus of elasticity and high elongation (similar to conventional cured products) to cured products having a high modulus of elasticity and tensile shear strength.

In other words, the curable rubber composition (13) of the present invention has high adhesiveness, and by changing the amount of the silane coupling agent added, not only can a cured product having a low elastic modulus and high elongation be obtained, but also a cured product having an improved matrix cohesion and a high elastic modulus and tensile shear strength can be obtained. Further, the curable rubber composition (13) of the present invention is high in curing speed and excellent in light resistance after curing. Therefore, the desired mechanical properties can be covered by a simple method of changing the amount of the silane coupling agent added, which is particularly suitable for adhesives, sealants and tackifiers.

Rubber composition (14)

The rubber composition (14) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), an epoxy resin (K3), a silicon compound (Q) containing a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group in the molecule and a silicon compound (R) containing at least two hydroxyl groups bonded to silicon atoms in the molecule.

The rubber composition (14) of the present invention contains preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

The epoxy resin (K3) used in the rubber composition (14) of the present invention includes epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin (such as tetrabromophenol A type glycidyl ether), novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A type epoxy propane adduct; glycidyl ester type epoxy resins such as diglycidyl p-hydroxybenzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, m-aminophenol based epoxy resins, diaminodiphenylmethyl epoxy resins, urethane-modified epoxy resins, various alicyclic epoxy resins, N-diglycidylaniline and N, N-diglycidylotolidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol (e.g., glycerol), hydantoin type epoxy resins and epoxidized unsaturated polymers such as oil-derived resins. The epoxy resin (K3) used in the present invention is not limited to the above-mentioned compounds, and a commonly used epoxy resin can be used.

Among these epoxy resins, the epoxy resins having at least two epoxy groups are more preferable because they are highly reactive to curing and can more easily obtain a network structure. Still more preferable ones include bisphenol A type epoxy resins, phthalate based diglycidyl esters, and novolak type epoxy resins.

In the present invention, a curing agent that promotes curing of the epoxy resin (K3) may be used. The epoxy resin curing agent used in the present invention includes agents generally used for curing epoxy resins. These curing agents include amines such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2, 4, 6-tris (dimethylaminomethyl) phenol; salts of tertiary amines; a polyamide resin; imidazole; dicyandiamide; boron trifluoride/amine complexes; carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylene/tetrahydrophthalic anhydride, dodecylsuccinic anhydride, pyromellitic anhydride, chlorendic anhydride; an alcohol; phenols and carboxylic acids.

The desired content of the curing agent varies depending on its type and the type of epoxy resin. However, for specific uses, the amount thereof added is in the range of 0.01 to 300 parts by weight per 100 parts by weight of the component (K3).

The component (Q) used in the present invention is a silicon compound containing a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group in the molecule.

Functional groups reactive with epoxy groups in the silicon compound include primary, secondary and tertiary amino groups, mercapto groups, epoxy groups and carboxyl groups. Any of the hydrolyzable silyl groups used for the (A2) component may be used as the hydrolyzable silyl group herein. Among them, the alkoxysilyl group is more preferable because it is easy to handle.

Specific examples of these silicon compounds include amino group-containing silanes such as γ -aminopropyltrimethoxysilane, γ -aminopropylmethyldimethoxysilane, γ - (2-aminoethyl) aminopropyltrimethoxysilane, γ - (2-aminoethyl) aminopropylmethyldimethoxysilane, γ - (2-aminoethyl) aminopropyltriethoxysilane, γ -ureidopropyltriethoxysilane, N- β - (N-vinylbenzylaminoethyl) - γ -aminopropyltrimethoxysilane and γ -anilinopropyltrimethoxysilane, mercapto group-containing silanes such as γ -mercaptopropyltrimethoxysilane, γ -mercaptopropyltriethoxysilane, γ -mercaptopropylmethyldimethoxysilane and γ -mercaptopropylmethyldiethoxysilane, epoxy bond-containing silanes such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropyltriethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and carboxy compounds such as β -carboxyethyltriethoxysilane, β -carboxyethylphenylbis (2-methoxyethoxy) silane and N-carboxyethyltrimethoxysilane (N-carboxyethyl) β -carboxyethyltrimethoxysilane (γ -aminoethyl) alone or in combination.

The component (R) of the present invention is a silicon compound having at least two (preferably 2 to 4) hydroxyl groups bonded to a silicon atom in the molecule.

These silicon compounds include polydimethyl siloxane having a silanol group at the terminal, polydiphenyl siloxane having a silanol group at the terminal, polydimethyl diphenyl siloxane having a diphenylsilanol group at the terminal, diphenylsilanediol, bis (hydroxydimethylsilyl) benzene, polytetramethyl p-silaphenylene siloxane, organosilicon compounds having a hydroxyl group atthe terminal, such as silicone varnish and organopolysiloxane.

The component (A2) in which hydrolyzable groups in the rubber-based organic polymer are converted into silanol groups can also be used as the component (R). Specific examples of these polymers include polypropylene oxide having dimethylsilanol groups at the molecular terminals. The amount of silanol-containing rubber-based polymer depends on its molecular weight and silanol content. In general, however, the amount to be added is preferably 10 to 100 parts by weight per 100 parts by weight of the component (A2). Among these compounds, the more preferable ones include diphenylsilanediol, which has a low molecular weight for every 1 hydroxyl group bonded to the silicon atom and is not likely to condense on itself. These compounds may be used alone or in combination.

The curable composition (14) can be obtained by mixing a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (component (A2)), an epoxy resin (component (K3)), a silicon compound (component (Q)) and a silicon compound (component (R)) as effective components.

When the component (R) having at least two hydroxyl groups bonded to silicon atoms in the molecule is mixed into the composition comprising the components (A2), (K3) and (Q), the curable composition (14) can be stably cured even in the case where moisture is insufficient in the ambient atmosphere, because the composition can be cured by the action of the silanol groups in the component (R). Therefore, the composition (14) of the present invention can be used even under conditions where moisture hardly enters the system, and is particularly suitable for sealants, adhesives and potting agents.

After the hydrolyzable silyl groups in components (a2) and (Q) are partially hydrolyzed, a condensation reaction is carried out in a composition comprising components (a2), (K3) and (Q). On the other hand, in the composition further comprising the component (R), the condensation reaction can be carried out in the presence of the silanol group in the component (R) without carrying out the hydrolysis step first.

The ratio of component (K3) to component (A2), i.e., (A2)/(K3), is preferably in the range of 100/1 to 100/200 (by weight). When the ratio is more than 100/1, the strength of the cured product tends to be insufficient, and when the ratio is less than 100/200, the rubber-like properties tend to be insufficient. The weight part of component (K3) per 100 parts by weight of component (A2) is preferably from 10 to 120/100, more preferably from 20 to 100/100, at which the rubber-like properties of the cured product are sufficiently exhibited, and the strength of the cured product is sufficiently improved, although the preferred ratio varies depending on the use of the curable composition.

The silicon compound used as the component (Q) is added in an amount of preferably from 100/0.1 to 100/20, more preferably from 100/0.2 to 100/10, in a weight ratio of (component (A2) + component (K3))/component (Q). When the weight ratio is more than 100/0.1, the strength of the cured product tends to be insufficient, and when the weight ratio is less than 100/20, the rubber-like properties tend to be insufficient.

The silicon compound used as the component (R) is added in an amount such that the weight ratio of the component (A2)/the component (R) is preferably from 100/0.1 to 100/100, more preferably from 100/0.2 to 100/50. When the weight ratio is more than 100/0.1, the cured product tends to lose stable properties under the influence of moisture in the ambient atmosphere, and when the weight ratio is less than 100/100, the rubber-like properties tend to be insufficient.

The method for producing the curable rubber composition (14) containingthe components (A2), (K3), (Q) and (R) is not limited. It can be prepared by a conventional method such as kneading these components at ordinary or high temperature with a mixer, a roller or a kneader, or mixing after dissolving the components in a small amount of a suitable solvent. The components may be sufficiently mixed with each other to obtain a one-liquid type or two-liquid type composition.

The rubber composition (14) of the present invention may be appropriately blended with one or more additives. The additives used in the present invention include adhesion promoters, property modifiers, storage stability improvers, plasticizers, fillers, aging inhibitors, ultraviolet absorbers, metal deactivators, ozone-induced aging inhibitors, light stabilizers, amine-based radical chaining inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments and foaming agents.

The adhesion promoter used in the present invention includes commonly used adhesives and others, in addition to the above-mentioned epoxy resin as the component (K3) and silicon compounds as the components (Q) and (R).

Specific examples of such adhesion promoters include phenol resins, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates, and when an adhesion promoter is used, it is preferably added in an amount of about 1 to 50 parts by weight, more preferably about 5 to 30 parts by weight, per 100 parts by weight of the component (A2).

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded, and esters of ortho-organic acids.

Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate. When the storage stability improver is used, it is incorporated preferably at about 0.5 to 20 parts by weight per 100 parts by weight of the (A2) component, more preferably about 1 to 10 parts by weight.

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. Preferably, the plasticizer should be compatible with each component of the rubber composition (14) of the present invention.

Specific examples of such plasticizers include hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene, chlorinated paraffin, phthalate esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butylphthaloyl butyl glycolate, non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, polyalkylene glycol esters such as diethylene glycol benzoate and triethylene glycol dibenzoate, and phosphate esters such as tricresyl phosphate and tributyl phosphate, which may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the rubber composition (14) of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

In the introduction of the reactive silicon group into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber, a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is preferably added in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the component (A2).

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc. When the filler is used, it is used in an amount of preferably about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the total of the components (A2), (K3), (Q) and (R).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4, 4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, laurylstearyl thiodipropionate and diethyl 2, 2-thio [ di-3 (3, 5-di-t-butyl-4-hydroxy]dipropionate, diethyl thiodipropionate, zinc di-butyl-3-thiodipropionate, zinc dithiobutyl-dithiobenzoate, zinc dithiobenzoate, e, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, e.g., dithiobutylthiodipropionate, dithiobutyl-bis (3-4-bis-4-butylthiodipropionate, dithiobutyl-dithiobenzoate, dithiobutyl-dithiobenzoate, dithiobenzoate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of rubber compositions of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the component (A2).

The rubber composition (14) of the present invention can be obtained by uniformly kneading the components by a kneader (e.g., an internal mixer, a planetary mixer, a Banbury mixer, a kneader or a two-roll apparatus).

The rubber composition (14) of the present invention is cured at room temperature to 200 ℃ for several minutes to several days because the composition can be cured rapidly. It is particularly preferred to crosslink the composition with moisture in air at room temperature.

[ use of rubber composition (14)]

The rubber composition (14) of the present invention is suitably used as a sealant, and also as an adhesive, a tackifier, a coating, a molding material, a spray material, a casting rubber material and a foaming material.

When it is used as a sealant, it may be a one-liquid type sealant composition which can be rapidly cured when exposed to moisture in the air while being applied to form a good rubber elastomer because the composition can be kept stable for a long period of time when stored under a closed condition after a curing catalyst is kneaded with other components under moisture-free conditions.

The rubber composition (14) of the present invention contains a curable composition, an ethylene/α -olefin/nonconjugated polyene random copolymer rubber containing a hydrolyzable silyl group as the component (A2), wherein the organic polymer (Z1) contains a hydrolyzable silyl group represented by the above general formula (1) and has substantially no unsaturated double bond in the main chain, as described above, the composition is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

The rubber composition (14) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

The curable rubber composition (14) of the present invention can be cured even at a low temperature around room temperature, and can be cured rapidly by raising the temperature to about 100 ℃ and 150 ℃. Thus, the composition can be cured and used over a wide temperature range from low to high temperatures, depending on the particular application. When the combination of epoxy resin/epoxy resin curing agent is selected from those curable at room temperature, the curable rubber composition (14) of the present invention can be cured at room temperature to give a high-strength product. When a liquid type epoxy resin is used, a cured product obtained from the solvent-free composition can be easily molded.

The method for molding the curable rubber composition (14) of the present invention is not limited. However, the method is preferably selected from a method commonly used for solid rubbers such as natural rubber, and a method used for rubber-based liquid polymers such as polyurethane. These molding methods can give cured products (e.g., molded rubbers and rubber-like foamed products) having modified properties (e.g., strength). The composition (14) is also suitable for use as a rubber-based adhesive, a sealant, a tackifier, etc. Particularly when the weight ratio of the components (a2)/(K3) is set to 100/20 to 100/100, a rubber-based adhesive having high peel strength and shear strength can be obtained.

The curable rubber composition (14) of the present invention can be stably cured, regardless of the atmosphere in which it is cured, even in theabsence of a sufficient amount of moisture. The composition also solves the problem of low strength associated with rubber-based cured products having hydrolyzable silyl groups. The composition also has other advantages of high hardness, improved weatherability of the cured product, and the like.

Rubber composition (15)

The rubber composition (15) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), calcium carbonate (L1) and talc (L2). The rubber composition (15) of the present invention contains preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2). The rubber composition (15) of the present invention is compounded with two kinds of inorganic fillers (L), i.e., calcium carbonate (L1) and talc (L2), for ensuring both good workability (spin-coatability) of the composition and good mechanical properties (particularly hardness) of the cured product.

Calcium carbonate as component (L1) is classified into two types: limestone powder produced by mechanically pulverizing/processing natural chalk, limestone, marble, etc., and light calcium carbonate produced from limestone, etc., as a raw material, by a wet process involving a chemical reaction, are called colloidal calcium carbonate, particularly when made into ultrafine colloidal particles under controlled conditions. Among these calcium carbonates, limestone powder is preferable because of its low cost, and colloidal calcium carbonate is preferable because of its remarkable effect of improving the workability (spin-coatability) of the composition. These may be used alone or in combination.

The limestone powder can be pulverized by a dry method or a wet method, which is not suitable for the present invention, because the storage stability of the rubber composition (15) of the present invention is generally deteriorated by the reaction product. The calcium carbonate as the component (L1) of the present invention is more preferably calcium carbonate treated with a surface-treating agent. The surface treatment of calcium carbonate as the component (L1) improves the adhesion of the composition (15) of the present invention and further improves the effect of improving the workability.

The surface treatment agent used in the present invention includes organic compounds such as fatty acids, fatty acid soaps, and fatty acid esters; various surfactants; and coupling agents such as silane coupling agents and titanate-based coupling agents.

Specific examples of these organic compounds include fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid; sodium and potassium salts of these acids; and alkyl esters of these acids.

Specific examples of the surfactant used in the present invention include polyoxyethylene alkyl ether sulfate and long-chain alcohol sulfate, sodium salts and potassium salts of these compounds as sulfate type anionic surfactants, alkylbenzene sulfonate, alkylnaphthalene sulfonate, paraffin sulfonate, α -olefin sulfonate and alkyl sulfosuccinate, and sodium salts and potassium salts thereof as sulfonate type anionic surfactants.

The calcium carbonate is treated with 0.1 to 20% by weight (based on calcium carbonate), more preferably 1 to 5% by weight, of a surface treating agent. When the amount of the agent is less than 0.1%, sufficient effects for improving workability, adhesion and weather resistance cannot be obtained, and when the amount of the agent exceeds 20%, storage stability of the curable composition may be deteriorated.

The component (L1) is incorporated preferably in an amount of 5 to 500 parts by weight, more preferably 20 to 350 parts by weight, still more preferably 40 to 200 parts by weight, per 100 parts by weight of the component (A2). When the amount added is less than 5 parts by weight, the effect of improving the workability (spin-coatability) of the rubber composition cannot be sufficiently obtained, and when the amount added exceeds 500 parts by weight, the adhesiveness may be deteriorated. These compounds may be used alone or in combination as component (L1).

Talc used as component (L2) is an inorganic filler obtained by mechanically pulverizing/processing/classifying a raw material called talc, and contains magnesium silicate (3 MgO.4SiO)₂·H₂O) as the main component. The talc as the component (L2) of the present invention may be untreated or surface-treated with a surface-treating agent. When subjected to surface treatment, the storage stability of the rubber composition (15) of the present invention can be improved.

The surface treatment agent for component (L2) was the same as that for component (L1).

The component (L2) is incorporated preferably in an amount of 5 to 300 parts by weight, more preferably 20 to 200 parts by weight, still more preferably 40 to 150 parts by weight, per 100 parts by weight of the component (A2). When the addition amount is less than 5 parts by weight, the component may not sufficiently improve mechanical properties of a cured product obtained from the composition, and when the addition amount exceeds 300 parts by weight, adhesiveness may be deteriorated. These compounds may be used alone or in combination as component (L2).

The rubber composition (15) of the present invention may contain various fillers in addition to calcium carbonate used as the component (L1) andtalc used as the component (L2). Specific examples of these fillers include: reinforcing fillers such as fumed silica, settling silica, silicic anhydride, silicon hydride, and carbon black; fillers such as diatomaceous earth, refractory earth, clay, talc, titanium oxide, bentonite, organic bentonite, iron oxide, zinc oxide, active zinc white; fibrous fillers, such as glass fibers or filaments.

The rubber composition (15) of the present invention may contain a silane coupling agent capable of improving the adhesive strength of the cured silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) to substrates and other objects, which is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as hydrolyzable silicon group) and one or more other functional groups.

Functional groups useful in the present invention include, in addition to hydrolyzable silicon groups: primary, secondary and tertiary amino groups, epoxy groups, carboxyl, vinyl, isocyanate, isocyanurate and halogen. Of these, primary, secondary and tertiary amino groups, mercapto groups, epoxy groups, isocyanate groups and isocyanurate groups are more preferable, and isocyanate groups and epoxy groups are most preferable.

The hydrolyzable silicon group is preferably bonded to other functional groups through a hydrocarbon group such as an alkylene group or an arylene group, but is not limited thereto.

The molecular weight of the silane coupling agent is 500 or less, particularly preferably 300 or less.

The silane coupling agents useful in the present invention include amino-containing silanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldiethoxysilane, gamma-ureidopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-benzyl-gamma-aminopropyltrimethoxysilane and N-vinylbenzyl-gamma-aminopropyltriethoxysilane, mercapto-containing silanes such as gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane, epoxy-containing silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, gamma-glycidyloxyethyltriethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, gamma-glycid.

Further, derivatives obtained by modifying some of the above-mentioned compounds may also be used as a silane coupling agent. They include: amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanate silanes, phenylamino-long chain-alkyl silanes, aminosilylated siloxanes and silylated polyesters.

The silane coupling agent is added in an amount of 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (A2). These silane coupling agents may be used alone or in combination.

The rubber composition (15) of the present invention may further contain a tackifier in addition to the silane coupling agent.

The rubber composition (15) of the present invention may be incorporated with a curing catalyst capable of promoting silanol condensation.

Specific examples of the catalyst used in the present invention include titanates such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octoate and tin naphthenate, reaction products between dibutyltin oxide and phthalic acid esters, dibutyltin bisacetylacetonate, organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate, chelates such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octoate, amino compounds, and salts of these compounds with carboxylic acid esters such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1, 8-diazabicyclo (5, 4, 0) undec-7 (DBU-7, 35u), known condensation catalysts between polyamine and polyamine, such as polyamine-epoxy, polyamine coupling catalysts, and polyamine, such as polyamine-epoxy resins, polyamine coupling agents.

When a curing catalyst is used, it is generally added in an amount of about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of the (A2) component. An excessively low catalyst content is disadvantageous because it results in a slow curing speed of the rubber composition product. An excessively high catalyst content is also disadvantageous because it deteriorates the tensile-related properties of the cured product.

The rubber composition (15) of the present invention may be appropriately blended with one or more additives. The additives used in the present invention include adhesion promoters, property modifiers, storage stability improvers, plasticizers, anti-aging agents, ultraviolet absorbers, metal deactivators, ozone-induced aging inhibitors, light stabilizers, amine-based radical chaining inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments and foaming agents.

The adhesion promoter used in the present invention includes a conventional adhesive and other adhesives, except for the silane coupling agent.

Specific examples of such adhesion promoters include phenol resins, epoxy resins, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanate and aromatic polyisocyanate, and when an adhesion promoter is used, it is preferably added in an amount of about 1 to 50 parts by weight, more preferably about 5 to 30 parts by weight, per 100 parts by weight of the component (A2).

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded, and esters of ortho-organic acids.

Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate. When the storage stability improver is used, it is incorporated preferably at about 0.5 to 20 parts by weight per 100 parts by weight of the (A2) component, more preferably about 1 to 10 parts by weight.

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. It is preferable that the plasticizer should be compatible with each component of the rubber composition (15) of the present invention.

Specific examples of such plasticizers include hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene, chlorinated paraffin, phthalate esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butylphthaloyl butyl glycolate, non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, polyalkylene glycol esters such as diethylene glycol benzoate and triethylene glycol dibenzoate, phosphate esters such as tricresyl phosphate and tributyl phosphate, which may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the rubber composition (15) of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

In the introduction of the reactive silicon group into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber, a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is preferably added in an amount of about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the component (A2).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4, 4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, laurylstearyl thiodipropionate and 2, 2-thio [ di-3- (3, 5-di-t-butyl-4-hydroxy]thiodipropionate, diethyl thiodipropionate, zinc di-butyl-3-4-thiodicarbamate, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, e, e.g., zinc dithiobutyl-thiodicarbamate, zinc dithiobenzoate, zinc dithiobutyl-3-dithiobenzoate, dithiobutyl-dithio, dithiobutyl-4-dithio, dithiobutyl-thiodicarbamate, dithiocarbamic acid, dithiocarbamic.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of rubber compositions of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the component (A2).

The effect of mixing calcium carbonate used as the component (L1) of the present invention and talc used as the component (L2) of the present invention was also observed even if the above-mentioned various additives were also mixed. More specifically, the curable rubber composition (15) of the present invention, when used as an elastomer sealant for construction, or a sealant for laminated glass, an SSG construction method, or a rust-proof or water-proof edge (cut portion) of wired glass or laminated glass, will have further improved workability (spin-coatability) and mechanical properties (hardness).

The rubber composition (15) of the present invention can be obtained by uniformly kneading the components by a kneader (e.g., an internal mixer, a planetary mixer, a Banbury mixer, a kneader or a two-roll apparatus).

The rubber composition (15) of the present invention is cured at room temperature to 200 ℃ for several minutes to several days because the composition can be cured rapidly. It is particularly preferred to crosslink the composition with moisture in air at room temperature.

[ rubber composition (15) and use thereof]

The rubber composition (15) of the present invention comprises a curable composition, a reactive silicon group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A2), as in the case of the rubber composition (11). more specifically, the rubber composition (15) of the present invention comprises an organic polymer (Z1), calcium carbonate (L1) and talc (L2), wherein the component (Z1) contains a hydrolyzable silyl group represented by the above general formula (1) and contains substantially no unsaturated double bond in the main chain.

The curable rubber composition (15) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

Curable composition (16)

The curable composition (16) of the present invention contains (a) a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), (b) a nickel-containing light stabilizer (S) and (c) a silane coupling agent (T).

The curable composition (16) of the present invention contains preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The curable composition (16) of the present invention exhibits excellent properties in curing speed and weather resistance, which are mainly derived from a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ light stabilizer (S) containing Nickel]

The present invention uses as light stabilizer (S) a light stabilizer (S) containing atomic nickel. Commercially available nickel-based light stabilizers are generally useful in the present invention as the stabilizer (S).

Specific examples of the light stabilizer include nickel dithiocarbamates such as nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate and nickel dibutyldithiocarbamate; nickel complexes such as [2, 2 ' -thiobis (4-tert-octylphenolate)]-n-butylaminonickel, [2, 2 ' -thiobis (4-tert-octylphenolate)]-2-ethylhexylamineonickel and [2, 2 ' -thiobis (4-tert-octylphenolate)]-triethanolamine nickel; other nickel compounds, such as nickel bis (octylphenyl) sulfide and nickel isopropyl xanthate. These light stabilizers may be used alone or in combination.

The component (S) is incorporated preferably at about 0.1 to 20 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), more preferably 1 to 10 parts by weight.

When the content of component (S) is less than the above range, the curable composition of the present invention may have poor weather-resistant adhesion to glass and other objects. The content exceeding the above range is disadvantageous in terms of cost. The nickel-containing light stabilizer (S) is considered to be capable of preventing the photo-deterioration of the adhesion improving effect obtained by the silane coupling agent used as the component (T). The nickel-containing light stabilizer (S) is considered to have the above-mentioned effects to a higher degree than other stabilizers.

[ silane coupling agent (T)]

The silane coupling agent, component (T), of the present invention is a silane coupling agent capable of improving the adhesive strength to a substrate or other objects of the cured silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). The agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referredto as a hydrolyzable silicon group) and one or more other functional groups.

Functional groups useful in the present invention include, in addition to hydrolyzable silicon groups: primary, secondary and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurate groups and halogens. Of these, primary, secondary and tertiary amino groups, epoxy groups, isocyanate groups and isocyanurate groups are more preferable, and isocyanate groups and epoxy groups are most preferable.

Specific examples of silane coupling agents useful in the present invention include amino-containing silanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldiethoxysilane, gamma-ureidopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-benzyl-gamma-aminopropyltrimethoxysilane and N-vinylbenzyl-gamma-aminopropyltriethoxysilane, mercapto-containing silanes such as gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane, epoxy-containing silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyldimethoxysilane, gamma-3-glycidoxypropyltrimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane, epoxy-silane, such as gamma-glycidoxypropyltrimethoxysilane, gamma-3-glycidoxypropyltrimethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, gamma-glycidyloxyethyl.

The silane coupling agent (T) is added in an amount of 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The rubber composition (16) of the present invention may be mixed with a tackifier in addition to the silane coupling agent. Examples of the tackifier other than the silane coupling agent include compounds having an epoxy group or an isocyanate group in the molecule, including isocyanate polymers.

[ other Components]

The composition (16) of the present invention may be incorporated with one or more additives as required. The additives used in the present invention include a curing catalyst capable of promoting silanol condensation, a storage stability improver capable of preventing curing of the composition (16) of the present invention upon storage, a plasticizer, a filler, an aging inhibitor, an ozone-induced aging inhibitor, a phosphorus-based peroxide decomposer, a lubricant and a foaming agent.

Specific examples of these catalysts used in the present invention include titanates such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octoate and tin naphthenate, reaction products between dibutyltin oxide and phthalates, dibutyltin bisacetylacetonate, organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate, chelates such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octoate, amino compounds, and salts of these compounds with carboxylic acid esters such as butylamine, octylamine, dodecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1, 8-diazabicyclo (5, 4, 0) bis (7-epoxypropyl) silane, reaction products of these compounds with carboxylic acid esters such as butylamine, octylamine, dodecylamine, dibutylamine, diethanolamine, triethanolamine, diethylenetriamine, 2-ethyl-4-methylimidazole, and 1, 8-diazabicyclo (5, 4, 0) bis (7-amino-propyl) silane, and other known amine-containing acidic polyamine coupling agents such as a polyamine, and a combination of these.

The curing catalyst is added in an amount of about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) component.

The storage stability improvers useful for the present invention include compounds having silicon to which a hydrolyzable group is bonded, and esters of ortho-organic acids.

Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate.

Plasticizers useful in the present invention include low molecular weight plasticizers (such as dioctyl phthalate), high molecular weight plasticizers, and high viscosity plasticizers.

Specific examples of the plasticizer used in the present invention include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butylphthaloyl butyl glycolate, nonaromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate, phosphoric acid esters such as tricresyl phosphate and tributyl phosphate, chlorinated paraffins, and hydrocarbon-based oils such as alkylbiphenyls, polybutenes, hydrogenated polybutenes, ethylene/α -olefin oligomers, α -methylstyrene oligomers, biphenyls, terphenyls, triaryldimethanes, alkyleneterphenyls, liquid polybutadienes, hydrogenated liquid polybutadienes, paraffin oils, naphthene oils, random polypropylenes and partially hydrogenated terphenyls.

Of these, hydrocarbon-based compounds free of unsaturated groups, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with the components of the composition (16) of the present invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and cheapness.

In the introduction of the reactive silicon group into the saturated hydrocarbon-based polymer, a plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is incorporated preferably in an amount of 1 to 400 parts by weight, more preferably 1 to 150 parts by weight, further preferably 10 to 120 parts by weight, particularly preferably 20 to 100 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate, quartz powder, glass beads, fine aluminum powder, flint powder, and zinc powder. Among these, thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable; and calcium carbonate, titanium oxide and talc. They may be used alone or in combination.

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4,4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, laurylstearyl thiodipropionate and 2, 2-thio [ di-3- (3, 5-di-t-butyl-4-hydroxy]thiodipropionate, diethyl thiodipropionate, zinc di-butyl-3-4-thiodicarbamate, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, e, e.g., zinc dithiobutyl-thiodicarbamate, zinc dithiobenzoate, zinc dithiobutyl-3-dithiobenzoate, dithiobutyl-dithio, dithiobutyl-4-dithio, dithiobutyl-thiodicarbamate, dithiocarbamic acid, dithiocarbamic.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than the other type of composition (16) of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

Curable composition (16) and use thereof

The curable composition (16) of the present invention comprises a curable composition, as the component (A1), a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, as described above, more specifically, the curable composition (16) of the present invention comprises:

(a) an organic polymer (Z) containing a hydrolyzable silyl group represented by the general formula [ III]and having substantially no unsaturated double bond in the main chain,

(b) a light stabilizer (S) containing nickel, and

(c) a silane coupling agent (T).

As described above, the composition is suitable for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

The curable composition (16) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

In other words, the present invention provides a sealant, a potting agent, a coating material or an adhesive composed of a curable composition containing (a) the organic polymer (Z), (b) the nickel-containing light stabilizer (S) and (c) the silane coupling agent (T).

Curable rubber composition (17)

The curable rubber composition (17) of the present invention contains a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a sulfur-based aging inhibitor (U).

As required, component (A1) which is the main component of the curable rubber composition (17) of the present invention is cured with a silanol condensing catalyst.

Specific examples of the condensation catalyst used in the present invention include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; a reaction product between dibutyltin oxide and a phthalate; dibutyl tin diacetone; organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and aluminum diisopropoxide ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octoate; amino compounds, and salts of these compounds with carboxylic acids, such as butylamine, monoethanolamine, triethylenetetramine, guanidine, 2-ethyl-4-methylimidazole, and 1, 3-diazabicyclo (5, 4, 6) undecene-7 (DBU); and other acidic or basic silanol condensation catalysts.

[ Sulfur-based aging inhibitor (U)]

The sulfur-based aging inhibitors useful as the component (U) in the present invention include mercaptans, thiolates, sulfides including sulfide carboxylate esters and hindered phenol-based sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptanes, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitor as the component (U) include:

thiols, such as 2-mercaptobenzothiazole;

mercaptides, such as the zinc salt of 2-mercaptobenzothiazole;

sulfides, such as 4,4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (2-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, terephthaloyl bis (2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and diethyl 2, 2-thio [ bis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate];

polysulfides, such as 2-benzothiazole disulfide;

dithiocarboxylates such as zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate and zinc dimethyldithiocarbamate;

thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolylthiourea and ethylenethiourea; and

thiophosphates, such as trilauryl trithiophosphate. Other compounds may also be used in the present invention as long as they are sulfur-based compounds having an anti-aging function.

The above-mentioned sulfur-based aging inhibitor (U) prevents decomposition and/or aging of the main chain under heating much more effectively than other types of agents than the composition (17) of the present invention, and controls problems such as residual surface tackiness.

The above-mentioned sulfur-based aging inhibitor (U) is added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). it sufficiently exhibits the effect of improving the heat resistance of the composition without causing any problems such as coloration.

One or more commonly used aging inhibitors may be used in combination with the sulfur-based aging inhibitor (U). These age inhibitors include: phenolic radical inhibitors, such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid methylen]methane; ultraviolet absorbers such as 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate; metal deactivators, inhibitors against ozone-induced ageing, light stabilizers, amine-based radical chaining inhibitors, phosphorus-based peroxide decomposers, citric acid and phosphoric acid.

Further, various silane compounds can be used as the property adjuster of the present invention to control strength, elongation and other properties of the cured product in a wide range. Specific examples of these compounds include silicon compounds having one or more silanol groups or other hydrolyzable groups, but are not limited thereto: (CH)₃)₃SiOH，(CH₃CH₂)₃SiOH，(CH₃CH₂CH₂)₃SiOH，(C₆H₅-)₃SiOH，(C₆H₅-)₂(CH₃-)SiOH，(CH₃-)₂(C₆H₅-)SiOH，

(p+q＝2～20)

(CH₃)₂Si(OCH₃)₂，(CH₃CH₂)₂Si(OCH₃)₂，(CH₃)₂Si(OCH₂CH₃)₂，(CH₃CH₂)₂Si(OCH₂CH₃)₂，(C₆H₅)₂Si(OCH₂CH₃)₂，(C₆H₅)₂Si(OCH₃)₂，(C₆H₅)₂Si(OH)₂，(CH₃-C₆H₅)₂Si(OCH₃)₂，(CH₃-C₆H₅)₂Si(OH)₂，(CH₃)₂Si(OCH₂CH₂OCH₃)₂，(CH₃CH₂)₂Si(OCH₂CH₂OCH₃)₂，(CH₃)(CH₃CH₂)Si(OCH₃)₂，(C₆H₅)(CH₃)Si(OH)₂，(C₆H₅)(CH₃CH₂)Si(OH)₂，(C₆H₅)(CH₃)Si(OCH₃)₂，(C₆H₅)(CH₃CH₂)Si(OH)₂，

(x+y＝0～18)

(x+y＝0～18)(CH₃)₃Si-NH-Si(CH₃)₃，(CH₃)₃Si-N(CH₃)₂，(CH₃)₃Si-NH-CO-NH-Si(CH₃)₃，

In the above formula, R is a hydrogen atom or a hydrocarbon group of 1 to 20 carbon atoms.

The methods of adding the silicon compound can be classified into three main groups.

The first method is to add only a silicon compound to the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), and in this method, the silicon compound is uniformly dispersed and dissolved by carefully setting conditions (such as temperature and stirring conditions) as required in consideration of the properties of the silicon compound.

The second method is to mix a given amount of silicon compound with the final product when it is used. For example, when the composition is used as a two-liquid component type sealing material, a silicon compound may be mixed as a third component with the base material and the curing agent of the composition.

The third method is to previously react a silicon compound with the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) in the presence of a silanol condensing catalyst if necessary, when the silicon compound reacts with moisture to form a compound having a silanol group in the molecule, a desired amount of water is added to the reaction system, followed by heating under vacuum to evaporate, thereby achieving the object of the invention.

The curable rubber composition (17) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a sulfur-based aging inhibitor (U) as essential components, and may be further added, as required, one or more additives such as the above-mentioned various silane compounds as property modifiers other additives used in the present invention include various fillers, plasticizers, silanol condensing catalysts capable of promoting the curing of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), aging inhibitors other than the sulfur-based aging inhibitor (U), ultraviolet absorbers, lubricants, pigments, foaming agents, tackifiers and water.

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder.

These fillers may be used alone or in combination.

Specific examples of such plasticizers include hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, process oil, paraffin oil, naphthene oil and partially hydrogenated terphenyl;

chlorinated paraffin;

phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;

esters of polyalkylene glycols, such as diethylene glycol benzoate and triethylene glycol dibenzoate; and

phosphoric acid esters such as tricresyl phosphate and tributyl phosphate, particularly preferred are saturated hydrocarbon-based compounds, which may be used alone or in combination, in the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) In the introduction of the hydrolyzable silyl group, a plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

Further, the curable rubber composition (17) of the present invention may be incorporated with various tackifiers to further improve the adhesiveness thereof.

Specific examples of the tackifier used in the present invention include silane coupling agents such as epoxy resins, phenol resins, aminosilanes and epoxysilane compounds; an alkyl titanate; and an aromatic polyisocyanate. These compounds may be used alone or in combination to improve the adhesion of the composition to various types of objects.

The curable rubber composition (17) of the present invention is suitable for various materials such as adhesives, tackifiers, coatings, sealant compositions, waterproofing materials, spray materials, shaping materials and casting rubber materials.

Curable rubber composition (17) and use thereof

As described above, the curable rubber composition (17) of the present invention comprises a curable composition, a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1), more specifically, the composition comprises an organic polymer (Z) and a sulfur-based aging inhibitor (U). As described above, the composition is suitable for use in the fields of electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure.

The curable rubber composition (17) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

Curable composition (18)

The curable composition (18) of the present invention comprises a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a compound (V) containing in the molecule an unsaturated group capable of causing polymerization by reacting with oxygen in the air and/or a photopolymerizable material.

The curable composition (18) of the present invention contains preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The curable composition (18) of the present invention exhibits excellent properties in curing speed and weather resistance, which are mainly derived from a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

[ oxidizable polymerizable Material and/or photopolymerizable Material (V)]

The curable composition (18) of the present invention is incorporated with a compound having an unsaturated group and/or a photopolymerizable material in the molecule capable of causing polymerization by reacting with oxygen in the air as the component (V) to enhance weather-resistant adhesion of the composition. They can exhibit their functions when used alone or in combination.

Among the above-mentioned materials used as the component (V), a compound having an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air in the molecule is simply referred to as an oxidatively polymerizable material.

Specific examples of oxidatively polymerizable materials include: ester compounds of unsaturated higher fatty acids and alcohols; diene-based polymers and copolymers (e.g., polymers and copolymers of 1, 2-polybutadiene, 1, 4-polybutadiene, and dienes of 5 to 8 carbon atoms); various modified products of these polymers and copolymers (e.g., modified with maleic acid or boiled oil). The reactivity of the oxidative polymerization depends, for example, on the reaction temperature, humidity and the presence or absence of light and additives.

Therefore, when a compound having an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air in the molecule is added as component (V), it acts more strongly as a weather-resistant adhesion promoter when irradiated with light, because it can form a harder coating film on the adhesion surface with an object such as glass. However, its initial adhesive strength did not deteriorate.

When an ester compound whose main component is an ester of an unsaturated higher fatty acid and an alcohol is blended as the component (V), the curable composition (18) can have significantly improved weather-resistant adhesion to various glasses such as heat ray reflective glasses. For the esters of unsaturated higher fatty acids and alcohols, the unsaturated higher fatty acid component preferably has at least 10 carbon atoms in the molecule, each molecule having at least one unsaturated group and a carboxyl group.

Specific examples of the ester compound of an unsaturated higher fatty acid include products obtained by condensing an unsaturated higher fatty acid such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, octadecatrien-4-oic acid, ricinoleic acid or arachidonicacid with an alcohol selected from monovalent alcohols (such as methanol and ethanol), divalent alcohols (such as ethylene glycol and propylene glycol), trivalent alcohols (such as trimethylolpropane and glycerol), tetravalent alcohols (such as pentaerythritol), hexavalent alcohols (such as sorbitol), and organic silicon compounds having a hydroxyl group bonded to a silicon atom through an organic group.

It is known that saturated fatty acid groups are much less reactive towards oxidative polymerization than unsaturated fatty acid groups, while the reactivity of unsaturated fatty acid groups increases proportionally with the number of double bonds it contains and the degree of conjugation. Therefore, among ester compounds of unsaturated higher fatty acids, more preferable are compounds having an iodine value of 100 or more, which are highly reactive.

The ester compound of an unsaturated higher fatty acid having an iodine value of 100 or more can be produced by a condensation reaction of an unsaturated higher fatty acid and an alcohol as described above. However, the cost of using drying oils in practice is more economical because of the availability of drying oils. These drying oils include compounds containing triglycerides as the main component, i.e., esters of unsaturated higher fatty acids with glycerol, such as linseed oil, tung oil, soybean oil, hemp seed oil, clothes oil, lacquer seed oil (urushi kernel oil), perilla oil, oiticica oil, coconut oil, walnut oil, poppy oil, cherry seed oil, pomegranate seed oil, safflower oil, tobacco seed oil, touhaze seed oil, rubber seed oil, sunflower seed oil, grape seed oil, balsam soybean oil, and petroselinum seed oil.

These drying oils may contain ester compounds of unsaturated higher fatty acids having 10 or more carbon atoms, ester compounds of unsaturated higher fatty acids having less than 10 carbon atoms, alcohols, unsaturated fatty acids and saturated fatty acids. The ester compound of an unsaturated higher fatty acid having 10 or more carbon atoms preferably accounts for at least 80% by weight, more preferably 100% by weight, of the drying oil.

As previously mentioned, the reactivity of the oxidative polymerization reaction increases in proportion to the degree of conjugation of the unsaturated fatty acid groups. Therefore, a drying oil having as a main component a triglyceride of a conjugated unsaturated higher fatty acid (such as eleostearic acid, octadecatrien-4-oic acid, punicic acid or canulupinic acid) is highly reactive to oxidative polymerization to more effectively improve the weather-resistant adhesion of the composition, and is therefore most desirable. Specific examples of the drying oil having as a main component a triglyceride of an unsaturated higher fatty acid having a conjugated group include tung oil, oiticica oil, pomegranate seed oil and balsam soybean oil.

These compounds having an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air in the molecule may be used alone or in combination.

Among the above-mentioned materials used as the component (V), the photopolymerizable material means, in short, a compound having an unsaturated group in which a double bond is activated to initiate polymerization when irradiated with light. A variety of materials are known to fall within this class, including organic monomers, oligomers, resins, and compositions containing one or more of these. Any relevant commercially available material may be used in the present invention. When used as the (V) component, the photopolymerizable material functions as a weather-resistant adhesion promoter because it can form a hard coating film on the adhesion surface with an object (e.g., glass) when irradiated with light. However, it did not show deterioration of the initial adhesive strength.

The photopolymerizable unsaturated group contained in the photosensitive resin for photopolymerization system is represented by vinyl, allyl, vinyl ether, vinyl thioether, vinyl amino, acetylenically unsaturated group, acryloyl, methacryloyl, styryl and cinnamoyl. Among them, acryloyl and methacryloyl are more preferable because of their high initial efficiency of polymerization.

Examples of the acryl-or methacryl-containing photosensitive resin used in the photopolymerization system include acrylamide derivatives, methacrylamide derivatives and (meth) acrylates, of which (meth) acrylates are more preferable because they are easily available in various types. The term (meth) acrylate in this specification is a class of materials that includes both acrylates and methacrylates.

When a monofunctional photopolymerizable material having (meth) acrylate as a main component has one photosensitive group (unsaturated group), only a linear polymer is formed by photopolymerization. On the other hand, in a polyfunctional (meth) acrylate having two or more photosensitive (unsaturated) groups, photopolymerization and photocrosslinking simultaneously occur to form polymer molecules having a network structure. Therefore, the (meth) acrylate is more preferable because a harder coating film can be formed on the adhesion interface to enhance the effect of improving the weather-resistant adhesion.

Specific examples of the polyfunctional (meth) acrylate include di (meth) acrylates (having two functional groups) of propylene glycol, butylene glycol or ethylene glycol; trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate (having 3 functional groups); and pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate (having 4 or more functional groups). Further, examples of the oligomer include oligoesters having a molecular weight of 10,000 or less, such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. The polyfunctional (meth) acrylate preferably has 2 or more, more preferably 3 or more, acrylic or methacrylic unsaturated groups. The unsaturated acrylic compound can obtain a higher effect of improving weather-resistant adhesion as the number of functional groups thereof increases.

Other examples of photopolymerizable materials include polyvinyl cinnamate and azide resins.

Polyvinyl cinnamates include cinnamate compounds of polyvinyl alcohol, known as photosensitive resins having cinnamoyl groups as photosensitive groups, and many other vinyl polycinnamate derivatives.

The azide resin includes a rubber photosensitive liquid, known as a photosensitive resin having an azide group as a photosensitive group and usually mixed with a diazide compound as a photosensitive group, and resins specified on pages 93, 106 and 117 of "photosensitive resin" published by Society of printing 1972, 3, 17. These materials may be used alone or in combination, or may be mixed with a photosensitizer as required.

These photopolymerizable materials may be used alone or in combination. When the component (V) is required to exhibit the effect of improving weather-resistant adhesion more safely and more rapidly, the addition of a photosensitizer is effective for the above purpose. When a compound having an unsaturated group capable of causing polymerization by reacting with oxygen in the air and/or a photopolymerizable material in the molecule is used as the component (V) to be added to the composition (18) of the present invention, the weather-resistant adhesion property of the curable composition containing a saturated hydrocarbon-based polymer having a reactive silicon group is greatly improved. Above all, component (V) does not adversely affect the properties of the cured composition. The component (V) is incorporated preferably in an amount of 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of the component (A1). When the content is less than 0.1 part by weight, the improvement of weather-resistant adhesion is insufficient. When the content exceeds 20 parts by weight, the storage stability of the sealant composition may be deteriorated.

The curable composition (18) of the present invention comprising component (A1) and component (V) is superior in adhesion to substrates and weather-resistant adhesion to substrates to the curable composition not containing component (V) because component (V) is cured by the action of oxygen and/or light. These characteristics are exhibited even when the composition does not contain a silane coupling agent, as described below. However, the composition shows better adhesion and weather-resistant adhesion when incorporated with a silane coupling agent.

The curable composition (18) of the present invention may be mixed with one or more additives as required. The additives used in the present invention include silane coupling agents, curing catalysts capable of promoting silanol condensation, property modifiers capable of modifying the properties of the cured product in relation to stretching, plasticizers, fillers, adhesion promoters, aging inhibitors, radical inhibitors, ultraviolet absorbers, metal deactivators, ozone-induced aging inhibitors, light stabilizers, phosphorus-based peroxide decomposers, lubricants, pigments and foaming agents.

The silane coupling agent which may be added as needed to the curable composition (18) of the present invention is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as hydrolyzable silicon group) and one or more other functional groups, and is capable ofimproving the adhesive strength of the cured silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) to a substrate or other object.

Specific examples include the above-mentioned groups as hydrolyzable groups, and methoxy and ethoxy are more preferable from the viewpoint of hydrolysis speed. The compound preferably has 2 or more hydrolyzable groups, more preferably 3 or more hydrolyzable groups.

Functional groups useful in the present invention include, in addition to hydrolyzable silicon groups: primary, secondary and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurate groups, and halogens. Of these, primary, secondary and tertiary amino groups, epoxy groups, isocyanate groups and isocyanurate groups are more preferable, and isocyanate groups and epoxy groups are most preferable.

Specific examples of silane coupling agents useful in the present invention include amino-containing silanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldiethoxysilane, gamma-ureidopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-benzyl-gamma-aminopropyltrimethoxysilane and N-vinylbenzyl-gamma-aminopropyltriethoxysilane, mercapto-containing silanes such as gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane, epoxy-containing silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyldimethoxysilane, gamma-3-glycidoxypropyltrimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane, epoxy-silane, such as gamma-glycidoxypropyltrimethoxysilane, gamma-3-glycidoxypropyltrimethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, gamma-glycidyloxyethylhexylethylhexyltrimethoxysilane, gamma-glycidyloxyethyltrimethoxysilane.

The silane coupling agent which can be optionally used in the present invention is preferably added in an amount of 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). these silane coupling agents may be used alone or in combination.the composition (18) of the present invention may further contain a tackifier other than a silane coupling agent.

In the case of the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) In the introduction of the hydrolyzable silyl group, a plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

Specific examples of these additives are described in, for example, japanese patent laid-open gazettes 69659/1992 and 108928/1995, and japanese patent laid-open gazettes 254149/1988 and 22904/1989.

The curable composition (18) of the present invention brings about an effect of significantly improving the adhesion of the composition to various objects, either in the presence of a primer layer or in the absence of a primer layer, and particularly the effect is more significant in the absence of a primer layer. Such as inorganic substrates of glass, aluminum, stainless steel, zinc, copper and plaster, organic substrates of vinyl chloride, acrylic, polyester, polyethylene, polypropylene and polycarbonate.

The curable composition (18) of the present invention can remarkably improve weather-resistant adhesion to various glasses such as ordinary inorganic glass (float glass), and is more effective particularly when used as a sealant composition for heat ray reflective glass. The heat ray reflective glass suitable for use with the curable composition (18) of the present invention means an optically functional glass coated on its surface with a film such as a metal, metal nitride or metal oxide to reflect or absorb light of a specific wavelength.

The effect of unsaturated compounds capable of reacting with oxygen in the air was also observed, even when various additives were incorporated.

More specifically, the curable composition (18) of the present invention, when used as an elastomer sealant for construction engineering, or a sealant for laminated glass, or a sealant for rust-proof or water-proof edges (cut portions) of wired glass or laminated glass, can further improve the adhesion and weather-resistant adhesion of the sealant to various objects when incorporated with the above-mentioned compounds.

Curable composition (18) and use thereof

As described above, the curable composition (18) of the present invention contains a curable composition, as the component (A1), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, more specifically, a composition comprising (a) an organic polymer (Z) and a compound having in the molecule an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air and/or a photopolymerizable material, as the component (V).

The curable composition (18) of the present invention preferably further comprises the above-mentioned silane coupling agent.

The curable composition (18)of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

In other words, the present invention provides a sealant, a potting agent, a coating material or an adhesive composed of a curable composition containing (a) the organic polymer (Z) and a compound having, in the molecule, an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air and/or a photopolymerizable material as the component (V).

When the curable composition is used as a sealant, a potting agent, a coating material and an adhesive, it is preferable to further contain the above-mentioned silane coupling agent.

Tackifier composition (19)

The tackifier composition (19) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), a tackiness imparting resin (W), and a curing catalyst composed of a specific organozirconium compound (H1) or a specific organoaluminum compound (H2).

[ tackiness-imparting resin (W)]

The tackiness-imparting resin (W) can be used in the present invention for adjusting the tackiness of the composition.

The tackifier (W) is not limited. These resins useful in the present invention include resins having an acidic group such as rosin ester resins, phenol resins, xylene/phenol resins and terpene/phenol resins; various petroleum-based resins, such as aromatic, aliphatic/aromatic copolymers or cycloaliphatic-based resins having relatively low polarity; and conventional tackiness imparting resins such as benzofuran resins, low molecular weight polyethylene resins and terpene resins.

Specific examples of such resins include, but are not limited to: resins with lower polarity, e.g. Petrosin801^TM(Mitsui Chemicals)，Neopolymer S^TM(NIPPON PETROCHEMICALS)，Tackiace A100^TM(Mitsui Chemicals)，Quintone 1500^TM(ZEON CORP.)，FTR6100^TM(Mitsui Chemicals)，Vicolastic A75^TM(Hercules)，Coumarone C-90^TM(Nippon Steel Chemical Group); resins having less polar groups, e.g. YS Polystar T-115^TMAnd YS Polystar S-145^TM(Yasuhara Yushi)，Steperite Ester 7^TM(Hercules), and Neopomymer E-100^TM(NIPPON PETROCHEMICALS)。

The content of the tackiness-imparting resin (W) depends on the type used, however, it is preferably at most 140 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). at more than 140 parts by weight, a composition having good tackiness cannot be obtained.

[ curing catalyst (H)]

The curing catalyst (H) of the present invention is represented by the following general formula [ VIII]An organozirconium compound represented by formula (H1) orThe following general formula [ IX]The organoaluminum compound (H2) shown. Using a curing catalyst [ H]]The releasability of the tackifier composition (19) of the present invention from silicone release paper can be greatly improved.

Wherein "n" is an integer of 0 to 4, R is a monovalent hydrocarbon group of 1 to 20 carbon atoms, Y is a group selected from the group consisting of hydrocarbon groups of 1 to 8 carbon atoms, halogenated hydrocarbon groups, cyanoalkyl groups, alkoxy groups, halogenated alkoxy groups, cyanoalkoxy groups and amino groups, which may be the same or different, andwherein "p"is an integer of 0 to 3, R is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Y is a group selected from the group consisting of a hydrocarbon group of 1 to 8 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, a cyanoalkoxy group and an amino group, which may be the same or different.

The organozirconium compound (H1) or the organoaluminum compound (H2) means an alkoxide-based compound or chelate compound of zirconium or aluminum, represented by the above general formula [ VIII]or [ IX], wherein an organic group is bonded to zirconium or aluminum. It may be a monomer or related compound.

Specific examples of such compounds include, but are not limited to: alkoxide-based compounds, e.g. (C)₂H₅O)₄Zr、(iso-C₃H₇O)₄Zr、(n-C₄H₉O)₄Zr、(C₈H₁₇O)₄Zr、(iso-C₃H₇O)₃Al、(iso-C₃H₇O)₂Al(sec-C₄H₉O) and (sec-C₄H₉O)₃Al; and chelates, e.g. Zr (acac)₄(zirconium tetraacetylacetonate, etc.), (n-C₄H₉O)₃Zr(acac)、(n-C₄H₉O)₂Zr(acac)₂、(n-C₄H₉O)Zr(acac)₃、(iso-C₃H₇O)₂Al(acac)、Al(acac)₃、(iso-C₃H₇O)₂Al (ethylacetoacetate) and Al (ethylacetate)Acylacetic acid radical)₃。

Even when the organozirconium compound (H1) or the organoaluminum compound (H2) is associated into a trimer or tetramer, it can be used. These curing catalysts (H) may be used alone or in combination.

The curing catalyst (H) is preferably added in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the amount is less than 0.01, the curing catalyst (H) does not sufficiently exhibit its catalytic effect, and when the amount exceeds 20 parts by weight, the catalytic reaction is excessively promoted to deteriorate the workability of applying the tackifier composition to a substrate.

The curing catalyst (H) of the present invention is at the same level in curing activity as the organotin-based compound which has been widely used as a curing catalyst, does not cause a problem of coloring of an adhesion promoter unlike the alkyl titanate-based compound used as a catalyst, and has excellent productivity and appearance.

[ other Components]

The tackifier composition (19) of the present invention may be incorporated, as required, with one or more additives within limits not adversely affecting the object of the present invention. The additives used in the present invention include adhesion promoters, property modifiers, storage stability improvers, plasticizers or softeners, fillers, aging inhibitors, ultraviolet absorbers, metal deactivators, ozone-induced aging inhibitors, light stabilizers, amine-based radical chaining inhibitors, phosphorus-based peroxide decomposers, antioxidants, lubricants, pigments, foaming agents and surfactants.

The adhesion promoter used in the present invention includes a conventional adhesive, a silane coupling agent such as an aminosilane compound and an epoxysilane compound, and other compounds specific examples of these adhesion promoters include a phenol resin, an epoxy resin, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, a benzofuran/indene resin, a rosin ester resin, a terpene/phenol resin, α -methylstyrene/vinyltoluene copolymer, polyethylmethylstyrene, an alkyl titanate and an aromatic polyisocyanate, and when the adhesion promoter is used, it is preferably added in an amount of about 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The storage stability improvers useful for the present invention include esters of ortho-organic acids.

When the storage stability improver is used, it is incorporated preferably at about 0.5 to 20 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), more preferably 1 to 10 parts by weight.

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. Preferably, the plasticizer should be compatible with the components of the rubber composition of the present invention.

Specific examples of these plasticizers include:

hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methylstyrene oligomer, biphenyl, terphenyl, triaryl dimethane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyl biphenyl, partially hydrogenated terphenyl, paraffin oil, naphthene oil and atactic polypropylene;

chlorinated paraffin;

phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, dioctyl phthalate and butyl phthalyl glycolyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;

esters of polyalkylene glycols, such as diethylene glycol benzoate and triethylene glycol dibenzoate;

phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; and

polypropylene glycol. Among them, the saturated hydrocarbon-based compounds are more preferable. They may be used alone or in combination.

Of these, hydrocarbon-based compounds free of unsaturated groups, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, for example, these compounds are well compatible with the respective components of the rubber composition of the present invention, have a limited effect on the curing speed of the rubber composition, and the resulting cured product is high in resistance to weather, and inexpensive.

When a hydrolyzable silyl group is introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) In the case of (3), a plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is incorporated preferably at about 10 to 500 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), more preferably at about 20 to 300 parts by weight.

Specific examples of the filler include wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder and zinc powder, among which thixotropic fillers such as settling silica, fumed silica and carbon black are more preferable, and calcium carbonate, titanium oxide and talc are used in an amount of preferably about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful for the present invention include:

thiols, such as 2-mercaptobenzothiazole;

mercaptides, such as the zinc salt of 2-mercaptobenzothiazole;

sulfides, such as 4,4 ' -thiobis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (2-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, terephthaloyl bis (2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and diethyl 2, 2-thio [ bis-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate];

polysulfides, such as 2-benzothiazole disulfide;

dithiocarboxylates such as zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate and zinc dimethyldithiocarbamate;

thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolylthiourea and ethylenethiourea; and

thiophosphates, such as trilauryl trithiophosphate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of agents for the curable rubber composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Solvents may be used, for example, to improve handling and to reduce viscosity. Solvents used for the above purpose include aromatic hydrocarbon-based solvents such as toluene and xylene; ester-based solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate; and ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone.

The tackifier composition (19) of the present invention is useful in a wide range of applications such as tapes, sheets, labels and foils. For example, the above-mentioned tackifier composition of a solventless liquid, a solvent type, an emulsion type or a hot melt type is applied to a substrate such as a synthetic resin or modified natural film, paper, any type of cloth, a metal foil, a metallized plastic foil, asbestos or a glass fiber cloth, and cured at normal or high temperature after being exposed to moisture or water.

Tackifier composition (19) and use thereof

As described previously, the tackifier composition (19) of the present invention comprises a tackifier composition, a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, the composition comprises an organic polymer (Z), a tackiness imparting resin (W), and a curing catalyst (H) composed of a specific organozirconium compound (H1) or a specific organoaluminum compound (H2). The composition is suitable for use in the fields of electric/electronic devices, transportation machines, and civil engineering/construction, medical care, and leisure, as described previously.

For the civil engineering/construction field, the tackifier composition (19) is useful, for example, as an adhesive, a waterproof or a vibration-proof plate.

Rubber composition (20)

The rubber composition (20) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a specific curing catalyst (H).

[ curing catalyst H]

The curing catalyst (H) includes: a mercaptide-type organotin compound having an Sn— S bond (H3), a sulfide-type organotin compound having an Sn ═ S bond (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds and a carboxylic acid-type organotin compound (H7).

For example, the mercaptide-type organotin compound having Sn — S bond (H3) includes compounds represented by the following chemical formula and structural formula:

having R₂Organotin compounds of the type ring Sn (-S … … COO-), for example:

having R₂Organotin compounds of the type ring Sn (-S … … S-), for example:

R₂Sn(-SCH₂COOR)₂organotin compounds of the type, for example: (n-C)₄H₉-)₂Sn(-SCH₂COO-iso-C₈H₁₇)₂And (n-C)₈H₁₇-)₂Sn(-SCH₂COO-n-C₁₂H₂₅)₂；

RSn(-SCH₂COOR)₃Organotin compounds of the type, for example: (n-C)₄H₉-)Sn(-SCH₂COO-iso-C₈H₁₇)₃And (n-C)₈H₁₇-)Sn(-SCH₂COO-n-C₁₂H₂₅)₃.

Sulfide-type organotin compounds having Sn ═ S bond (H4) include R₂Sn ═ S type compounds, e.g. (n-C)₈H₁₇-)₂Sn＝S。

Organic carboxylic acids (H5) include benzoic acid, phthalic acid, succinic acid, adipic acid, pyromellitic acid, formic acid, and acetic acid.

Organic carboxylic anhydrides (H6) include acetic anhydride, maleic anhydride,phthalic anhydride, succinic anhydride, and pyromellitic anhydrides.

The carboxylic acid type organotin compound (H7) mixed with one of the above-mentioned compounds (H3) to (H6) used for the curing catalyst (H) includes compounds represented by the following chemical formula, for example, Sn (-OCO-n-C)₈H₁₇)₂(n-C₄H₉)₂Sn(-OCO-n-C₁₁H₂₃)₂，(n-C₄H₉)₂Sn(-OCOCH＝CHCOOCH₃)₂，(n-C₈H₁₇)₂Sn(-OCO-n-C₁₁H₂₃)₂And (n-C)₈H₁₇)₂Sn(-OCOCH＝CHCOO-n-C₄H₉). Tin (IV) compounds are preferred to tin (II) compounds for the purposes of the present invention.

For the ratio of the mercaptide-type organotin compound having Sn — S bonds (H3) to the carboxylate-type organotin compound (H7) of the present invention, i.e., (H3)/(H7), the ratio of the sulfide-type organotin compound having Sn ═ S bonds (H4) to the carboxylate-type organotin compound (H7), i.e., (H4)/(H7), the ratio of the organic carboxylic acid (H5) to the carboxylate-type organotin compound (H7), i.e., (H5)/(H7), the ratio of the organic carboxylic acid anhydride (H6) to the carboxylate-type organotin compound (H7), i.e., (H6)/(H7), each is 0.1 to 20, preferably 0.1 to 10.

The curing catalyst (H) is added in an amount of about 0.01 to 10 parts by weight, preferably about 0.1 to 10 parts by weight, per 100 parts by weight of the silyl group containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the amount is in the above range, the curing catalyst can give a rubber composition having an improved pot life in an open atmosphere.

[ other Components]

The rubber composition (20) of the present invention may be incorporated, as required, with at least one compound selected from the group consisting of trialkyl orthoformates, hydrolyzable organosiloxane compounds, hydrolyzable ester compounds and alkyl alcohols within limits not adversely affecting the object of the present invention.

The trialkyl orthoformates useful in the present invention include trimethyl orthoformate and triethyl orthoformate.

Hydrolyzable organosiloxane compounds useful in the present invention include tetramethyl orthosilicate and tetraethyl orthosilicate.

Hydrolyzable ester compounds useful in the present invention include methyltriethoxysilane, methyltriacetoxysilane, and vinyltrimethoxysilane.

Alkyl alcohols useful in the present invention include methanol, butanol, pentanol, and cellosolve.

The rubber composition of the present invention may further contain one or more additives, such as various fillers, pigments and plasticizers, within limits not adversely affecting the object of the present invention.

Fillers and pigments useful in the present invention include various silicas, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, and glass fibers.

The plasticizer used in the present invention includes process oils, paraffin oils, naphthene oils, polybutadienes and ethylene/α -olefin oligomers when hydrolyzable silyl groups are introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A)₀) In the case of (3), a plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

Rubber composition (20) and use thereof

As described above, the rubber composition (20) of the present invention contains a curable composition, a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1). more specifically, the composition contains an organic polymer (Z) and a specific curing catalyst (H) comprising a mercaptide-type organotin compound having Sn-S bonds (H3), a sulfide-type organotin compound having Sn-S bonds (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds and a carboxylic acid-type organotin compound (H7). The composition is suitable for use in electric/electronic parts, transportation machines, civil engineering/construction, medical and leisure areas, as described above.

The rubber composition (20) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

Curable composition (21)

The curable composition (21) of the present invention contains a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) and a specific curing catalyst (H8).

[ curing catalyst (H8)]

The copolymer rubber (A1) was crosslinked/cured by condensation when its hydrolyzable silicon group was hydrolyzed in the presence of moisture. The curing catalyst (H8) used in the present invention functions to greatly accelerate the curing of the copolymer rubber (A1).

As the curing catalyst (H8), a catalyst represented by the general formula Q₂Sn(OZ)₂Or [ Q₂Sn(OZ)]₂A compound represented by O, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn therein. Specific examples of such compounds include, but are not limited to:(C₄H₉)₂Sn(OCH₃)₂，(C₄H₉)₂Sn(OC₄H₉)₂，(C₄H₉)₂Sn(OC₈H₁₇)₂，(C₄H₉)₂Sn(OC₁₂H₂₅)₂，

[，(C₈H₁₇)₂Sn(OC₄H₉)₂，(C₄H₉)₂Sn(OCH₂CH₂CH₂NH₂)₂，(C₄H₉)₂Sn(OCH₂CH₂NH₂)₂，(C₄H₉)₂Sn[OCH₂CH₂CH₂N(CH₃)₂]₂，(C₄H₉)₂Sn(OCH₂CH₂CH₂SH)₂，

these curing catalysts (H8) may be used singly or in combination, the curing catalyst (H8) is usually added in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1). when the amount added is less than 0.01 part by weight, the composition (21) cannot be cured at a practical speed, and when the amount added exceeds 10 parts by weight, there are problems associated with cost.

The curing catalyst (H8) used in the present invention can significantly improve the activityof rapid curing as compared with conventionally used organotin-based compounds, does not cause the problem of coloring of the composition unlike alkyl titanate-based compounds used as catalysts, and has excellent productivity and appearance.

The curable composition (21) of the present invention, which contains component (A1) and component (H8), cures very rapidly, starts curing from the surface in several minutes to 1 hour when exposed to air at room temperature, and becomes tack-free. After standing for two or three days, the elastomer is cured to penetrate into the interior of the elastomer and is converted into a solid rubber-like elastomer. The cured product has excellent heat resistance and acid resistance.

[ other Components]

The copolymer rubber (A1) of the present invention can be modified when blended with various fillers.

Specific examples of the filler used in the present invention include: reinforcing fillers such as fumed silica, settling silica, silicic anhydride, silicon hydride, and carbon black; other fillers such as calcium carbonate, magnesium carbonate, diatomaceous earth, refractory clay, talc, titanium oxide, bentonite, organic bentonite, iron oxide, zinc oxide, activated zinc white, hydrogenated castor oil, and silas spheres; fibrous fillers, such as asbestos and glass fibers or filaments.

When a high strength curable composition is to be prepared, a filler selected from the group consisting essentially of: fumed silica, precipitated silica, silicic anhydride, silicon hydride, carbon black, surface-treated finely divided calcium carbonate, fireclay, clay, and active zinc white. The filler can bring about an advantageous effect when it is added in an amount of 1 to 100 parts by weight per 100 parts by weight of the copolymer rubber as the component (A1). On the other hand, when a cured product having low strength andhigh elongation is to be produced, a filler mainly selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, iron oxide, zinc oxide, and silas spheres is used. The filler is added in an amount of 5 to 200 parts by weight per 100 parts by weight of the copolymer rubber as the component (A1) to bring about advantageous effects. Needless to say, these fillers may be used alone or in combination.

When a plasticizer is used in combination with the filler, the curable composition (21) of the present invention has one or more additional advantages such as further improved elongation of the cured product, and a larger amount of the filler can be mixed.

Specific examples of such plasticizers include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butyl phthalyl butyl glycolate, nonaromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate, phosphoric acid esters such as tricresyl phosphate and tributyl phosphate, chlorinated paraffins, and hydrocarbon-based compounds such as polybutene, hydrogenated polybutene, ethylene/α -olefin oligomer, α -methyl styrene oligomer, biphenyl, terphenyl, triaryl dimethyl alkane, alkylene terphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atactic polypropylene and partially hydrogenated terphenyl.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the curable composition (21) of the present invention, limited influence on curing speed of the curable composition, high resistance to weather of the cured product, and cheapness.

When the reactive silicon group is introduced into the saturated hydrocarbon-based polymer, the plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

The plasticizer brings about an advantageous effect when added in an amount of 100 parts by weight or less per 100 parts by weight of the component (A1).

The method for preparing the curable composition (21) of the present invention is not limited. It can be prepared by a conventional method such as kneading these components at ordinary or high temperature with a mixer, a roller or a kneader, or mixing after dissolving the components in a small amount of a suitable solvent. Each component can be sufficiently mixed with the other components to produce mainly a two-liquid type composition.

The curable composition (21) of the present invention can be cured into a solid having a rubber-like elasticity containing a three-dimensional network structure by the action of moisture when exposed to air.

The curable composition (21) of the present invention may be suitably mixed with one or more additives as required at the time of use. The additives used in the present invention include another curing catalyst (e.g., dodecylamine or lead octylate), an adhesion promoter, a property adjuster, a storage stability improver, an ultraviolet absorber, a metal deactivator, an ozone-induced aging inhibitor, a light stabilizer, an amine-based radical chaining inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment and a foaming agent.

Specific examples of other curing catalysts useful in the present invention include titanates such as tetrabutyl titanate and tetrapropyl titanate, organoaluminum compounds such as aluminum triacetylacetate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate, chelates such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octanoate, amino compounds, and salts of these compounds with carboxylic acids such as butylamine, octylamine, dodecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1, 8-diazabicyclo (5, 4, 0) undec-7 (DBU), low molecular weight polyamide resins produced by the reaction between an excess of polyamine and a polybasic acid, products of the reaction between an excess of polyamine and an epoxy compound, amino-containing silane coupling agents such as gamma-aminopropyltrimethoxysilane and N- (β) ethyl-aminopropylsilane, and other basic amino silane condensation catalysts or other basic amino silane condensation catalysts.

The adhesion promoter used in the present invention includes conventional adhesives, silane coupling agents such as aminosilane compounds and epoxysilane compounds; and other compounds.

Specific examples of such adhesion promoters include phenolic resins, epoxy resins, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) aminopropylmethyldimethoxysilane, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates.

The storage stability improvers useful for the present invention include compounds having a silicon atom to which a hydrolyzable group is bonded, and esters of ortho-organic acids.

Specific examples of the storage stability improvers include: methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate.

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4,4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, laurylstearyl thiodipropionate and diethyl 2, 2-thio [ di-3 (3, 5-di-t-butyl-4-hydroxy]dipropionate, diethyl thiodipropionate, zinc di-butyl-3-thiodipropionate, zinc dithiobutyl-dithiobenzoate, zinc dithiobenzoate, e, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, e.g., dithiobutylthiodipropionate, dithiobutyl-bis (3-4-bis-4-butylthiodipropionate, dithiobutyl-dithiobenzoate, dithiobutyl-dithiobenzoate, dithiobenzoate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of themain chain under heating much more effectively than other types of agents than the composition of the present invention, and controls problems such as residual surface tackiness.

Free radical inhibitors useful in the present invention include phenolic free radical inhibitors such as 2, 2-methylenebis (4-methyl-6-tert-butylphenol) and tetrakis [ methylene 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]methane, and amino free radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

Curable composition (21) and use thereof

As described above, the curable composition (21) of the present invention contains a curable composition, as the component (A1), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, more specifically, the composition contains an organic polymer (Z) and a curing catalyst (H8). The composition is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, as described above.

The curable composition (21) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

In other words, the present invention provides sealants, potting agents, coating materials or adhesives composed of a curable composition comprising the organic polymer (Z) and the curing catalyst (H8).

Curable rubber composition (22)

The curable rubber composition (22) of the present invention contains a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), a titanate (Y) and, if necessary, a silanol condensing catalyst.

[ titanate (Y)]

The titanate (Y) of the present invention is a specific component of the present invention for improving the adhesive strength of the hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) to various substrates such as glass, metal and mortar, and further, it functions as a silanol condensation catalyst for promoting the silanol condensation of hydrolyzable silyl groups with each other in the hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The titanate (Y) used in the present invention includes organic titanates, titanium chelates, titanium silicates, titanium-based coupling agents, and partially hydrolyzed condensates thereof.

Specific examples of the titanate (Y) used in the present invention include tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetraoctadecyl titanate, tetramethyl titanate, diethoxydi (acetylacetonate) titanium, diisopropylbis (ethylacetoacetate) titanium, isopropyl (2-ethyl-1, 3-hexanediol) titanium, bis (2-ethylhexyloxy) bis (2-ethyl-1, 3-hexanediol) titanium, di-n-butoxybis (triethanolamine) titanium (di-n-butoxybis (triethanolamine) titanium), titanium tetraacetylacetonate, titanium hydroxybis (lactate) titanium, and hydrolysis condensates thereof.

Specific examples of the titanium-based coupling agent used in the present invention include compounds represented by the following general formula and water thereofAnd (3) a decomplexation product:

of the above titanates (Y), more preferred is a titanate having the general formula Ti (OR)₄The compound represented by (A) is particularly high in the effect of improving adhesion, wherein R's are each a hydrocarbon group of 1 to 20 carbon atoms, and may be substituted or unsubstituted.

These titanates (Y) may be used alone or in combination.

The titanate (Y) is added in an amount of 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of the component (A1). When the amount is less than 0.1 part by weight, the adhesion cannot be sufficiently improved, and when the amount exceeds 20 parts by weight, the storage stability of the sealant composition may be deteriorated.

[ silanol condensing catalyst]

A silanol condensing catalyst may be used for the curable rubber composition (22) of the present invention. Silanol condensation catalysts useful in the present invention include divalent or tetravalent tin-based, aluminum-based, and amine-based curing catalysts. Of these catalysts, the tetravalent tin-based compound is more preferable because of its high catalytic activity. The tetravalent tin-based catalyst and specific examples thereof are similar to the tetravalent tin compound (C) used hereinbefore as one of the components of the curable rubber composition (2).

Silanol condensation catalysts other than tetravalent tin-based curing catalysts may also be used in the present invention.

Specific examples of these catalysts for use in the present invention include stannous-based curing catalysts such as tin octoate, aluminum-based curing catalysts such as aluminum triacetoacetate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate, zirconium tetraacetylacetonate, lead octoate, amino-based curing catalysts such as butylamine, octylamine, dodecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU), and salts of these compounds with carboxylic acids, low molecular weight polyamide resins produced by the reaction between an excess of polyamine and a polybasic acid, products of the reaction between an excess of polyamine and an epoxy compound, amino-containing silane coupling agents such as gamma-aminopropyltrimethoxysilane and N- (β -dimethoxypropyl) amino-propyl-based curing catalysts, and other basic condensation catalysts or acidic silanes.

These catalysts may be used alone or in combination. The silanol condensing catalyst is added preferably in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the component (A1). A catalyst content lower than the above range is disadvantageous because it results in insufficient curing speed and insufficient extent of curing reaction. The catalyst content above the above range is also disadvantageous in that local overheating or foaming occurs during curing, making it difficult to obtain a cured product having good properties, and the pot life is deteriorated to an unacceptable level, which is also disadvantageous in workability of the composition.

[ other Components]

The silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) itself has a high viscosity and sometimes causes problems concerning workability, and therefore, it is preferable to add various plasticizers to the copolymer rubber to the extent that the adhesiveness of the curable rubber composition (22) of the present invention is not impaired, for lowering the viscosity of the copolymer rubber and thereby improving the workability.

The plasticizer to be used in the present invention is not limited, and a conventional plasticizer can be used, and preferably, these plasticizers should be compatible with each component of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) of the present invention.

Specific examples of these plasticizers include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butyl phthalyl butyl glycolate, nonaromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, esters of polyalkylene glycols such as diethylene glycol benzoate and triethylene glycol dibenzoate, phosphoric acid esters such as tricresyl phosphate and tributyl phosphate, chlorinated paraffins, and hydrocarbon-based compounds such as alkylbiphenyls, polybutenes, hydrogenated α -olefin oligomers, ethylene/α -olefin oligomers, α -methylstyrene oligomers, biphenyls, terphenyls, triaryldimethanes, alkylenebiphenyls, liquid polybutadienes, hydrogenated liquid polybutadienes, paraffin oils, naphthenic oils, atactic polypropylenes and partially hydrogenated terphenyls.

Of these, hydrocarbon-based compounds free of unsaturated groups, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, hydrogenated α -olefin oligomer, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with the respective components of the rubber composition (22) of thepresent invention, limited influence on the curing speed of the rubber composition, high resistance to weather of the cured product, and inexpensiveness.

When the reactive silyl group is introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene random copolymer rubber, the solvent may be replaced with a plasticizer to adjust the reaction temperature and the viscosity of the reaction system, the amount of the plasticizer added is preferably from 10 to 150 parts by weight, more preferably from 30 to 100 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), the amount of the plasticizer added is not sufficient to lower the viscosity if it is less than 10 parts by weight, and the amount of the plasticizer added is more than 150 parts by weight to deteriorate the mechanical and adhesive properties of the composition, and the curable rubber composition (22) of the present invention may further contain various antioxidants.

The anti-aging agent used in the present invention comprises: phenol-based antioxidants, aromatic amine-based antioxidants, sulfur-based hydroperoxide decomposers, phosphorus-based hydroperoxide decomposers, benzotriazole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, hindered amine-based light stabilizers, and nickel-based light stabilizers.

Specific examples of the phenol-based antioxidant include: 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 5-di-tert-butylhydroquinone, n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 4 ' -butylidenebis (3-methyl-6-tert-butylphenol) and 4,4 ' -thiobis (3-methyl-6-tert-butylphenol).

Specific examples of the aromatic amine-based antioxidant include: n, N' -diphenyl-p-phenylenediamine and 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline.

Specific examples of the thiohydroperoxide decomposer include didodecyl 3, 3 ' -thiodipropionate, ditridecyl 3, 3 ' -thiodipropionate and dioctadecyl 3, 3 ' -thiodipropionate.

Specific examples of the phosphorus-based hydroperoxide decomposer include: diphenylisooctyl phosphite and triphenyl phosphite.

Specific examples of the benzotriazole-based ultraviolet absorber include: 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole and 2- (5-methyl-2-hydroxyphenyl) benzotriazole.

Specific examples of salicylate-based ultraviolet absorbers include: 4-tert-butylphenyl salicylate and 2, 4-di-tert-butylphenyl 3, 5 '-di-tert-butyl-4' -hydroxybenzoate.

Specific examples of the benzophenone-based ultraviolet absorber include: 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-benzyloxy benzophenone.

Specific examples of hindered amine-based light stabilizers include: bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, 1- {2- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]ethyl } -4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]-2, 2, 6, 6-tetramethylpiperidine and 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine.

Specific examples of the nickel-based light stabilizer include: nickel dibutyldithiocarbamate, [2, 2 '-thiobis (4-tert-octylphenolate)]-nickel (II) 2-ethylhexylamine and [2, 2' -thiobis (4-tert-octylphenolate)]-nickel (II) n-butylamine.

Particularly, the combination of the phenol-based antioxidant, the salicylate-based ultraviolet absorber and the hindered amine-based light stabilizer greatly improves the weather resistance of the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber as the component (A1), and therefore, is desirable.

The age resister is preferably added in an amount of 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the component (A1). If the amount is less than 0.1 part by weight, the weather resistance of the curable rubber composition cannot be sufficiently improved, whereas if it exceeds 10 parts by weight, the economy and adhesion are deteriorated.

The curable rubber composition (22) of the present invention may be incorporated with an adhesion promoter other than the titanate (Y) as required.

The adhesion promoters useful in the present invention include epoxy resins, phenolic resins, various silane coupling agents and aromatic polyisocyanates.

Specific examples of the silane coupling agent used in the present invention include:

amino-containing silanes, such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldiethoxysilane, gamma-ureidopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-benzyl-gamma-aminopropyltrimethoxysilane and N-vinylbenzyl-gamma-aminopropyltriethoxysilane;

mercapto group-containing silanes such as gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane;

epoxy-containing silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane;

carboxysilanes, such as β -carboxyethyltriethoxysilane, β -carboxyethylphenylbis (2-methoxyethoxy) silane and N- β - (carboxymethyl) aminoethyl- γ -aminopropyltrimethoxysilane;

vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane and gamma-acryloxypropylmethyltriethoxysilane;

halogen-containing silanes, such as gamma-chloropropyltrimethoxysilane; and

silane isocyanurates, such as tris (trimethoxysilyl) isocyanurate;

and isocyanate-containing silanes such as gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-isocyanatopropylmethyldiethoxysilane and gamma-isocyanatopropylmethyldimethoxysilane.

Further, derivatives obtained by modifying some of the above-mentioned compounds may also be used as a silane coupling agent. They include: amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanate silanes, phenylamino-long chain-alkyl silanes, aminosilylated siloxanes and silylated polyesters.

The silane coupling agent is added in an amount of preferably 0.1 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the component (A1).

If the amount is less than 0.1 partby weight, the adhesion cannot be sufficiently improved, and if it exceeds 20 parts by weight, the storage stability of the sealant composition may be deteriorated. These silane coupling agents may be used alone or in combination.

The curable rubber composition (22) of the present invention may be incorporated with various fillers as required.

Specific examples of the filler include: wood powder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, white clay, fumed silica, settling silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder. Among them, preferred are precipitated silica, fumed silica, carbon black and calcium carbonate, titanium oxide and talc. These fillers may be used alone or in combination.

The filler is incorporated preferably in an amount of 5 to 500 parts by weight, more preferably 20 to 350 parts by weight, most preferably 40 to 200 parts by weight, per 100 parts by weight of component (A1).

In addition to the above-mentioned components (A) and (Y), silanol condensing catalyst, plasticizer, aging inhibitor, adhesion promoter and filler, the curable rubber composition (22) of the present invention may be incorporated with one or more additives as required. The additives used in the present invention include property modifiers for modifying the properties of the cured product in relation to stretching, weather-resistant adhesion improvers, radical inhibitors, metal deactivators, ozone-induced aging inhibitors, sagging inhibitors, phosphorus-based peroxide decomposers, solvents, lubricants, pigments and foaming agents.

Specific examples of these additives are described in Japanese patent publication Nos. 69659/1992 and 108928/1995,Japanese patent publication No. 2,512,468 and Japanese patent laid-open publication No. 22904/1989.

The effect of the titanate (Y) of the present invention can be observed even when an additive is incorporated. More specifically, the curable rubber composition (22) of the present invention, when used as a sealant for construction work, laminated glass, or rust-proof or water-proof edges (cut portions) of wired glass or laminated glass, can further improve the adhesion of the sealant to various objects when it is mixed with titanate (Y).

Curable rubber composition (22) and use thereof

As described above, the curable rubber composition (22) of the present invention contains a curable composition, as component (A1), a hydrolyzable silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber, more specifically, the curable rubber composition contains an organic polymer (Z) and a titanate (Y), and the composition is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, as described above.

The curable rubber composition may further incorporate the silanol condensing catalyst described above.

The curable composition (22) of the present invention can be used as sealants, potting agents, coating materials or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

In other words, the present invention provides a sealant, a potting agent, a coating material or an adhesive composed of a curable composition comprising the organic polymer (Z) and the titanate (Y).

The above-mentioned sealing material, potting agent, coating material or adhesive may further be mixed with the above-mentioned silanol condensing catalyst.

Curable composition (23)

The curable composition (23) of the present invention, which contains the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), is suitable for use in electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, as described previously.

The curable composition (23) of the present invention may be further incorporated, as required, with one or more additives such as a curing catalyst, a plasticizer and a filler. The curing catalyst used in the present invention is not limited, but a general silanol condensing catalyst may be used.

Specific examples of the curing catalyst used in the present invention include organotin, organotitanate, organoaluminum, organozirconium, amine compound and acid phosphate, a product between acid phosphate and amine compound, a saturated or unsaturated polyvalent carboxylic acid and its anhydride, a reaction product between carboxylate and amine compound, and lead octylate.

Specific examples of the organotin compounds include: tin carboxylates such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin phthalate, tin octylate and tin naphthenate; chelates, such as dibutyltin diacetylacetonate; dibutyl tin methoxide; and the reaction product between dibutyltin oxide and a phthalic acid ester.

Specific examples of the organic titanate compound include: titanates such as tetrabutyl titanate, tetraisopropyl titanate, tetrapropyl titanate and triethanolamine titanate; chelates, such as titanium tetraacetylacetonate.

Specific examples of the organoaluminum compound include aluminum triacetylacetonate, aluminum triethylacetoacetate and aluminum diisopropoxide ethylacetoacetate.

Specific examples of the organozirconium compound include: organozirconium compounds, such as tetraisopropoxyzirconium and tetrabutoxyzirconium, chelates, such as zirconium tetraacetylacetonate.

Specific examples of the amine compound include: butylamine, monoethanolamine, triethylenetriamine, guanidine, 2-ethyl-4-methylimidazole and 1, 8-diazabicyclo (5, 4, 0) undecene-7 (DBU).

Acid phosphate refers to a phosphate containing a-O-P (═ O) (OH) -moiety. Examples are acid phosphates, for example of the formula (RO)_d-P(＝O)-(OH)_3-dAn organic acid phosphate represented by wherein "d" is 1 or 2; r is an organic residue.

Organic acid phosphates include the following compounds:

(CH₃O)₂P(＝O)OH，

(CH₃O)P(＝O)(OH)₂，

(C₂H₅O)₂P(＝O)OH，

(C₂H₅O)P(＝O)(OH)₂，

[(CH₃)₂CHO]₂P(＝O)OH，

(CH₃)₂CHOP(＝O)(OH)₂，

(C₄H₉O)₂P(＝O)OH，

(C₄H₉O)P(＝O)(OH)₂，

(C₈H₁₇O)₂P(＝O)OH，

(C₈H₁₇O)P(＝O)(OH)₂，

(C₁₀H₂₁O)₂P(＝O)OH，

(C₁₀H₂₁O)P(＝O)(OH)₂，

(C₁₃H₂₇O)₂P(＝O)OH，

(C₁₃H₂₇O)P(＝O)(OH)₂，

(HOC₈H₁₆O)₂P(＝O)OH，

(HOC₈H₁₆O)P(＝O)(OH)₂，

(HOC₆H₁₂O)₂P(＝O)OH，

(HOC₆H₁₂O)P(＝O)(OH)₂，

[(CH₂OH)(CHOH)O]₂P(＝O)OH，

[(CH₂OH)(CHOH)O]-P(＝O)(OH)₂，

[(CH₂OH)(CHOH)C₂H₄O]₂p (═ O) OH and

[(CH₂OH)(CHOH)C₂H₄O]P(＝O)(OH)₂。

the curing catalyst is added in an amount of about 0 to 20 parts by weight per 100 parts by weight of the hydrolyzable silyl group containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The plasticizer used in the present invention is not limited, and a conventional plasticizer can be used. Preferably, these plasticizers should be compatible with the components of the curable composition (23) of the present invention. Specific examples of these plasticizers include:

phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate and butyl phthalyl butyl glycolate, nonaromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate, phosphoric acid esters such as tricresyl phosphate and tributyl phosphate, chlorinated paraffins, and hydrocarbon-based compounds such as alkylbiphenyls, polybutylenes,hydrogenated polybutylenes, ethylene/α -olefin oligomers, α -methylstyrene oligomers, biphenyls, terphenyls, triaryldimethanes, alkylene terphenyls, liquid polybutadienes, hydrogenated liquid polybutadienes, paraffin oils, naphthene oils, atactic polypropylenes and partially hydrogenated terphenyls.

Of these, hydrocarbon-based compounds free of unsaturated group, such as hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, are more preferable for various reasons, such as good compatibility with each component of the composition (23) of the present invention, limited influence on curing speed of the curable composition, high resistance to weather of the cured product, and cheapness.

When the reactive silicon group is introduced into the saturated hydrocarbon-based polymer, the plasticizer may be used instead of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

The plasticizer brings about an advantageous effect when added in an amount of 100 parts by weight or less per 100 parts by weight of the component (A1).

Specific examples of the filler include inorganic fillers such as calcium carbonate, talc, diatomaceous earth, mica, kaolin, magnesium carbonate, vermiculite, titanium oxide, graphite, alumina, silica, glass spheres, silas spheres, silica spheres, calcium oxide, magnesium oxide and silica, organic fillers such as hollow particles of powdery rubbers, recycled rubbers, fine powders of thermosetting or thermosetting resins, polyethylene and the like, and the filler is added in an amount of about 3 to 300 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors useful in the present invention include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc 2-mercaptobenzothiazole, sulfides such as 4,4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, nickel 2, 2 ' -thiobis (4-octylphenol), dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, laurylstearyl thiodipropionate and 2, 2-thio [ di-3- (3, 5-di-t-butyl-4-hydroxy]thiodipropionate, diethyl thiodipropionate, zinc di-butyl-3-4-thiodicarbamate, zinc dithiobutyl-3-dithiobenzoate, zinc dithiobenzoate, e, e.g., zinc dithiobutyl-thiodicarbamate, zinc dithiobenzoate, zinc dithiobutyl-3-dithiobenzoate, dithiobutyl-dithio, dithiobutyl-4-dithio, dithiobutyl-thiodicarbamate, dithiocarbamic acid, dithiocarbamic.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of agents for the composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is added in an amount of about 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1).

Other additives useful in the present invention include sagging inhibitors, such as hydrogenated castor oil; organobentonite and calcium stearate; a colorant, a tackifier and a solvent.

The thus-obtained curable composition (23) containing component (A1) is useful as a coating material (particularly, a coating material for underbody) and a sealing material for automobile bodies for rust prevention and vibration prevention, and can satisfy the requirements of the automobile industry in recent years.

Curable composition (23) and use thereof

The curable composition (23) of the present invention contains, as the component (A1), an ethylene/α -olefin/nonconjugated polyene random copolymer rubber containing a hydrolyzable silyl group.

For example, the curable composition (23) of the present invention is suitable as sealants, potting agents, coating materials for uses other than vehicles, or adhesives for electric/electronic device members, transportation machines, and civil engineering/construction, and leisure areas.

The curable composition (23) of the present invention is contained in a coating material (23) ' for vehicles, a sealing material (24) ', a potting material (24) ', a coating material (24) ' for uses other than vehicles, and an adhesive (24 ') all of which are the composition of the present invention.

Sealant (25) 'for laminated glass'

The sealant (25)' for laminated glass of the present invention comprises a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), a curing catalyst (H), and water or a hydrate of a metal salt (B11).

The sealant (25)' for laminated glass of the present invention comprises preferably 5 to 50% by weight, particularly preferably 5 to 40% by weight, of a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

The curing catalyst (H) of the present invention may be a known silanol condensing catalyst. Specific examples of the curing catalyst used in the present invention are as described above.

The curing catalyst (H) is preferably added in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2). A catalyst content below the above range results in insufficient curing speed and insufficient extent of curing reaction.

The water or metal salt hydrate (B11) of the present invention serves as a water source necessary for condensation/curing of the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) to promote the formation of a crosslinked structure.

When the water source is other than water, a wide variety of commercially available metal hydrates can be used. These hydrates include hydrates of alkaline earth metals and other metals. Among them, the hydrates of alkali metals and alkaline earth metals are more preferable. More specifically, MgSO₄·7H₂O、Na₂CO₃·10H₂O、Na₂SO₄·10H₂O、Na₂S₂O₃·5H₂O、Na₃PO₄·12H₂O and Na₂B₄O₇·10H₂O。

Water is added as the component (B11) in an amount of preferably 0.01 to 25 parts by weight, more preferably 0.05 to 15 parts by weight, still more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

The metal salt hydrate as the component (B11) is incorporated preferably in an amount of 0.01 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, still more preferably 1 to 10 parts by weight, per 100 parts by weight of the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

Water and hydrates of metallic salts may be used alone or in combination.

The sealant (25)' for laminated glass of the present invention may be incorporated with various additives.

Representative additives are adhesion promoters, represented by silane coupling agents. Needless to say, an adhesion promoter other than the silane coupling agent may be used. The silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as hydrolyzable silicon group) and one or more other functional groups. The hydrolyzable group is more preferably methoxy group, ethoxy group or the like in view of hydrolysis speed. The compound preferably has2 or more hydrolyzable groups, more preferably 3 or more hydrolyzable groups.

Functional groups useful in the present invention include, in addition to hydrolyzable silicon groups: primary, secondary and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurate groups and halogens. Of these, primary, secondary or tertiary amino groups, epoxy groups, isocyanate groups and isocyanurate groups are more preferable, and isocyanate groups and epoxy groups are most preferable.

Specific examples of the silane coupling agent used in the present invention include:

amino group-containing silanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, gamma-ureidopropyltrimethoxysilane, N- β - (N-vinylbenzylaminoethyl) -gamma-aminopropyltriethoxysilane and gamma-anilinopropyltrimethoxysilane;

mercapto group-containing silanes such as gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldimethoxysilane and gamma-mercaptopropylmethyldiethoxysilane;

epoxy-containing silanes, such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane;

carboxysilanes, such as β -carboxyethyltriethoxysilane, β -carboxyethylphenylbis (2-methoxyethoxy) silane and N- β - (N-carboxymethylaminoethyl) - γ -aminopropyltrimethoxysilane;

vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane and gamma-acryloxypropylmethyltriethoxysilane;

halogen-containing silanes, such as gamma-chloropropyltrimethoxysilane;

silane isocyanurates, such as tris (trimethoxysilyl) isocyanurate; and

isocyanate-containing silanes such as gamma-isocyanatopropyltrimethoxysilane and gamma-isocyanatopropyltriethoxysilane.

Further, derivatives obtained by modifying some of the above-mentioned compounds may also be used as a silane coupling agent. These compounds include: amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanate silanes, phenylamino-long chain-alkyl silanes, aminosilylated siloxanes and silylated polyesters. These silane coupling agents can be easily hydrolyzed in the presence of moisture, but remain stable when incorporated into the component (A2) for the sealant (25)' for laminated glass of the present invention.

Specific examples of the tackifiers other than the silane coupling agent used in the present invention include conventional adhesives and other compounds, and specific examples of these tackifiers include phenolic resins, epoxy resins, coumarone/indene resins, rosin ester resins, terpene/phenol resins, α -methylstyrene/vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates and aromatic polyisocyanates.

The tackifier is added in an amount of 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

The sealant (25)' for laminated glass of the present invention may be further mixed with various types of fillers to further improve its properties. The filler used in the present invention comprises: reinforcing fillers such as fumed silica, settling silica, silicic anhydride, silicon hydride, talc and carbon black; other fillers such as limestone powder, colloidal calcium carbonate, diatomaceous earth, refractory earth, clay, titanium oxide, bentonite, organic bentonite, iron oxide, zinc oxide and active zinc white; fibrous fillers, such as glass fibers or filaments.

When a reinforcing filler, mainly fumed silica, settling silica, silicic anhydride, silicon hydride, talc or carbon black, is used when a curable sealing material having high strength is to be produced, a cured product having excellent mechanical properties in terms of strength and modulus can be obtained when added in an amount of 1 to 100 parts by weight per 100 parts by weight of the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

On the other hand, when a cured product having a low modulus and a high elongation is to be produced, it is recommended to add other types of fillers such as limestone powder, gelled calcium carbonate, diatomaceous earth, refractory earth, clay, titanium oxide, bentonite, organobentonite, iron oxide, zinc oxide or active zinc white in an amount of 5 to 400 parts by weight per 100 parts by weight of the silyl group-containing ethylene/α -olefin/unconjugated polyene random copolymer rubber (A2).

Needless to say, these fillers may be used alone or in combination.

The filler may be added to the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), or to the curing catalyst as the component (H), or to both.

When a plasticizer and a filler are mixed, the sealant (25)' for laminated glass of the present invention may have one or more additional advantages such as further improvement of elongation of the cured product and mixing of a larger amount of the filler.

It is preferable that these plasticizers should be compatible with the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2).

Specific examples of the plasticizer include process oil, polybutene, hydrogenated polybutene, α -methylstyrene oligomer, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil and atactic polypropylene, and among them, hydrocarbon-based compounds free of unsaturated groups, such as process oil, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil and naphthene oil, are more preferable.

When a reactive silicon group is introduced into the above-mentioned ethylene/α -olefin/nonconjugated polyene copolymer rubber, a plasticizer may be used in place of the solvent to adjust the reaction temperature and the viscosity of the reaction system.

When the plasticizer is used, it is incorporated preferably at about 10 to 500 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), more preferably at about 20 to 300 parts by weight.

The sealant (25)' of the present invention for laminated glass may be appropriately blended with various additives such as an age resistor, a light stabilizer, a flame retardant, a thixotropic enhancer, a pigment and a surfactant as required.

The aging inhibitors useful for the present invention include commonly known ones such as sulfur-based ones, radical inhibitors and ultraviolet absorbers.

The sulfur-based aging inhibitors useful for the present invention include mercaptans, thiolates, sulfides (including sulfide carboxylate esters and hindered phenol-based sulfides), polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, and sulfoxides.

Specific examples of the sulfur-based aging inhibitors include mercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such as zinc salt of 2-mercaptobenzothiazole, sulfides such as 4,4 ' -thiobis (3-methyl-6-t-butylphenol), 4 ' -thiobis (2-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (2, 6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2 ' -thiobis (4-octylphenol) nickel, dilauryl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, β ' -dioctadecyl thiodibutyrate, lauryloctadecyl thiodipropionate and 2, 2-thio [ di-3- (3, 5-di-t-butyl-4-hydroxyphenol) diethyl thiodipropionate], diethyl dithiobenzoate, zinc dithiobutyldithiocarbamate, such as zinc dithiobutyl-dithiobenzoate, zinc dithiobenzoate and zinc dithiobutyldithiocarbamate.

The above-mentioned sulfur-based aging inhibitor prevents decomposition and/or aging of the main chain under heating much more effectively than other types of agents for the rubber composition of the present invention, and controls problems such as residual surface tackiness.

The radical inhibitors useful in the present invention include phenolic radical inhibitors such as 2, 2-methylene-bis (4-methyl-6-tert-butylphenol) and tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl idene propionate]methane, and amino radical inhibitors such as phenyl- β -naphthylamine, α -naphthylamine and N, N '-sec-butyl-p-phenylenediamine, phenothiazine and N, N' -diphenyl-p-phenylenediamine.

The ultraviolet absorbers used in the present invention include 2- (2 ' -hydroxy-3 ', 5 ' -di-t-butylphenyl) benzotriazole and bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

When the age resistor is used, it is incorporated preferably at about 0.1 to 20 parts by weight per 100 parts by weight of the silyl group functionalized ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), more preferably at about 1 to 10 parts by weight.

Sealant (26) 'for laminated glass'

The sealant (26)' for laminated glass of the present invention comprises a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), a hot-melt resin (X), a curing catalyst (H), and water or a hydrate of a metallic salt (B11).

The silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) is a hydrocarbon-based polymer having good moisture barrier properties and water-repellent properties, and is highly adhesive to various inorganic substrates such as glass and aluminum to give a cured product which is well moisture-barrier.

The sealant (26)' of the present invention for laminated glass contains 5 to 50% by weight, preferably 10 to 50% by weight, of an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) to ensure sufficient tackiness (initial adhesiveness) when a spacer (spacer) is temporarily bonded to glass in a laminated glass production line.

The hot melt resin (X) used in the present invention is not limited, and a general hot melt resin may be used, including, for example, EVA hot melt resin, polyamide hot melt resin, polyester hot melt resin, polyurethane hot melt resin, acrylic hot melt resin, butyl rubber hot melt resin, and polyolefin-based hot melt resin.

From the viewpoint of workability, the softening temperature of the hot-melt resin is preferably about 100 ℃ to 250 ℃, although not limited thereto.

Morepreferably, it comprises a butyl rubber-based hot-melt resin (hot-melt butyl). The hot melt butyl used in the present invention is not limited, and conventional hot melt butyl groups may be used, which may contain no additives, or one or more additives (e.g., fillers). The hot melt resins useful in the present invention include butyl rubber having an unsaturation of about 0.5 to 5.0(IIR), Vistanex Series (Exxon Mobil), Terostat Series (Teroson), and Hamatite Series (Yokohama rubber).

The hot melt resin (X) of the present invention, such as a hot melt butyl, can be used as it is without vulcanization.

The sealant (26)' for laminated glass of the present invention contains the hot-melt resin (X) preferably in an amount of 20 to 95% by weight, more preferably 50 to 90% by weight, for ensuring sufficient tackiness (initial adhesiveness) in temporarily adhering the spacer (spacer) to the glass in the laminated glass production line.

The curing catalyst (H) is added preferably in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the component (A2), in order to prevent local overheating or foaming from occurring and to ensure a sufficient pot life at a sufficient curing speed.

Water is added as component (B11) in an amount of preferably 0.01 to 25 parts by weight, more preferably 0.05 to 15 parts by weight, still more preferably 0.2 to 5 parts by weight, per 100 parts by weight of component (A2).

The metal salt hydrate is added as component (B11) in an amount of preferably 0.01 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, still more preferably 1 to 10 parts by weight, per 100 parts by weight of component (A2).

Water and the hydrate of the metal salt as the component (B11) may be used alone or in combination.

Effects of the invention

(1) The curable elastomer composition (1) of the present invention contains a curable composition, the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber specified above as the component (A1). more specifically, the composition comprises an organic polymer (Z) containing a specific hydrolyzable silyl group and having substantially no unsaturated double bond in the main chain, and a compound (B1) having a silanol group and/or a compound which can react with moisture to form a compound having a silanol group in the molecule (B1). As a result, the composition can improve elongation and residual tackiness on the surface of the cured product, cures rapidly, and can give a cured product of high weather resistance.

Therefore, the curable elastomer composition (1) of the present invention is suitable for use as adhesives, tackifiers, coatings, sealants, waterproofing materials, spray materials, shaping materials and casting rubber materials.

(2) The curable rubber composition (2) of the present invention comprises an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a specific silyl group, more specifically, an organic polymer (Z) containing a specific hydrolyzable silyl group and having substantially no unsaturated double bond in the main chain, a tetravalent tin compound (C), a specific silicon compound (B2). The composition is highly weather-resistant, rapidly cures, and is capable of greatly improving adhesion to various objects, and when an additive is added, the curable rubber composition (2) of the present invention can further improve adhesion to various substrates.

The curable rubber composition (2) of the present invention is particularly suitable for elastomer sealants, for example, sealants for laminated glass, electrical insulators (e.g., insulating coatings for electric wires and cables), which particularly require very rapid curing.

(3) The present invention can provide a curable composition (3) which is cured rapidly and is excellent in residual elasticity, weather resistance and adhesion to a coating layer.

(4) The curable composition (4) of the present invention can form a rubber-like elastomer which is excellent in storage stability, high in curing speed, excellent in tensile properties, free from residual tackiness and excellent in weather resistance.

(5) The rubber composition (5) curable at ordinary temperatures of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), or an organic polymer (Z) containing a specific hydrolyzable silyl group and having substantially no unsaturated double bond in the main chain, and a specific silane compound (B5). As a result, the composition can be cured rapidly and is excellent in weather resistance, and a cured product (cured coating film) excellent in adhesion can be obtained.

The rubber composition (5) curable at ordinary temperatures of the present invention has particularly good adhesion to coating films of conventional paints such as melamine alkyd resins and melamine acrylic resins, and is suitable for use as a paint for repairing automobiles.

(6) The curable rubber composition (6) of the present invention comprises an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a specific hydrolyzable silyl group, or an organic polymer (Z) which has a specific hydrolyzable silyl group and is substantially free of unsaturated double bonds in the main chain, a specific amine (D) and a specific silane coupling agent (B6). The composition can be easily cured at room temperature or under heating with moisture in the air without adversely affecting the properties of the cured product.

Therefore, the curable rubber composition (6) of the present invention can be widely used as a coating curable at room temperature or under heating, and is particularly suitable for repairing automobiles, new car production lines, precoated metals, glass, rust prevention of heavy construction structures (such as bridges) and building materials, and also for coating materials, adhesives and sealants.

(7) The curable composition (7) of the present invention can be cured rapidly to give a cured product greatly improved in adhesive strength and weather-resistant adhesion while maintaining a low modulus.

(8) The curable composition (8) of the present invention can be cured rapidly, and the adhesive strength and weather-resistant adhesion of the cured product can be greatly improved while maintaining a low modulus. Also shows excellent properties in terms of storage stability.

(9) The curable rubber composition (9) of the present invention contains a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), or an organic polymer (Z) which contains a specific hydrolyzable silyl group and has substantially no unsaturated double bond in the main chain, an alcohol (B9) and/or a hydrolyzable ester compound (I), a hydrolyzable organosilicon compound (B10), and a curing accelerator added as required.

The curable rubber composition (9) of the present invention can be used for coating materials, can be cured rapidly at room temperature, and gives a coating film excellent in surface gloss the addition of ethyl silicate to the ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) enables free adjustment of the surface hardness of the coating film.

Further, the curable rubber composition (9) of the presentinvention is useful not only as a coating material but also as a coating composition (for example, for aircraft, construction and automobile), a sealant composition and a surface treatment agent for various inorganic materials.

(10) The curable rubber composition (10) of the present invention contains water or a hydrate of a metallic salt as a water source required for the curing reaction, and a silanol condensing catalyst. The composition shows substantially no deterioration in curability (curing rate) after storage, and is high in curing rate and excellent in weather resistance. Further, the curable rubber composition (10) of the present invention may be blended with a compound having a reactive silicon group which can easily react with moisture (e.g., a silane coupling agent). The composition is hardly crosslinked upon storage, thereby preventing an increase in viscosity.

(11) The rubber composition (11) of the present invention comprises an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) having a hydrolyzable silyl group represented by the above chemical formula (1) in the molecule and an organosilicon compound (K1). The composition can be handled well, cured sufficiently quickly, and a cured product excellent in various properties such as weather resistance, heat resistance, water resistance, strength and elongation is obtained.A polysiloxane having 2 or more silanol groups is added to bring about an advantage that curability in the deep inside of the composition is very high.accordingly, the rubber composition (11) of the present invention is particularly suitable for use as a sealing material, an adhesive, a coating material, a waterproof material, a spray material, a molding material and a casting rubber material.

(12) The rubber composition (12) of the present invention comprises an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) having a hydrolyzable silyl group represented by the above chemical formula (1) in the molecule, an organic rubber (K2) and a crosslinking agent (M) for the organic rubber (K2). The composition can be rapidly vulcanized to give a vulcanized curable rubber elastomer excellent in various properties such as weather resistance, heat resistance, chemical resistance and mechanical strength.

(13) The present invention enables not only to obtain a cured product excellent in adhesion, having a greatly varying layered structure, low elasticity and high elongation; and a cured product having a high modulus of elasticity and tensile shear strength can be obtained by decreasing the particle size of the epoxy resin dispersed in the matrix to increase the content thereof. The rubber composition (13) of the present invention can be cured sufficiently rapidly to give a cured product having high weather resistance.

(14) The present invention provides a high-strength cured product, the toughness and strength of which are improved so as not to be affected by moisture amount. The curable rubber composition (14) of the present invention can be cured sufficiently rapidly to give a cured product of high weather resistance.

(15) The curable rubber composition (15) of the present invention contains an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2), calcium carbonate (L1) and talc (L2) having a hydrolyzable silyl group represented by the above chemical formula (1) in the molecule, and therefore, the composition achieves a good balance between workability and mechanical properties of the cured product, cures sufficiently rapidly to give a cured product excellent in weather resistance, and therefore, the composition is suitable as a sealant for laminated glass, and also useful for other applications such as a sealant for elastomer for construction, a sealant for SSG construction method, a sealant for a wiredor laminated glass for rust-proof or water-proof edges (cut portions).

(16) The curable composition (16) of the present invention exhibits good weather-resistant adhesion even to transparent objects for which conventional compositions do not have weather-resistant adhesion, such as various surface-treated heat ray reflective glasses. Moreover, the composition cures rapidly and gives a cured product having high weather resistance.

(17) The curable rubber composition (17) of the present invention can be cured rapidly, has high weather resistance, and gives a cured product having high heat resistance.

The curable rubber composition (17) of the present invention is suitable for use as adhesives, tackifiers, coatings, sealant compositions, water repellents, spray materials, shaping materials and casting rubber materials.

(18) The curable composition (18) of the present invention cures rapidly, and adhesion to various objects and various glass substrates, particularly weather-resistant adhesion to heat-ray reflective glass, is greatly improved. The composition is also excellent in weather resistance. When added with various additives, the curable composition (18) of the present invention is particularly suitable for elastomer sealants, such as sealants for laminated glass and SSG construction methods, which are required to adhere to various objects and have weather-resistant adhesion to vitreous substrates.

(19) The tackifier composition (19) of the present invention contains a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) or an organic polymer (Z) which contains a specific hydrolyzable silyl group and has substantially no unsaturated double bond in the main chain, a specific curing catalyst (H1 or H2) for condensation reaction between groups having hydrolyzable silicon in the component (Z) and a tackiness-imparting resin (W).

The tackifier composition (19) of the present invention is useful as a product requiring peeling from silicone release paper or release film (e.g., double-sided tape, label, sheet).

(20) The rubber composition (20) of the present invention contains an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a hydrolyzable silyl group in a terminal or a side chain or an organic polymer (Z) which contains a specific hydrolyzable silyl group and has substantially no unsaturated double bond in the main chain, and a specific curing catalyst (one of H3 to H7).

The rubber composition (20) of the present invention can be cured at ordinary temperature or low temperature and thus can be used as a coating material or a coating material.

Further, the rubber composition (20) of the present invention may be mixed with various resins used for conventional paints and coating materials, such as a varnish resin, an acrylic varnish resin, a thermosetting acrylic resin, an alkyd resin, a melamine resin and an epoxy resin, in an appropriate ratio. After mixing, the properties (e.g., adhesion and weatherability) of conventional coatings and coating materials are improved.

Further, the rubber composition (20) of the present invention can be used for coating and sealing material compositions for aircrafts, structures, automobiles and glasses, and also as a surface treating agent for various inorganic materials.

(21) The curable composition (21) of the present invention comprising a specific copolymer rubber as component (A1) and a specific curing catalyst as component (H8) cures significantly faster than conventional curable compositions and has greatly improved weather resistance.

The curable composition (21) of the present invention having the above-mentioned effects is useful not only as a tackifier and a sealing material but also as an adhesive, a molding material, a vibration insulator, a foaming material, a coating material and a spray material.

(22) The curable rubber composition (22) of the present invention is excellent in weather resistance, and can greatly improve curing speed and adhesion to various objects. When incorporated with various additives, the curable rubber composition (22) of the present invention is particularly suitable for elastomer sealants, such as for laminated glass and SSG building process sealants, which are required to have adhesion to various objects.

(23) The curable composition (23) of the present invention is suitable for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas, and is particularly suitable for use as a coating material (23)' for vehicles, and also for other uses such as sealants, potting agents, and coating materials other than vehicles, adhesives, all within the scope of the composition.

(23) ' the coating composition for vehicles of the present invention can satisfy the requirements of the automobile industry: reduce the weight of the automobile and save resources and energy by reducing the temperature and the baking time. Further, the composition can give a film excellent in rust prevention, vibration isolation and weather resistance even when it is produced under curing conditions of low temperature and short time.

(25) ' the sealant for laminated glass of the present invention comprises an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) having a hydrolyzable silyl group represented by the above chemical formula (1) in the molecule, a curing catalyst (H) and water or a metal salt hydrate (B11). The composition has various advantageous properties such as weather resistance, heat resistance, non-staining property, low moisture permeability, weather-resistant adhesion and little odor, and is excellent in mechanical properties and can be produced at low cost.

(26) ' the sealant for laminated glass of the present invention comprises an ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) having a hydrolyzable silyl group represented by the above chemical formula (1) in the molecule, a hot-melt resin (X), a curing catalyst (H) and water or a metal salt hydrate (B11). As compared with the conventional hot-melt resin, the temperature dependence of structural strength and adhesion to a substrate are improved while maintaining vapor barrier properties.

Examples

The present invention is illustrated by examples, but the present invention is not limited to these examples.

<example A series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in each of examples and comparative examples were determined by the following methods.

(1) Composition of copolymer rubber

By using¹³The composition of the copolymer rubber was determined by the C-NMR method.

(2) Iodine value of copolymer rubber

The iodine value of the copolymer rubber was determined by titration.

(3) Intrinsic viscosity [ η]

The intrinsic viscosity of the copolymer rubber was measured in decalin maintained at 135 deg.C [ η].

(4) Molecular weight distribution (Mw/Mn)

The molecular weight distribution (Mw/Mn) of the copolymer rubber is determined by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), both measured by Gel Permeation Chromatography (GPC), using GMH-HT or GMH-HTL (TOSOH CORP.) as a column and o-dichlorobenzene as a solvent.

For examples and comparative examples, a curing speed test and an accelerated weather resistance test were conducted in the following manner.

(1) Curing speed test

The curable composition (blank) was cured in a mould (dimensions 20X 80X 5 mm) at 50 ℃ and 50% RH (relative humidity) for 24 hours.

The cured product was then taken out of the mold, and the curing speed was evaluated by measuring the thickness of the cured portion with a micrometer having a spring force as weak as 0.1mm, which was represented by ◎ when the thickness was 1mm or more, by △ when the thickness was 0.5 to 1mm, and by x when the thickness was less than 0.5 mm.

(2) Accelerated weather resistance test

The weather resistance was measured by a Sun Carbon Arc weatherometer in accordance with JIS B-7753.

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 250 hours

Preparation examplesProduction of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2dl/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) adding 2% of chloroplatinic acidA toluene solution (0.3 g) and 1.5 g of methyldimethoxysilane were reacted with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a mixture containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Reference example A1

N-butyl acrylate 128 g (1 mol), 0.74 g (0.005 mol) of vinyltrimethoxysilane and 1.44 g (0.008 mol) of γ -mercaptopropylmethyldimethoxysilane were mixed with each other, 0.3 g of α '-azobisisobutyronitrile was added thereto and dissolved therein by stirring, a part of the mixed solution (30 g) was added to a 300 ml four-necked flask equipped with a condenser, a dropping funnel and a stirrer, thereafter purged with dry nitrogen, heated in a nitrogen atmosphere with an oil bath (80 ℃), polymerization occurred within two to three minutes, heat was generated, and the mixed solution was thickened, the remaining mixed solution was added dropwise with a funnel after the heat release was settled, these mixed solutions were completely added within about 3 hours, 60 ml of a 20% by weight acetone solution of α' -azobisisobutyronitrile was added 15 minutes and 30 minutes after the addition of the mixed solution was stirred under heating for 30 minutes to terminate the polymerization, the polymer thus obtained was colorless, transparent and viscous, and had a viscosity at 23 ℃ as measured by gas chromatography, an average gel content of GPC monomer content of 15% by GPC (21,000).

Reference examples A2-A7

A polymer was prepared in the same manner as in reference example A1, except that the components listed in Table A1 were used. The viscosity, residual monomer content and average molecular weight of each polymer are listed in Table A1.

TABLE A1

(preparation of organic vinyl Polymer)

	Reference example
							A2	A3	A4	A5	A6	A7
	Monomer (g) as main component	BA (50)	BA (100)	BA (128)	BA (128)	BA (128)							BA (128)
Other monomers (gram)							2EHA (50) MAPDMS (0.50)	VAc (20) MAPDMS (0.50)	HDDA (1.70)	TMPA (1.78)	NPCDA (2.12) MAPDMS (0.70)	FA-731A (4.24)
	Chain transfer agent (gram)	MPTES (5.50)	MPDMS (3.50)	MPDMS (1.70)	MPDMS (3.25)	MPDMS (3.61)							MPDMS (4.93)
Polymerization initiator (g)							AIBN (0.35)	AIBN (0.35)	AIBN (0.41)	AIBN (0.41)	AIBN (0.35)	AIBN (0.35)
	Viscosity (poise, 23 ℃ C.)*1	180	230	670	350	250							430
Residual monomer (%)*2							1.5	1.7	1.6	2.1	1.8	1.3
	Average molecular weight*3	6000	8000	15000	10000	8000							12000

^*1: measured with type B Binder^*2: measured by gas chromatography (internal standard method)^*3: measured by GPC

BA: acrylic acid n-butyl ester

2 EHA: 2-ethylhexyl acrylate

VAc: ethyl acetate

HDDA：CH₂＝CH-CO-O(CH₂)₆O-CO-CH＝CH₂

TMPA：(CH₂＝CH-CO-O)₃C-CH₂CH₃

NPCDA：CH₂＝CH-CO-OCH₂-C(CH₃)₂-CH₂O-CO-CH＝CH₂

FA-731A：

MAPDMS：CH₂＝C(CH₃)-CO-O(CH₂)₅-Si(OCH₃)₂(CH₃)

MAPTMS：CH₂＝C(CH₃)-CO-(CH₂)₅-Si(OCH₃)₃

MPDMS: gamma-mercaptopropylmethyldimethoxysilane

MPTES: gamma-mercaptopropyltriethoxysilane

AIBN α' -azobisisobutyronitrile

Example A1

A mixture of 30 g of the silyl group functionalized ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in preparation example and 0.43 g of triphenyl silanol became completely transparent and uniform after stirring at 90 ℃ for 2 hours. To the above mixture was added 0.9 g of NO918 (a 2: 1 mixture of heat-treated dibutyltin oxide and di-2-ethylhexyl phthalate, SANKYOORGANIC CHEMICALS) as a curing catalyst. The resulting mixture was thoroughly stirred and mixed, centrifuged at 3,000rpm for 10 minutes to defoam the mixture, placed in a polyethylene mold frame (11X 8X 0.3 cm), and the composition was cured in the mold at room temperature for 3 days and at 50 ℃ for 4 days. A colorless transparent cured sheet was obtained which had no rubber-like elasticity.

The cured sheet was punched out to form a dumbbell-shaped test piece (No. 3 according to JIS K-6301). Tensile tests were carried out with an Autograph at a tensile speed of 200 mm/min to determine the elongation and the breaking strength. The results are shown in Table A2.

As shown in Table A2, the addition of triphenyl silanol can greatly improve the tensile characteristics and can improve the elongation of the cured acrylic-based polymer which tends to be insufficient in elongation.

Comparative examples A1-A23

For each comparative example, a mixture of 30 g of the organic polymer (1) obtained in referential example A1 and 0.43 g of triphenyl silanol was prepared. The mixture became completely transparent and homogeneous after stirring for 2 hours at 90 ℃. To the above mixture was added 0.9 g of NO918 (a 2: 1 mixture of heat-treated dibutyltin oxide and di-2-ethylhexyl phthalate, SANKYO ORGANICCHEMICALS) as a curing catalyst. The resulting mixture was stirred well to mix, defoamed by centrifugation at 3,000rpm for 10 minutes, placed in a polyethylene mold frame (11X 8X 0.3 cm), and the composition was cured in the mold at room temperature for 3 days and at 50 ℃ for 4 days. A colorless transparent cured sheet was obtained which had no rubber-like elasticity.

The cured sheet was punched out into a dumbbell-shaped test piece (No. 3 according to JIS K-6301). Tensile tests were carried out with an Autograph at a tensile speed of 200 mm/min to determine the elongation and the breaking strength. The results are shown in Table A2 together with the results for the cured sheet without triphenylsilanol.

Cured sheets were prepared from the organic polymers (2) to (7) obtained in referential examples A2 to A7 and tested. The results are also shown in Table A2 together with the results for the cured sheet without triphenyl silanol.

As shown in Table A2, the addition of triphenyl silanol can greatly improve the tensile characteristics and can improve the elongation of the cured acrylic-based polymer which tends to be insufficient in elongation.

A cured sheet was prepared in the same manner as in comparative example A1, except that (CH) capable of forming a compound having 2 or more silanol groups in the molecule was used₃)₂Si(OCH₃)₂(hereinafter referred to as dimethoxy compound) or CH₂＝CHSi(OCH₃)₃(hereinafter referred to as trimethoxy compound) instead of triphenyl silanol, the elongation and breaking strength of the cured sheet were analyzed. The results are shown in Table A3 (comparative examples A8-A15) and Table A4 (comparative examples A16-A23).

Comparing the results in Table A2 with those in tables A3 and A4, it can be seen that a compound having only one silanol group (e.g., triphenyl silanol) can greatly improve the elongation of the cured sheet in a particular manner.

TABLE A2

		Examples	Comparative example
										A1	A1	A2	A3	A4	A5	A6	A7
		Copolymer rubber or polymer		Production example	Reference to Example A1	Reference to Example A2	Reference to Example A3	Reference to Example A4	Reference to Example A5									Reference to Example A6	Reference to Example A7
Amount of triphenylsilanols (g)										0.43	0.43	0.39	0.29	0.38	0.45	0.71	0.24
		Triphenyl silanol ratio (mol%)*		50	50	20	25	40	40									50	15
Speed of curing										◎	×	×	×	×	×	×	×
		Weather resistance		A	B	C	C	B	B									B	C
Elongation (%)										620	500	300	350	450	520	350	250
		Breaking Strength (kg/cm)3)		3.0	2.3	2.0	2.3	1.9	1.8									2.0	1.8
Triphenylsilane-free Alcohol addition	Elongation (%)									310	260	120	150	190	240	110	130
		Breaking Strength (kg/cm)3)	2.9	2.5	2.1	2.3	2.1	1.8	2.2									1.9

^*: evaluation of weather resistance in mol% based on the silicon-containing compound used in preparing the copolymer rubber or the organic polymer: a: no crack or no molten portion was found; b: small cracks or melting portions found, but slight C: cracks or fused portions were observed.

TABLE A3

(Effect of adding dimethoxy Compound)

	Comparative example
									A8	A9	A10	A11	A12	A13	A14	A15
	Copolymer rubber or polymer	Manufacture of Example (b)	Reference to Example A1	Reference to Example A2	Reference to Example A3	Reference to Example A4	Reference to Example A5	Reference to Example A6									Reference to Example A7
Amount of dimethoxy compound (g)									0.21	0.21	0.17	0.13	0.17	0.20	0.31	0.10
	Proportion of dimethoxy compound (mol%)*	50	50	20	25	40	40	50									15
Speed of curing									◎	△	×	×	△	△	△	×
	Weather resistance	A	B	C	C	B	B	B									C
Elongation (%)									320	250	130	180	230	270	120	130
	Breaking Strength (kg/cm)3)	3.2	2.5	2.0	2.4	2.3	1.9	2.1									2.0

^*: evaluation of weather resistance in mol% based on the silicon-containing compound used in preparing the copolymer rubber or the organic polymer: a: no crack or no molten portion was found; b: small cracks or melting portions found, but slight C: cracks or fused portions were observed.

TABLE A4

(Effect of adding trimethoxy Compound)

	Comparative example
									A16	A17	A18	A19	A20	A21	A22	A23
	Copolymer rubber or polymer	Manufacture of Example (b)	Reference to Example A1	Reference to Example A2	Reference to Example A3	Reference to Example A4	Reference to Example A5	Reference to Example A6									Reference to Example A7
Amount of trimethoxy Compound (g)									0.27	0.27	0.21	0.16	0.20	0.24	0.38	0.13
	Proportion of trimethoxy Compound (mol%)*	50	50	20	25	40	40	50									15
Speed of curing									◎	△	×	×	△	△	△	×
	Weather resistance	A	B	C	C	B	B	B									C
Elongation (%)									270	200	100	130	180	210	90	110
	Breaking Strength (kg/cm)3)	2.5	2.1	1.9	2.0	2.0	1.6	1.8									1.7

^*: evaluation of weather resistance in mol% based on the silicon-containing compound used in preparing the copolymer rubber or the organic polymer: a: no crack or no molten portion was found; b: small cracks or melting portions found, but slight C: cracks or fused portions were observed.

Examples A2-A4

For each of examples A2-A4, a cured sheet was prepared and subjected to a tensile test in the same manner as in example A1, except that each silanol compound shown in Table A5 was used in place of triphenyl silanol, and was added to the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) obtained in production example. The results are shown in Table A5.

As shown in the table, each silanol compound achieved high elongation.

Comparative examples A24-A26

For each of comparative examples A24-A26, a cured sheet was prepared and subjected to a tensile test in the same manner as in comparative example A1, except that each silanol compound listed in Table A5 was added to the organic polymer (1) prepared in the reference example in place of triphenyl silanol. The results are shown in Table A5.

As shown in the table, each silanol compound achieved high elongation.

TABLE A5

	Examples			Comparative example
							A2	A3	A4	A24	A25	A26
	Copolymer rubber or polymer	Production example	Production example	Production example	Reference example A1	Reference example A1							Reference example A1
Silanol compound type							MeSiOH	EtSiOH	Ph(Me)SiOH	MeSiOH	EtSiOH	Ph(Me)SiOH
	Dosage (gram)	0.09	0.09	0.36	0.09	0.09							0.36
Proportion (mol%)*							30	20	50	30	20	50
	Speed of curing	◎	◎	◎	△	△							△
Weather resistance							A	A	A	B	B	B
	Elongation (%)	480	520	660	390	400							480
Breaking Strength (kg/cm)3)							2.9	3.1	2.6	2.4	2.5	2.0

^*: evaluation of weather resistance in mol% based on the silicon-containing compound used in preparing the copolymer rubber or the organic polymer: a: no crack or no molten portion was found; b: small cracks or melting portions found, but slight C: cracks or fused portions were observed.

Examples A5-A7

For each of examples A5-A7, a cured sheet was prepared and subjected to a tensile test in the same manner as in example A1, except that each silanol compound capable of reacting with moisture to form a silanol-containing compound shown in Table A6 was added in place of triphenyl silanol to the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) obtained in production example. The results are shown in Table A6.

As shown in the table, the addition of each compound capable of reacting with moisture to form a silanol-containing compound brings about approximately the same effect as the addition of a silanol compound, greatly improving the elongation of the cured acrylic-based polymer which tends to be insufficient in elongation.

Comparative examples A27-A29

For each of comparative examples A27-A29, a cured sheet was prepared and subjected to a tensile test in the same manner as in comparative example A1, except that each of the silicon compounds capable of reacting with moisture to form a silanol-containing compound shown in Table A6 was added to the organic polymer (1) obtained in comparative example A1 in place of triphenyl silanol. The results are shown in Table A6.

As shown in the table, the addition of each compound capable of reacting with moisture to form a silanol-containing compound brings about approximately the same effect as the addition of a silanol compound, greatly improving the elongation of the cured acrylic-based polymer which tends to be insufficient in elongation.

TABLE A6

	Examples			Comparative example
							A5	A6	A7	A27	A28	A29
	Copolymer rubber or polymer	Production example	Production example	Production example	Reference example A1	Reference example A1							Reference example A1
Silanol compound type							Si(1)	Si(2)	Si(3)	Si(1)	Si(2)	Si(3)
	Dosage (gram)	0.16	0.27	0.22	0.16	0.27							0.22
Proportion (mol%)*							30	40	50	30	40	50
	Speed of curing	◎	◎	◎	×	△							△
Weather resistance							A	A	A	C	B	B
	Elongation (%)	550	590	620	420	480							480
Breaking Strength (kg/cm)3)							2.9	2.5	2.6	2.4	2.2	2.2

^*: mol% Si (1) based on the silicon-containing compound used in the preparation of the copolymer rubber or the organic polymer: me₃SiNHSiMe₃Si(2)：Me₃SiO-C(CH₃)NSiMe₃Si(3)：CH₃-CO-NHSiMe₂Evaluation of weather resistance: a: no crack or no molten portion was found; b: small cracks or melting portions found, but slight C: cracks or fused portions were observed.

<example B series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

The accelerated weather resistance test was carried out in the following manner.

[ accelerated weather resistance test]

The weather resistance was measured by a Sun Carbon Arc weatherometer in accordance with JIS B-7753.

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 1000 hours

The analysis method comprises the following steps: in accordance with JIS K-6301

Production example B1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a mixture containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) Is/are as followsEthylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example B2

Into a 500 ml nitrogen-purged pressure-resistant glass reactor equipped with a three-way stopcock, 54 ml of ethylcyclohexane (at least standing overnight and dried with molecular sieve 3A), 126 ml of toluene (at least standing overnight and dried with molecular sieve 3A) and 1.16 g (5.02 mmol) of p-DCC represented by the following formula were charged by syringe.

Then, a pressure-resistant glass liquefied gas collecting tube equipped with a needle valve and containing 56 ml of an isobutylene monomer was connected to the above-mentioned three-way cock. The polymerization reactor was cooled in a dry ice/ethanol bath maintained at-70 ℃ and the gas phase was evacuated with a vacuum pump. The needle valve was then opened to allow the isobutylene monomer to pass through the liquefied gas collection tube into the polymerization reactor and the reactor was returned to atmospheric pressure with nitrogen from one port of the three-way stopcock.

Subsequently, 0.093 g (1.0 mmol) of 2-methylpyridine was added to the reaction system, followed by 1.65 ml (15.1 mmol) of titanium tetrachloride, to initiate polymerization. Thereafter, at 70 minutes after the reaction was initiated, 1.22 g (10.8 mmol) of allyltrimethylsilane was added to chemically introduce an allyl group into the terminal of the polymer. The reaction solution obtained 120 minutes after the initiation of the reactionwas washed 4 times with 200 ml of water each time, and the solvent was distilled off to prepare an isobutylene-based polymer having an allyl group at the terminal.

Next, 40 g of an isobutylene polymer having an allyl group at the terminal thereof was dissolved in 20 ml of n-heptane, the mixture was heated to about 70 ℃ and 1.5[ eq/vinyl]was added thereto]Methyldimethoxysilane and 1X 10^-4[ equivalent/vinyl group]]The platinum/vinylsiloxane complex of (a), to carry out a hydrosilylation reaction. The reaction was followed by FT-IR. About 4 hours in 1640 cm^-1The absorption peak of the olefin(s) disappeared.

The reaction solution was concentrated under vacuum to prepare an isobutylene polymer having reactive silicon groups at both terminals represented by the following formula:

the yield of the polymer was estimated from the yield. Also, Mn and Mw/Mn were analyzed by GPC, and by comparing protons associated with each structure with each other¹The intensity of resonance signals (proton from initiator: 6.5-7.5ppm, methyl proton from polymer terminal attached to silicon atom: 0.0-0.1ppm, methoxy proton: 3.4-3.5) of H-NMR-analysis analyzed terminal structure.

Using a Varian Gemini 300 (Pair)¹H is 300 megahertz) in CDCl₃In the middle of¹H-NMR analysis.

FT-IR analysis was performed with an analyzer (Shimadzu IR-408), and GPC analysis was performed with a Waters LC Module 1 as a liquid transfer system and Shodex K-804 as a column. Molecular weights were calculated by comparison with polystyrene standards. The polymer thus produced had an Mn of 11,400, an Mn/Mw of 1.23 and an Fn (silyl) of 1.76, wherein the number average molecular weight was expressed in terms of polystyrene molecular weight and the number of terminal silyl functional groups was the number of terminal silyl functional groups per 1 mole of the isobutylene polymer.

Production example B3

An isobutylene-based polymer having a reactive silicon group was prepared in the same manner as in preparation example B2, except that p-DCC and allyltrimethylsilane were added in different amounts of 2.32 g (10.0 mmol) and 14.4 g (126.0 mmol), respectively.

The polymer thus prepared had Mn of 5,780, Mw/Mn of 1.28 and Fn (silyl) of 1.93.

Examples B1 and B2, and comparative examples B1-B3

A mixture containing the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in preparation example B1 was prepared. It consists of the following substances: 100 parts of copolymer rubber (A-1) and 90 parts of paraffin Process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO320B 10)^TM)50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of Talc (Fuji Talc Kogyo, Talc LMR)^TM) 3 parts as light stabilizerNickel dimethyldithiocarbamate (Sanshin Chemical induuscry Co. Sandant) of agentNBC^TM)5 parts of impregnation inhibitor (Kusumoto Kasei, Disparlon # 305)^TM) 1 part of hindered phenol antioxidant (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of a salicylate ultraviolet absorber (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of hindered amine light stabilizer (Sankyo, SanolLS-765)^TM) 3 parts of dipentaerythritol pentaacrylate and hexaacrylate (TOAGOSEI, Aronix M-400) as a photocurable compound^TM)2 parts of gamma-glycidoxypropyltrimethoxysilane (Nippon Unicar, Silane Coupling Agent A-187), 4 parts of gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, Silane Coupling Agent A-1310) as the isocyanate-containing Silane Coupling Agent of the present invention, and parts of the silicon compound shown in Table B2, all parts being by weight. The respective mixtures were kneaded well by a 3-paint roll unit to prepare the main component.

For examples B1 and B2, and comparative example B1, diphenyldimethoxysilane (Shin-Etsu Chemical, LS-5300) was incorporated in parts as indicated in Table B1^TM) Which is a silanol-free silicon compound as component B2 of the present invention. For comparative examples B2 and B3, the incorporation fractions of diphenyldisilanol (Chisso Co., D6150) are indicated in Table B1^TM) As silanol-containing silicon compounds.

The curing agent was prepared by the following method: in the disposable cup, a mixture comprising: 16 parts of paraffin Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 10 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM)2 parts of water and parts of the silanol condensation catalyst shown in Table B1 below, all parts being by weight, the mixture was stirred 3 times at 10,000 rpm for 10 minutes each with a homogenizer (Nihon Seiki sesakusho Co., Ltd.

Examples B1 and B2, and comparative examples B2 and B3 incorporated 4 parts by weight of component C according to the inventionThe tetravalent tin compound, dibutyltin dimethoxide (Aldrich Chemical), was used as a silanol condensing catalyst, and comparative example B1 incorporated 4 parts by weight of a divalent tin compound, tin octylate (NITTO KASEI, U-28)^TM)。

After kneading the above main component and curing agent, curability of each composition was evaluated by the following hardness of the cured product.

A sample containing 16 parts of the main component and 1 part of the curing catalyst (all by weight) was used for the measurement, the mixture was thoroughly kneaded and cured in a mold of 12 × 12 × 50 mm under a constant temperature bath maintained at 25 ℃, and a teflon sheet was used as a liner. The hardness of a rectangular parallelepiped test piece cured at 25 ℃ was measured with a durometer (Shimadzu, durometer 200) according to spring type hardness test A of JIS K-6301/1975. Curability was determined by measuring the time required for the composition to reach 20 hardness immediately after kneading of the main component and the curing agent. The results are shown in Table B1.

TABLE B1

	Silanol condensation catalysis Agent (dosage)	Silicon compound (amount)	Required to reach 20 hardness Time of (hours)	Weather resistance
					Example B1	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	1	No cracking was observed Or molten parts
Example B2	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (1.0 parts by weight)	1	No cracking was observed Or molten parts
					Comparative example B1	Sn(OCOC7H15)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	3	No cracking was observed Or molten parts
Comparative example B2	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OH)2 (0.5 parts by weight)	2	No cracking was observed Or molten parts
					Comparative example B3	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OH)2 (1.0 parts by weight)	2	No cracking was observed Or molten parts

Reference examples B1-B6

In the polymer produced in production example B2, which is a saturated hydrocarbon polymer, the following components were incorporated, wherein the amounts of the components are expressed in parts by weight per 100 parts by weight of the polymer: 90 parts of paraffin Process Oil (IdemitsuKosan, Diana Process Oil PS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO320B 10)^TM)50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of Talc (FujiTalc Kogyo, Talc LMR)^TM) 3 parts of nickel dimethyldithiocarbamate as light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC)^TM)5 parts of impregnation inhibitor (Kusumoto Kasei, Disparlon # 350)^TM) 1 part of hindered phenol antioxidant (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of a salicylate ultraviolet absorber (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of hindered amine light stabilizer (Sankyo, Sanol LS-765)^TM) 3 parts of dipentaerythritol pentaacrylate and hexaacrylate (TOAGOSEI, Aronix M-400) as a photocurable compound^TM)2 parts of gamma-glycidoxypropyltrimethoxysilane (Nippon Unicar, silane coupling agent A-187), 4 parts of gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, silane coupling agent A-1310) as the isocyanate-containing silane coupling agent of the present invention, and the following silicon compounds in parts shown in Table B2. The mixture was kneaded well with a 3-paint roll unit to prepare the main component.

For reference example B1-B3 was prepared by incorporating the parts of diphenyldimethoxysilane (Shin-Etsu Chemical, LS-5300) shown in Table B2^TM) Which is a silanol-free silicon compound as component B2 of the present invention. Reference example B4 did not incorporate a silicon compound. For reference examples B5 and B6 were prepared by incorporating the parts of diphenyldisilanol shown in table B2 (Chisso co.,D6150^TM) As silanol-containing silicon compounds.

The curing agent was prepared by the following method: in the disposable cup, a mixture comprising:16 parts of paraffin Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 10 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM)2 parts of H₂O and the following silanol condensation catalystin parts shown in Table B2, all parts being by weight, the mixture was stirred 3 times at 10,000 rpm for 10 minutes each with a homogenizer (Nihon Seiki sesakusho Co., Ltd. excel. autohomogenizer).

Reference examples B1-B2 and B4-B6 incorporated 4 parts by weight of dibutyltin dimethoxide (Aldrich Chemical) as component C of the present invention as a silanol condensing catalyst, and reference example B3 incorporated 4 parts by weight of a divalent tin compound tin octylate (NITTO KASEI, U-28)^TM)。

After kneading the above main component and curing agent, curability of each composition was evaluated by the following hardness of the cured product.

A sample containing 16 parts of the main component and 1 part of the curing catalyst (all by weight) was used for the measurement, the mixture was thoroughly kneaded and cured in a mold of 12 × 12 × 50 mm under a constant temperature bath maintained at 25 ℃, and a teflon sheet was used as a liner. The hardness of a rectangular parallelepiped test piece cured at 25 ℃ was measured with a durometer (Shimadzu, durometer 200) according to spring type hardness test A of JIS K-6301/1975. Curability was determined by measuring the time required for the composition to reach 20 hardness immediately after kneading of the main component and the curing agent. The results are shown in Table B2.

TABLE B2

	Silanol condensation catalysis Agent (dosage)	Silicon compound (amount)	Required to reach 20 hardness Time of (hours)	Weather resistance
					Reference example B1	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	2.1	Slight observation was made Molten part of (2)
Reference example B2	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (1.0 parts by weight)	2.0	Slight observation was made Molten part of (2)
					Reference example B3	Sn(OCOC7H15)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	＞12	Slight observation was made Molten part of (2)
Reference example B4	(C4H9)2Sn(OCH3)2 (4 parts by weight)	Is not used (0 part by weight)	4.0	Slight observation was made Molten part of (2)
					Reference example B5	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OH)2 (0.5 parts by weight)	3.8	Slight observation was made Molten part of (2)
Reference example B6	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OH)2 (1.0 parts by weight)	3.5	Slight observation was made Molten part of (2)

Reference examples B7-B9

The adhesion improving effect of the isocyanate-containing silane coupling agent of the present invention was evaluated by the adhesion test described below.

Test pieces for tensile adhesion test were prepared according to the method prescribed in JIS A-5758/1992, and glass substrates formed into H-shapes were filled with the compositions (reference example B7 was a 16: 1 mixture of the main component and the curing agent prepared in reference example B1, and reference example B8 was a 16: 1 mixture of the main component and the curing agent prepared in reference example B2, in the exact weight ratio), while breaking the bubbles in each composition with a spatula. Each composition was cured in an oven at 23 ℃ for 7 days +50 ℃ for 7 days. The substrate used for the H-shape tensile test was aluminum (Taiyu Kizai, A1100P, size3X 5X 0.2 cm) according to JIS H-4000. It was washed with methyl ethyl ketone (Wako-Junyaku Kogyo, Special grade) and wiped with clean cotton cloth, then it was filled with the composition. It is not coated with a primer.

The adhesion test of reference example B9 was conducted in the same manner as reference example B7, except that no gamma-isocyanatopropyltriethoxysilane was used.

After the sample of the H-shaped tensile test prepared above was cured, its tensile adhesion was tested, and its adhesion in the absence of the primer layer was evaluated by comparing the tensile characteristics and the failure form.

According to the method for testing tensile adhesiveness of JIS A-5758/1992, a tensile adhesiveness test was conducted at a tensile rate of 50 mm/min in a thermostatic chamber maintained at 23 ℃ and RH (relative humidity) of 50. + -. 5% using Autograph AG-2000A of Shimadzu.

The results are shown in Table B3.

Examples B3-B5

Adhesion tests of examples B3 to B5 were carried out in the same manner as in reference examples B7 to B9, except that the silyl group-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example B1 was used in place of the polymer prepared in production example B2.

The results are shown in Table B4.

TABLE B3

	Silanol condensation catalysis Agent (dosage)	Silicon compounds (dosage)	Isocyanate-containing silanes Coupling agent (dosage)	Adhesion test of Bad form	Weather resistance
						Reference example B7	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	OCNC3H6Si(OCH3)3 (4 parts by weight)	Cohesive failure	Slight observation Molten part
Reference example B8	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (1.0 parts by weight)	OCNC3H6Si(OCH3)3 (4 parts by weight)	Cohesive failure	Slight observation Molten part
						Reference example B9	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	Is not used (0 part by weight)	Interfacial destruction	Slight observation Molten part

TABLE B4

	Silanol condensation catalysis Agent (dosage)	Silicon compounds (dosage)	Isocyanate-containing silanes Coupling agent (dosage)	Adhesion test of Bad form	Weather resistance
						Example B3	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	OCNC3H6Si(OCH3)3 (4 parts by weight)	Cohesive failure	No cracking or cracking was observed Molten part
Example B4	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (1.0 parts by weight)	OCNC3H6Si(OCH3)3 (4 parts by weight)	Cohesive failure	No cracking or cracking was observed Molten part
						Example B5	(C4H9)2Sn(OCH3)2 (4 parts by weight)	(C6H5)2Si(OCH3)2 (0.5 parts by weight)	Is not used (0 part by weight)	Interfacial destruction	No cracking or cracking was observed Molten part

The cured products prepared in examples B1-B5, comparative examples B1-B3 and reference examples B1-B9 were subjected to a weather resistance test in accordance with the following method. The results are shown in tables B1-B4.

<example C series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

Production example

[ production of ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 liters and equipped with stirring blades (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously introduced from the side of the reactor into the liquid phase at rates of 60 liters/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, andhydrogen and VO (OEt) as a catalyst were continuously fed at 700 l/h, 45 mmol/h and 315 mmol/h₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 parts by weight of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% toluene solution of chloroplatinic acid (0.3 part by weight) and 1.5 parts by weight of methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)in the effluent were distilled off. This gave 101.5 parts by weight of a compound containing dimethoxymethylsilyl (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Example C1

The mixture containing the ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in the above production example was stirred in a sealable kneader (planetary mixer) at 120 ℃ under vacuum for 2 hours and dehydrated, the mixture was composed of 100 parts of the copolymer rubber (A-1), 55 parts of diisodecyl phthalate (DIDP) as a plasticizer, 120 parts of surface-treated colloidal calcium carbonate as a filler, 20 parts of titanium oxide, 2 parts of aliphatic amide wax as an impregnation inhibitor, 1 part of an ultraviolet absorber and 1 part of a light stabilizer, all parts being by weight, the mixture was cooled to room temperature, and 2 parts of vinyltrimethoxysilane as a viscosity stabilizer, 2 parts of a curing catalyst (NITTO KASEI, U-220) and 3 parts of N- (β -aminoethyl) - γ -aminopropyltrimethylsilyloxydimethoxysilane as a surface modifier were incorporated, all parts being by weight, the resulting mixture was stirred at room temperature and placed in a closed container to give a single liquid component (i.e. -liquid type) and the composition was also evaluated for each of the following C3 days after storage in the example composition was prepared.

Each composition was spread to a thickness of 3 mm, allowed to cure at 23 ℃ and 55% relative humidity, and after 1 day, a total of 5 commercially available commercial solvent-based acrylic coatings (3 acrylic urethane coatings, 1 acrylic varnish, and 1 acrylic enamel) were applied with a brush. After 7 days, the composition was evaluated by testing with cellophane tape (Nichiban) in a pattern of 25 meshes (2 mm squares) and by the percentage of the number of meshes remaining on the surface of the sealing material to the total number of meshes.

Each composition was spread to a thickness of 3 mm and cured at 23 ℃ and 55% relative humidity for 1 and 7 days, and the residual tackiness of each composition was evaluated by touching the mold to cure the surface with a finger, and also the tensile properties of each composition were evaluated according to JIS K-6251. The results are shown in Table C1.

Each composition was tested for curing speed and weather resistance by the following methods. The results are shown in Table C1.

(1) Testing of curing speed

Each composition was spread to a thickness of 3 mm and cured under conditions of 23 ℃ and 55% relative humidity, and its curing speed, which is defined as the time required for the composition to reach 20 hardness (JIS A), was measured.

(2) Weather resistance test (ozone-induced aging test)

The test for accelerated weather resistance was carried out under the following conditions in accordance with JIS B-7753:

an analyzer: sunshine Carbon Arc weather thermometer

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 1000 hours

Examples C2 and C3

Compositions of each of examples C2 and C3 were prepared in the same manner as in example C1, except that the amount of N- (β -aminoethyl) - γ -aminopropyltrimethylsiloxydimethoxysilane was changed to the amount shown in Table C1, and N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane (A-1120) which isa commonly used adhesion promoter was incorporated.

Comparative examples C1 and C2

Respective compositions of comparative examples C1 and C2 were prepared in the same manner as in example C1, except that N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane (A-1120) which was used as a conventional tackifier was used in place of N- (β -aminoethyl) - γ -aminopropyltrimethylsilyloxydimethoxysilane.

As shown in Table C1, each of the compositions of the present invention was excellent in residual tackiness on the cured surface and adhesion to the coating material. It also shows the unapproved phenomenon that the adhesiveness of the composition changes with storage.

Reference example C1

Will contain an average of 2.1 methyldimethoxysilyl [ Si (CH)]in the molecule₃)(OCH₃)₂]A mixture of propylene oxide polymers having a number average molecular weight of 17,000 was stirred in a sealable kneader (planetary mixer) under vacuum at 120 ℃ for 2 hours, and dehydrated. The mixture consisted of the following: 100 parts of the above polymer, 55 parts of diisodecyl phthalate (DIDP) as a plasticizer, 120 parts of surface-treated colloidal calcium carbonate as a filler, 20 parts of titanium oxide, 2 parts of aliphatic amide wax as an impregnation inhibitor, 1 part of an ultraviolet absorber, and 1 part of a light stabilizer, all parts being by weight. The mixture was allowed to cool to room temperatureAnd 2 parts of vinyltrimethoxysilane as a viscosity stabilizer, 2 parts of a curing catalyst (NITTO KASEI, U-220) and 3 parts of N- (β -aminoethyl) -gamma-aminopropyltrimethylsilyloxydimethoxysilane as a surface modifier were incorporated, all parts being by weight the resulting mixture was stirred at room temperature and placed in a closed container to give a one-liquid type curable composition.

The above composition was tested in the same manner as in example C1. The results are shown in Table C1.

TABLE C1

		Examples			Comparative example
								C1	C2	C3	C1	C2	C3
		Additive agent	N- (β -aminoethyl) -gamma-amino Aminopropyl trimethylsiloxy Dimethoxysilane	3	3	4									3
A-1120								1	1	3	5
			Adhesion of coating	Initial (%)	85	100	100						5	5	90
After storage (%)	65	90						85	40	50	70
				Residual tackiness	After 1 day	◎	◎					◎	○	○	◎
After 7 days	◎	◎	◎					◎	◎	◎
					Stress at 100% elongation (MPa)		1.0				1.1	1.0	0.9	0.9	1.0
Breaking Strength (MPa)		3.0	3.2	2.9				2.5	2.2	2.5
					Elongation at Break (%)		550				500	580	490	450	450
Time (hours) required to reach 20 hardness		3.0	2.5	2.5				6.0	7.0	3.0
					Weather resistance		Not observed Cracking or melting Fused part				Not observed Cracking or melting Fused part	Not observed Cracking or melting Fused part	Not observed Cracking or melting Fused part	Not observed Cracking or melting Fused part	Observe to break Cracking or melting In part

^*◎ No residual tack ○ was observed, very slight residual tack △ was observed, slight residual tack x was observed

Examples C4-C8

A mixture containing the ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) having a hydrolyzable silyl group prepared in the above preparation example was prepared for each of examples C4 to C8. This mixture consisted of the following: 100 parts of copolymer rubber (A-1), 55 parts of diisodecyl phthalate (DIDP) as a plasticizer, 120 parts of surface-treated colloidal calcium carbonate as a filler, 20 parts of titanium oxide, 2 parts of aliphatic amide wax as an impregnation inhibitor, 1 part of an ultraviolet absorber, 1 part of a light stabilizer, 2 parts of vinyltrimethoxysilane as a viscosity stabilizer, 2 parts of acuring catalyst (NITTO KASEI, U-220), and a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule as a surface modifier shown in Table C2, all parts being by weight. Stirring each composition at room temperature; unlike the compositions prepared in examples C1-C3, they were dehydrated under vacuum and placed in a closed container

Each composition was spread to a thickness of 3 mm, cured at 23 ℃ and 55% relative humidity, and after 1 day, a total of 5 commercially available solvent-based acrylic coatings for industrial use were applied with a brush. After 7 days, the composition was evaluated by testing with cellophane tape (Nichiban) in a pattern of 25 meshes (2 mm squares) and by the percentage of the number of meshes remaining on the surface of the sealing material to the total number of meshes. The results are shown in Table C2.

Each composition was again tested for residual tack, tensile properties, cure speed and weatherability. The results are also shown in Table C2.

Comparative examples C3 and C4

Comparative examples C3 and C4 were carried out in the same manner as in example C4, except that N- (β -aminoethyl) - γ -aminopropyltrimethylsiloxydimethoxysilane (comparative example C4) was not used, or N- (β -aminoethyl) - γ -aminopropyltrimethylsiloxydimethoxysilane (comparative example C3) was replaced with 3 parts by weight of N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane (A-1120). The results are shown in Table C2.

TABLE C2

		Examples C4	Examples C5	Examples C6	Examples C7	Examples C8	Comparative example C3	Comparative example C4
									Additive agent	N- (β -aminoethyl) -gamma-aminopropyl Trimethylsiloxy dimethoxy silicon Alkane (I) and its preparation method	3			2.5	1.5
Gamma-aminopropyltrimethylsiloxy group Dimethoxysilane		3
								N, N-dimethyl-gamma-aminopropyl trimethyl Silyloxy dimethoxysilane				3
A-1120				3	3	3
								Paint adhesion (%)		98	85	100	86	80	0	0
Residual tackiness	After 1 day	◎	◎	◎	◎	◎	○										△
									After 2 days	◎	◎	◎	◎	◎	○	○
Stress at 100% elongation (MPa)		0.70	0.55	0.30	0.80	0.75	0.70										0.40
								Breaking Strength (MPa)		3.10	2.50	1.40	3.50	3.20	2.20	1.40
Elongation at Break (%)		630	750	950	560	590	430										570
								Time (hours) required to reach 20 hardness		2.5	3.0	3.5	3.0	3.0	6.0	7.0
Weather resistance		Not observed To melting In part	Not observed To melting In part	Not observed To melting In part	Not observed To melting In part	Not observed To melting In part	Not observed To melting In part										Not observed To melting In part

Example C9 and comparative example C5

A mixture of the ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) containing the hydrolyzable silyl group prepared in the above-mentioned production example was prepared for each of example C9 and comparative example C5. the mixture was composed of 100 parts by weight of the copolymer rubber (A-1), 2 parts by weight of a curing catalyst (NITTOKASEI, U-220) and N- (β-aminoethyl) - γ -aminopropyltrimethylsiloxysilane (example C9) or N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane (A-1120) (comparative example C5) as a surface modifier, each composition was stirred at room temperature, each composition was spread to a thickness of 3 mm, cured at 23 ℃ and 55% relative humidity, a total of 5 commercially available industrial use solvent-based coating materials were applied with a brush after 1 day, and after 7 days, a cellophane tape (Nichiban) was used to evaluate the percentage of the surface pattern on a grid number of 25 grids (2 mm) as shown in Table 3.

Each composition was tested for residual tack, tensile properties, cure speed and weather resistance as in the case of example C1. The results are also shown in Table C3.

TABLE C3

		Example C9	Comparative example C5
				Additive agent	N- (β -aminoethyl) amide Radical) -gamma-aminopropyl radical Trimethylsiloxy group Dimethoxysilane	3
A-1120		3
			Paint adhesion (%)			90	0
Residual tackiness	After 1 day	◎		△
			After 2 days		◎	○
	Tensile stress at 100% elongation (MPa)			0.40			0.50
Breaking strength (MPa)			0.52		0.58
		Elongation at Break (%)		220		150
Time required to reach 20 hardness					2.5		4
		Weather resistance		No cracking was observed		Cracking was observed

<example D series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

Production example

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 parts by weight of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% toluene solution of chloroplatinic acid (0.3 part by weight) and 1.5 parts by weight of methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 parts by weight of a compound containing dimethoxymethylsilyl (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Example D1

The copolymer prepared in the above preparation example was added to 100 g1.75 g of (CH) was incorporated in the rubber (A-1)₃)₃SiOC₆H₅The resulting mixture was stirred at 80 ℃ for 2 hours. Then 150 grams of a fatty acid (Shiraishi K.K., CCR) was added^TM) Treated colloidal calcium carbonate, 65 grams dioctyl phthalate, 1gram hindered phenolic antioxidant (Ouchishinsko Chemical Industrial Co., Nocrac NS-6)^TM) 3 g of tin octylate and 1 g of laurylamine, and the resultant mixture was kneaded thoroughly with a 3-roll coater.

The thus-prepared composition was used to form a H-2 type specimen (substrate: anodized alumina, undercoat: APZ-730 of Nippon Unicar) according to JIS A-5758, which was cured under the given conditions and its H-shape stretchability was measured by a tensile tester. Its tackiness was also tested by touching with a finger. The storage stability was evaluated from the viscosity (type B viscosity at 23 ℃ C., poise) ratio, i.e., the ratio of the viscosity of the composition stored at 50 ℃ for one week to the viscosity of the as-prepared composition. The results are shown in Table D1.

The curing speed and weather resistance of each composition were measured by the following methods. The results are shown in Table D1.

(1) Testing of curing speed

The curable composition was cured in a 20X 80X 5mm mold for 24 hours at 23 ℃ and 50% relative humidity.

Then, the cured product was taken out of the mold, and the thickness of the cured portion was measured with a micrometer having a weak spring force of 0.1mm to evaluate the curing speed, which was recorded as ○ when the thickness was not less than 1mm and as X when the thickness was less than 1 mm.

(2) Test of weather resistance

The weather resistance was measured under the following conditions in accordance with JIS B-7753:

an analyzer: sunshine Carbon Arc weather thermometer

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 250 hours

The weather resistance was evaluated by visually observing the surface aging (cracked and melted portions). the composition was marked ○ when no cracked or melted portions were observed and marked X when surface aging was observed.

The results are shown in Table D1, where M₁₅₀Is the modulus at 150% elongation of the specimen, T_BIs modulus of rupture, E_BIs elongation at break, the tack evaluation "A" is a tack comparable to that of the composition without organosilicon compound (comparative example D1), and "B" is a tack higher than that of the above composition. With respect to storage stability, the lower the number, the better the storage stability.

Comparative examples D1-D3

A composition of comparative example D1 was prepared in the same manner as in example D1, except that C was not used₆H₅OSi(CH₃)₃And tested in the same manner. The results are shown in Table D1.

Compositions of comparative examples D2 and D3 were prepared in the same manner as in example D1, except that the same amount of (CH) was used₃)₃SiOH or (C)₆H₅)₃SiOH replacing C₆H₅OSi(CH₃)₃And tested in the same manner. The results are also shown in Table D1.

TABLE D1

	Organosilicon compounds	Characteristics of
									H-shape stretchability			Viscosity of (touch)	Is stored stably Characterization of nature	Curing Speed of rotation	Weather resistance
		M150 (kg/cm) Rice and its production process2)	TB (kg- Centimeter2)	EB (kg/cm) Rice and its production process2)
					Practice of Example D1	(CH3)3SiOC6H5	2.6	6.0	720	A	1.01					○	○
Comparison Example D1	Is not used	5.3	7.7	320								A	1.25	○	○
					Comparison Example D2	(CH3)3SiOH	3.0	6.1	460	A	0.97					○	○
Comparison Example D3	(C6H5)3SiOH	2.5	5.8	690								B	0.97	○	○

The results shown in Table D1 demonstrate the inclusion of (CH)₃)₃The SiOH composition has excellent adhesion but low improvement in modulus and elongation, and contains (C)₆H₅)₃The SiOH composition has improved modulus and elongation but poor adhesion. On the other hand, Contains (CH)₃)₃SiOC₆H₅The composition of (A) has improved modulus and elongation and is excellent in adhesion.

Examples D2-D5, and comparative examples D4-D6

The compositions of the above examples were prepared in the same manner as in example D1, except that the organosilicon compound shown in Table D2 was used in place of C₆H₅OSi(CH₃)₃And tested in the same manner. The results are shown in Table D2, along with the results for the composition made in example D1.

TABLE D2

The results shown in Table D2 demonstrate that each of the compositions of the present invention is excellent in curing speed, modulus, tackiness, storage stability and weather resistance, while the composition using an organosilicon compound that generates a compound (e.g., ammonia or an amine) that functions as a silanol condensation catalyst is poor in storage stability.

Reference example D1

A composition was prepared in thesame manner as in example D1, except thatAlso, 100 g of the copolymer rubber (A-1) was replaced with a propylene oxide polymer containing 3 dimethoxysilyl groups represented by the following formula on average in the molecule and having an average molecular weight of 9,600, and the test was carried out in the same manner. The results are shown in Table D4.

Reference examples D2-D4

The composition of reference example D2 was prepared in the same manner as in example D1, except that C was not used₆H₅OSi(CH₃)₃And tested in the same manner. The results are shown in Table D3.

The compositions of reference examples D3 and D4 were prepared in the same manner as in example D1, except that the same amount of (CH) was used₃)₃SiOH or (C)₆H₅)₃SiOH replacing C₆H₅OSi(CH₃)₃And tested in the same manner. The results are also shown in Table D3.

TABLE D3

	Organosilicon compounds	Characteristics of
									H-shape stretchability			Viscosity of (touch)	Is stored stably Characterization of nature	Curing Speed of rotation	Weather resistance
		M150 (kg/cm) Rice and its production process2)	TB (kg- Centimeter2)	EB (kg/cm) Rice and its production process2)
					Reference to Example D1	(CH3)3SiOC6H5	2.5	5.8	710	A	0.92					○	×
Reference to Example D2	Is not used	5.2	7.6	340								A	1.22	○	×
					Reference to Example D3	(CH3)3SiOH	3.5	6.3	490	A	0.92					○	×
Reference to Example D4	(C6H5)3SiOH	2.5	5.9	680								B	0.92	○	×

Reference examples D5-D11

The compositions of the above examples were prepared in the same manner as in reference example D1, except that the organosilicon compounds shown in Table D4 were used in place of C₆H₅OSi(CH₃)₃And tested in the same manner. The results are shown in Table D4 together with those of the composition prepared in reference example D1.

TABLE D4

<example E series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

Each composition was tested for curing speed and accelerated weather resistance by the following methods.

(1) Testing of curing speed

(1A)

The frequency change of the composition in each cure was followed by a scanning VNC (SVNC, RPRA TECHNOLOGY LTD.). The frequency increased and became stable with time, and the frequency after stabilization was set to 100%, and the curing speed was 95% in accordance with the time required for the frequency change amount. The tests were carried out at room temperature according to the instructions described in the following manual:

(i) manuals for scanning, vibrating probe solidification tester (scanning VNC) vibration (software version 2.2) for RAPRA

(ii) RAPRA aware scanning, vibrating stylus solidification tester (scanning VNC) (RTL/2844)

(1B)

The curable composition (blank) was cured in a 20X 80X 5mm mould for 24 hours at 23 ℃ and 50% relative humidity.

Then, the cured product was taken out ofthe mold, and the thickness of the cured portion was measured with a micrometer having a weak spring force of 0.1mm to evaluate the curing speed, which was recorded as ○ when the thickness was not less than 1mm and as X when the thickness was less than 1 mm.

(2) Accelerated weathering test

The weather resistance was measured by a Sun Carbon Arc weatherometer in accordance with JIS B-7753.

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

Production example E1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization.The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) containing 68 mol% of ethylene, measured in decalin maintained at 135 ℃To obtain the intrinsic viscosity [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This is achieved by101.5 g of a compound containing dimethoxymethylsilyl groups (-SiCH) were produced₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example E2

[ production of silyl-containing vinyl Polymer]

340 g of xylene were charged into a reactor equipped with a stirrer, a thermometer, a nitrogen-supplying port, a dropping funnel and a condenser, and heated at 110 ℃.

Then, a solution of 140 g of styrene, 166 g of butyl acrylate, 467 g of methyl methacrylate, 100 g of stearyl methacrylate, 117 g of gamma-methacryloxypropyltrimethoxysilane, 10 g of N-methylolacrylamide, 30 g of gamma-mercaptopropyltrimethoxysilane and 30 g of azobisisobutyronitrile was continuously charged into the reactor over a period of 3 hours.

After the completion of the addition of the monomers, 3 g of azobisisobutyronitrile, which was separately prepared, was dissolved in 200 g of toluene, and the resulting solution was added to the above mixture for 1 hour, followed by 1 hour of polymerization to prepare a silyl group functionalized vinyl resin.

The silyl group functionalized vinyl resin solution thus prepared contained 65% of non-volatile substances. The number average molecular weight of this resin was 4,400 as determined by GPC.

Production example E3

[ production of reaction product of epoxy Compound and acid phosphate]

50 g of monobutyl phosphate having an acid value of 670 (Daihachi Kagaku, MP-4) was charged into a reactor equipped with a stirrer, a thermometer, a nitrogen supply port, a dropping funnel and a condenser, and 70.5 g of gamma-glycidoxypropyltrimethoxysilane was slowly added dropwise with stirring in a nitrogen atmosphere. After no further exotherm was observed, the reaction was continued by heating the mixture at 80 ℃ for a further 1 hour. The effluent was mixed with 12 g of methyl orthoacetate, 12 g of methanol and 96.5 g of xylene, and cooled to prepare a curing catalyst containing 50% of active component (curing catalyst 1).

Production example E4

[ production of copolymer containing acid phosphate]

In a reactor equipped with a stirrer, a thermometer, a nitrogen gas supply port, a dropping funnel and a condenser, 170 g of isopropyl alcohol and 170 g of butyl acetate were charged, and heated at 110 ℃.

Then, a solution of 200 g of styrene, 300 g of butyl acrylate, 380 g of methyl methacrylate, 100 g of α -acid phosphooxyethyl methacrylate (α -acid phosphoethyl methacrylate) (Daihachi Kagaku, MR-200), 20 g of acrylic acid and 30 g of azobisisobutyronitrile was continuously charged into the reactor for 3 hours.

After the addition of the monomers was completed, a solution of 3 g of azobisisobutyronitrile, whichwas separately prepared, dissolved in 200 g of butyl acetate was added to the above mixture for 1 hour, and polymerization was further carried out for 1 hour. An additional 350 grams of isopropanol was added to make a copolymer containing the acid phosphate ester, which contained 50% resin solids (curing catalyst 2).

Production example E5

138 g of 1, 9-decadiene were introduced into a pressure-resistant reactor, and 256 g of trimethoxysilane and 1.04 g of a 10% isopropanol solution of chloroplatinic acid were introduced under a nitrogen atmosphere and reacted with one another at 90 ℃ for 4 hours. The product was analyzed by infrared absorption spectroscopy once the reaction was complete. Allyl groups were found at 1640 cm^-1The absorption peak at (a) disappeared. Unreacted trimethoxysilane was distilled off under vacuum (5 torr) at 100 ℃ to obtain a liquid having (CH)₃O)₃Si(CH₂)₁₀Si(OCH₃)₃A silane compound (B-1) having the structure.

Production example E6

In a pressure-resistant reactor, 252 g of 1-octadecene were charged, and 142 g of trichlorosilane and 0.5 g of chloroplatinic acid in 10% isopropanol were added under a nitrogen atmosphere, and they were reacted with each other at 90 ℃ for 4 hours. The product was analyzed by infrared absorption spectroscopy once the reaction was complete. Allyl groups were found at 1640 cm^-1The absorption peak at (a) disappeared. Unreacted trichlorosilane was distilled off under vacuum (5 torr) at 100 ℃. 192 g of methanol were added to the effluent, treated under vacuum to remove the hydrogen chloride gas formed, and 100 g of methyl orthoformate was added at 60 ℃ for 2 hours for transesterification and treated under vacuum (5 torr) to distill the volatiles to obtain a methanol having (CH)₃O)₃Si(CH₂)₁₇CH₃A silane compound (B-2) having the structure.

Production example E7

In a pressure resistant reactor, 270 g of 1-octadecanol were charged, 14 g of hexane were added thereto, and the mixture was degassed at 90 ℃ for 1 hour under vacuum (5 torr) to remove water.

257 g of gamma-isocyanatopropyltriethoxysilane were added under nitrogen and reacted with one another at 90 ℃ for 2 hours and then at 110 ℃ for 1 hour. The product was analyzed by infrared absorption spectroscopy. Isocyanate is in 2270 cm^-1The absorption peak disappears and is 1530 cm^-1Where an absorption peak associated with the urethane bond was observed. Thus, it was judged that the silane compound (B-6) having the following structure was formed.

Production example E8

500 g of hydrogenated polybutadiene diol having a hydroxyl value of 63.6 (Nippon soda Co., Ltd., NISSO-PB GI-1000) was charged in a pressure-resistant reactor, 25 g of hexane was added thereto, and the mixture was degassed at 90 ℃ for 1 hour under vacuum (5 torr) to remove water.

Then, 126 g of a 28% methanol solution of sodium methoxide was added to the above composition, and the reactants were reacted with each other for 4 hours while distilling off methanol at 140 ℃ under vacuum. Then, 52.5 g of allyl chloride was added dropwise to the above system, and they were reacted at 110 ℃ for 2 hours. The effluent was distilled under vacuum at 110 ℃ to remove volatiles. After the effluent was cooled, 1.5 liters of hexane and 50 g of aluminum silicate were added thereto, allowed to stand, filtered through celite to remove salts, and distilled under vacuum to remove hexane, to obtain hydrogenated polybutadiene having allyl groups at both terminals.

Then, 300 g of the above product was charged in a pressure-resistant reactor, 15 g of hexane was added thereto, and the mixture was degassed at 90 ℃ under vacuum to remove water. Then, 49.9 g of trimethoxysilane and 0.21 g of a 10% isopropyl alcohol solution of chloroplatinic acid were added to the above composition, and they were reacted with each other at 90 ℃ for 4 hours.

Once the reaction was complete, the effluent was distilled under vacuum at 100 ℃ to remove volatiles. This produced a hydrogenated polybutadiene having trimethoxysilyl groups at both terminals (silane compound B-3).

Examples E1 to E7

Compositions of examples E1-E7 were prepared which contained the dimethoxymethylsilyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber prepared in preparation example E1. Other components were a silane compound (B) having a long chain of polyolefin prepared in one of preparation examples E5 to E8, a curing catalyst (C) prepared in preparation example E3 or E4, or a commercially available tin compound (dioctyltin maleate, Sakai Kagaku, TN801^TM). The compositions of the examples are shown in Table E1. It was diluted with xylene to give it sufficient viscosity for coating.

A coating film of a thermosetting resin was formed by the following method. Coated with a two-liquid type polyurethane surface coating (Isamu Toryo, Hiprisurf 2C)^TM) The mild steel plate was rubbed with #240 sandpaper, dried and then rubbed with #400 sandpaper, and a varnish of melamine acrylic resin (Kansai Paint co., ltd., magiclon m-77)^TM) And (4) coating. The coating film was baked at 150 ℃ for 30 minutes and treated with a medium beat compound to form a base (base).

The compositions prepared in each of examples E1 to E7 were formed into coatings by a usual method, andthen they were spray-coated with a coating film of a thermosetting resin, forcibly dried at 60 ℃ for 30 minutes, and allowed to stand at room temperature for 7 days to form cured coating films.

The adhesion was evaluated by placing a cellophane tape on a2 mm square grid pattern cut with a knife, and then removing the tape to visually observe the peeling of the surface.

Then, the sample was placed in a foaming test chamber, allowed to stand at 50 ℃ and 98% relative humidity for 3 days, and its adhesiveness was evaluated according to the standard provided by Nippon Paint, Inspection and Testing Association (10 th point: no peeling of the coating film, 0 th point: complete peeling of the coating film).

The results are shown in Table E1.

TABLE E1

	Examples
								E1	E2	E3	E4	E5	E6	E7
	Containing dimethoxysilyl groups EPDM(1)	100	100	100	100	100	100								100
Silane compounds with long polyolefin chains Thing (B) B-1 (preparation E5)								6.5	-	-	-	-	-	-
	B-2 (preparation E6)	-	6.5	-	-	6.5	6.5								6.5
B-3 (preparation E7)								-	-	6.5	-	-	-	-
	B-4 (preparation E8)	-	-	-	6.5	-	-								-
Curing catalyst (C) AP-8*								-	-	-	-	1	-	-
	Curing catalyst 1 (preparation example E3)	2	2	2	2	-	-								-
Curing catalyst 2 (preparation example E4)								-	-	-	-	-	10	-
	TN801**	-	-	-	-	-	-								2
Adhesive disposable								10	10	10	10	10	10	10
	Two times	10	10	10	10	10	10								10
Curing Rate (1A) [ Hr] (1B)								6 ○	7 ○	8 ○	9 ○	7 ○	8 ○	10 ○
	Weather resistance	A	A	A	A	A	A								A

AP-8 (trade name), Daihachi Kagaku, a mixture of dioctyl phosphate and monooctyl phosphate

TN801 (trade name), Sakai Kagaku, dioctyltin maleate

Evaluation of weather resistance: a: no cracking or melting of the part was observed, B: although slight, small cracks or melted portions were observed, C: cracked or fused portions were observed.

Comparative examples E1-E11

Compositions containing the silyl-containing vinyl resin prepared in production example E2 of comparative examples E1 to E11 were prepared. Other components were a silane compound (B) having a long chain of polyolefin prepared in one of preparation examples E5 to E8, a curing catalyst (C) prepared in preparation example E3 or E4, or a commercially available tin compound (dioctyltin maleate, Sakai Kagaku, TN801^TM). The compositions of the examples are shown in Table E1. It was diluted with xylene to make it sufficiently viscous for coating.

The adhesion of each composition was evaluated in the same manner as in example E1.

The results are shown in Table E2.

The curing speed and weather resistance of the compositions prepared in each of examples E1-E7 and comparative examples E1-E11 were tested according to the aforementioned methods.

The results are shown in tables E1 and E2.

TABLE E2

		Examples
													E1	E2	E3	E4	E5	E6	E7	E8	E9	E10	E11
		Vinyl containing silyl groups Base resin (preparation E2)		100	100	100	100	100	100	100	100	100												100	100
With long polyolefin chains Silane Compound (B) B-1 (preparation E5)													6.5	-	-	-	-	-	-	-	-	-	-
		B-2 (preparation E6)		-	6.5	-	-	6.5	6.5	6.5	-	-												-	-
B-3 (preparation E7)													-	-	6.5	-	-	-	-	-	-	-	-
		B-4 (preparation E8)		-	-	-	6.5	-	-	-	-	-												-	-
Curing catalyst (C) AP-8*													-	-	-	-	1	-	-	1	-	-	-
		Curing catalyst 1 Production example E3		2	2	2	2	-	-	-	-	2												-	-
Curing catalyst 2 Production example E4													-	-	-	-	-	10	-	-	-	10	-
		TN801**		-	-	-	-	-	-	2	-	-												-	2
Adhesion Property	At a time												10	10	10	10	9	8	8	1	2	0	0
		Two times	9	9	9	9	8	7	7	0	0	0												0
	Curing Rate Hr] (1A) (1B)												18 ×	20 ×	24 ×	22 ×	14 ×	16 ×	18 ×	24 ×	36 ×	20 ×	48 ×
Weather-resistant material			B	B	B	B	C	C	C	C	C	C												C

AP-8 (trade name), Daihachi Kagaku, a mixture of dioctyl phosphate and monooctyl phosphate

TN801 (trade name), Sakai Kagaku, dioctyltin maleate

Evaluation of weather resistance: a: no cracking or melting of the part was observed, B: although slight, small cracks or melted portions were observed, C: cracked or fused portions were observed.

<example F series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

The curing speed test and weather resistance test of examples and comparative examples were conducted by the following methods.

(1) Testing of curing speed

The curable composition (blank) was cured in a 20X 80X 5mm mould for 24 hours at 23 ℃ and 50% relative humidity.

Then, the cured product was taken out of the mold, and the thickness of the cured portion was measured with a micrometer having a weak spring force of 0.1mm to evaluate the curing speed, which was designated ◎ when the thickness was not less than 2 mm, △ when the thickness was 1 to 1.9 mm, and X when the thickness was less than 0.9 mm.

(2) Test of weather resistance

The weather resistance was measured by a Sun Carbon Arc weatherometer in accordance with JIS B-7753.

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

Production example F1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization carried out under the above conditions produces ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a mixture containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example F2

148 g of phthalic anhydride, 46.6 g of propylene oxide, 22.8 g of acryloyl glycidyl ether, 11.6 g of allyl alcohol and 0.5 g of dimethylbenzylamine were charged into a 1-liter metal autoclave, and they were reacted with each other at 100 ℃ for 3 hours, 46 g of propylene oxide was charged thereinto, and the reaction was continued for 1 hour. Then, excess propylene oxide was removed to obtain a polyester having a molecular weight of 1,200.

Then, 100 g of the polyester thus prepared was reacted with 9.5 g of acetic anhydride at 120 ℃ for 2 hours, and the hydroxyl groups in the polyester were treated after removing the excess acetic anhydride. Subsequently, 22.2 g of the polyester bearing the treated hydroxyl groups were reacted with 0.0035 g of chloroplatinic acid and 8.65 g of methyldichlorosilane at 80 ℃ for 3 hours. Excess methyldichlorosilane was removed under vacuum. Then, 20 ml of methanol and 20 ml of methyl orthoformate were added to the above effluent, and the mixture was stirred at room temperature under vacuum for 1 hour to remove low boiling substances. This gives a silyl-containing polyester.

Production example F3

A solution of 2 g of azobisisobutyronitrile dissolved in 30 g of styrene, 16 g of allyl methacrylate, 20 g of methyl methacrylate, 19 g of n-butyl methacrylate, 14 g of n-butyl acrylate, 1 g of acrylic acid and 2 g of n-dodecylmercaptan was added dropwise to 100 g of toluene as a solvent, and they were heated at 90 ℃ to react with each other for 10 hours, to obtain a vinyl polymer having a molecular weight of 8,000 and containing an allylic unsaturated group.

Infrared absorption peak of vinyl polymer 1648 cm^-1The carbon-carbon double bond at (A) is involved.

To 20 g of the vinyl polymer having an allylic unsaturated group thus prepared, 1.5 g of methyldimethoxysilane and 0.0005 g of chloroplatinic acid dissolved in isopropanol were added and they were reacted with each other at 90 ℃ for 6 hours under a sealed condition. In the infrared absorption spectrum chart, the product has no infrared absorption peak at 1648 cm<-1>. Thus, it was judged that a silyl group-containing vinyl polymer was produced.

Production example F4

A silyl-containing diallyl phthalate-based copolymer was prepared in the same manner as in preparation example F3, except that 16 g of allyl methacrylate was replaced with 31 g of diallyl phthalate.

Production example F5

A solution of 2 g of azobisisobutyronitrile dissolved in 30 g of styrene, 27 g of gamma-methacryloxypropyltrimethoxysilane, 20 g of methyl methacrylate, 19 g of n-butyl methacrylate, 14 g of n-butyl acrylate, 1 g of acrylic acid and 2 g of n-dodecylmercaptan was added dropwise to 100 g of toluene as a solvent and heated at 100 ℃ to obtain a vinyl polymer having a molecular weight of 9,000 containing silyl groups.

Production example F6

100 g of a diallyl phthalate prepolymer having an iodine value of about 80 (DAISO Co. Ltd., DAISO DAP L)^TM) 0.00001 g of chloroplatinic acid and 1 g of hydroquinone were dissolved in 100 ml of toluene, and 35 ml of methyldiethoxysilane was added to reactthem with each other at 90 ℃ for 3 hours to obtain a silyl group-containing diallyl phthalate prepolymer.

Production example F7

[ production of silyl-containing Polymer]

In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and N₂In a reactor having a gas supply port and a dropping funnel, 45.9 parts by weight of xylene in N was charged₂It was heated to 110 ℃ under a gas flow, and the following mixture (a) was added dropwise thereto at a constant rate through a dropping funnel for 5 hours:

a mixture (a); styrene 12.8 parts by weight of methyl methacrylate 50.1 parts by weight of stearyl methacrylate 6.9 parts by weight of gamma-methacryloxypropyltrimethoxysilane 30.2 parts by weight of xylene 13.5 parts by weight of 2, 2' -azobisisobutyronitrile 4.5 parts by weight

Once the addition of the above mixture (a) was completed, 0.5 parts by weight of 2, 2' -azobisisobutyronitrile and 5 parts by weight of toluene were further added at a constant rate for 1 hour. The resulting resin solution was solidified at 110 ℃ for 2 hours and cooled, to which xylene was added to adjust the solid content to 60%.

The characteristics of the resin solution A thus obtained are shown in Table F1.

Production example F8

[ production of acrylic resin for coating]

A resin solution B was produced in the same manner as in production example F7, except that 31.8 parts by weight of butyl acetate and 9.5 parts by weight of xylene were added, in place of the mixture (a), to which the following mixture (B) was added:

mixture (b) xylene 18.0 parts by weight of styrene 28.3 parts by weight of methyl methacrylate 6.9 parts by weight of n-butyl acrylate 47.6 parts by weight of methacrylic acid 0.3 parts by weight of 2-hydroxyethyl methacrylate 16.9 parts by weight of 2, 2' -azobisisobutyronitrile 1.8 parts by weight

Once the addition of the above mixture (b) was completed, 0.5 parts by weight of 2, 2' -azobisisobutyronitrile and 3.8 parts by weight of toluene were further added at a constant rate for 1 hour. The resulting resin solution was solidified at 110 ℃ for 2 hours and cooled, to which xylene was added to adjust the solid content to 60%.

The characteristics of the resin solution B thus obtained are shown in Table F1.

TABLE F1

	Resin solution A	Resin solution B
			Characteristics of Non volatile matter [% ]]	60	60
Viscosity (23 ℃ C.) (centipoise)	900	4400
			Acid number (KOH/g solid)	0	2.0
Hydroxyl number (KOH/g solid)	0	73
			Color number (Gardner)	＜1	＜1

Examples F1-F8, and comparative examples F1-F14

A mild steel plate as a sample substrate was degreased, rubbed with #240 sandpaper, coated with a polyurethane surface coating, and baked at 80 ℃ for 30 minutes. Then, the coated surface was rubbed with #600 sandpaper, coated with varnish (clear paint) of each of examples F1 to F8 and comparative examples F1 to F14 described in Table F2, and baked at 140 ℃ for 30 minutes to prepare a test piece.

After each sample was baked under the above conditions, it was allowed to stand at room temperature for 30 minutes. Their properties are shown in Table F2.

The following are the notes 1-4 in table F2:

*1: q-631 is a modified cycloaliphatic polyamine manufactured by Mitsui Chemicals, Inc.

*2: the hardness was measured in accordance with JIS K-5400.

*3: for the toluene dropping test, several drops of toluene were dropped on the coating film, and the coating filmwas observed after standing and drying at room temperature.

The resistance of the coating film to the solvent was evaluated according to the following four-stage system.

<four-stage System for evaluating solvent resistance>

◎ No change was observed at all on the surface of the coating film

○ No change was observed in the surface of the coating film

△ marks on the surface of the coating film

X: dissolution of coating film

*4: evaluation of weather resistance

A: no cracking or melting portions were observed.

B: although slight, small cracks or melted portions were observed.

C: cracked or fused portions were observed.

Watch F2(1)

	Examples
									F1	F2	F3	F4	F5	F6	F7	F8
	Composition [ parts by weight] Silyl group-containing copolymer Production example F1	100	100	100	100	100	100	100									100
Acrylic resin Production example F8									80	-	-	-	-	-	-	-
	Thermosetting acrylic coating (Belcoat No.5200)	-	80	-	-	-	80	-									80
Alkyd paint (Hariphthal SFC42-60X)									-	-	40	-	-	-	-	-
	Epoxy-based coating (Epikote 1001)	-	-	-	40	-	-	-									-
Organopolysiloxane (Z6018)									-	-	-	-	40	-	40	-
	Amines (B) Q-631 *1	-	-	-	-	-	2	2									-
Piperidine derivatives									-	-	-	-	-	-	-	3
	Monoethanolamine	2	2	2	2	2	-	-									-
Silane coupling agent (C) N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane									-	-	-	-	-	1	1	-
	Gamma-aminopropyltriethoxysilane	-	-	-	-	-	-	-									1.5
Gamma-mercaptopropionic acidTriethoxysilane									1	1	1	1	1	-	-	-
	Test of Hardness 2	3H	3H	3H	3H	3H	3H	3H									3H
Toluene drop test 3									○ to ◎	○ to ◎	○ to ◎	○ to ◎	○ to ◎	○ to ◎	○ to ◎	○ to ◎
	Curing speed (tension of coating film)	◎	◎	◎	◎	◎	◎	◎									◎
Weather resistance 4									A	A	A	A	A	A	A	A

TABLE F2(2)

	Comparative example
								F1	F2	F3	F4	F5	F6	F7
	Composition [ parts by weight] Silyl group-containing copolymer Production example F3
-								-	-	-	-	100	100
		Production example F4	-	-	-	-	-							-	-
Production example F5	100							100	100	100	100	-	-
		Acrylic resin Production example F8	80	-	-	-	-							-	-
Thermosetting acrylic coating (Belcoat No.5200)	-							80	-	-	-	80	-
		Alkyd paint (Hariphthal SFC42-60X)	-	-	40	-	-							-	-
Epoxy-based coating (Epikote 1001)	-							-	-	40	-	-	40
		Organopolysiloxane (Z6018)	-	-	-	-	40							-	-
Amines (B) Q-631*1	-							-	-	-	-	2	2
		Piperidine derivatives	-	-	-	-	-							-	-
Monoethanolamine	2							2	2	2	2	-	-
		Silane coupling agent (C) N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane	-	-	-	-	-							1	1
Gamma-aminopropyltriethoxysilane	-							-	-	-	-	-	-
		Gamma-mercaptopropyltriethoxysilane	1	1	1	1	1							-	-
Test of Hardness 2	2H							2H	2H	2H	2H	2H	2H
		Toluene drop test 3	○	○	○	○	○							○	○
Curing speed (tension of coating film)	×							×	△	△	△	×	×
		Weather resistance 4	B	B	B	B	B							B	B

Watch F2(3)

	Comparative example
								F8	F9	F10	F11	F12	F13	F14
	Composition [ parts by weight] Silyl group-containing copolymer Production example F2	-	-	-	-	-	-								100
Production example F3								-	-	-	-	-	-	-
	Production example F4	100	-	-	-	-	-								-
Production example F5								-	100	100	-	-	-	-
	Acrylic resin Production example F8	-	-	-	-	-	-								80
Thermosetting acrylic coating (Belcoat No.5200)								80	-	80	180	-	-	-
	Alkyd paint (Hariphthal SFC42-60X)	-	-	-	-	-	-								-
Epoxy-based coating (Epikote 1001)								-	-	-	-	140	-	-
	Organopolysiloxane (Z6018)	-	-	-	-	-	140								-
Amines (B) Q-631 *1								-	-	-	-	-	-	-
	Piperidine derivatives	3	-	-	-	-	-								-
Monoethanolamine								-	2	-	2	2	2	2
	Silane coupling agent (C) N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane	-	-	-	-	-	-								-
Gamma-aminopropyltriethoxysilane								1.5	-	-	-	-	-	-
	Gamma-mercaptopropyltriethoxysilane	-	1	-	1	1	1								1
Test of Hardness 2								2H	HB	6B	2H	2H	2H	3H
	Toluene drop test 3	○	△	×	○	○	○								○ to ◎
Curing speed (tension of coating film)								×	×	×	×	×	×	◎
	Weather resistance 4	B	C	C	B to C	B to C	B to C								C

Reference examples F1-F5, and reference comparative examples F1-F5

A mild steel plate as a sample substrate was degreased, rubbed with #240 sandpaper, coated with a polyurethane surface coating, and baked at 80 ℃ for 30 minutes. Then, the coated surface was rubbed with #600 sandpaper, coated with the varnishes of respective reference examples F1 to F5 and reference comparative examples F1 to F5 described in Table F3, and baked at 140 ℃ for 30 minutes to prepare test specimens.

After each sample was baked under the above conditions, it was allowed to stand at room temperature for 30 minutes. Their properties are shown in Table F3.

The following are notes 1-11 in table F3:

*1: thermosetting acrylic coating made by NOF corp.

*2: soybean fatty acid short oil type alkyd resin manufactured by Harima Chemicals.

*3: epoxy resins manufactured by Shell.

*4: organopolysiloxane manufactured by Dow Corning.

*5: dioctyltin maleate from Sakai Kagaku Kogyo.

*6: an amino group-containing silane coupling agent manufactured by UCC.

*7: an epoxy group-containing silane coupling agent manufactured by UCC.

*8: dioctyl acid phosphate manufactured by Daihachi Kagaku.

*9: hardness measured according to JIS K-5400.

*10: for the toluene dropping test, several drops of toluene were dropped on the coating film, and the coating film was observed after standing and drying at room temperature.

The resistance of the coating film to the solvent was evaluated according to the following four-stage system.

<four-stage System for evaluating solvent resistance>

◎ No change was observed at all on the surface of the coating film

○ No change was observed in the surface of the coating film

△ marks on the surface of the coating film

X: dissolution of coating film

*11: evaluation of weather resistance

A: no cracking or melting portions were observed.

B: although slight, small cracks or melted portions were observed.

C: cracked or fused portions were observed.

Watch F3(1)

	Reference example
						F1	F2	F3	F4	F5
	Composition [ parts by weight] Silyl group-containing copolymer Production example F7	100	100	100	100						100
Acrylic resin production example F8						80	-	-	-	-
	Thermosetting acrylic coating (Belcoat No.5200，Clear S)*1	-	80	-	-						-
Alkyd paint (Hariphthal SFC42-60X)*2						-	-	40	-	-
	Epoxy-based coating (Epikote 1001)*3	-	-	-	40						-
Organopolysiloxane (Z6018)*4						-	-	-	-	40
	Curing catalyst TN801*5	4	4	-	-						-
A-1120*6						1	1	-	-	-
	A-187*7	1	1	-	-						-
DP-8*8						-	-	1	1	1
	N, N-dimethyl-N-dodecylamine	-	-	1	1						1
Test for Test (experiment) Hardness 9						2H	2H	2H	2H	2H
	Toluene drop test 10	○	○	○	○						○
Curing speed (tension of coating film)						×	×	×	×	×
	Weather resistance of 11	B	B	B	B						B

TABLE F3(2)

	Reference comparative example
						F1	F2	F3	F4	F5
	Composition [ parts by weight] Silyl group-containing copolymer Production example F7	100	100	-	-						-
Acrylic resin production example F8						-	80	-	-	-
	Thermosetting acrylic coating (Belcoat No.5200，Clear S) *1	-	-	180	-						-
Alkyd paint (Hariphthal SFC42-60X)*2						-	-	-	-	-
	Epoxy-based coating (Epikote 1001)*3	-	-	-	140						-
Organopolysiloxane (Z6018)*4						-	-	-	-	140
	Curing catalyst TN801*5	4	-	4	-						-
A-1120*6						1	-	1	-	-
	A-187*7	1	-	1	-						-
DP-8*8						-	-	-	1	1
	N, N-dimethyl-N-dodecylamine	-	-	-	1						1
Test for Test (experiment) Hardness 9						HB	6B	2H	2H	2H
	Toluene drop test 10	△	×	○	○						○
Curing speed (tension of coating film)						×	×	×	×	×
	Weather resistance of 11	C	C	C	C						C

<example G series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

Production example

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously discharged from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 parts by weight of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% toluene solution of chloroplatinic acid (0.3 part by weight) and 1.5 parts by weight of methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. Distilled offExcess methyldimethoxysilane and solvent (toluene) in the effluent. This gave 101.5 parts by weight of a compound containing dimethoxymethylsilyl (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Examples G1 to G8, and reference example G1

A mixture containing the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer prepared in the preparation example was prepared in each of the above examples. It consists of the following substances: 100 g of copolymer rubber (A-1), 120 g of calcium carbonate as filler (Shiraishi K.K., CCR)^TM) 20 grams of titanium dioxide (Ishihara Sangyo kaisha. ltd., R820)^TM)2 g of dibutyltin diacetylacetonate (NITTO KASEI, U-220) as a curing accelerator^TM) 50G of the paraffinic Process oils of examples G1-68 and reference G1 as plasticizers (Idemitsu Kosan, Diana Process Oil PW-380)^TM) 2G of a monovalent silanol compound as shown in Table G1, and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane (H) as trifunctional and difunctional aminosilane compounds₂NCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃) And N- (β -aminoethyl) -gamma-aminopropylmethyldimethoxysilane (NH)₂CH₂CH₂NHCH₂CH₂CH₂Si(CH₃)(OCH₃)₂) (the amounts are shown in Table G1). Filling with 3-applicator roll deviceThe components were kneaded, mixed, and put into an H-shaped test piece prepared in accordance with JIS A-5758 to determine its tensile characteristics, adhesive strength and weather resistance (weather resistance) of adhesive strength when the test piece is exposed to light. It was also analyzed for curing speed and weather resistance (ozone-induced aging test). The results are shown in Table G1. The following test methods were used.

(tensile Property)

The thus-prepared composition was put into an H-shaped test piece (substrate: anodized alumina) prepared in accordance with JIS A-5758 and cured at 23 ℃ and a relative humidity of 60% for 14 days. The cured product was further cured at 30 ℃ for 14 days, and a tensile test was conducted at a rate of 30 mm/min.

(adhesive Strength)

The samples that broke in the tensile test were observed for failure. When the cured product itself was broken (cohesive failure, CF), it was judged that its adhesive strength to the substrate was high, and when the cured product and the substrate were separated from each other at the adhesive interface, it was judged that the adhesive strength was low (adhesive failure, AF).

(weather resistance adhesion)

An H-shaped test piece (substrate: glass) was prepared in accordance with JIS A-5758, and subjected to an accelerated exposure test with a Sunshine weatherometer (Sugashikenki, WEL-3-HC) for 480 hours and a tensile test with an Autograph (Shimadzu, IS-5000).

(curing speed test)

The curable composition was cured in a 20X 80X 5mm mold for 24 hours at 23 ℃ and 50% relative humidity.

Then, the cured product was taken out of the mold, and the curing speed was evaluated by measuring the thickness of the cured portion with a micrometer having a weak spring force of 0.1mm, which was designated as ○ when the thickness was more than 1mm, △ when the thickness was 0.5 to 1mm, and x when the thickness was less than 0.5 mm.

(weather resistance test)

An accelerated weather resistance test was carried out under the following conditions in accordance with JIS B-7753.

An analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The test specimen after the test was visually evaluated for weather resistance according to the following four grades:

◎ No cracking or melting part observed

○ although slight, cracked or melted portions were observed

△ some degree of cracking or melting of the parts was observed

X: severe cracking or melting of the parts was observed

Table G1

In the table, "-" was used for a sample in which the composition was separated from the substrate and the properties of the cured product itself could not be measured.

The results of a comprehensive evaluation of the compositions prepared in examples G1-G8 and reference example G1 are given in Table G2, where those with good properties are denoted ○, those without are denoted x, and those between are denoted △.

Table G2

	Monovalent silanol group Compound (I)	Trifunctional aminosilanes (grams)	Modulus of elasticity	Bonding Strength of	Weather-resistant adhesive Compatibility of the materials	Curing Speed of rotation	Weather-proof Property of (2)
								Bifunctional aminosilanes (grams)
		Example G1							Use of	0.5/3.0	○	○	○	○	○
Example G2	Use of		1.0/3.0	○	○	○	○	○
		Example G3							Use of	0.5/3.0	○	○	○	○	○
Example G4	Is not used		0.5/3.0	△	○	○	△	△
		Example G5							Use of	3.0/0	×	○	○	△	△
Reference example G1	Use of		0/3.0	○	○	×	△	△
		Example G6							Use of	0/0	×	×	×	△	△
Example G7	Is not used		0/3.0	×	×	×	△	△
		Example G8							Is not used	3.0/0	×	×	×	△	△

Comparative production example

In a pressure resistant reactor equipped with a stirrer, 800 g of a 97% polyoxypropylene-based polymer having allyl ether groups at the total terminals and an average molecular weight of about 8,000 was charged, and 19 g of methyldimethoxysilane was added to the mixture. Then, the mixture was mixed with 0.34 ml of 8.9 g of chloroplatinic acid (H)₂PtCl₆·6H₂O) was dissolved in 18 ml of isopropanol and 160 ml of tetrahydrofuran and allowed to react with each other at 80 ℃ for 6 hours.

Quantitative analysis by IR spectrum showed that almost no silicon hydride groups remained in the reaction solution. The reactive silicon group was quantitatively analyzed by NMR, and it was confirmed that the resulting polyoxypropylene polymer (CA-1) had an average of about 1.7 terminal groups of the group represented by the following formula in one molecule.

Reference examples G2-G10

Curable compositions of reference examples G2 to G10 were each prepared in the same manner as in examples G1 to G8 and reference example G1, except that the polymer (CA-1) prepared in comparative production example was used in place of the silyl-containing ethyleneAn olefin/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared by substituting a polyoxypropylene having an allyl ether group at the terminal, Mn of 5,200 and Mw/Mn of 1.6 for reference examples G2-G3 and G5-G10 or a 2-ethylhexyl phthalate (Daihachi Kagaku) for reference example G4 in place of a paraffin Process Oil (Idemitsu Kosan, Diana Process Oil PW-380) as a plasticizer^TM). The properties of these compositions were evaluated. The results are shown in Table G3.

Table G3

In the table, the values in the parentheses () are for the samples in which the composition was separated from the substrate at the adhesion interface and thus the properties of the cured product itself could not be measured.

The results of a comprehensive evaluation of the compositions prepared in examples G2-G10 are shown in Table G4, wherein those with good properties are denoted ○, none are denoted x, and those between are denoted △.

Table G4

		Monovalent silanols Class I Compound (I)	Trifunctional aminosilanes (g)	Modulus of elasticity	Adhesive strength	Weather-resistant adhesive Compatibility of the materials	Speed of curing	Weather resistance
									Difunctional aminosilanes (g)
			Reference example G							2	Use of	0.1/2.0	○	○	○	×	×
3	Use of	0.5/2.0		○	○	○	×	×
									4	Use of	0.5/2.0	○	○	○	×	×
5	Is not used	0.5/2.0		×	○	○	×	×
									6	Use of	2.0/0	×	○	○	×	×
7	Use of	0/2.0		○	○	×	×	×
									8	Use of	0/0	-	×	×	×	×
9	Is not used	0/2.0		×	○	×	×	×
									10	Is not used	2.0/0	×	○	○	×	×

<example H series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

Production example

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 parts by weight of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% toluene solution of chloroplatinic acid (0.3 part by weight) and 1.5 parts by weight of methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 parts by weight of a compound containing dimethoxymethylsilyl (-SiCH)₃(OCH₃)₂) Ethylene/propylene/5-ethaneAn alkenyl-2-norbornene random copolymer rubber (A-1).

Example H1 and comparative example H1

Using the silyl group functionalized ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in the production example, a one-liquid type curable composition was prepared, and its storage stability and weatherresistance of the cured product were evaluated. Their compositions are shown in Table H1 (parts by weight), and the evaluation results are shown in Table H2.

Evaluation was carried out by the following method.

(viscosity and curing speed (tack free time))

These were carried out according to JIS A-5758.

(curing speed test)

The curable composition was cured in a 20X 80X 5mm mold for 24 hours at 23 ℃ and 50% relative humidity.

Then, the cured product was taken out of the mold, and the curing speed was evaluated by measuring the thickness of the cured portion with a micrometer having a spring force as weak as 0.1mm, wherein the thickness was ○ when the thickness was not less than 1mm and X when the thickness was less than 1.0 mm.

(weather resistance test)

An accelerated weather resistance test was carried out under the following conditions in accordance with JIS B-7753.

An analyzer: sun Garbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The test piece after the visual inspection was evaluated for weather resistance according to a two-stage system of ○: no crack or molten portion observed, x: crack or molten portion observed.

(storage stability)

The storage stability of the curable composition was evaluated from the viscosity, i.e., the ratio of the viscosity of the composition after storagein a nitrogen-purged container at 50 ℃ for 4 weeks to the viscosity of the composition immediately after preparation.

The closer the ratio of the composition is to 1, the better its storage stability is.

Reference examples H1-H3

Using a compound having about 2 dimethoxymethylsilyl groups (-Si (CH) in the molecule₃)(OCH₃)₂) And oxypropylene having an average molecular weight of 9,000 (KANEKA CORP., MS Polymer, hereinafter referred to as CA-1) and polyoxypropylene having about 1.5 dimethoxysilyl groups in the molecule and an average molecular weight of 8,000 (KANEKACORP., MS Polymer, hereinafter referred to as CA-2) were prepared into one-liquid type curable compositions of each of reference examples H1-H3 and evaluated in the same manner as in example H1. Their compositions are shown in Table H1 (parts by weight), and their evaluation results are shown in Table H2.

TABLE H1

		Examples	Comparative example	Reference example	Reference example	Reference example
								Components	H1	H1	H1	H2	H3
Polymer rubber	A-1	100	100	0	0	0
							CA-1	0	0	50	50	50
	CA-2	0	0	50	50	50
							Filler material	Colloidal calcium carbonate	120	120	120	120	120
Titanium oxide	20	20	20	20	20
						Plasticizer		Paraffin oil	50	50	50	50	50
Dehydrating agent	VTMO*4	3	3	3	3		3
						Tackifier		DAMO*5	2	2	2	2	2
Curing catalyst	U-220*6	1	1	1	1		1
						Organic carboxylic acids		2-BAcetic acid anhydride	0.2	0	0.2	0	0
Stearic acid	0	0	0	0.4	0

^*1 CALFORT-S(STURGE)^*2 TIOFWE R85(TDF)^*3 Paraffin Oil (Idemitsu Kosan, Diana Process Oil PW-3)^TM)^*4 DYNASYLAN VTMO(Huls)^*5 DYNA SYLAN DAMO(Huls)^*6 Dibutyltin diacetylacetate (NITTO KAGAKU)

TABLE H2

	Characteristics of	Example H1	Comparative example H1	Reference example H1	Reference example H2	Reference example H3
							Immediately after the sample is prepared	Viscosity (poise)	12000	11000	13000	11000	9500
Tack free time (hours)	4	2.5	5.5	4.5	2.5
						Speed of curing		○	○	○	○	○
Weather resistance	○	○	×	×	×
						Samples were at 50 deg.C After storing for 4 weeks		Viscosity (poise)	14000	15000	13000	13000	13000
Tack free time (hours)	4	8	5.5	5.0	＞10
							Speed of curing	○	○	○	○	×
Weather resistance	○	○	×	×	×
							Storage stability	Viscosity ratio	1.17	1.36	1.18	1.18	1.37

<example J series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and reference examples were determined by the aforementioned methods.

The curing speed and accelerated weather resistance of the examples and the reference examples were tested by the following methods.

(1) Curing speed test

The curable composition (blank) was cured in a 20X 80X 5mm mould for 24 hours at 23 ℃ and 50% relative humidity.

Then, the cured product was taken out of the mold, and the curing speed was evaluated by measuring the thickness of the cured portion with a micrometer having a weak spring force of 0.1mm, wherein the thickness was ○ when the thickness was not less than 1mm and X when the thickness was less than 1 mm.

(2) Accelerated weather resistance test

Weather resistance test was carried out in accordance with JIS B-7753 using a Sun Carbon Arc weatherometer.

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

And (3) performance measurement: in accordance with JIS K-6301

Production example J1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) contains68 mol% ethylene, intrinsic viscosity measured in decalin maintained at 135 ℃ [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a compound containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example J2

0.2 mol of methyl methacrylate, 0.086 mol of allyl methacrylate and 5 g of n-dodecylmercaptan were dissolved in 70 ml of toluene, 0.5 g of azobisisobutyronitrile was added thereto, and they were allowed to react with each other at 80 ℃ for 4 hours (the toluene solution was directly used for the subsequent hydrosilylation reaction). The solvent was distilled off under vacuum to obtain an acrylic polymer having a molecular weight of about 2,000 and containing an allylic unsaturated group.

Analysis of the far infrared absorption spectrum shows that the acrylic polymer prepared from the acrylic polymer is 1648cm^-1Has an absorption peak related to carbon-carbon double bond at 1730 cm^-1There is a strong absorption peak associated with the ester.

Production example J3

0.2 mol of methyl methacrylate, 0.086 mol of allyl acrylate and 5 g of n-dodecylmercaptan were dissolved in 70 ml of toluene, and 0.5 g of azobisisobutyronitrile was added thereto, and they were reacted with each other at 80 ℃ for 4 hours. This produces an acrylic polymer having a molecular weight of about 2,000 and containing allylic unsaturation.

Analysis of the far infrared absorption spectrum shows that the acrylic polymer prepared from the acrylic polymer is 1648cm^-1There is an absorption peak associated with the carbon-carbon double bond.

Productionexample J4

0.1 mol of methyl methacrylate, 0.1 mol of styrene, 0.86 mol of allyl methacrylate and 5 g of n-dodecylmercaptan were dissolved in 70 ml of toluene, and 0.5 g of azobisisobutyronitrile was added thereto, and they were reacted with each other at 80 ℃ for 4 hours. This produced a vinyl copolymer having a molecular weight of about 2,000.

Analysis of the far infrared absorption spectrum showed that the copolymer produced thereby was found to be 1648cm^-1There is also an absorption peak associated with the carbon-carbon double bond.

Example J1

A mixture composed of 100 parts by weight of the ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) containing a hydrolyzable silyl group prepared in production example J1, 10 parts by weight of methanol (B-1) and 4 parts by weight of methyl orthoformate (B-2) was stirred 3 times at a speed of 10,000 rpm by a homogenizer (Nihon Seiki Sesakusho Co., Ltd., excel autohomogenizer) for 10 minutes each to prepare a composition. It was diluted to 35% with toluene and incorporated with 2,000ppm of moisture, and then tested for its storage stability at room temperature. The results of the samples after 3 weeks of storage are shown in table J2.

Reference example J1

To a toluene solution of 20 g of the acrylic polymer prepared in preparation example J2, 1.6 ml of methyldichlorosilane and 0.00001 g of chloroplatinic acid were added, and they were reacted with each other at 90 ℃ for 3 hours under a closed condition. 5 ml of methanol and 5 ml of methyl orthoformate were added to the effluent, and the mixed solution was stirred continuously until the solution became neutral.

The infrared absorption spectrum of the hydrosilylation product is 1648cm^-1The infrared absorption peak at (a) completely disappeared.

The results of gas chromatography analysis of the polymer solution are shown in Table J1.

TABLE J1

Results of gas chromatography analysis of Polymer solution
		Methyltrimethoxysilane	3.8％
Ortho-formic acid methyl ester	5.0％
		Methanol	10.5％

The polymer solution thus prepared was diluted to 35% with toluene and incorporated with 2,000ppm of moisture, and then tested for its storage stability at room temperature. The results of the samples after 3 weeks of storage are shown in table J2.

TABLE J2

	Viscosity (23 ℃ C.; centipoise)		Change in viscosity (21 days/initial)
				Initial	After 21 days
	Example J1	300				520	1.7
Reference example J1			10	21	2.1

*: the viscosity is measured with a B-type viscometer at 23 DEG C

As shown in table J2, the compositions prepared in example J1 and reference J1 have good storage stability.

Reference example J2

The hydrosilylation reaction was carried out in the same manner as in reference example J1, except that 1.8 ml of methyldiethoxysilane was used instead of 1.6 ml of methyldichlorosilane. 1648cm in the infrared absorption spectrum of the hydrosilylation product^-1The infrared absorption peak at (E) also disappeared completely, and it was judged that the silyl group functionalized acrylic polymer was produced.

Reference examples J3 and J4

The hydrosilylation reactions of each of the above examples were carried out in the same manner as in referential example J1, except that the copolymer rubber (a-1) was replaced with the polymer produced in each of production examples J3 and J4 to produce a resin curable at ordinary temperature.

Reference examples J5-J8

To 100 parts by weight of each of the resins prepared in referential examples J1 to J4, 2 parts by weight of dibutyltin maleate was added, and each composition was spread on a mild steel plate to evaluate its ability to form a coating film and other characteristics. The results are shown in Table J3.

TABLE J3

Resin composition	Tack free time [ min ] Clock (CN)]	Time for sample to stand Hour (h)]	Surface gloss
				Example J1	20	48	Superior food
Reference example J1	30	48	Superior food
				**	35	48	Superior food
Reference example J2	40	48	Superior food
				Reference example J3	30	48	Superior food
Reference example J4	45	72	Superior food

*: standing at 25 deg.C and RH 70%

**: resin prepared in reference example J1 further incorporating 30% by weight of ethyl silicate

Further, the curing speed and the weather resistance of the cured product of each of the compositions prepared in example J1 and reference examples J5 to J8 were tested in accordance with the following methods. The results are shown in Table J4.

TABLE J4

	Speed of curing	Weather resistance
			Example J1	○	No cracking was observed
Reference example J5	×	Slight cracking was observed
			Reference example J6	×	Slight cracking was observed
Reference example J7	×	Slight cracking was observed
			Reference example J8	×	Slight cracking was observed

<example K series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and reference examples were determined by the aforementioned methods.

The curing speed and accelerated weather resistance of the examples and the reference examples were tested by the following methods.

(1) Curing speed test

The curable composition (blank) was cured in a 20X 80X 5mm mould for 24 hours at 23 ℃ and 50% relative humidity.

Then, the cured product was taken out of the mold, and the curing speed was evaluated by measuring the thickness of the cured portion with a micrometer having a weak spring force of 0.1mm, wherein the thickness was ○ when the thickness was not less than 5mm and X when the thickness was less than 5 mm.

(2) Accelerated weather resistance test

Weather resistance test was carried out in accordance with JIS B-7753 using a Sun Carbon Arc weatherometer.

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

Production example K1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5Continuously carrying out the ternary polymerizationShould be used.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a compound containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example K2

[ production of saturated Hydrocarbon Polymer]

A1 liter pressure-resistant glass autoclave equipped with a stirring blade, a three-way cock and a vacuum line was charged with 7.5 mmol of p-DCC represented by the following formula Compound A. The autoclave was then purged with nitrogen.

Then, 330 ml of toluene dried with molecular sieves and 141 ml of hexane were added as a solvent by a syringe to the autoclave, and then 3 mmol of α -methylpyridine was added while supplying nitrogen through one side of the three-way cock.

Next, a pressure-resistant liquefied gas collecting tube made of glass equipped with a needle valve and containing 113 g of isobutylene was passed through a column equipped with barium oxide for dehydration and connected to a three-way cock. The autoclave was then used as a polymerization reactor, immersed in a dry ice/acetone bath maintained at-70 ℃, and the solution was allowed to cool for 1 hour with internal stirring. After cooling, the polymerization reactor was evacuated by a vacuum line, and isobutylene was fed from a liquefied gas collecting tube by opening a needle valve. Thereafter, the inside of the reactor was returned to normal pressure by introducing nitrogen gas through the three-way cock.

After confirming that the inside of the reactor was maintained at-70 deg.C, byThe polymerization reactor was filled with 7.18 g (3.8 mmol) TiCl using a three-waystopcock syringe₄The polymerization is initiated. After 2 hours, 2.57 g (22.5 mmol) of allyltrimethylsilane were added to the reactor. The reaction was further carried out for 1 hour, and water was added to the reaction mixture to deactivate the catalyst. Then, the organic layer was washed three times with pure water, and after removing water, the solvent was distilled off under vacuum, which yielded an isobutylene polymer having allyl terminal groups.

Compound a is represented by the following structural formula:

then, 100 g of an isobutylene polymer having an allyl terminal was dissolved in 50 ml of n-heptane, the solution was heated to about 70 ℃ and 1.2[ eq/allyl group]was added to the solution]Methyldimethoxysilane and 1X 10^-4[ equivalent/allyl group]]Platinum (vinylsiloxane) complexes for carrying out hydrosilylation reactions. The reaction course was followed by FT-IR at 1640cm for determining the production of olefins^-1After the absorption peak disappeared, the reaction was stopped at about 4 hours.

The reaction solution was concentrated under vacuum to give an isobutylene polymer having silicon reactive at both terminal groups represented by the following formula:

the polymer yield was estimated from the production. The number average molecular weight (Mn) and Mw/Mn were also analyzed by GPC, and measured by proton correlation with each structure¹H-NMR-analysis the intensities of resonance signals (proton from initiator: 6.5-7.5ppm, methyl proton from polymer end group attached to silicon atom: 0.0-0.1ppm, and methoxy proton: 3.5-3.4) were compared with each other to analyze the end group structure. The polymer had Mn of 11,416, Mn/Mw of 1.47 and Fn (silyl) of 1.95 (number average molecular weight is relative to standard polystyrene molecular weight, Fn (silyl) is the number of terminal silyl functional groups in one isobutylene polymer molecule).

Example K1

Preparation of an ethylene/propylene copolymer containing silyl groups prepared in preparation K15-vinyl-2-Ice-falling substanceA mixture of the flat olefin random copolymer rubber (A-1). It consists of the following substances: 100 parts of copolymer rubber (A-1) and 90 parts of paraffin Process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO 320B)^TM) 50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of talc (Maruo Calcium, LMR)^TM) 1 part of an antiaging agent 1 (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of another aging inhibitor as aging inhibitor 2 (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of an anti-aging agent 3 and an anti-aging agent (Sankyo, Sanol LS-765)^TM) 3 parts of light stabilizer (Sanshin KagakuKogyo, Sandant NBC)^TM) 3 parts of a photocurable resin (TOAGOSEI, Aronix M-400)^TM) 5 parts of thixotropic agent (Kusumoto Kasei, Disparlon # 305)^TM) And 4 parts of gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, Y-9030) as a silane coupling agent^TM) All parts are by weight. The main component of reference example K1 was prepared by kneading the mixture well with a 3-paint roll unit.

The curing agent of example K1 was prepared by the following method: in the disposable cup, a mixture comprising: 4 parts of dibutyltin acetylacetonate (NITTO KASEI, U-220) as a silanol condensing catalyst^TM) 4 portions of mirabilite (Na)₂SO₄·10H₂O), 10 parts of paraffin process Oil (Idemitsu Kosan, DianaProcess Oil PS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) The mixture was stirred 3 times by weight for 10 minutes at 10,000 rpm using a homogenizer (Nihon Seiki sesakusho co., ltd. excel autohomogenizer).

The above composition placed in a sealed glass bottle was stored in a good oven maintained at 50 ℃ for one month, and the viscosity of the main component was measured.

The viscosity was measured at 23 ℃ by a viscometer type B (Tokyo Keiki, type BS) using a No. 7 spindle.

Its viscosity was measured at 10rpm as 8,525 poise immediately after preparation and 9,020 poise also after storage at 10 rpm.

Reference examples K1 and K2

A mixture containing the polymer prepared in preparation K2 was prepared for reference examples K1 and K2. It consists of the following substances: 100 parts of polymer, 90 parts of paraffin process oil (Idemitsu Kosan, DianaProcess OilPS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO 320B)^TM) 50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of talc (Maruo Calcium, LMR)^TM) 1 part of an antiaging agent 1 (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of another aging inhibitor as aging inhibitor 2 (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of an anti-aging agent 3 and an anti-aging agent (Sankyo, Sanol LS-765)^TM) 3 parts of light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC)^TM) 3 parts of a light-curable resin (TOAGOSEI,Aronix M-400^TM) 5 parts of thixotropic agent (Kusumoto Kasei, Disparlon # 305)^TM) And 4 parts of gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, Y-9030) as a silane coupling agent^TM) All parts are by weight. The main component of reference example K1 was prepared by kneading the mixture well with a 3-paint roll unit.

The curing agent of example K1 was prepared by the following method: in the disposable cup, a mixture comprising: 4 parts of dibutyltin acetylacetonate (NITTO KASEI, U-220) as a silanol condensing catalyst^TM) 4 portions of mirabilite (Na)₂SO₄·10H₂O), 10 parts of paraffin process Oil (Idemitsu Kosan, DianaProcess Oil PS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) All parts by weight were measured using a homogenizer (Nihon Seiki sesakusho Co., Ltd. excel)Autohomogenizer) the mixture was stirred 3 times for 10 minutes at 10,000 rpm.

The main component and the curing agent used in referential example K2 were prepared in the same manner as in referential example K1, except that 4 parts of Natrii sulfas (Na) was added to the former₂SO₄·10H₂O) and omitted from the latter, the compositions produced were tested in the same way.

Each of the above compositions placed in a sealed glass bottle was stored in a good oven maintained at 50 ℃ for one month, and the viscosity of the main component was measured.

The viscosity was measured at 23 ℃ by a viscometer type B (Tokyo Keiki, type BS) using a No. 7 spindle.

The viscosity of these compositions was measured immediately after their preparation at 10rpm as 7,632 poise (reference K1) and 8,928 poise (reference K2), respectively, and after storage, also at 10rpm, as 9,072 poise and above 12,000 poise (over a measurable range). This result indicates that the main component has a higher viscosity when incorporated into a hydrate of the metal salt than when not incorporated, and the viscosity increases when the main component is stored.

Example K2

A mixture containing the ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example K1 was prepared. It consists of the following substances: 100 parts of copolymer rubber (A-1) and 90 parts of paraffin Process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO 320B)^TM) 50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of talc (Maruo Calcium, LMR)^TM) 1 part of an antiaging agent 1 (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of another aging inhibitor as aging inhibitor 2 (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of an anti-aging agent 3 and an anti-aging agent (Sankyo, Sanol LS-765)^TM) 3 parts of light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC)^TM) 3 parts of a photocurable resin (TOAGOSEI, Aronix M-400)^TM) 5 parts of thixotropic agent (KusumotoKasei, Disparlon # 305)^TM) 4 portions of gamma-isocyanate propyl triethoxy as a silane coupling agentSilane (Nippon Unicar, Y-9030)^TM) And 2 parts of gamma-glycidoxypropyltrimethoxysilane (Nippon unicar, A-187)^TM) All parts are by weight. The mixture was well kneaded by a 3-roll coater (3-paintroll unit) to prepare the main component of referential example K2.

The curing agent of example K2 was prepared by the following method: in the disposable cup, a mixture comprising: 4 parts of dibutyltin acetylacetonate (NITTO KASEI, U-220) as a silanol condensing catalyst^TM) 4 portions of mirabilite (Na)₂SO₄·10H₂O), 10 parts of paraffin process Oil (Idemitsu Kosan, DianaProcess Oil PS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM)The mixture was stirred 3 times by weight for 10 minutes at 10,000 rpm using a homogenizer (Nihon Seiki sesakusho co., ltd. excel autohomogenizer).

The above composition, placed in a sealed glass bottle, was stored for one month in a good oven maintained at 50 ℃, and its adhesion to the respective substrate and its mechanical properties were measured as a function of time, immediately after the preparation and after the storage. The results are shown in tables K1 and K2.

Preparing a sample for a tensile test according to JIS A-5758/1992 which specifies a method for preparing a tensile test sample; the composition comprising the main component and the curing agent in the given weight ratio was well kneaded, and it was placed in an H-shaped glass or aluminum substrate and cured in an oven.

The curing conditions were 23 ℃ X7 days +50 ℃ X7 days for each composition.

Three materials are used for preparing a base material for an H-shaped tensile test; float glass (Koen-sha specified by Japan Serial Industry Association, size 3X 5X 0.5 cm) in accordance with JIS A-5758/1992, pure aluminum (Taiyu Kizai, A1100P, size 5X 0.2 cm) in accordance with JIS H-4000, and heat ray reflective glass (KLS)^TM5X 0.6 cm). Nail for useEach of these H-shaped substrates was washed with ethyl ketone (Wako-Junyaku Kogyo, Special grade) and wiped with clean cotton cloth, then it was filled with the composition.

The H-shaped test piece thus prepared, in which the test piece was cured at a tensile rate of 50 mm/min in a thermostatic chamber maintained at 23 ℃ and a relative humidity of 65. + -. 5%, was tested in accordance with the method for testing tensile adhesion of JIS A-5758/1992. The ratio of Cohesive Failure (CF)/film failure (TCF)/adhesive failure of the K-series shown in the table was determined by visual inspection of the cross section of the tensile specimen.

Reference examples K3 and K4

A mixture containing the polymer prepared in preparation K2 was prepared for reference examples K3 and K4. It consists of the following substances: 100 parts of polymer, 90 parts of paraffin process oil (Idemitsu Kosan, DianaProcess OilPS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO 320B)^TM) 50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of talc (Maruo Calcium, LMR)^TM) 1 part of an antiaging agent 1 (Ciba-Geigy Japan, Irganox 1010)^TM)，1 part of another age resister as age resister 2 (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of an anti-aging agent 3 and an anti-aging agent (Sankyo, Sanol LS-765)^TM) 3 parts of light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC)^TM) 3 parts of a photocurable resin (TOAGOSEI, Aronix M-400)^TM) 5 parts of thixotropic agent (Kusumoto Kasei, Disparlon # 305)^TM) 4 parts of gamma-isocyanate propyl triethoxysilane (Nippon Unicar, Y-9030) as a silane coupling agent^TM) And 2 parts of gamma-glycidoxypropyltrimethoxysilane (Nippon Unicar, A-187)^TM) All parts are by weight. The main component of reference example K3 was prepared by kneading the mixture well with a 3-paint roll unit.

The curing agent of reference example K3 was prepared by the following method: in the disposable cup, a mixture comprising: 4 parts of dibutyltin acetylacetonate (NITTO KASEI,U-220^TM) 4 portions of mirabilite (Na)₂SO₄·10H₂O), 10 parts of paraffin process Oil (Idemitsu Kosan, DianaProcess Oil PS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) The mixture was stirred 3 times by weight for 10 minutes at 10,000 rpm using a homogenizer (Nihon Seiki sesakusho co., ltd. excel autohomogenizer).

The main component and the curing agent used in referential example K4 were prepared in the same manner as in referential example K3, except that 4 parts of mirabilite (Na)₂SO₄·10H₂O) was added to the main component of reference example K3 and omitted from the curing agent of reference example K3, and the resulting composition was tested in the same manner.

The above composition, placed in a sealed glass bottle, was stored for one month in a good oven maintained at 50 ℃, and its adhesion to the respective substrate and its mechanical properties were measured as a function of time, immediately after the preparation and after the storage. The results are shown in tables K1 and K2.

Preparing a sample for a tensile test according to JIS A-5758/1992 which specifies a method for preparing a tensile test sample; the composition comprising the main component and the curing agent in the given weight ratio was well kneaded, and it was placed in an H-shaped glass or aluminum substrate and cured in an oven.

The curing conditions were 23 ℃ X7 days +50 ℃ X7 days for each composition.

Three materials are used for preparing a base material for an H-shaped tensile test; float glass (Koen-sha specified by Japan Serial Industry Association, size 3X 5X 0.5 cm) in accordance with JIS A-5758/1992, pure aluminum (Taiyu Kizai, A1100P, size 5X 0.2 cm) in accordance with JIS H-4000, and heat ray reflective glass (KLS)^TM5X 0.6 cm). Each of these H-shaped substrates was washed with methyl ethyl ketone (Wako-Junyaku Kogyo, Special grade) and wiped with clean cotton cloth, then it was filled with the composition.

The H-shaped test piece thus prepared, in which the test piece was cured at a tensile rate of50 mm/min in a thermostatic chamber maintained at 23 ℃ and a relative humidity of 65. + -. 5%, was tested in accordance with the method for testing tensile adhesion of JIS A-5758/1992. The ratio of Cohesive Failure (CF)/film failure (TCF)/adhesive failure of the K-series shown in the table was determined by visual inspection of the cross section of the tensile specimen.

TABLE K1 (H-shaped tensile test results from freshly prepared compositions)

	Base material	M50	TB	EB	Failure (%)
								Kilogram force/cm2	Kilogram force/cm2	％	CF	TCF	AF
		Example K2	FL	6.22	6.60	68	100							0	0
pAl	5.10							6.80	72	100	0	0
			KLS	5.20	6.61	68	100						0	0
Reference example K3	FL							6.14	7.80	79	100	0			0
		pAl	5.56	7.96	88	100	0						0
	KLS							5.97	7.79	82	99	1		0
		Reference example K4	FL	5.48	7.49	85	99						1		0
pAl	4.94							8.13	107	94	5	1
			KLS	5.39	7.82	95	99						1	0

(Note) FL: float glass, pAl: pure aluminum, KLS: heat-ray reflective glass, M₅₀: 50% tensile stress, T_B: tensile breaking strength, E_B: elongation at tensile break

TABLE K2 (H-shaped tensile test results obtained with the stored compositions)

	Base material	M50	TB	EB	Failure (%)
								Kilogram force/cm2	Kilogram force/cm2	％	CF	TCF	AF
		Example K2	FL	5.20	7.10	79	100							0	0
pAl	5.12							7.32	85	98	2	0
			KLS	5.24	7.06	77	98						2	0
Reference example K3	FL							5.94	8.88	91	100	0			0
		pAl	5.47	8.39	93	97	0						3
	KLS							6.50	9.01	81	98	2		0
		Reference example K4	FL	-	2.62	30	1						0		99
pAl	-							1.85	23	0	0	100
			KLS	-	1.32	15	0						0	100

(Note) FL: float glass, pAl: pure aluminum, KLS: heat-ray reflective glass, M₅₀: 50% tensile stress, T_B: tensile breaking strength, E_B: elongation at tensile break

Example K3

A curing agent was prepared in the same manner as in example K2, except that 4 parts by weight of dibutyltin dimethoxide (Aldrich Chemical) was used in place of U-220 as the silanol condensing catalyst and that the main component of example K2 was also tested in the same manner as in example K2. The results are shown in tables K3 and K4.

Reference example K5

A curing agent was prepared in the same manner as in referential example K3, except that 4 parts by weight of dibutyltin dimethoxide (Aldrich Chemical) was used in place of U-220 as the silanol condensing catalyst and that the test was also conducted in the same manner as referential example K3 using the main components of referential example K3. The results are shown in tables K3 and K4.

TABLE K3 (H-shaped tensile test results from freshly prepared compositions)

	Base material	M50	TB	EB	Failure (%)
								Kilogram force/cm2	Kilogram force/cm2	％	CF	TCF	AF
		Example K3	FL	3.78	6.53	113	100							0	0
pAl	3.69							6.70	120	98	2	0
			KLS	3.82	6.74	122	98						2	0
Reference example K5	FL							4.42	7.70	130	100	0			0
		pAl	4.23	8.32	144	97	3						0
	KLS							4.60	7.26	127	97	3		0

(Note)

FL: float glass, pAl: pure aluminum, KLS: heat-ray reflective glass, M₅₀: the tensile stress of the film is 50 percent,

T_B: tensile breaking strength, E_B: elongation at tensile break

TABLE K4 (H-shaped tensile test results obtained with the stored compositions)

	Base material	M50	TB	EB	Failure (%)
								Kilogram force/cm2	Kilogram force/cm2	％	CF	TCF	AF
		Example K3	FL	3.86	7.09	116	100							0	0
pAl	3.76							7.22	122	99	1	0
			KLS	3.86	7.33	126	100						0	0
Reference example K5	FL							4.50	8.34	133	98	0			2
		pAl	4.32	8.46	139	100	0						0
	KLS							4.69	8.41	125	100	0		0

(Note) FL: float glass, pAl: pure aluminum, KLS: heat-ray reflective glass, M₅₀: the tensile stress of the film is 50 percent,

T_B: tensile breaking strength, E_B: elongation at tensile break

Examples K4-K7

A mixture containing the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example K1 was prepared and used in each of examples K4 to K7. It is prepared from the following materialsConsists of the following components: 100 parts of copolymer rubber (A-1) and 90 parts of paraffin process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO 320B)^TM) 50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of talc (Maruo Calcium, LMR)^TM) 1 part of an antiaging agent 1 (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of another aging inhibitor as aging inhibitor 2 (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of an anti-aging agent 3 and an anti-aging agent (Sankyo, Sanol LS-765)^TM) 3 parts of light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC)^TM) 5 parts of thixotropic agent (Kusumoto Kasei, Disparlon # 305)^TM) 4 parts of silane coupling agent 1(Nippon Unicar, Y-9030)^TM) And 2 parts of silane coupling agent 2(Nippon Unicar, A-187)^TM) All parts are by weight. The mixture was well kneaded by a 3-paint roll unit to prepare the main components of reference examples K6 to K9.

The curing agent of example K4 was prepared by the following method: in the disposable cup, a mixture comprising: 4 parts of a silanol condensation catalyst (NITTO KASEI, U-220)^TM) 4 portions of mirabilite (Na)₂SO₄·10H₂O), 10 parts of paraffin Process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) All parts are by weight, the mixture is stirred 3 times with a homogenizer (Nihon Seikisesakusho co., ltd. excel autohomogenizer) at 10,000 rpm for 10 minutes each.

Each of the compositions of examples K4-K7 was prepared in the same manner as in example K2, except that the salt cake (Na) was replaced with a hydrate of another metal salt for the curing agent₂SO₄·10H₂O), example K5 is carried out using 6 parts of sodium thiosulfate pentahydrate (Na)₂S₂O₃·5H₂O), example K6 using 6 parts of magnesium sulfate (MgSO)₄·7H₂O), for example K7With 4 parts of sodium phosphate (Na)₃PO₄·12H₂O) was prepared and tested in the same manner as in example K2, the results of which are shown in tables K5 and K6.

Reference examples K6-K9

A mixture containing the polymer prepared in preparation K2 was prepared for reference examples K6-K9. It consists of the following substances: 100 parts of polymer, 90 parts of paraffin process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 180 parts of limestone powder (Shiraishi Calcium, PO 320B)^TM) 50 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of talc (Maruo Calcium, LMR)^TM) 1 part of an antiaging agent 1 (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of another aging inhibitor as aging inhibitor 2 (Sumitomo Chemical, Sumisorb 400)^TM) 1 part of the extractThe anti-aging agent 3 further comprises an anti-aging agent (Sankyo, Sanol LS-765)^TM) 3 parts of light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC)^TM) 5 parts of thixotropic agent (Kusumoto Kasei, Disparlon # 305)^TM) 4 parts of silane coupling agent 1(Nippon Unicar, Y-9030)^TM) And 2 parts of silane coupling agent 2(Nippon Unicar, A-187)^TM) All parts are by weight. The mixture was kneaded well with a 3-paint roll unit to prepare the main component.

The curing agent of reference example K6 was prepared by the following method: in the disposable cup, a mixture comprising: 4 parts of a silanol condensation catalyst (NITTO KASEI, U-220)^TM) 4 portions of mirabilite (Na)₂SO₄·10H₂O), 10 parts of paraffin Process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) All parts are by weight, the mixture is stirred 3 times with a homogenizer (Nihon Seikisesakusho co., ltd. excel autohomogenizer) at 10,000 rpm for 10 minutes each.

Prepared by the same method as in reference example K3 and used for making ginsengComposition as in K7-K9, except that another metal salt hydrate is used in place of Natrii sulfas (Na) for the curative₂SO₄·10H₂O), example K7 is carried out using 6 parts of sodium thiosulfate pentahydrate (Na)₂S₂O₃·5H₂O), example K8 using 6 parts of magnesium sulfate (MgSO)₄·7H₂O), example K9 was repeated using 4 parts of sodium phosphate (Na)₃PO₄·12H₂O) was prepared and tested in the same manner as in reference example K3, the results of which are shown in tables K5 and K6.

The compositions comprising the main components and the curing agent prepared in each of examples K1-K7 and reference examples K1-K9 were subjected to the curing speed and weather resistance tests in the manner as described above.

The results are shown in Table K7.

TABLE K5 (H-shaped tensile test results from freshly prepared compositions)

	Base material	M50	TB	EB	Failure (%)
								Kilogram force/cm2	Kilogram force/cm2	％	CF	TCF	AF
		Example K4	FL	4.32	5.94	83	100							0	0
KLS	4.36							5.80	78	100	0	0
			Example K5	FL	4.85	6.20	72						100	0	0
KLS	4.90	6.04						68	100	0	0
				Example K6	FL	4.59	6.80					88	100	0	0
KLS	4.60	6.62	83					100	0	0
					Example K7	FL	4.18				6.20	91	100	0	0
KLS	4.23	6.00	86	100				0	0
						Reference example K6	FL			4.92	7.40	94	100	0	0
KLS	5.20	7.29	83	99	1			0
							Reference example K7		FL	5.51	7.71	80	100	0	0
KLS	5.63	7.45	74	100	0	0
								Reference example K8	FL	5.22	8.45	99	100	0	0
KLS	5.31	7.94	87	100	0	0
							Reference example K9		FL	4.78	7.69	102	100	0	0
KLS	5.12	7.76	96	100	0	0

(Note)

FL: float glass, KLS: heat-ray reflective glass, M₅₀: the tensile stress of the film is 50 percent,

T_B: tensile breaking strength, E_B: elongation at tensile break

TABLE K6 (H-shaped tensile test results obtained with the stored compositions)

	Base material	M50	TB	EB	Failure (%)
								Kilogram force/cm2	Kilogram force/cm2	％	CF	TCF	AF
		Example K4	FL	4.33	6.25	84	100							0	0
KLS	4.34							6.34	91	100	0	0
			Example K5	FL	4.87	6.70	80						100	0	0
KLS	4.88	6.80						77	100	0	0
				Example K6	FL	4.58	7.00					92	100	0	0
KLS	4.54	7.42	94					100	0	0
					Example K7	FL	4.22				6.80	95	100	0	0
KLS	4.32	6.90	102	100				0	0
						Reference example K6	FL			4.92	7.40	90	100	0	0
KLS	5.20	7.29	83	99	1			0
							Reference example K7		FL	5.51	7.71	80	100	0	0
KLS	5.63	7.45	74	100	0	0
								Reference example K8	FL	5.22	8.45	99	100	0	0
KLS	5.31	7.94	87	100	0	0
							Reference example K9		FL	4.78	7.69	102	100	0	0
KLS	5.12	7.76	96	100	0	0

(Note)

FL: float glass, KLS: heat-ray reflective glass, M₅₀: the tensile stress of the film is 50 percent,

T_B: tensile breaking strength, E_B: elongation at tensile break

TABLE K7

	Freshly prepared composition		Compositions after storage
					Speed of curing	Weather resistance	Speed of curing	Weather resistance
	Example K1	○	No cracking or cracking was observed Molten part	○					No cracking or cracking was observed Molten part
Reference example K1					×	No cracking or cracking was observed Molten part	×	No cracking or cracking was observed Molten part
	Reference example K2	×	No cracking or cracking was observed Molten part	×					No cracking or cracking was observed Molten part
Example K2					○	No cracking or cracking was observed Molten part	○	No cracking or cracking was observed Molten part
	Reference example K3	×	No cracking or cracking was observed Molten part	×					No cracking or cracking was observed Molten part
Reference example K4					×	No cracking or cracking was observed Molten part	×	No cracking or cracking was observed Molten part
	Example K3	○	No cracking or cracking was observed Molten part	○					No cracking or cracking was observed Molten part
Reference example K5					×	No cracking or cracking was observed Molten part	×	No cracking or cracking was observed Molten part
	Example K4	○	No cracking or cracking was observed Molten part	○					No cracking or cracking was observed Molten part
Example K5					○	No cracking or cracking was observed Molten part	○	No cracking or cracking was observed Molten part
	Example K6	○	No cracking or cracking was observed Molten part	○					No cracking or cracking was observed Molten part
Example K7					○	No cracking or cracking was observed Molten part	○	No cracking or cracking was observed Molten part
	Reference example K6	×	No cracking or cracking was observed Molten part	×					No cracking or cracking was observed Molten part
Reference example K7					×	No cracking or cracking was observed Molten part	×	No cracking or cracking was observed Molten part
	Reference example K8	×	No cracking or cracking was observed Molten part	×					No cracking or cracking was observed Molten part
Reference example K9					×	No cracking or cracking was observed Molten part	×	No cracking or cracking was observed Molten part

<example L series>

Production example 1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber]

In a stainless polymerization reactor having a basic capacity of 100 liters and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norice were continuously fed from the side of the reactor into the liquid phase at rates of 60 liters/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively(ii) limonene, and hydrogen and VO (OEt) as a catalyst were continuously fed in at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization reaction conducted under the above conditions produces an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in the form of a homogeneous solution.

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thus prepared contained 68 mol% of ethylene, and had an intrinsic viscosity [ η]of 0.2dl/g, an Iodine Value (IV) of 10 (g/100 g) and an Mw/Mn of 15 as measured in decalin maintained at 135 ℃.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a dimethoxymethylsilyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber.

Examples L1-L4, and comparative example L1

Using the components shown in Table L1 and the ratios also shown in Table L1, homogeneous rubber compositions of examples L1 to L4 and comparative example 1, respectively, were prepared, and the viscosities thereof were measured. The results are shown in Table L1.

Each of the resulting compositions was cast into 3mm thick sheets and cured at room temperature for 4 days and then at 50 ℃ for 4 days.

The cured sheet was evaluated for tackiness, heat resistance, curing speed and weather resistance by the following methods.

Both cure speed (film expandability) and weatherability were measured using different example aliquots. The results are shown in Table L2.

1) Viscosity of

◎ the feeling of stickiness to the touch is not felt

○ slight stickiness to the touch

△ feeling sticky to the touch

2) Heat resistance

The heat resistance of the sheet was evaluated by the time required for the surface of the sheet to start melting at 130 ℃.

3) Weather resistance

In the accelerated weathering test using a Sunshine weatherometer, the weather resistance was evaluated by the time required for the surface of the sheet to begin to melt.

4) Curing speed test

The film expandability, i.e., curing speed, of the composition comprising the main component and the catalyst at room temperature was measured.

Adjusted to 23 ℃ and 50% RH, the composition and the mould (20X 80X 5 mm) and the mould were left to stand overnight before filling the mould with the composition. After the cured composition was allowed to stand for 24 hours therein, the cured product was then taken out from the mold, and the thickness of the cured portion was measured with a micrometer having a spring force as weak as 0.1mm, to evaluate the curing speed thereof.

(evaluation criteria)

X: when the thickness of the cured part is less than 1mm

○ when the thickness of the cured part is not less than 1 mm.

5) Weather resistance test

An accelerated weather resistance test was carried out in accordance with JIS B-7753.

An analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The surface condition of the test piece after the test was visually observed, and its weather resistance was evaluated according to the following three grades:

○ No cracking or melting part observed

△slight cracking or melting of parts was observed

X: cracks or molten portions were observed

Reference examples L1-L6

Three reactive silicon group-containing polymers were prepared by the method described in production examples 1 to 3 (columns 16 to 18) of Japanese patent laid-open publication No. 252670/1989.

Homogeneous rubber compositions were prepared using these polymers and the other components shown in Table L1, respectively. The ratios of these compositions are listed in table L1.

The properties of these rubber compositions and those cured products produced in examples were evaluated in the same manner as in examples. The results are shown in Table L1.

TABLE L1

Composition comprising a metal oxide and a metal oxide (share)	Examples L1	Examples L2	Reference example L1	Reference example L2	Examples L3	Examples L4	Reference example L3	Reference example L4	Comparative example L1	Reference example L5	Reference example L6
												Component (A2) Production example L1 Production example L2 (Note 6) Production example L3 (Note 7)	80 - -	80 - -	- 80 -	- 80 -	100 - -	100 - -	- - 100	- - 100	100 - -	- 100 -	- - 100
Component (K1) PS340.5 (Note 1) PS084 (Note 2) PS080 (Note 3)	20 - -	- 20 -	20 - -	- 20 -	- - 24 (Note 4)	- - 35 (Note 5)	- - 80 (Note 4)	- - 90 (Note 5)	- - -	- - -	- - -
												Tin octylate	3	3	3	3	3	3	3	3	3	3	3
Laurylamine	0.75	0.75	0.75	0.75	0.75	0.75	0.75	0.75	0.75	0.75	0.75
												Curable composition (days, 23 ℃ C.) Viscosity of Heat resistance (days) Weather resistance (days)	○ ◎ 110 ○	○ ◎ 105 ○	× ◎ 45 △	× ◎ 48 △	○ ◎ 120 ○	○ ◎ 115 ○	× ◎ 40 △	× ◎ 41 △	○ ○ 115 ○	× △ 50 △	× ○ 43 △

Notes of Table L1:

(Note 1) PS 340.5: silanol terminated polydimethylsiloxane (Chisso Corp.)

(Note 2) PS 084: polydimethyldiphenylsiloxane with diphenylsilanol termination (Chisso Corp.)

(Note 3) PS 080: polydiphenylsiloxane having silanol end groups (Chisso Corp.)

(Note 4) ratio of silanol groups in the polysiloxane to methoxysilyl groups in the polymer: 1 equivalence ratio

(Note 5) ratio of silanol groups in the polysiloxane to methoxysilyl groups in the polymer: 1.2 equivalence ratio

(Note 6) a reactive silicon group-carrying polymer synthesized according to the method described in column 1 (16-18) of production example 1 of Japanese patent laid-open publication No. 252670/1989.

(Note 7) a reactive silicon group-carrying polymer synthesized according to the method described in column 3 (16-18) of production example 3 of Japanese patent laid-open publication No. 252670/1989.

<example M series>

Production example M1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization reaction conducted under the above conditions produces an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in the form of a homogeneous solution.

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

To 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, a 2% toluene solution of chloroplatinic acid (0.3 g) and 1.5 g of methyldimethoxysilane were added and reacted with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a dimethoxymethylsilyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber.

Examples M1-M5

Rubber compositions of each of examples M1 to M5 were prepared using the components shown in Table M1 and the ratios also shown in M1. It comprises the following components: as component (a2), the dimethoxymethylsilyl-containing copolymer rubber prepared in production example M1; and polybutadiene rubber, styrene/butadiene copolymer rubber, acrylic rubberAr101, a hydrolyzable silyl polypropylene glycol (KANEKA corp., MS polymer, MS203^TM) Or an organic rubber of nitrile rubber (JSR corp., N230S) as component (K2). The mixture was kneaded at 120 ℃ for 5 minutes by a Banbury mixer (Kobe Steel, Ltd.1.9) and further kneaded by an 8-inch roll mill in the presence of a vulcanizing agent. The vulcanization speed T of a test piece of the rubber composition was measured in accordance with JIS K-6300/1994₉₀。

Further, it was extruded into a sheet by a twin-screw extruder and heated at 180 ℃ for continuous vulcanization for 1 hour to prepare a vulcanized rubber sheet.

The vulcanized sheet was evaluated for tensile elongation, heat resistance, surface weather resistance, curing speed and weather resistance by the following methods. The results are shown in Table M1.

(evaluation method)

1) Tensile test

Tensile test was carried out at 23 ℃ in accordance with JIS 6251 using JIS No.1 dumbbell-shaped test pieces.

2) Weather resistance test

An accelerated weather resistance test was carried out in accordance with JIS B-7753 to determine weather resistance:

an analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The surface condition of the test piece after the test was visually observed, and its weather resistance was evaluated according to the following three grades:

○ No cracking or melting part observed

△ slight cracking or melting of parts was observed

X: cracks or molten portions were observed

Reference examples M1-M5

Each of the vulcanized rubber sheets of reference examples M1 to M5 was produced and tested in the same manner as in the corresponding examples, except that a silyl group-containing copolymer rubber as component (A2) was replaced with a compound A (represented by the following general formula) having a number average molecular weight of 10,600, a molecular weight distribution (Mw/Mn) of 1.2 and a number of terminal dimethoxymethylsilyl functional groups of 1.9 synthesized in the manner described in Japanese patent laid-open publication No. 105005/1988. The results are shown in Table M1.

Compound A

Wherein "r" and "s" are each an integer.

TABLE M1

	Examples					Reference example
												M1	M2	M3	M4	M5	M1	M2	M3	M4	M5
Composition (parts by weight) Component (A2) Silyl group-containing copolymer size A Component (K2) Polybutadiene rubber Styrene/butadiene copolymer rubber Acrylic rubber MS Polymer, MS203 Nitrile rubber Other Components Asahi#60G Vulcanizing agent (M) Dicumyl peroxide	50 50 40 2.7	50 50 40 2.7	50 50 40 2.7	50 50 40 2.7	50 50 40 2.7	100 40 2.7	100 40 2.7	100 40 2.7	100 40 2.7	100 40 2.7
											Curing speed of rubber composition: t90(170 ℃ C.) for a minute Properties of cured product Tensile elongation (%) Weather resistance	5.6 400 ○	5.8 420 ○	6.2 480 ○	6.9 500 ○	6.5 490 ○	6.8 250 △	6.5 280 △	8.2 290 △	10.5 300 △	8.6 310 △

Notes

MS Polymer MS203^TM: a hydrolyzable silyl group-containing polypropylene glycol, KANEKA Corp.

Asahi # 60G: FEF grade Carbon black, Asahi Carbon

As shown in Table M1, the curing speed of the rubber compositions prepared in the respective examples and the surface weather resistance, weather resistance and heat resistance of the cured products thereof were all superior to those of the respective reference examples.

<example N series>

Production example 1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization reaction conducted under the above conditions produces an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in the form of a homogeneous solution.

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A0-1) thus prepared contained 68 mol% of ethylene, and had an intrinsic viscosity [ η]of 0.2dl/g, an Iodine Value (IV) of 10 (g/100 g) and an Mw/Mn of 15 as measured in decalin maintained at 135 ℃.

To 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, a 2% toluene solution of chloroplatinic acid (0.3 g) and 1.5 g of methyldimethoxysilane were added and reacted with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a dimethoxymethylsilyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber.

Reference examples 1 to 6

The respective polymers of reference examples 1 to 6 were prepared according to the methods of production examples 1 to 6 disclosed in Japanese patent laid-open publication Nos. 292616/1992[0036]- [0037].

Examples N1-N4, and reference examples N1-N6

Curable resin compositions of each of examples N1 to N4 were prepared using the components shown in Table N1 and the weight ratios also shown in Table N1. The composition consists of the following components: preparation of copolymer rubber containing Dimethoxysilyl group, Epichlorohydrin-bisphenol A type Epoxy resin (Yuka Shell Epoxy, Epikote # 828) prepared in example 1^TMEpoxy equivalent: about 190), gamma- (2-aminoethyl) aminopropyltrimethoxysilane (Nippon Unicar, Al 122) as a silane coupling agent^TM) Dibutyl oxide as a silanol condensation catalyst50/50 mixture of tin and dioctyl phthalate (Sankyo Organic Chemicals, Ltd., # 918)^TM) And 2, 4, 6-tris (dimethylaminomethyl) phenol (kayaku nooly co., ltd., DMP 30) as an epoxy resin curing catalyst^TM). Compositions were also prepared in the same manner as described above except that the polymers prepared in comparative preparation examples 1 to 6 were used in comparative examples N1 to N6, respectively.

The curable resin compositions prepared in examples N1 to N4 and comparative examples N1 to N6 were each evaluated by the following methods.

1) Tensile test Using dumbbell test specimens

The curable resin composition was cured in a Teflon frame at 23 ℃ for 3 days and further at 50 ℃ for 4 days, and molded into a sheet. The cured sheet was die-cut into No. 3 dumbbell test pieces in accordance with JIS K-6301. The tensile strength was measured at 200 mm/min and the modulus (M) at 50 and 100% elongation was determined₅₀And M₁₀₀) Breaking strength (T)_B) And elongation at break (E)_B)。

2) Measurement of tensile shear Strength

The test was carried out in accordance with JIS K-6850. An aluminum plate (A-1050P aluminum plate, size 100X 25X 2 mm, defined by JIS H-4000) was lightly wiped with acetone, and the curable resin composition was spread with a spatula thereon to an area of 25X 12.5 mm and a thickness of 0.05 mm. The coated surfaces of the two panels were bonded face to face and pressed against each other by hand. The coated specimens were fixed and the resin was cured at 23 ℃ for 3 days and then fixed at 50 ℃ for 4 days. Then, they were pulled apart from each other at 5 mm/min until the cured resin was broken. The tensile shear strength was obtained by dividing the maximum load value measured when the cured resin broke by the coated area.

Thecuring speed and the weather resistance were measured by the following methods:

3) speed of curing

The film expandability, i.e., curing speed, of the composition comprising the main component and the catalyst at room temperature was measured.

The curable composition was cured in a mold (20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours, and the thickness of the cured portion was measured with a micrometer having a spring force as weak as 0.1mm to evaluate the curing speed.

(evaluation criteria)

X: when the thickness of the cured part is less than 1mm

○ when the thickness of the cured part is not less than 1 mm.

4) Weather resistance test

The weather resistance was determined by conducting an accelerated weather resistance test in accordance with JIS B-7753.

An analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: the surface condition of the test piece after 500 hours visual inspection was evaluated for weather resistance according to the following three grades:

○ No cracking or melting part observed

△ slight cracking or melting of parts was observed

X: cracks or molten portions were observed

The results are given in Table N1.

TABLE N1

	Examples	Reference example
			1 2 3 4	1 2 3 4 5 6
	Silyl group-containing polymersArticle (A) Production example 1 Comparative production example 1 Comparative production example 2 Comparative production example 3 Comparative production example 4 Comparative production example 5 Comparative production example 6	100 100 100 100 - - - - - - - - - - - - - - - - - - - - - - - -			- - - - - - 100 - - - - - - 100 - - - - - - 100 - - - - - - 100 - - - - - - 100 - - - - - - 100
Epoxy resin #828			50 50 50 50	50 50 50 50 50 50
	Silane coupling agent	1 2 5 7.5			2 2 2 2 2 2
Silanol condensation catalyst			1 1 1 1	1 1 1 1 1 1
	Epoxy curing catalyst	5 5 5 5			5 5 5 5 5 5
M50 M100			14.9 30.1 23.7 21.6 29.7 55.4 51.3 50.7	32.7 36.9 27.4 24.9 37.9 10.7 59.6 64.4 46.3 41.8 67.1 21.2
	TB(kilogram force/cm)2)	78.1 86.3 80.1 77.7			90.5 77.7 74.4 112 121 68.2
EB(％)			180 131 111 107	158 125 180 314 189 250
	Shear strength (kilogram force/centimetre) Rice and its production process2)	91 138 133 131			147 180 100 143 92 100
Speed of curing			○ ○ ○ ○	○ ○ ○ ○ ○ ○
	Weather resistance	○ ○ ○ ○			× × × × × ×

<example O series>

Production example 1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization reaction conducted under the above conditions produces an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in the form of a homogeneous solution.

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) contains 68 mol% of ethylene, measured in decalin maintained at 135 ℃Intrinsic viscosity [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

To 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, a 2% toluene solution of chloroplatinic acid (0.3 g) and 1.5 g of methyldimethoxysilane were added and reacted with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a dimethoxymethylsilyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber.

Reference production examples 1 and 2

The polymers of reference production examples 1 and 2 were prepared according to the methods of production examples 1 and 3, respectively, disclosed in Japanese patent laid-open publication No. 280217/1987.

Example O1, and reference examples O1 and O2

A mixture of example O1 containing the copolymer rubber prepared in production example 1 as component (A2) was prepared. The composition consists of the following components: 100 parts of copolymer rubber, 50 parts of bisphenol A type epoxy resin (Yuka Shell epoxy, Epikote # 828)^TM) 1 part of a bisphenol type antioxidant (Ouchishinsko chemical Industrial Co., Nocrac NS-6)^TM) 1 part of N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane (silicon compound as the component (Q) of the present invention), 1 part of diphenylsilanediol (silicon compound as the component (R) of the present invention), 2 parts of an organotin-based compound as a silanol condensing catalyst (Sankyo organic Chemicals, Ltd., # 918)^TM) 5 parts of 2, 4, 6-tris (dimethylaminomethyl) phenol as an epoxy resin curing catalyst and 0.4 part of water, all parts being by weight. The components are mixed well with each other and the mixture is poured carefully into a polyethylene frame to prevent foaming on entry into the frameCuring was carried out at 23 ℃ in a frame for 1 day and at 50 ℃ for 3 days to form a 3mm thick sheet. Similar procedures were repeated to produce mixtures and sheets containing the polymers produced in reference production examples 1 and 2 (reference examples O1 and O2).

The compositions prepared in example O1 and reference examples O1 and O2 were subjected to a tensile test using a dumbbell-shaped specimen in the following manner, and their curing speed and weather resistance were also measured. The results are shown in Table O1.

1) Tensile test Using dumbbell test specimens

The cured sheet was die-cut into No. 3 dumbbell test pieces in accordance with JIS K-6301. The tensile strength at break (TB) and elongation at break (EB) were determined at 500 mm/min.

The curing speed and the weather resistance were measured by the following methods:

1) speed of curing

The film expandability, i.e., curing speed, of the composition comprising the main component and the catalyst at room temperature was measured.

The curable compositions of each example and comparative example were cured in a mold (20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours, and the thickness of the cured portion was measured with a micrometer having a spring force as weak as 0.1mm to evaluate the curing speed.

(evaluation criteria)

X: when the thickness of the cured part is less than 1mm

○ when the thickness of the cured part is not less than 1 mm.

2) Weather resistance test

The weather resistance wasdetermined by conducting an accelerated weather resistance test in accordance with JIS B-7753.

An analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The surface condition of the test piece after the test was visually observed, and its weather resistance was evaluated according to the following three grades:

○ No cracking or melting part observed

△ slight cracking or melting of parts was observed

X: cracks or molten portions were observed

TABLE O1

	Tensile Properties		Speed of curing	Weather resistance
					TB(kg/cm)2)	EB(％)
	Example O1	35					380	○	○
Reference example O1			48	410	○	×
	Reference example O2	25					210	×	×

Examples O2-O4, and reference examples O3-O5

Examples O2-O4 were each prepared in the same manner as example O1 except that 0.5 part of bis (hydroxydimethylsilyl) benzene and 0.5 part of polydimethyl-diphenylsiloxane having diphenylsilanol groups as terminal groups were used (Petrarch Systems Inc., PS-084)^TM) Or 0.5 partof a silicone varnish having silanol groups (Shin-Etsu Chemical Co., Ltd., KR-212)^TM) (all by weight) in place of diphenylsilanediol as component (R) of the present invention to measure T_BAnd E_B. Each of the cured sheets of referential examples O3 to O5 was also prepared from the composition prepared in referential example O1. The results are shown in Table O2.

TABLE O2

	Component type (R)	Tensile Properties		Speed of curing	Weather resistance
						TB(kg/cm)2)	EB(％)
		Example O2	Bis (hydroxydimethyl methyl) Silyl) benzene					67	550	○	○
Example O3	PS-084			65	800	○	○
		Example O4	KR-212					73	720	○	○
Reference example O3	Bis (hydroxydimethyl methyl) Silyl) benzene			55	510	○	×
		Reference example O4	PS-084					55	750	○	×
Reference example O5	KR-212			63	660	○	×

Examples O5-O8, and reference examples O7-O12

In examples O5 to O8, adhesive specimens were prepared from the compositions prepared in each of examples O1 to O4 by the following methods, and their adhesive strengths were measured. The results are shown in Table O3.

Method for preparing sample and method for testing tensile shear Strength (according to JIS K-6850)

An aluminum plate (A-1050P aluminum plate, size 100X 25X 2 mm, defined by JIS H-4000) was lightly wiped with acetone, and the resin composition was spread on the surface to an area of 25X 12.5 mm and a thickness of 0.05 mm with a spatula. The coated surfaces of the two panels were bonded face to face and pressed against each other by hand. The coated specimens were fixed and the resin was cured at 23 ℃ for 1 day and then fixed at 50 ℃ for 3 days. Then, they were pulled apart from each other at 5 mm/min until the cured resin was broken. The tensile shear strength was obtained by dividing the maximum load value measured when the cured resin broke by the coated area.

Preparation method of sample and T-shaped peeling Strength (releasing Strength)

An aluminum plate (A-1050P aluminum plate, size 200X 25X 2 mm, defined by JIS H-4000) was lightly wiped with acetone, and the resin composition was spread on the surface to an area of 100X 25 mm and a thickness of 0.3 mm with a spatula. The coated surfaces of the two panels were bonded face-to-face and pressed against each other 5 times with a 5 kg hand roller in a manner to avoid back and forth motion. The resin composition was cured at 23 ℃ for 1 day and then fixed at 50 ℃ for 3 days. Then, the thus-prepared specimen was fixed in a tensile tester in a T-shape manner and stretched at 200 mm/min until the bonded portion was broken. The strength measured when the bonded portion was broken was taken as the T-shaped peel strength.

TABLE O3

		Compositions for use Type (B)	Adhesive strength
					Tensile shear strength (kg/cm)2)	T-shaped peel strength (kg/25 mm)
			Examples	05 06 07 08			Example 1	142	13.2
Example 2	116	10.7
					Example 3	104	11.1
Example 4	105	8.9

Example O9

The curable resin composition of example O1 was prepared using the polymer prepared in preparation example 1. The composition consists of the following components: 100 parts of polymer, 50 parts of Epikote #828^TM1 part of Nocrac NS-6^TM1 part of N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, 1 part of diphenylsilanediol and 2 parts of #918^TMAnd 5 parts of 2, 4, 6-tris (dimethylaminomethyl) phenol. These components were well mixed with each other in a nitrogen atmosphere to prevent moisture from being mixed into the air.

Using the above-mentioned method for preparing a sample, a sample was prepared from the above-mentioned composition, cured at 23 ℃ for 1 day and further cured at 50 ℃ for 3 days, and its adhesive strength was measured. It has a tensile shear strength of 126 kg/cm²T-Peel Strength of 9.0 kg/25 mm (example O9)

<example P series>

Production example 1

[ preparation of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber]

In a stainless polymerization reactor having a basic capacity of 100 liters and equipped with a stirring blade (stirring rotation: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 liters/hr, 2.5 kg/hr, 4.0kg/hr and 380 g/hr, respectively, and hydrogen and VO (OC) as a catalyst were continuously fed at rates of 700 liters/hr, 45 mmol/hr and 315 mmol/hr, respectively₂H₅)₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization reaction conducted under the above conditions produces an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in the form of a homogeneous solution.

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thus prepared contained 68 mol% of ethylene, and had an iodine value of 10, an intrinsic viscosity [ η]of 0.2dl/g and an Mw/Mn of 15.

To 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, a 2% toluene solution of chloroplatinic acid (0.3 g) and 1.5 g of methyldimethoxysilane were added and reacted with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and solvent in the effluent were distilled off. This gave 101.5 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber containing a dimethoxymethylsilyl group.

Examples P1 and P2, comparative examples P1 to P3

For each of examples P1 and P2 and comparative examples P1 to P3, a mixture containing the dimethoxysilyl-containing copolymer rubber obtained in production example P1 was prepared. The mixture comprises the above copolymer rubber, a paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) Colloidal calcium carbonate (Shiraishi K., EDS-D10A)^TM) Limestone powder (Maruo Calcium, Snowlite SS)^TM) Talc (Fuji TalcKogyo, Talc LMR)^TM)、Na₂SO₄·10H₂O (Wako Jun-yaku Kogyo) and gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, Y-9030) as a silane coupling agent^TM). Each component is given in parts by weight in Table P1. The mixture was well kneaded with a 3-roll coater to prepare the main component of each example.

U the threadlike behavior (thread property) of each main component was evaluated with a spatula.

Dibutyl tin diacetylacetonate (NITTO KASEI Co., Neostan U-220) was added to the main component^TM) To obtain a mixture with a weight ratio of 404/2. The components are well kneaded by hand,the resulting mixture was formed into a sheet in a2 mm thick aluminum frame lined with a polytetrafluoroethylene sheet while breaking the bubbles in the composition with a spatula. The sheet was oven cured at 23 ℃ for 7 days and then at 50 ℃ for 7 days. The cured sheet was punched out into 3 pieces in accordance with JIS K-6251-1993 "tensile test method for vulcanized rubberDumbbell specimen, which was stretched at a rate of 500 mm/min with an Autograph (Shimadzu, Autograph AG-2000A) in a thermostatic chamber maintained at 23 ℃ and 50. + -. 10% RH.

Cured samples for hardness measurement were prepared as follows. Adding curing catalyst (NITTO KASEI, Neostan U-220) to the main component^TM) To obtain a mixture with a weight ratio of 404/2. The hardness was measured by kneading the components well and curing the resulting mixture in a frame lined with a polytetrafluoroethylene sheet (size 12X 50 mm) to form a rectangular sample, under standard curing conditions of 7 days at 23 ℃ and 7 days at 50 ℃. The hardness of the bar-shaped test piece was measured by a spring-type hardness test A method using a rubber-type hardness meter (Shimadzu, Hardnessmeter 200) in accordance with JIS K-6301/1975. A total of 5 measurements were made for each composition and the average values are reported.

Table P1 shows the composition of the main components, the viscosity (at 10 rpm), and the threadlike properties, dumbbell tensile test results, hardness, curing speed and weather resistance of each composition.

The line properties were rated on two scales:

○ the threadlike character of the composition is low and can be easily trimmed with a spatula

X: the composition has high linear performance and is difficult to trim by a scraper

M50, T in Table P1_maxAnd E_maxRespectively, 50% tensile stress, maximum tensile stress, and elongation at maximum load.

The curing speed and weather resistance were measured by the following methods.

1) Speed of curing

The film expandability, i.e., curing speed, of the composition comprising the main component and the catalyst at room temperature was measured.

The curable composition was cured in a mold (dimensions 20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours, and the thickness of the cured portion was measured with a micrometer having a spring force as weak as 0.1 mm.

(evaluation criteria)

X: when the thickness of the cured part is less than 1mm

○ when the thickness of the cured portion is 1mm or more

2) Weather resistance test

An accelerated weather resistance test was conducted in accordance with JIS B-7753 to determine the weather resistance:

an analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The surface state of the test specimen was visually observed, and the weather resistance was evaluated according to the following three grades:

○ No cracks or no melting portions were found

△ slight cracks or melted portions were observed

X: cracks or melted portions were observed

The results are shown in Table P1.

Comparative examples P4-P8

An isobutylene polymer having a reactive silicon group was synthesized according to the method described in paragraph 0049-0055 of Japanese patent laid-open publication No. 316804/1998.

Each of the compositions of comparative examples P4 to P8 was prepared in the same manner as in examples P1 and P2 and comparative examples P1 to P3, respectively, except that the dimethoxysilyl-containing copolymer rubber was replaced with an isobutylene polymer having a reactive silicon group. Various properties of these compositions were measured and the results are shown in Table P2.

TABLE P1

Composition comprising a metal oxide and a metal oxide	Additive agent	Example P		Comparative example P
							1	2	1	2	3
		Main component (parts by weight)	Polymerization obtained in production example Article (A)	100	100	100						100	100
PS-32	100						100	100	100	100
			EDS-D10A	100	50	200					-	-
Snowlite SS	50						200	-	300	-
			LMR	100	100	-					-	200
Na2SO4·10H2O	2						2	2	2	2
			Y-9030	2	2	2					2	2
Curing catalyst (parts by weight)	U-220						2	2	2	2			2
		Linear behavior		○	○	○					×	×
Stretch characteristics	M50(kgf/cm2)						7.90	7.91	3.52	4.12			9.69
		Tmax(kgf/cm2)	11.7	12.6	11.6	8.8					13.1
	Emax(％)						85	83	215	118		62
		JIS hardness A Speed of curing Weather resistance		34 ○ ○	34 ○ ○	24 ○ ○					28 ○ ○		38 ○ ○

TABLE P2

Composition comprising a metal oxide and a metal oxide	Additive agent	Comparative example P
							4	5	6	7	8
		Main component (parts by weight)	Note (1)	100	100	100						100	100
PS-32	100						100	100	100	100
			EDS-D10A	200	-	-					100	50
Snowlite SS	-						300	-	50	200
			LMR	-	-	200					100	100
Na2SO4·10H2O	2						2	2	2	2
			Y-9030	2	2	2					2	2
Curing catalyst (parts by weight)	U-220						2	2	2	2			2
		Linear behavior		○	×	×					○	○
Stretch characteristics	M50(kgf/cm2)						4.1	4.8	11.3	9.0			9.2
		Tmax(kgf/cm2)	13.8	10.4	15.4	13.8					14.7
	Emax(％)						248	132	70	93		95
		JIS hardness A Speed of curing Weather resistance		29 × △	33 × △	39 × △					38 × △		38 × △

Note (1): polymers used in examples described in Japanese patent laid-open publication No. 316804/1998

From the results shown in tables P1 and P2, it is apparent that the following findings can be derived.

Examples P1 and P2 had excellent workability of the compositions made with the silyl-containing copolymer rubber. The cured product has excellent mechanical strength and hardness, and these properties are well balanced. And also has sufficient weather resistance and curing speed.

Each of the compositions prepared in comparative examples P1 to P3 contained no calcium carbonate or talc but contained a silyl-containing copolymer rubber. These compositions have a poor balance between the above properties.

Each of the compositions prepared in comparative examples P4 to P8 did not contain a silyl group containing copolymer rubber, and the balance between these properties was poor, and the weather resistance was low or the curing speed was low.

<example Q series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in examples and comparative examples were measured by the aforementioned methods.

Production example

[ preparation of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped witha stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2dl/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 parts by weight of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) adding a 2% solution of chloroplatinic acid in toluene (0.3 part by weight)) And 1.5 parts by weight of methyldimethoxysilane, which were allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 parts by weight of a compound containing dimethoxymethylsilyl (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Example Q1

Example Q1A mixture containing the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example was prepared. The mixture contained 100 parts of copolymer rubber (A-1), 90 parts of paraffin-based Process oil (Idemitsu Kosan, Diana Process OilPS-32) as a plasticizer^TM) 360 parts of limestone powder as filler (Shiraishi Calcium, Whiton SB)^TM) And 5 parts of mirabilite Na serving as a water source₂SO₄·10H₂O, 1 part of methylene tetrakis [3- (3 ', 5' -di-tert-butyl-4-hydroxyphenyl) propionate as an antiaging agent]Methane (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of 2- (2 ' -hydroxy-3 ', 5 ' -tert-butyl) -5-chlorobenzotriazole (Ciba-Geigy Japan, Tinuvin327 as stabilizer^TM) 1 part of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate (Sankyo, SanolLS-770)^TM) 5 parts of thixotropy-imparting agent (kusumoto Kasei, Disparlon # 305)^TM)2 parts of gamma-isocyanate propyl triethoxysilane (Nippon Unicar, Y-9030) as a silane coupling agent^TM) And 3 parts of nickel dimethyldithiocarbamate (Sanshin) represented by the following structural formula as a light stabilizerKagaku Kogyo，Sandant NBC^TM) All parts are parts by weight. The major component was prepared by kneading sufficiently with a 3-roll coater to mix these components.

The curing agent was prepared by the following method: manually kneading a mixture comprising: 10 parts of a paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 25 parts of limestone powder (Shiraishi Calcium, Whiton SB)^TM) 4 parts of tetravalent tin compound (NITTO KASEI, U-220) as a curing agent^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) All parts are in parts by weight, and the mixture is repeatedly stirred with a Homogenizer (Nihon Seiki Sesakusho, Excel Auto Homogenizer) at 10,000 rpm for 3 times for 10 minutes each.

Samples were prepared in accordance with JIS A-5758-; the composition comprising 14 parts by weight of the above main component and 1 part by weight of the curing agent was put into an H-shaped frame of a glass or aluminum substrate after sufficiently kneading. The composition was allowed to cure in an oven at 23 ℃ for 7 days and 50 ℃ for 7 days. Sputter coating the surface with TiO₂The heat ray reflective Glass sheet (Central Glass, SGY-32)^TMAnd TCB-35^TMAnd 5 × 5 × 0.6 cm) was used as a substrate for the H-shaped frame. Each H-shaped frame was washed with methyl ethyl ketone (Wako-Junyaku, tex) and wiped dry with clean cotton before filling the composition.

The H-shaped test pieces thus obtained were subjected to a light-resistant adhesion test, and the H-shaped mechanical properties before and after the test were measured, and the results are shown in Table Q1. In this test, an H-shaped tensile specimen was placed in a Sunshine ultra-long life aging machine (Suga Shikenki, WEL-SUN-HC) in which the temperature of a black substrate was maintained at 63 ℃ and irradiated with light from a daylight-type carbon arc as a light source, and the H-shaped tensile specimen was taken out from the analyzer after 480 hours.

The H-shaped test piece thus obtained was tested in accordance with JIS A-5758/1992 by the tensile adhesion test method at a tensile rate of 50 mm/min in a thermostatic chamber maintained at 23 ℃ and 65. + -. 5% RH. The ratio of Cohesive Failure (CF)/Thin Coating Failure (TCF)/Adhesive Failure (AF) shown in the table was determined by visual inspection of a cross section of the tensile specimen.

Cohesive failure refers to the fracture of the cured composition itself, rather than the failure at the interface between the substrate and the cured composition, indicating that the cured composition is bonded to the substrate with high bond strength. Adhesive failure refers to the separation of the substrate and the cured composition from each other at the interface, indicating that the cured composition adheres to the substrate with poor adhesive strength. Thin coating failure is cohesive failure at the interface, indicating an adhesive strength intermediate between the two failure modes described above.

Weather resistance tests were carried out in the following manner, and the results are shown in Table Q1.

Weather resistance test

An accelerated weather resistance test was carried out in accordance with JIS B-7753 under the following conditions.

An analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

Comparative examples Q1-Q3

The same procedure as used in example Q1 was repeated, except that in comparative example Q1, 3 parts by weight of nickel dimethyldithiocarbamate (Sanshin Kagaku Kogyo, Sandant NBC) as a light stabilizer was not added^TM) (ii) a In comparative example Q2, 3 parts by weight of 2- (2 ' -hydroxy-3 ', 5 ' -tert-butyl) -5-chlorobenzotriazole (Ciba-Geigy Japan, Tinuvin327^TM) As a non-nickel based stabilizer; in comparative example Q3, 5 parts by weight of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate (Sankyo, Sanol LS-770) was added^TM) As a non-nickel based stabilizer. The results are shown in Table Q1.

TABLE Q1

Before testing	M50 (kgf/cm2)	Tmax (kgf/cm2)	Emax (％)	Failure (%)			Weather resistance
								CF	TFC	AF
				Example Q1	4.4	5.8					60	100	0	0	No cracks were observed Or molten parts
Comparative example Q1	4.3	5.9	62				99	1	0	No cracks were observed Or molten parts
				Comparative example Q2	4.3	5.8					63	100	0	0	No cracks were observed Or molten parts
Comparative example Q3	4.3	5.6	60				100	0	0	No cracks were observed Or molten parts
				After the test	M50 (kgf/cm2)	Tmax (kgf/cm2)					Emax (％)	Failure (%)
CF	TFC	AF
			Example Q1				3.2	4.7	75	100		0	0
Comparative example Q1	3.0	3.2		52	0	2					98
			Comparative example Q2				2.9	3.4	54	0		1	99
Comparative example Q3	3.1	3.1		50	1	0					99

As shown in Table Q1, each of examples Q1 and comparative example Q1The compositions prepared from-Q3 all showed good adhesion to surface treated SGY-32 glass substrates prior to the weather resistant adhesion test. After the test, only the sample prepared in example Q1 showed cohesive failure, while the other samples showed adhesive failure. These results show that the addition of Ni-based stabilizer (Sandant NBC)^TM) The light-resistant adhesion can be improved.

Example Q2 and comparative example Q4

EXAMPLE Q2 the same procedure as in example Q1 was repeated, except that 3 parts by weight of [2, 2' -thiobis (4-tert-octylphenolate) represented by the following formula]-Nickel n-butylamine (ACC, SYASORB UV1084) in place of 3 parts by weight of nickel dimethyldithiocarbamate (Sanshin Kagaku Kogyo, Sandant NBC)^TM) Also as Ni-based light stabilizers:

comparative example Q4 the same procedure as used in example Q2 was repeated, except that 3 parts by weight of n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate represented by the following formula (ACC, SYASORB UV 2908)^TM) Instead of 3 parts by weight of [2, 2' -thiobis (4-tert-octylphenolate)]-nickel n-butylamine (ACC, SYASORBUV 1084)^TM) As non-Ni-based light stabilizers:

the results are shown in Table Q2.

Example Q3 and comparative example Q5

Example Q3 the same procedure as used in example Q1 was repeated except that limestone powder (Shiraishi Calcium Whiton SB) was added^TM) The amount of (c) is reduced from 25 parts by weight to 20 parts by weight. Comparative example Q5 the same procedure as used in example Q3 was repeated, except that 3 parts by weight of 2, 4-dibutylphenyl 3 ', 5 ' -di-tert-butyl-4 ' -hydroxybenzoate (ACC, SYASORB) represented by the following formula as a non-Ni-based light stabilizer was used712^TM) Instead of 3 parts by weight of nickel dimethyldithiocarbamate (Sanshin Kagaku Kogyo, Sandant NBC) as a Ni-based light stabilizer^TM)：

The results are shown in Table Q2.

TABLE Q2

	M50 (kgf/cm2)	Tmax (kgf/cm2)	Emax (％)	Failure (%)			Weather resistance
								CF	TFC	AF
				Example Q2	3.2	4.4					78	100	0	0	No cracks were observed Or molten parts
Example Q3	3.3	4.8	80				100	0	0	No cracks were observed Or molten parts
				Comparative example Q4	3.0	3.2					52	0	1	99	No cracks were observed Or molten parts
Comparative example Q5	3.2	3.2	50				0	2	98	No cracks were observed Or molten parts

<example R series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in each example and comparative example 1 were measured by the aforementioned methods.

The curing speed and weather resistance tests were carried out in theexamples and comparative examples by the following methods:

(1) curing speed test

The compositions prepared in examples and comparative examples were cured in a mold (having a size of 20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours and then taken out of the mold, the thickness of the cured portion was measured with a micrometer having a weak spring force of 0.1mm, and the curing speed was evaluated, which was represented by ○ when the thickness was 1mm or more, by △ when the thickness was 0.5 to 1mm, and by X when the thickness was less than 0.5 mm.

(2) Weather resistance test

Weather resistance was measured by a Sun Carbon Arc weatherometer according to JIS B-7753 to determine weather resistance.

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

<evaluation criteria for weather resistance>

○ No cracks or fused portions were found on one side of the sample

△ slight cracks or melted portions were observed on one side of the sample

X: cracks or melted portions were observed on one side of the sample

Preparation example R1

[ preparation of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 liters and equipped with stirring blades (stirring speed: 250 rpm), the liquid phasewas separated from the side of the reactorHexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed at rates of 60 l/h, 2.5 kg/h, 4.0 kg/h and 380 g/h, and hydrogen, VO (OEt) as a catalyst, were continuously fed at rates of 700 l/h, 45 mmol/h and 315 mmol/h, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2dl/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a mixture containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Preparation example R2

Into a 500 ml four-necked flask was charged 200 g of polypropylene oxide (97% of all terminal groups thereof haveallyl ether groups and an average molecular weight of 5,000), to which was added 100. mu.l of a 10% ethanol solution of chloroplatinic acid, followed by dropwise addition of methyldimethoxysilane at 50 ℃ and allowing them to react with each other at 80 ℃ for about 3 hours.

According to¹H-NMR analysis revealed that the reaction product was obtained in 1 minPolypropylene oxide having 1.7 structures of the formula having an average molecular weight of about 5,200:

(CH₃O)₂Si(CH₃)(CH₂)₂CH₂O-

examples R1 to R6

For each of examples R1 to R6, a homogeneous toluene solution of a composition was prepared using the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example R1.

Each solution was cured in a frame of about 3mm thickness at room temperature for 1 day, at 50 ℃ for another 4 days, and then treated at 50 ℃ under a vacuum of 2-3mmHg for 2 hours to completely evaporate the toluene.

The obtained cured sheet was put into a hot air type dryer maintained at 150 ℃ for 20 days, and changes in properties with time (heat resistance measurement) were observed, the results are shown in Table R1. the heat resistance in the Table was rated by the following three grades ○: no crack or molten portion was observed, △: crack or molten portion was slightly observed, x: crack or molten portion was observed, NISSAN DLTP: sulfide carboxylate-based antioxidant (NOF Corp.), Nocrac 300: sulfur-containing hindered phenol (Ouchishinsko Chemical Industries Co., Ltd.) and Irgano 1010: hindered phenol (Ciba Geigy, Japan).

TABLE R1

Practice of Example (b)	Component (parts by weight)							Performance of
											Component (A1)	Component (U)		Tin octylate	Dodecane Amine amines	Toluene	Water (W)	Heat resistance	Weather resistance	Curing speed Degree of rotation
	R1	100	NISSAN DLTP	1	3	0.75	50	0.5	○	○											○
R2											100	NISSAN DLTP	3	3	0.75	50	0.5	○	○	○
	R3	100	NISSAN DLTP	5	3	0.75	50	0.5	○	○											○
R4											100	Nocrac 300	1	3	0.75	50	0.5	○	○	○
	R5	100	Nocrac 300	3	3	0.75	50	0.5	○	○											○
R6											100	Nocrac 300	5	3	0.75	50	0.5	○	○	○

Component (a 1): ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)

Examples R7 to R9 and comparative example R1

For examples R7 to R9 and comparative example R1, a sheet having a thickness of 1mm was prepared in the same manner as in example R1 except that the sulfur-based aging inhibitor was replaced with the additives listed in Table R2 to prepare a composition. The time required for the sheet to completely decompose and begin to flow at 150 ℃ was measured with a test tube type rubber weatherometer.

The results are shown in Table R2.

Comparative example R2

A sheet of comparative example R2 was prepared in the same manner as in example R7 except that the polymer prepared in production example R2 was used in place of the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example R1, and the test was conducted in the same manner. The results are shown in Table R2.

TABLE R2

	Example R			Comparative example R
						7	8	9	1	2
	NISSAN DLTP parts by weight]	1	-	1	-						1
Nocrac300 [ parts by weight]						-	1	1	-	-
	Heat resistance	○	○	○	△						△
Weather resistance						○	○	○	△	×
	Speed of curing	○	○	○	○						○

The cured compositions obtained in examples R1 to R9 and comparative examples R1 and R2 were subjected to weather resistance tests in accordance with the foregoing methods. As a result, cracks were not observed in the samples prepared in examples R1 to R9, but cracks were observed in the samples prepared in comparative examples R1 and R2.

<example S series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were measured in accordance with the above-mentioned methods.

Production example

[ preparation of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 liters and equipped with stirring blades (stirring speed: 250 rpm), 60 liters/hr, 2.5 kg/hr and 4.0 kg/hr, respectively, were introduced from the side of the reactor into the liquid phaseHexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed at a rate of 380 g/hr and at a rate of 700L/hr, 45 mmol/hr and 315 mmol/hr, respectively, hydrogen, VO (OEt) as a catalyst₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) contains 68 mol% of ethyleneIntrinsic viscosity [ η]measured in decalin maintained at 135 ℃ []0.2dl/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 parts by weight of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% toluene solution of chloroplatinic acid (0.3 part by weight) and 1.5 parts by weight of methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 parts by weight of a compound containing dimethoxymethylsilyl (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Examples S1 to S5

Each of examples S1 to S5 produced a mixture containing the polymer produced in the preparation example. The mixture contained 100 parts of polymer, 90 parts of paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 30 parts of limestone powder (Maruo Clacimum, Snowlite SS)^TM) 100 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A)^TM) 100 parts of Talc (Fuji Talc Kogyo, Talc LMR)^TM) 6 parts of Na₂SO₄·10H₂O, 6 parts of tung oil as the compound having an unsaturated group polymerizable upon reaction with oxygen in the air and component (V) of the present invention, 3 parts of dipentaerythritol pentaacrylate and hexaacrylate as the photopolymerizable compound (TOAGOSEI, Aronix M-400)^TM) And the tackifiers listed in table S1 (the amounts also given in table S1), all parts being parts by weight. The mixtures were kneaded well with a 3-roll coater to prepare the main components of the examples.

The adhesionpromoter used in examples S1 to S3 was gamma-glycidoxypropyltrimethoxysilane (Nippon unicar, silane coupling agent A-187)^TM) As the silane coupling agent of the present invention, and/or gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, silane coupling agent Y-9030)^TM) The amounts are given in table S1. Example S4 used no tackifier, while example S5 used 4 parts by weight of epoxy resin as a tackifier (excluding silane) free of hydrolyzable silicon groupOther than coupling agent) (Yuka Shell Epoxy, Epikote #828^TM)。

The curing agent was prepared by the following method: manually kneading a mixture comprising: 10 parts of a paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 20 portions of stoneLimestone powder (Maruo Calcium, Snowlite SS)^TM) 4 parts of curing catalyst (NITTO KASEI, U-220)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) All parts are in parts by weight, and each mixture is stirred 3 times at 10,000 rpm for 10 minutes each with a Homogenizer (Nihon Seiki Seisakusho co., ltd., Excel Auto homogenerator).

A cured sample for tensile adhesion measurement was prepared in accordance with JIS A-5758/1992 by the following method. The curing agent was mixed into the main component to prepare a mixture in a weight ratio of 12/1. The components were well kneaded, and the resulting mixture was put into an H-shaped glass substrate while breaking the bubbles in the composition with a spatula. Each composition was cured in an oven at 23 ℃ X1 day +50 ℃ X5 days. The substrate used for the H-type tensile test was float Glass (Koen-sha, designated by Japan Serial Industrial Association, having a size of 3X 5X 0.5 cm) or heat ray reflective Glass (Central Glass, KLS) coated with hot-melt TiOx according to JIS A-5758/1992^TMAnd the dimensions are 5 × 5 × 0.6 cm). Each of these H-shaped substrates was washed with methyl ethyl ketone (Wako-Junyaku, Special grade) and wiped with a cleaning cotton cloth, then filled with the composition. No primer coating was applied.

The H-shaped test piece for tensile test thus obtained was cured without a primer layer and then tested by the tensile adhesion test method in JIS A-5758/1992. The test was conducted in a constant temperature chamber maintained at 23 ℃ and 50. + -. 10% RH using an Autograph (Shimadzu, Autograph AG-2000A) at a tensile rate of 50 mm/min, and adhesion without the undercoat layer was evaluated by comparing the tensile characteristics and the fracture morphology. The results are shown in Table S1, in which the cross section of each tensile test sample was visually observed to determine the ratio of Cohesive Failure (CF)/Thin Coating Failure (TCF)/Adhesive Failure (AF).

The curing speed and weather resistance were measured according to the following methods. The results are shown in Table S7.

(1)Curing speed test

The curable composition was cured in a mold (dimensions 20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours and then taken out of the mold, the thickness of the cured portion was measured with a micrometer having a spring force as weak as 0.1mm, and the curing speed was evaluated, which was represented by ○ when the thickness was 1mm or more and by X when the thickness was less than 1 mm.

(2)Weather resistance test

An accelerated weather resistance test was conducted in accordance with JIS B-7753 in order to determine the weather resistance.

An analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 1000 hours

TABLE S1

Practice of Example (b)	Tackifier (amount added)	Substrate	At maximum load Elongation (c) of*1	Destruction morphology (%)*2
							CF	TCF	AF
				S1	A-187 (4 parts)	Float glass				○	100	0	0
Heat ray reflective glass: KLS	○	100	0				0
						S2		Y-9030 (4 parts)	Float glass	○	100	0	0
Heat ray reflective glass: KLS	○	100	0	00
					S3		A-187(2 parts) Y-9030(4 shares)		Float glass	○	100	0	0
Heat ray reflective glass: KLS	○	100	0	0
						S4		Is not used	Float glass	×	0	0	100
Heat ray reflective glass: KLS	×	0	0	100
					S5		Epikote 828 (4 parts)		Float glass	△	0	0	100
Heat ray reflective glass: KLS	△	0	0	100

^*1 ○ elongation 80% or more, △ elongation less than 80%, x elongation less than 60%^*2 CF: cohesive failure, TCF: thin coating failure, AF: adhesive failure

Examples S6 to S9 and comparative example S1

Each of examples S6 to S9 and comparative example S1 prepared a mixture containing the polymer prepared in the production example. The mixture contained 100 parts of polymer, 90 parts of paraffin-based process Oil (Idemitsu Kosan, DianaProcess Oil PS-32)^TM) 30 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) 100 parts of colloidal calcium carbonate (Shiraishi K.K. EDS-D10A)^TM) 100 parts by weight of Talc (Fuji TalcKogyo, Talc LMR)^TM) 6 parts of Na₂SO₄·10H₂O, 3 parts of nickel dimethyldithiocarbamate as light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC)^TM) 3 parts of [2, 2' -thiobis (4-tert-octylphenolate)]-nickel n-butylamine (ACC, CYASORB UV-1084), 1 part of antioxidant (Ciba-GeigyJapan, Irganox 1010)^TM) 1 part of ultraviolet absorber (Ciba-Geigy Japan, Tinuvin 327)^TM) 1 part of a light stabilizer (Sankyo, Sanol, LS-770)^TM) And 2 parts of gamma-glycidoxypropyltrimethoxysilane (Nippon Unicar, silane coupling agent A-187) as a silane coupling agent of the present invention^TM) And 4 parts of gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, silane coupling agent Y-9030)^TM) All parts are parts by weight. Tung oil was also added as the compound having an unsaturated group polymerizable upon reaction with oxygen in the air of the present invention and component (V), dipentaerythritol pentaacrylate and hexaacrylate as the photopolymerizable compound (TOAGOSEI, Aronix M-400)^TM) The amounts are given in Table S2. The mixtures were kneaded well with a 3-roll apparatus to give the respective solidsMain components of the examples.

The curing agent was prepared by the following method: manually kneading a mixture comprising:10 parts of a paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS), 4 parts of curing catalyst (NITTO KASEI, U-220)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) All parts are parts by weight, and the mixture is stirred 3 times with a Homogenizer (Nihon Seiki Sesakusho co., ltd., Excel Auto homogenerator) at 10,000 rpm for 10 minutes each.

H-shaped test pieces were prepared in the above manner except that the curing conditions were 23 ° c. × 7 days +50 ° c. × 7 days. The H-shaped tensile specimen was put into a Sunshine ultra-long life aging machine (Suga Shikenki, WEL-SUN-HC) in which the temperature of a black substrate was kept at 63 ℃ and was placed under the light from a daylight-type carbon arc as a light source in a weather resistance tester (SWOM) for a period of time listed in Table S2, and the specimen was taken out from the tester and subjected to a tensile adhesion test. Weather-resistant adhesion was evaluated by comparing tensile properties and failure morphology. The results are shown in Table S2.

The tensile adhesion of the H-shaped specimens was also determined before they were subjected to the weather resistance test and used as a reference. The results are shown inTable S3.

The curing speed and weather resistance of the compositions prepared in examples S6 to S9 were measured in the same manner as in examples S1 to S3. The results are shown in Table S7.

TABLE S2

	Can react with oxygen in the air Unsaturation of gas reaction Compound (addition amount)	Photopolymerizable material Material (adding amount)	Substrate	SWOM Exposure time	Maximum load Elongation at time Rate of change*1	Destruction morphology (%)*2
									CF	TCF	AF
						Comparison Example S1	Is not used	Is not used				Float glass	3000	×	0	0	100
Heat ray reflective glass: KLS	500	×	100	0	0
									Practice of Example S6	Is not used	AronixM400 (3 parts)	Float glass	3000	×	50	50	0
Heat ray reflective glass: KLS	600	×	0	0	100
						Practice of Example S7	Is not used	AronixM400 (6 parts)				Heat radiationLinear reflective glass: KLS	500	○	100	0	0
Practice of Example S8	Tung oil (6 shares)	Is not used	Float glass	3000	○				100	0	0
						Heat ray reflective glass: KLS	1000	○				100	0	0
			Practice of Example S9	Tung oil (6 shares)	AronixM400 (3 parts)				Float glass	3000	○				100	0	0
Heat ray reflective glass: KLS	1000	○				100	0	0

^*1 ○ elongation 80% or more, △ elongation less than 80%, x elongation less than 60%^*2 CF: cohesive failure, TCF: thin coating failure, AF: adhesive failure

TABLE S3

	Can react with oxygen in the air Corresponding unsaturated compounds (amount added)	Photopolymerizable materials (amount added)	Substrate	Maximum loadTime of flight Elongation (c) of*1	Destruction morphology (%)*2
								CF	TCF	AF
					Comparative example S1	Is not used	Is not used				Float glass	△	100	0	0
Heat ray reflective glass: KLS	△	100	0	0
								Examples S6	Is not used	AronixM400 (3 parts)	Float glass	△	100	0	0
Heat ray reflective glass: KLS	○	100	0	0
					Examples S7	Is not used	AronixM400 (6 parts)				Heat ray reflective glass: KLS	△	100	0	0
Examples S8	Tung oil (6 shares)	Is not used	Float glass	○				100	0	0
					Heat ray reflective glass: KLS	△	100				0	0
			Examples S9	Tung oil (6 shares)				AronixM400 (3 parts)	Float glass	○			100	0	0
Heat ray reflective glass: KLS	○	100			0	0

^*1 ○ elongation 80% or more, △ elongation less than 80%, x elongation less than 60%^*2 CF: cohesive failure, TCF: thin coating failure, AF: is adhered to

Reference production example

Into a 500 ml nitrogen-purged pressure-resistant glass reactor equipped with a three-way stopcock, 54 ml of ethylcyclohexane (dried at least one night with molecular sieve 3A), 126 ml of toluene (dried at least one night with molecular sieve 3A), and 1.16 g (5.02 mmol) of p-DCC represented by the following formula were charged by syringe.

Then, a pressure-resistant glass liquefied gas collecting tube equipped with a needle valve and containing 56 ml of an isobutylene monomer was connected to the above-mentioned three-way cock. The polymerization reactor was then immersed in a dry ice/ethanol bath maintained at-70 ℃ to cool the solution and evacuated to vacuum. Then the needle valve is opened to make the isobutene monomer enter into the polymerization reactor through the liquefied gas collecting pipe, and the reactor is returned to normal pressure by introducing nitrogen through the rotary three-way cock. To the reactor, 0.093 g (1.0 mmol) of 2-methylpyridine was added, followed by 1.65 ml (15.1 mmol) of titanium tetrachloride, to initiate polymerization. After 70 minutes, 1.22 g (10.8 mmol) of allyltrimethylsilane was added to the reactor, introducing an allyl group at the polymer end. After the reaction for 120 minutes, the reaction solution was washed 4 times with 200 ml of water each time, and the solvent was distilled off to obtain an isobutylene-based polymer having allyl terminal groups.

Next, 40 g of the isobutylene-based polymer having allyl terminal group obtained above was dissolved in 20 ml of n-heptane, the mixture was heated to about 70 ℃ and 1.5[ eq/vinyl]was added thereto]Methyldimethoxysilane and 1X 10^-4[ equivalent/vinyl group]]The platinum/vinylsiloxane complex of (a), to carry out a hydrosilylation reaction. The reaction was followed by FT-IR. About 4 hours in 1640cm^-1The olefin absorption peak at (a) disappeared.

The reaction solution was concentrated under vacuum to prepare an isobutylene polymer having reactive silicon groups at both terminals represented by the following formula:

the yield of the polymer was estimated from the yield. The Mn and Mw/Mn were also analyzed by GPC, comparing the protons 300MHz associated with each structure with each other¹H-NMR-analysis of the resonance signal intensity (proton derived from initiator: 6.5 to 7.5ppm, methyl proton derived from the terminal of polymer attached to siliconatom: 0.0 to 0.1ppm, methoxy proton: 3.4 to 3.5ppm) to analyze the terminal structure.

Using a Varian Gemini 300 (Pair)¹H is 300MHz) in CDCl₃In the middle of¹H-NMR analysis.

FT-IR analysis was performed with an IR analyzer (Shimadzu IR-408), and GPC analysis was performed with a Waters LC Module 1 as a liquid transfer system and Shodex K-804 as a column. Molecular weight is the molecular weight relative to polystyrene standards. The polymer thus produced had an Mn of 11,400, an Mn/Mw of 1.23 and an Fn (silyl) of 1.76, wherein the number average molecular weight was expressed in terms of polystyrene molecular weight and the number of terminal silyl functional groups was the number of terminal silyl functional groups per 1 mole of the isobutylene polymer.

Reference examples S1 to S5

Each of reference examples S1 to S5 prepared a mixture containing the polymer prepared in the reference preparation example. The mixture comprises: 100 parts of polymer, 90 parts of paraffin-based Process oil (Idemitsu Kosan, Diana Process OilPS-32)^TM) 30 portions of limestonePowder (Maruo Calcium, Snowlite SS)^TM) 100 parts of colloidal calcium carbonate (Shiraishi K.K. EDS-D10A^TM) 100 parts of Talc (Fuji Talc Kogyo, Talc LMR)^TM) 6 parts of Na₂SO₄·10H₂O, 6 parts of tung oil as the compound having an unsaturated group polymerizable upon reaction with oxygen in the air and component (V) of the present invention, 3 parts of dipentaerythritol pentaacrylate and hexaacrylate as the photopolymerizable compound (TOAGOSEI, Aronix M-400)^TM) And the tackifiers listed in table S4 (the amounts also given in table S4), all parts being parts by weight. The mixtures were kneaded well with a 3-applicator roll apparatus to prepare the main components of theexamples.

The adhesion promoter used in reference examples S3 to S5 was gamma-glycidoxypropyltrimethoxysilane (Nippon unicar, silane coupling agent A-187)^TM) As a silane coupling agent, and/or gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, silane coupling agent Y-9030)^TM) The amounts are given in table S1. Reference example S1 used no tackifier, while reference example S2 used 4 parts by weight of Epoxy resin as a tackifier (except silane coupling agent) having no hydrolyzable silicon group (Yuka Shell Epoxy, Epikote # 828)^TM)。

The curing agent was prepared by the following method: manually kneading a mixture comprising: 10 parts of a paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) 4 parts of curing catalyst (NITTO KASEI, U-220)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB # 30)^TM) All parts are in parts by weight, and each mixture is stirred 3 times at 10,000 rpm for 10 minutes each with a Homogenizer (Nihon Seiki Seisakusho co., ltd., Excel Auto homogenerator).

Preparing a test piece for tensile adhesion measurement according to JIS A-5758/1992; 12 parts by weight of the main component and 1 part by weight of the curing agent were well kneaded, and the resulting mixture was put into an H-shaped glass substrate while breaking the bubbles in the composition with a spatula. Each composition was allowed to cure in an oven under curing conditionsThis was 23 ℃ X1 day +50 ℃ X5 days. According to JIS A-5758/1992, the substrate used for the H-type tensile test was float glass (Koen-sha, designated by Japan Serial Industry Association, having dimensions of 3X 5X 0.5 cm), or coated with hot-melt TiO_xHeat ray reflective Glass (KLS)^TMDimension of 5X 5X 0.6 cm). Each of these H-shaped substrates was washed with methyl ethyl ketone (Wako-Junyaku, Special grade) and wiped with a cleaning cotton cloth, then filled with the composition. No primer coating was applied.

The H-shaped test piece for tensile test thus obtained was cured without a primer layer and then tested by the tensile adhesion test method in JIS A-5758/1992. The test was conducted in a constant temperature chamber maintained at 23 ℃ and 50. + -. 10% RH using an Autograph (Shimadzu, Autograph AG-2000A) at a tensile rate of 50 mm/min, and the adhesion without the undercoat layer was evaluated by comparing the tensile characteristics and the fracture morphology. The results are shown in Table S4, in which the cross section of each tensile test sample was visually observed to determine the ratio of Cohesive Failure (CF)/Thin Coating Failure (TCF)/Adhesive Failure (AF).

The curing speed and weather resistance of reference examples S3 to S5 were measured as described in examples S1 to S3. The results are shown in Table S7.

TABLE S4

	Tackifier (amount added)	Substrate	At maximum load Elongation (c) of*1	Destruction morphology (%)*2
							CF	TCF	AF
				Reference to Example S1	Is not used	Float glass				×	0	0	100
Heat ray reflective glass: KLS	×	0	0				100
						Reference to Example S2		Epikote 828 (4 parts)	Float glass	×	0	0	100
Heat ray reflective glass: KLS	×	0	0	100
					Reference to Example S3		A-187 (4 parts)		Float glass	○	100	0	0
Heat ray reflective glass: KLS	○	100	0	0
						Reference to Example S4		Y-9030 (4 parts)	Float glass	△	100	0	0
Heat ray reflective glass: KLS	△	100	0	0
					Reference to Example S5		A-187(2 parts) Y-9030(4 shares)		Float glass	○	100	0	0
Heat generationRay-reflective glass: KLS	△	100	0	0

^*1 ○ elongation 80% or more, △ elongation less than 80%, x elongation less than 60%^*2 CF: cohesive failure, TCF: thin coating failure, AF: adhesive failure

Reference examples S6 to S10

Mixtures of the respective reference examples S6 to S10 which contained the polymers produced in the reference production examples were prepared in the same manner as in examples S6 to S9 and comparative example S1. The mixture contained 100 parts of polymer, 90 parts of paraffin-based Process Oil (Idemitsu Kosan, Diarna Process Oil PS-32)^TM) 30 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) 100 parts of colloidal calcium carbonate (Shiraishi K.K. EDS-D10A)^TM) 100 parts by weight of Talc (Fuji Talc Kogyo, Talc LMR)^TM) 6 parts of Na₂SO₄·10H₂O、3 parts of nickel dimethyldithiocarbamate (Sanshin Kagaku Kogyo, Sandant NBC) as a light stabilizer^TM) 3 parts of [2, 2' -thiobis (4-tert-octylphenolate)]-nickel n-butylamine (ACC, CYASORB UV-1084), 1 part of antioxidant (Ciba-Geigy Japan, Irganox 1010)^TM) 1 part of ultraviolet absorber (Ciba-Geigy Japan, Tinuvin 327)^TM) 1 part of a light stabilizer (Sankyo, Sanol, LS-770)^TM) And 2 parts of gamma-glycidoxypropyltrimethoxysilane (Nippon Unicar, silane coupling agent A-187) as a silane coupling agent^TM) And 4 parts of gamma-isocyanatopropyltriethoxysilane (Nippon Unicar, silane coupling agent Y-9030)^TM) All parts are by weightAnd (4) portions are obtained. Tung oil was also added as the compound having an unsaturated group polymerizable upon reaction with oxygen in the air of the present invention and component (V), dipentaerythritol pentaacrylate and hexaacrylate as the photopolymerizable compound (TOAGOSEI, Aronix M-400)^TM) The amounts are given in Table S5. The mixtures were kneaded well with a 3-applicator roll apparatus to prepare the main components of the examples.

The curing agent was prepared by the following method: manually kneading a mixture comprising: 10 parts of a paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32)^TM) 20 parts of limestone powder (Maruo Calcium, Snowlite SS)^TM) 4 parts of curing catalyst (NITTO KASEI, U-220)^TM) And 2.5 parts of carbon black (Mitsubishi Chemical, CB# 30)^TM) All parts are parts by weight, and the mixture is stirred 3 times with a Homogenizer (Nihon Seiki Sesakusho co., ltd., Excel Auto homogenerator) at 10,000 rpm for 10 minutes each.

H-shaped test pieces were prepared in the above manner except that the curing conditions were 23 ° c. × 7 days +50 ° c. × 7 days. The H-shaped tensile specimen was put into a Sunshine ultra-long life aging machine (Suga Shikenki, WEL-SUN-HC) in which the temperature of a black substrate was kept at 63 ℃ and was placed under the light from a daylight-type carbon arc as a light source in a weather resistance tester (SWOM) for a period of time listed in Table S5, and the specimen was taken out from the tester and subjected to a tensile adhesion test. Weather-resistant adhesion was evaluated by comparing tensile properties and failure morphology. The results are shown in Table S5.

The tensile adhesion was also determined before the H-shaped specimens prepared as above were subjected to the weather resistance test and used as a reference. The results are shown in Table S6.

The curing speed and weather resistance of the compositions prepared in referential examples S7 to S10 were measured in the same manner as in examples S1 to S3. The results are shown in Table S7.

TABLE S5

	Can react with oxygen in the air Unsaturation of gas reaction Compound (addition amount)	Photopolymerizable material Material (adding amount)	Substrate	SWOM Exposure time	At maximum load Elongation (c) of*1	Destruction morphology (%)*2
									CF	TCF	AF
						Reference to Example S6	Is not used	Is not used				Float glass	3000	△	100	0	0
Heat ray reflective glass: KLS	500	△	0	0	100
									Reference to Example S7	Is not used	AronixM400 (3 parts)	Float glass	3000	△	100	0	0
Heat ray reflective glass: KLS	600	△	70	0	30
						Reference to Example S8	Is not used	AronixM400 (6 parts)				Heat ray reflective glass: KLS	500	×	50	0	50
Reference to Example S9	Tung oil (6 shares)	Is not used	Float glass	3000	△				100	0	0
						Heat ray reflective glass: KLS	1000	△				100	0	0
			Reference to Example S10	Tung oil (6 shares)	AronixM400 (3 parts)				Float glass	3000	△				100	0	0
Heat ray reflective glass: KLS	1000	△				100	0	0

^*1 ○ elongation 80% or more, △ elongation less than 80%, x elongation less than 60%^*2 CF: cohesive failure, TCF: thin coating failure, AF: adhesive failure

TABLE S6

	Can react with oxygen in the air Corresponding unsaturated compounds (amount added)	Photopolymerizable materials (amount added)	Substrate	At maximum load Elongation (c) of*1	Destruction morphology (%)*2
								CF	TCF	AF
					Reference example S6	Is not used	Is not used				Float glass	△	97	3	0
Heat ray reflective glass: KLS	△	100	0	0
								Reference example S7	Is not used	AronixM400 (3 parts)	Float glass	△	98	2	0
Heat ray reflective glass: KLS	×	98	2	0
					Reference example S8	Is not used	AronixM400 (6 parts)				Heat ray reflective glass: KLS	×	100	0	0
Reference example S9	Tung oil (6 shares)	Is not used	Float glass	△				100	0	0
					Heat ray reflective glass: KLS	△	100				0	0
			Reference example S10	Tung oil (6 shares)				AronixM400 (3 parts)	Float glass	×			100	0	0
Heat ray reflective glass: KLS	×	100			0	0

^*1 ○ elongation 80% or more, △ elongation less than 80%, x elongation less than 60%^*2 CF: cohesive failure, TCF: thin coating failure, AF: adhesive failure

TABLE S7

	Speed of curing*	Weather resistance
			Example S1	○	No cracks or fused portions were observed
Example S2	○	No cracks or fused portions were observed
			Example S3	○	No cracks or fused portions were observed
Example S6	○	No cracks or fused portions were observed
			Example S7	○	No cracks or fused portions were observed
Example S8	○	No cracks or fused portions were observed
			Example S9	○	No cracks or fused portions were observed
Reference example S3	×	Cracks or melted portions were observed
			Reference example S4	×	Cracks or melted portions were observed
Reference example S5	×	Cracks or melted portions were observed
			Reference example S7	×	Cracks or melted portions were observed
Reference example S8	×	Cracks or melted portions were observed
			Reference example S9	×	Cracks or melted portions were observed
Reference example S10	×	Cracks or melted portions were observed

^*○ fully workable, △ tack residue, x uncured

<example T series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

The compositions obtained in the respective examples and comparative examples were determined for their peeling resistance, residual tackiness, curing speed and weather resistance to silicone release paper by the following methods.

(1) Peel resistance to silicone release paper

Adhesive tapes were prepared and placed on commercially available silicone release paper to make samples. The sample was kept at 50 ℃ for 7 days, 14 days or 21 days, subjected to accelerated adhesion, taken out and allowed to return to normal temperature, and tested for peel resistance. The peel resistance is defined as the resistance of the tape when the tape is peeled from the silicone release paper at 180 ° at a tensile speed of 300 mm/min.

(2) Residual tackiness

Adhesive tapes were prepared and placed on commercially available silicone release paper to make samples. The sample was kept at 50 ℃, and the adhesive tape was peeled off to measure the adhesiveness. The definition of residual tack is the above-mentioned tack relative to the initial tack, expressed as a percentage.

(3) Viscosity of

Adhesive tapes were prepared and placed on stainless steel plates to prepare test specimens. The sample was held at 23 ℃ for 60 minutes and tested for tack. The tack is defined as the peel strength of the tape when peeled from a stainless steel plate at a tensile speed of 300 mm/min at an angle of 180 ° at 23 ℃.

(4) Speed of curing

The curable composition was cured in a mold (dimensions 20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours.

The cured composition was taken out of the mold, and the thickness of the cured portion of the composition was measured with a micrometer having a spring force as weak as 0.1mm, which was labeled ○ when the thickness was 1mm or more and X when the thickness was less than 1 mm.

The time required to cure the composition at 120 ℃ and 50% RH was also measured the composition cured at less than 5 minutes is marked ○, the composition cured between 5 and 10 minutes is marked △ and the composition cured more than 10 minutes is marked x.

(5) Weather resistance

Weather resistance test was carried out according to JIS B-7753 using a Sun Carbon Arc weatherometer, and the weather resistance was measured:

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

Production example T1

[ preparation of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thus prepared contained 68 mol% of ethylene, had an Iodine Value (IV) of 10 (g/100 g), and had an intrinsic viscosity [ η]of 0.2dl/g and Mw/Mn of 15 as measured in decalin maintained at 135 ℃.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a mixture containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example T2

Into a pressure-resistant reactor equipped with a stirrer, 800 g of polypropylene oxide (prepared from polypropylene glycol as a raw material) was charged, the polypropylene oxide having all terminals thereof98% of the total amount of the polymer having allyl ether groups had an average molecular weight of about 8,000. To this was added 20 g of methyldimethoxysilane followed by 0.34 ml of chloroplatinic acid in catalyst solution (8.9 g H)₂PtCl·6H₂O was dissolved in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran), they were allowed to react with each other at 80 ℃ for 6 hours.

The conversion was determined by quantitative analysis of unreacted silane by gas chromatography and infrared analysis. The results showed that 84% of all the terminals of the polypropylene oxide produced carried the groups shown below:

production example T3

38.3 g (0.1 mol) of zirconium tetra-n-butoxide was dissolved in 88 g of toluene, and 10.0 g (0.1 mol) of acetylacetone was slowly added thereto with stirring. Zirconium tri-n-butoxide acetylacetonate is thus obtained with the concomitant generation of heat. The mixed toluene solution hereinafter refers to the catalyst of production example 3.

Production example T4

38.3 g (0.1 mol) of zirconium tetra-n-butoxide was dissolved in 87 g of toluene, and 20.0 g (0.2 mol) of acetylacetone was slowly added thereto with stirring. Zirconium di-n-butoxide diacetylacetonate was thus obtained with the concomitant generation of heat. The mixed toluene solution hereinafter refers to the catalyst of production example 4.

Production example T5

38.3 g (0.1 mol) of zirconium tetra-n-butoxide was dissolved in 86 g of toluene, and 30.0 g (0.3 mol) of acetylacetone was slowly added thereto with stirring. Zirconium di-n-butoxide triacetylacetone is thus obtained with the concomitant generation of heat. The mixed toluene solution hereinafter refers to the catalyst of production example 5.

Production example T6

128 g (1.0 mol) of n-butyl acrylate, 3.48 g (0.015 mol) of γ -methacryloxypropylmethyldimethoxysilane, 2.46 g (0.015 mol) of γ -mercaptopropylmethyldimethoxysilane and 0.25 g of α' -azobisisobutyronitrile were mixed and dissolved, and 30 g of the resulting mixed solution was introduced into a 300 ml four-necked flask purged with nitrogen, and slowly heated in an oil bath maintained at 70 ℃ with stirring, the polymerization was started immediately, and the remaining mixed solution was slowly dropped into the reaction solution with stirring by means of a dropping funnel for 2.5 hours, the reaction solution was continuously stirred for 1 hour after completion of dropping of the mixed solution, and the polymerization was completed, whereby a colorless transparent viscous substance having a viscosity of 350P (23 ℃) was obtained at a polymerization rate of 97%.

Examples T1 to T9

For each of examples T1 to T9, 100 parts by weight of the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in preparation example T1 was compounded with 80 parts by weight of a tackifier resin as given in Table T1 to prepare a toluene solution having a solid content of 80%.

The solution was mixed with the curing catalyst obtained in Table T1, and the resulting composition was coated on a polyester substrate (Toray Industries, LumirrorFilm) having a thickness of 25 μm with a coater to a thickness of 25 μm (calculated as a dry coating), and cured with a dryer at 120 ℃ for 0.5 to 5 minutes.

The obtained adhesive tape was measured for releasability from silicone release paper (Soken Industries, inc., EK-130R). Curing speed and weather resistance tests were conducted in accordance with the methods described above to evaluate curing speed and weather resistance. The results are shown in Table T1.

In Table T1, YS Polymer T-115 and YS Polymer S-145 are terpene phenolic resins (Yasuhara Yushi Kogyo) and Stepelite Ester 7 is a hydrogenated rosin Ester resin (Hercules).

Zr (acac) in Table T1₄Is zirconium tetraacetylacetonate.

TABLE T1

Practice of Example (b)	Tackifier resin	Curing catalyst		120℃ Fixed in time Chemical velocity	Peel resistance [ g/cm ]]			Adhesive force (original) [g/cm]	Residual adhesion [% ]]			At room temperature Curing of Speed of rotation	Weather-proof Property of (2)*4
														Type (B)	Content (wt.) (parts by weight)	50℃× 7 days	50℃× 14 days	50℃× 21 days	50℃× 7 days	50℃× 14 days	50℃× 21 days
		T1	YS Polyster T-115		Production example 3 Catalyst and process for preparing same*1	5	○		4	3	2											430	94	96	92	○	◎
T2	YS Polyster T-115			Production example 4 Catalyst and process for preparing same*2				5				○	3	5	3	440	92	94	94	○	◎
		T3	YS Polyster T-115		Production example 5 Catalyst and process for preparing same*3	5	○		4	4	3											420	97	99	98	○	◎
T4	YS Polyster S-145			Production example 5 Catalyst and process for preparing same*3				5				○	4	4	3	800	98	99	96	○	◎
		T5	Stepelite Ester 7		Production example 5 Catalyst and process for preparing same*3	5	○		2	2	3											220	90	88	87	○	◎
T6	YS Polyster T-115			Zr(acac)4				5				○	4	3	2	410	86	84	82	○	◎
		T7	YS Polyster T-115		(n-Buo4)Zr	5	○		5	5	6											400	87	85	86	○	◎
T8	YS Polyster T-115			Al(acac)3				5				○	3	4	4	390	90	88	87	○	◎
		T9	YS Polyster T-115		Ethylacetoacetic acid Diisopropoxyaluminum	5	○		6	6	5											405	88	90	90	○	◎

^*1 is (n-BuO)₃Zr(acac)，^*2 is (n-BuO)₂Zr(acac)₂，^*3: is (n-Buo) Zr (acac)₃ ^*4 weather resistance evaluation criteria: ◎: no change was found, ○: slight cracks or melted portions were observed, △: cracks or melted portions were observed, x: cracks or melted portions were found over a wide range.

Reference examples T1 to T9

For reference examples T1 to T9, to 100 parts by weight of the hydrolyzable silicon group-containing polyalkylene oxide prepared in manufacturing example T2 was mixed 80 parts by weight of the tackifier resin listed in table T2 to prepare a toluene solution having a solid content of 80%.

The solution was mixed with the curing catalyst listed in Table T2, and the resulting composition was applied to a polyester substrate (Toray Industries, LumirrorFilm) having a thickness of 25 μm by a coater to a thickness of 25 μm (calculated as a dry coating), and cured at 120 ℃ for 1 to 19 minutes by a dryer.

The obtained adhesive tape was measured for releasability from silicone release paper (Soken Industries, inc., EK-130R). Curing speed and weather resistance tests were conducted in accordance with the methods described above to evaluate curing speed and weather resistance. The results are shown in Table T2.

In Table T2, YS Polymer T-115 and YS Polymer S-145 are terpene phenolic resins (Yasuhara Yushi Kogyo) and Stepelite Ester 7 is a hydrogenated rosin Ester resin (Hercules).

Zr (acac) in Table T2₄Is zirconium tetraacetylacetonate.

Comparative examples T1 to T3

Adhesive tapes of comparative examples T1 to T3 were produced in the same manner as in comparative example T1, except that the organotin compounds shown in Table T2 were used as curing catalysts and the releasability thereof was measured. Curing speed and weather resistance tests were conducted in accordance with the methods described above to evaluate curing speed and weather resistance. The results are shown in Table T2.

TABLE T2

	Tackifier resin	Curing catalyst		120℃ Fixed in time Chemical velocity	Peel resistance [ g/cm ]]			Adhesive force (original) [g/cm]	Residual adhesion [% ]]			Curing Speed of rotation	Weather resistance *4
														Type (B)	Content (wt.) (parts by weight)	50℃× 7 days	50℃× 14 days	50℃× 21 days	50℃× 7 days	50℃× 14 days	50℃× 21 days
		Reference to Example T1	YS Polyster T-115		Production example 3 Catalyst and process for preparing same*1	5	○		3	3	2											360	90	92	90	○	△
Reference to Example T2	YS Polyster T-115			Production example 4 Catalyst and process for preparing same*2				5				○	2	4	3	365	89	92	92	○	△
		Reference to Example T3	YS Polyster T-115		Production example 5 Catalyst and process for preparing same*3	5	○		2	3	3											360	94	97	95	○	△
Reference to Example T4	YS Polyster S-145			Production example 5 Catalyst and process for preparing same*3				5				○	3	3	4	750	92	93	91	○	X to △
		Reference to Example T5	Stepelite Ester 7		Production example 5 Catalyst and process for preparing same*3	5	○		3	3	3											160	84	80	78	○	△
Reference to Example T6	YS Polyster T-115			Zr(acac)4				5				○	2	3	3	360	74	78	74	○	△
		Reference to Example T7	YS Polyster T-115		(n-Buo4)Zr	5	△		4	4	5											370	77	76	75	○	×
Reference to Example T8	YS Polyster T-115			Al(acac)3				5				○	2	3	3	350	80	78	81	○	△
		Reference to Example T9	YS Polyster T-115		Ethylacetoacetic acid Diisopropoxyaluminum	5	○		5	6	6											375	78	80	80	○	△
Comparison Example T1	YS Polyster T-115			Dibutyl dilaurate Tin base				5				×	260	Must not Measuring	Must not Measuring	365	50	-	-	×	×
		Comparison Example T2	YS Polyster T-115		Monononyl phenol bis Butyl tin	5	○		250	Must not Measuring	Must not Measuring											360	34	-	-	○	×
Comparison Example T3	YS Polyster T-115			Dimethoxy dibutyl Tin base				5				○	240	Must not Measuring	Must not Measuring	355	32	-	-	○	×

^*1 as (n-BuO)₃Zr(acac)，^*2 as (n-BuO)₂Zr(acac)₂，^*3: as (n-Buo) Zr (acac)₃ ^*4 weather resistance evaluation criteria: ◎: no change was found, ○: slight cracks or melted portions were observed, △: cracks or melted portions were observed, x: cracks or melted portions were found over a wide range.

As shown in table T2, the adhesive tapes having the compositions prepared in respective reference examples T1 to T9 were superior in releasability from silicone release paper to the adhesive tapes having the compositions prepared in respective comparative examples T1 to T3.

Reference examples T10 to T15

For reference examples T10 to T15, 50 parts by weight of YS Polyster T-115 was mixed with 100 parts by weight of the hydrolyzable silicon group-containing acrylate copolymer prepared in preparation example T6 to prepare a toluene solution having a solid content of 80%.

The solution was mixed with a curing catalyst as listed in Table T3, and the resulting composition was applied to a polyester substrate (Toray Industries, LumirrorFilm) having a thickness of 25 μm to a thickness of 25 μm (calculated as a dry coating), and cured at 120 ℃ for 3 minutes to obtain an adhesive tape.

The releasability of the resultant adhesive tape from the silicone release paper was measured in the same manner as in comparative example T1. Curing speed and weather resistance tests were conducted in accordance with the methods described above to evaluate curing speed and weather resistance. The results are shown in Table T3.

Comparative examples T4 and T5

Adhesive tapes of respective comparative examples T4 and T5 were produced in the same manner as in referential example T10, except that the organotin compound shown in Table T3 was used in place of the curing catalyst, and the releasability thereof was measured. Curing speed and weather resistance tests were conducted in accordance with the methods described above to evaluate curing speed and weather resistance. The results are shown in Table T3.

TABLE T3

	Curing catalyst		Peel resistance [ g/cm ]]			Adhesive force (original) [g/cm]	Residual adhesion [% ]]			Speed of curing [ Normal temperature]	Weather resistance*4
												Type (B)	Content (wt.) (parts by weight)	50℃ X 7 days	50℃× 14 days	50℃× 21 days	50℃ X 7 days	50℃× 14 days	50℃× 21 days
	Reference example T10	Production example 3 Catalyst and process for preparing same*1	5	3	3		3	320	84											80	81	○	△ to
Reference example T11						Production example 4 Catalyst and process for preparing same*2				5	3	2	3	330	78	79	81	○	△ to
	Reference example T12	Production example 5 Catalyst and process for preparing same*3	5	2	3		3	3 1 5	82											82	80	○	△ to
Reference example T13						Zr(acac)4				5	3	4	4	340	77	76	77	○	△ to
	Reference example T14	Al(acac)3	5	4	6		5	355	79											79	80	○	△
Reference example T15						Ethylacetoacetate diiso Aluminium propoxide				5	3	4	4	345	80	81	81	○	△
	Comparative example T4	Dibutyl tin dilaurate	5	120	250			360	45											33	-	○	×
Comparative example T5						Mono-nonyl phenol dibutyl ester Tin (Sn)				5	65	170		355	38	24	-	○	×

^*1 is (n-BuO)₃Zr(acac)，^*2 is (n-BuO)₂Zr(acac)₂，^*3: is (n-Buo) Zr (acac)₃ ^*4 weather resistance evaluation criteria: ◎: no change was found, ○: slight cracks or melted portions were observed, △: cracks or melted portions were observed, x: cracks or melted portions were found over a wide range.

<example U series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

The gel fraction measurement and weather resistance test in each of examples and reference examples were conducted in accordance with the following methods.

(1) Gel fraction measurement test

The cured coating film was immersed in acetone maintained at 20 ℃ for 24 hours, giving the weight of the undissolved portion relative to the weight of the film before the test, when the weight percentage was less than 60%, it was marked with X, 60% or more but less than 80% was marked with △, 80% or more but less than 90% was marked with ○, and 90% or more was marked with ◎.

(2) Weather resistance test

Weather resistance test was carried out according to JIS B-7753 using a Sun Carbon Arc weatherometer, and the weather resistance was measured:

<test conditions>

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 250 hours

<evaluation criteria for weather resistance>

○ No cracks or fused portionswere found on one side of the sample

△ slight cracks or melted portions were observed on one side of the sample

X: cracks or melted portions were observed on one side of the sample

Example U

[ preparation of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen, VO as a catalyst, (OEt) was continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Ethylene/propylene/5-vinyl-2-norbornene random copolymer thus preparedRubber (A)₀-1) containing 68 mol% of ethylene, having an Iodine Value (IV) of 10 (g/100 g), and having an intrinsic viscosity measured in decalin maintained at 135 ℃ [ η]0.2dl/g and Mw/Mn of 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a mixture containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Reference example U1

A solution of azobisisobutyronitrile (2 g) dissolved in styrene (30 g), allyl methacrylate (16 g), methyl methacrylate (20 g), n-butyl methacrylate (19 g), butyl acrylate (14 g), maleic anhydride (4 g) and dodecyl mercaptan (2 g) was added dropwise to xylene (90 g) maintained at 90 ℃ as a solvent, and these were reacted with each other for 10 hours to give a vinyl polymer having a molecular weight of 8,000 and containing an allylic unsaturated group. In the infrared absorption spectrum of the polymer, at 1648cm^-1And 1780cm^-1Has absorption peaks of carbon-carbon double bond and acid anhydride respectively. The polymer solution was distilled under vacuum to remove 40 grams of solvent.

To 16 g of a vinyl polymer having an allylic unsaturated group, 1.5 g of trimethoxysilane and 0.0005 g of a solution of chloroplatinic acid in isopropanol were added and allowed to react with each other in a sealed system at 90 ℃ for 6 hours. The infrared absorption spectrum of the reaction product is 1648cm^-1There was no infrared absorption peak, from which it was judged that a silyl group functionalized vinyl polymer was produced.

Reference example U2

A solution of 2 g of azobisisobutyronitrile dissolved in 30 g of styrene, 22 g of gamma-methacryloxypropyltrimethoxysilane, 22 g of methyl methacrylate, 15 g of n-butyl methacrylate and 18 g of butyl acrylate was added dropwise to 70 g of xylene kept at 90 ℃ as a solvent, and these compounds were reacted with each other for 10 hours to give a silyl group-containing vinyl polymer having a molecular weight of 16,000.

Reference example U3

A solution of 2 g of azobisisobutyronitrile dissolved in 30 g of styrene, 22 g of gamma-methacryloxypropyltrimethoxysilane, 22 g of methyl methacrylate, 15 g of n-butyl methacrylate, 18 g of butyl acrylate and 2 g of n-dodecylmercaptan was added dropwise to 70 g of xylene kept at 90 ℃ as a solvent, and these compounds were reacted with each other for 10 hours to give a silyl-containing vinyl polymer having a molecular weight of 9,000.

Reference example U4

A solution of 2 g of azobisisobutyronitrile dissolved in 30 g of styrene, 22 g of gamma-methacryloxypropyltrimethoxysilane, 52 g of methyl methacrylate, 15 g of n-butyl methacrylate, 18 g of butyl acrylate, 4 g of acrylamide, 10 g of n-butanol and 4 g of n-dodecylmercaptan was added dropwise to 70 g of xylene kept at 70 ℃ as a solvent, and these compounds were reacted with each other for 10 hours to give a silyl group-containing vinyl polymer having a molecular weight of 6,000.

Reference example U5

A solution of 2 g of azobisisobutyronitrile dissolved in 30 g of styrene, 22 g of gamma-methacryloxypropyltrimethoxysilane, 22 g of methyl methacrylate, 15 g of n-butyl methacrylate, 18 g of butyl acrylate, 4 g of 2-hydroxyethyl methacrylate and 4 g of n-dodecylmercaptan was added dropwise to 70 g of xylene kept at 90 ℃ as a solvent, and these compounds were reacted with each other for 10 hours to give a silyl group-containing vinyl polymer having a molecular weight of 6,000.

Reference example U6

A silyl-containing vinyl polymer having a molecular weight of 5,000 was prepared in the same manner as in reference example U4, except that 6 g of n-dodecylmercaptan, 4 g of acrylamide, 2 g of maleic anhydride and 10 g of n-butanol were used in place of 4 g of n-dodecylmercaptan and 4 g of 2-hydroxyethyl methacrylate in reference example U5.

The resin solutions prepared in each of examples U and reference examples U1-U6 were mixed with the additives and curing catalyst listed in Table U1, diluted with xylene to a resin viscosity (Ford cup viscosity: 15 seconds), and measured for pot life before peeling or gelling under open conditions.

Further, the resin solutions prepared in each of examples U and reference examples U1-U6 and the mixtures of the additives and curing catalysts listed in Table U1 were subjected to gel fraction measurement tests in accordance with the above-mentioned methods.

The mixture was left in a glass petri dish having a diameter of 2 cm and a depth of 1.5 cm, cured at room temperature, and the weather resistance of the cured composition was measured by the above-described method.

The results are shown in Table U1.

Watch U1

	Practice of Example U	Reference to Example U1	Reference to Example U2	Reference example U3		Reference to Example U4	Reference example U5		Reference to Example U6
										(1)	(2)	(1)	(2)
				Curing catalyst [ parts by weight]
Stann JF-9B(*1)	3	3	3			2.4			-	3	-	-	3
				Phthalic acid	-		-	-						-	-	-	-	1	-
Dibutyl dilaurate Tin (Sn)	-	-	-			-			-	-	3	3	-
				Tin octylate	-		-	-						0.6	1	-	-	-	-
Additive (parts by weight)]	-	-	-			-			-	-	-	-	-
				Methanol	10		10	10						-	-	-	10	10	10
Tetraethyl orthosilicate	10	10	-			10			10	-	10	10	10
				Trimethyl orthoformate	-		-	-						-	-	-	-	-	1
Storage under open conditions Shelf life	10 is small Less than or equal to	10 is small Less than or equal to	10 is small Less than or equal to			10 is small Less than or equal to			3 hours Internal peeling	10 is small Less than or equal to	3 hours Internal peeling	10 is small Less than or equal to	10 is small Less than or equal to
				Evaluation of gel fraction	◎		×	△						×	○	△	○	×	△
Evaluation of weather resistance	○	△	△			△			×	△	×	△	×

(x1) Stann JF-98: stabilizers for vinyl chloride (Sankyo Organic Chemials, Ltd.)

The chemical formula of the main component is as follows: (n-C)₄H₉-)₂Sn(-SCH₂COOR)₂(R: C4-C12) (. about.2) parts by weight of a curing catalyst and additives per 100 parts by weight of the resin.

<example V series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

Production example V1

[ preparation of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 liters and equipped with stirring blades (stirring speed: 250 rpm), the liquid phase was separated from the side of the reactorHexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed at rates of 60 l/h, 2.5 kg/h, 4.0 kg/h and 380 g/h, respectively, and hydrogen, VO (OEt) as a catalyst, were continuously fed at rates of 700 l/h, 45 mmol/h and 315 mmol/h, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

Thecopolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) containing 68 mol% of ethylene, having an Iodine Value (IV) of 10 (g/100 g), and having an intrinsic viscosity measured in decalin maintained at 135 ℃ [ η]0.2dl/g and Mw/Mn of 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a mixture containing dimethoxymethylsilyl groups (-SiCH)₃(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example V2

[ preparation of saturated Hydrocarbon-based Polymer (D-1)]

A uniformly mixed solution of 560 ml of methylene chloride, 1,160 ml of n-hexane, 940 mg of α -methylpyridine and 22 g of p-dicumyl chloride, all dried, was formed in a four-necked flask equipped with a stirrer and a nitrogen line and cooled to-70 deg.C, to which 570 ml of isobutylene monomer was added under vacuum through a molecular sieve tube.

To the above reaction solution maintained at-70 ℃ was immediately and completelyadded a previously cooled polymerization catalyst solution (containing 14 ml of titanium tetrachloride and 80 ml of methylene chloride) with stirring to initiate polymerization. The reaction solution was heated to-54 ℃ and then cooled to-70 ℃ over about 17 minutes.

About 20 minutes after the initiation of the polymerization reaction, 132 g of 1, 9-decadiene was added to the reaction solution, and stirring was continued at-70 ℃ for 4 hours.

The thus-prepared pale yellow turbid reaction solution was put into 3 liters of hot water (about 45 ℃) and stirred for about 2 hours. Then, the organic layer was separated and washed 3 times with pure water. The resulting colorless transparent organic layer was concentrated under vacuum to give about 400 g of an isobutylene oligomer having vinyl groups at both ends.

Next, 400 g of an isobutylene oligomer having vinyl groups at both ends was dissolved in 200 ml of n-heptane. The resulting solution was heated to about 70 ℃ and 1.5[ equivalents/vinyl group was added thereto]Methyldimethoxysilane and 1X 10^-4[ equivalent/vinyl group]]The platinum/vinylsiloxane complex of (a), to carry out a hydrosilylation reaction. The reaction was followed by FT-IR. 1640cm^-1The olefin absorption peak disappeared in about 4 hours.

The reaction solution was concentrated under vacuum to obtain the objective isobutylene oligomer (D-1) having reactive silicon groups at both terminals.

[ structural formula (II b)]]

Production example V3

[ preparation of saturated Hydrocarbon-based Polymer (D-2)]

The same procedure used in preparation example V2 was repeated in preparation example V3, except that 1, 9-decadiene was replaced with 24 g of allylmethylsilane to obtain an isobutylene oligomer (D-2) having a partially different intermediate structure formed.

[ structural formula (II b)]]

Production example V4

[ preparation of saturated Hydrocarbon-based Polymer (D-3)]

A uniformly mixed solution of 560 ml of methylene chloride, 1,160 ml of n-hexane, 940 mg of α -methylpyridine and 22 g of p-dicumyl chloride, all dried, was formed in a four-necked flask equipped with a stirrer and a nitrogen line and cooled to-70 deg.C, to which 570 ml of isobutylene monomer was added under vacuum through a molecular sieve tube.

To the above reaction solution maintained at-70 ℃ was immediately and completely added a previously cooled polymerization catalyst solution (containing 14 ml of titanium tetrachloride and 80 ml of methylene chloride) with stirring to initiate polymerization. The reaction solution was heated to-54 ℃ and then cooled to-70 ℃ over about 17 minutes. After the initiation of the polymerization reaction, the reaction solution was continuously stirred for about 60 minutes. The yellow turbid reaction solution thus obtained was put into 3 liters of hot water (about 45 ℃) and stirred for about 2 hours. Then, the organic layer was separated and washed 3 times with pure water. The resulting colorless transparent organic layer was concentrated under vacuum to give about 400 g of an isobutylene oligomer having a chlorinedione group at both ends.

Then, the isobutylene oligomer was continuously heated at 170 ℃ for 2 hours under vacuum to perform a thermal dehydrochlorination reaction, thereby obtaining an isobutylene oligomer having isopropenyl groups at both ends.

Next, 400 g of the isobutylene oligomer having isopropenyl groups at both ends obtained as above was dissolved in 200 ml of n-heptane. The resulting solution was heated to about 100 ℃ in a pressure vessel, to which was added 1.5[ equivalents/vinyl group]And 1X 10 of methyldichlorosilane^-4[ equivalent/vinyl group]]The platinum/vinylsiloxane complex of (a), to carry out a hydrosilylation reaction. The reaction was followed by FT-IR. 1640cm^-1The olefin absorption peak disappeared in about 10 hours. The reaction solution was cooled to 60 ℃, methanol in excess of methyldichlorosilane was added, and the mixture was stirred for about 4 hours to complete the methoxylation reaction. The reaction solution was concentrated under vacuum to obtain the objective isobutylene oligomer (D-3) having a structure with reactive silicon groups at both ends.

[ structural formula (II b)]]

Example V1

A mixture comprising the polymer (A-1) obtained in production example V1 as a silane-modified ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) was prepared, the mixture comprising 100 parts of the polymer rubber (A-1), 120 parts of calcium carbonate (Shiraishi K.K.CCR)^TM) 90 parts of paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32) as a plasticizer^TM) 30 parts of titanium dioxide, 5 parts of sodium hydrogensulfate and 3 parts of dibutyltin diacetylacetonate as curing agent (H8), all parts being parts by weight. These components were uniformly kneaded to obtain a curable composition.

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. The composition cured within 16 minutes.

Dibutyltin diacetylacetonate

Comparative example V1

A curable composition was prepared in the same manner as in comparative example V1, except that tin dioctoate was used in place of the curing catalyst (H8).

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. It is not cured even after 700 minutes or more.

Tin dioctoate

Reference example V1

A mixture containing the polymer (D-1) obtained in production example V2 as a saturated hydrocarbon-based polymer component was prepared. The mixture comprises 100 parts of polymer (D-1), 120 parts of calcium carbonate (Shiraishi K.K.CCR)^TM) 90 parts of paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32) as a plasticizer^TM) 30 parts of titanium dioxide, 5 parts of sodium hydrogensulfate and 3 parts of dibutyltin diacetylacetonate as a curing catalyst (H8), all parts being parts by weight. These components are uniformly kneaded to obtain a curable composition.

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. The composition cured within 25 minutes.

Reference example V2

A mixture containing the polymer (D-2) obtained in production example V3 as a saturated hydrocarbon-based polymer component was prepared. The mixture comprises 100 parts of polymer (D-2), 120 parts of calcium carbonate (Shiraishi K.K.CCR)^TM) 90 parts of paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32) as a plasticizer^TM) 30 parts of titanium dioxide, 5 parts of sodium hydrogensulfate and 3 parts of dibutyltin diacetylacetonate as a curing catalyst (H8), all parts being parts by weight. These components are uniformly kneaded to obtain a curable composition.

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. The composition cured within 30 minutes.

Reference example V3

A mixture containing the polymer (D-3) obtained in production example V4 as a saturated hydrocarbon-based polymer component was prepared. The mixture comprises 100 parts of polymer (D-3), 120 parts of calcium carbonate (Shiraishi K.K.CCR)^TM) 90 parts of paraffin-based Process Oil (Idemitsu Kosan, Diana Process Oil PS-32) as a plasticizer^TM) 30 parts of titanium dioxide, 5 parts of sodium hydrogensulfate and 3 parts of dibutyltin diacetylacetonate as a curing catalyst (H8), all parts being parts by weight. These components are uniformly kneaded to obtain a curable composition.

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. The composition cured within 30 minutes.

Reference example V4

A curable composition was prepared in the same manner as in referential example V1, except that tin dioctoate was mixed into the polymer (D-1) prepared in production example V2 as the saturated hydrocarbon-based polymer in place of the curing catalyst (H8).

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. The composition does not cure even after 700 minutes or more has elapsed.

Reference example V5

A curable composition was prepared in the same manner as in referential example V2, except that tin dioctoate was mixed intothe polymer (D-2) prepared in production example V3 as the saturated hydrocarbon-based polymer in place of the curing catalyst (H8).

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. The composition does not cure even after 700 minutes or more has elapsed.

Reference example V6

A curable composition was prepared in the same manner as in referential example V3, except that tin dioctoate was mixed into the polymer (D-3) prepared in production example V4 as the saturated hydrocarbon-based polymer in place of the curing catalyst (H8).

The curability (tack free time) of the resulting composition was measured in accordance with JIS A-5758. The composition does not cure even after 700 minutes or more has elapsed.

For examples and comparative examples, a curing speed test and an accelerated weather resistance test were conducted in the following manner.

(1) Curing speed test

The curable composition was cured in a mold (dimensions 20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours.

The cured product was then taken out of the mold, and the curing speed was evaluated by measuring the thickness of the cured portion with a micrometer having a spring force as weak as 0.1mm, which was marked with ○ when the thickness was 1mm or more and with x when the thickness was less than 1 mm.

(2) Weather resistance test

The accelerated weather resistance test was carried out under the following conditions in accordance with JIS B-7753.

The instrument comprises the following steps: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 250 hours

The test specimen was visually observed, and when no deterioration (crack or molten portion) was observed, it was marked as ○, and when deterioration was observed, it was marked as ×.

TABLE V1

		Examples	Comparative example
						V1	V1
Silyl-containing ethylene/α -olefin/nonconjugated polyethylene Copolymer rubber (A-1)		100	100
				Curing catalyst	Curing catalyst (H8)	3	-
Tin dioctoate	-	3
			Calcium carbonate		120	120
Operating oil		90					90
			Titanium dioxide		30	30
Sodium hydrogen sulfate		5					5
			Without stickiness (minute)Clock)		16	＞700
Curable composition		○					×
			Weather resistance		○	○

TABLE V2

		Reference example V
								1	2	3	4	5	6
		Saturated hydrocarbon-based polymer	D-1	100	-	-	100							-	-
D-2	-							100	-	-	100	-
			D-3	-	-	100	-						-	100
Curing catalyst	Curing catalyst (H8)							3	3	3	-	-			-
		Tin dioctoate	-	-	-	3	3						3
	Calcium carbonate							120	120	120	120	120		120
Operating oil			90	90	90	90	90						90
		Titanium dioxide						30	30	30	30	30		30
Sodium hydrogen sulfate				5	5	5	5						5		5
		Without stickiness (minutes)						25	30	30	＞700	＞700		＞700
Curable composition				×	×	×	×						×		×
		Weather resistance						○	○	○	○	○		○

<example W series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

The curing speed and weather resistance of the compositions prepared in examples, comparative examples and reference examples were tested by the following methods.

(1) Curing speed test

The curable composition was cured in A mold (80X 12.5 mm) at 23 ℃ and 50% relative humidity, and after the surface tackiness disappeared, the hardness thereof was measured with A JIS-A durometer, and the time required until the hardness reached 20 was recorded.

(2) Weather resistance test

Accelerated weather resistance test:

it was carried out according to JIS B-7753.

An analyzer: sunshine Carbon Arc weathering tester.

Light/rain cycle: illumination 120 min/rainfall 18 min

Black floor temperature: 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

Production example W1

Production example 1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OEt) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) intrinsic viscosity, measured in decalin maintained at 135 ℃, containing 68 mol% of ethylene [ η]0.2 deciliter/g, Iodine Value (IV) 10 (g/100 g), Mw/Mn 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) to a 2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were addedThey were reacted with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a compound containing dimethoxymethylsilyl groups (-Si (CH)₃)(OCH₃)₂) The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1).

Production example W2

138 ml of ethylcyclohexane (dried at least one night over molecular sieve 3A), 1012 ml of toluene (also dried at least one night over molecular sieve 3A) and 8.14 g (35.2 mmol) of p-DCC represented by the following formula were introduced by syringe into a2 l nitrogen-purged pressure-resistant glass reactor equipped with a three-way stopcock.

Then, a pressure-resistant glass liquefied gas collecting tube equipped with a needle valve and containing 254 ml (2.99 mol) of isobutylene monomer was connected to the above-mentioned three-way cock. The reactor for polymerization was then immersed in a dry ice/ethanol bath maintained at-70 ℃, the solution was allowed to cool, and a vacuum was drawn off with a vacuum pump. The needle valve was then opened to allow isobutylene monomer to pass from the liquefied gas collection tube into the polymerization reactor and the reactor was returned to atmospheric pressure with nitrogen from the other port of the three-way stopcock. Then, 0.387 g (4.15 mmol) of 2-methylpyridine was added to the reactor, followed by 4.90 ml (44.7 mmol) of titanium tetrachloride, to initiate polymerization. After 70 minutes, 9.65 g (13.4 mmol) of allyltrimethylsilane were charged into the reactor, and allyl groups were introduced at the polymer end groups. After 120 minutes of the reaction, the reaction mixture was washed 4 times with 200 ml of water each time, and the solvent was distilled off to prepare an isobutylene polymer having an allyl terminal.

Next, 200 g of the isobutylene polymer having allyl end groups thus obtained was mixed with 60g of paraffin process oil (Idemitsu Kosan, Diana Process oil PS-32) as a hydrocarbon plasticizer^TM) Mixing, heating the mixture to about 75 deg.C, adding 1.5[ equivalent/vinyl group []]Methyldimethoxysilane and 5X 10^-5[ equivalent/vinyl group]]The platinum/vinylsiloxane complex of (a), to carry out a hydrosilylation reaction. The reaction was followed by FT-IR. About 20 hoursOlefin in 1640cm time^-1The absorption peak at (a) disappeared.

This produced a mixture of an isobutylene polymer (represented by the following formula) having reactive silicon groups at both terminals and PS-32 as a plasticizer:

the yield of the polymer was estimated from the yield. The Mn and Mw/Mn were also analyzed by GPC and compared with each other at 300MHz for protons associated with each structure¹H-NMR-analysis the intensity of resonance signals (proton from initiator: 6.5-7.5ppm, methyl proton from polymer terminal attached to silicon atom: 0.0-0.1ppm, methoxy proton: 3.4-3.5ppm) analyzes the terminal structure. In CDCl with Varian Gemini 300 (300 MHz for 1H)₃In the middle of¹H-NMR analysis.

FT-IR analysis was performed with an IR analyzer (Shimadzu IR-408), and GPC analysis was performed with a Waters LC Module 1 as a liquid transfer system and Shodex K-804 as a column. Molecular weight is the molecular weight relative to the standard value for polystyrene. The polymer thus produced had an Mn of 5, 780, an Mn/Mw of 1.28 and an Fn (silyl) of 1.93, wherein the number average molecular weight was expressed as polystyrene molecular weight and the number of terminal silyl functional groups was the number of terminal silyl functional groups per 1 mole of isobutylene polymer.

Example W1

130 parts of the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in preparation example W1 and paraffin-based process oil(Idemitsu Kosan, Diana process oil PS-32)^TM) (wherein the silyl group-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) is 100 parts), 5 parts of tetra-n-butyl titanate (Wako-Junyaku) as a titanate of the component (Y), 2 parts of dibutyltin diacetylacetonate (NITTO KASEI, Neostan U-220) as a silanol condensing catalyst, were incorporated^TM) And 1 part of H₂O, so the parts are all by weight, to prepare a curable rubber composition.

The above composition was spread to a thickness of 5mm on an unprimed float glass substrate washed with methyl ethyl ketone (Wako-Junyaku) and cured in an oven. The cured compositions were subjected to a peel test using manual peeling with a cutter knife cutting the adhesive surface. The composition containing 5 parts by weight of titanate adhered well to the float glass substrate and showed cohesive failure. Curing speed and weather resistance tests were also carried out as described previously. It took 18 hours to reach a hardness of 20 in the curing speed test and showed no cracking in the weather resistance test.

Comparative example W1

A composition was prepared in the same manner as in example W1, except that the addition of the titanate ester as component (Y) was omitted and the test was conducted in the same manner. The composition exhibits insufficient adhesion to float glass substrates and exhibits adhesive failure. In addition, it took 72 hours for its hardness to reach 20 in the cure speed test and showed some cracking visible to the naked eye in the weather resistance test.

Reference example W1

A composition was prepared in the same manner as in comparative example W1, except that the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber prepared in production example W1 was replaced with the reactive silyl group-containing saturated hydrocarbon polymer prepared in production example W2, and a test was conducted in the same manner. The manual peel test indicated that the adhesion of the composition to float glass was insufficient and it showed adhesive failure. In addition, it took 48 hours for its hardness to reach 20 in the cure speed test, and showed slight but macroscopic cracking and melting portions in the weather resistance test.

Reference example W2

A composition was prepared in the same manner as in example W1, except that the silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber prepared in production example W1 was replaced with the reactive silyl group-containing saturated hydrocarbon polymer prepared in production example W2, and a test was conducted in the same manner. The manual peel test showed that the composition adhered well to the float glass and it showed cohesive failure. However, it reached a hardness of 20 to 36 hours in the curing speed test, and showed slight cracking and melting portions in the weather resistance test.

<example X series>

The composition, iodine value, intrinsic viscosity [ η], and molecular weight distribution (Mw/Mn) of the copolymer rubbers used in the respective examples and comparative examples were determined by the aforementioned methods.

Production example X1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 3.0 kg/hr, 9.0 kg/hr and 550 g/hr,respectively, and hydrogen and VOCl as a catalyst were continuously fed at rates of 70 l/hr, 95 mmol/hr, 443 mmol/hr and 127 mmol/hr, respectively₃、Al(Et)₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization conducted under the above conditions produced an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A) in the form of a homogeneous solution₀-1)。

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

Thus prepared ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) containing 68 mol% of ethylene, having an Iodine Value (IV) of 15 (g/100 g), and having an intrinsic viscosity measured in decalin at 135 ℃ [ η]0.2 deciliter/gram and Mw/Mn of 15. The yield was 3.5 kg/h.

At 100 parts by weight of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% toluene solution of chloroplatinic acid (0.3 part by weight) and 1.5 parts by weight of methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This is achieved by101.5 g of a compound containing dimethoxymethylsilyl groups (-SiH (OCH)₃)₂) An ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber.

Production example X2

[ production of saturated Hydrocarbon Polymer (CA-1)]

In a four-necked flask equipped with a stirrer and a nitrogen line, cooled to-70 ℃, a homogeneous mixed solution was formed from 560 ml of methylene chloride, 1,160 ml of n-hexane, 940 mg of α -methylpyridine and 22 g of p-diisopropylphenyl chloride, all dried, to which 570 ml of isobutylene monomer was added through a molecular sieve tube under vacuum.

To the above reaction solution maintained at-70 ℃ was immediately added all of the polymerization catalyst solution (containing 14 ml of titanium tetrachloride and 80 ml of methylene chloride) cooled in advance while stirring to initiate polymerization. The reaction was heated to-54 ℃ and then cooled to-70 ℃ over about 17 minutes. After the polymerization was initiated for about 20 minutes, 132 g of 1, 9-decadiene was added to the reaction solution, and the mixture was continuously stirred at-70 ℃ for 4 hours.

The thus-prepared yellow turbid reaction liquid was placed in3 liters of hot water (about 45 ℃ C.) and stirred for about 2 hours. Then, the organic layer was separated and washed 3 times with pure water. The resulting colorless transparent organic layer was concentrated under vacuum to obtain about 400 g of an isobutylene oligomer having vinyl groups at both terminals.

Then, 400 g of an isobutylene oligomer having vinyl groups at both terminals was dissolved in 200 ml of n-heptane. The resulting solution was heated to about 70 ℃ and 1.5[ equivalents/vinyl group was added thereto]Methyldimethoxysilane and 1X 10^-4[ equivalent/vinyl group]]The platinum/vinylsiloxane complex of (a), to carry out a hydrosilylation reaction. The reaction was followed by FT-IR. Olefin at 1640cm^-The absorption peak at 1 disappeared in about 4 hours.

The reaction solution was concentrated under vacuum to obtain an isobutylene oligomer having reactive silicon groups at both terminals (represented by the following formula).

Production example X3

[ production of saturated Hydrocarbon Polymer (CA-2)]

The same procedure as used in production example X2 was repeated in production example X3, except that 1, 9-decadiene was replaced with 24 g of allylmethylsilane to obtain an isobutylene oligomer (represented by the following formula) having a partially different internal structure.

Production example X4

[ production of saturated Hydrocarbon Polymer (CA-3)]

In a four-necked flask equipped with a stirrer and a nitrogen line cooled to-70 deg.C, a homogeneous mixed solution was formed from 560 ml of methylene chloride, 1,160 ml of n-hexane, 940 mg of α -methylpyridine and 22 g of p-diisopropylphenyl chloride (all dried), to which 570 ml of isobutylene monomer was added through a molecular sieve tube under vacuum.

To the above reaction solution maintained at-70 ℃ was added all of the previously cooled polymerization catalyst solution (containing 14 ml of titanium tetrachloride and 80 ml of methylene chloride) while stirring to initiate polymerization. The reaction was heated to-54 ℃ and then cooled to-70 ℃ over about 17 minutes. After the initiation of the polymerization reaction, the reaction solution was continuously stirred for about 60 minutes. The thus-prepared yellow turbid reaction liquid was placed in3 liters of hot water (about 45 ℃ C.) and stirred for about 2 hours. Then, the organic layer was separated and washed 3 times with pure water. The resulting colorless transparent organic layer was concentrated under vacuum to obtain about 400 g of an isobutylene oligomer having both terminal vinylidene chloride groups.

Then, the isobutylene oligomer was continuously heated at 170 ℃ under vacuum to perform a thermal dehydrochlorination reaction, to obtain an isobutylene oligomer having isopropenyl groups at both terminals.

400 g of an isobutylene oligomer having isopropenyl groups at both terminals was dissolved in 200 ml of n-heptane. In a pressure vessel, the resulting solution was heated to about 100 ℃ and 1.5[ equivalents/vinyl group was added thereto]Methyldichlorosilane and 1X 10^-4[ equivalent/vinyl group]]The platinum/vinylsiloxane complex of (a), to carry out a hydrosilylation reaction. The reaction was followed by FT-IR. Olefin at 1640cm^-1The absorption peak disappeared in about 10 hours. The reaction liquid was cooled to 60 ℃, methanol in excess to methyldichlorosilane was added thereto, and the mixture was stirred for about 4 hours to complete the methoxylation reaction. The reaction liquid was concentrated under vacuum to obtain an isobutylene oligomer having a structure represented by the following formula with reactive silicon groups at both terminals.

Synthesis example 1

[ Synthesis of copolymer (B)]

A solution of 5.7 g of butyl acrylate, 65.1 g of methyl methacrylate, 13.3 g of stearyl methacrylate, 5.6 g of gamma-methacryloxypropyltrimethoxysilane, 8.0 g of gamma-mercaptopropyltrimethoxysilane, 5.0 g of azobisisobutyronitrile and 22 g of xylene was added dropwise over a period of 6 hours in 20 g of a xylene solvent heated at 110 ℃. They were allowed to react with each other to polymerize for 2 hours, yielding a copolymer (B) having a solid content of 70% and a number average molecular weight (Mn) of 2,100 (in terms of polystyrene molecular weight) as determined by GPC.

Examples X1-X5

The silyl group-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example X1 was blended with the copolymer (B) prepared in Synthesis example 1 in a solid weight ratio of 60/40, and the mixture was subjected to evaporation treatment with an evaporator at 110 ℃ under vacuum to obtain a transparent viscous liquid having a solid content of not less than 99%.

100 grams of the blended, evaporated polymer was thoroughly kneaded with a planetary mixer: 100 g of limestone powder, 50 g of colloidal calcium carbonate, 5 g of glass beads (average particle diameter: 70 μm), 100 g of diisononyl phthalate, 5 g of silicic anhydride, 2 g of hindered phenol type antiaging agent, 10 g of calcium oxide, 2 g of aluminum chelate type curing catalyst, 1 g of aminosilane compound and silicon type reaction diluent (Shin-etsu silicone, AFP-1), the samples (A-1) of examples X1 to X5 were obtained.

Reference examples X1-X9

For reference examples X1-X9

Blended evaporation-treated polymers were prepared in the same manner as in examples X1 to X5, except that the silyl group-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1) prepared in production example X1 was replaced with the saturated hydrocarbon polymers (CA-1) to (CA-3) prepared in production examples X2 to X4, respectively, and that the samples (CA-1) to (CA-3) of reference examples X1 to X9 were prepared in the same manner as in examples X1 to X5.

Comparative examples X1-X3

100 g of vinyl chloride resin was completely kneaded with the following using a planetary mixer: 100 g of limestone powder, 50 g of colloidal calcium carbonate, 5 g of glass spheres (average particle diameter: 70 μm), 100 g of diisononyl phthalate, 3 g of a lead-based dehydrochlorination inhibitor and 5 g of a polyurethane prepolymer wereused to obtain a sample (CA-4) of comparative example X1-X3.

These samples were each spread on a cationically plated steel plate under different conditions as shown in table X1 to a thickness also shown in table X1 and cured to investigate their resistance to chipping (chipping), spraying saline and vibration. The weather resistance and curing speed of the coating film were evaluated by the following methods. The results are shown in Table X1.

The test methods are described below

(chipping resistance)

Three nuts (Nut M-4) were dropped from a height of 2M to a specimen inclined at 45 ℃ until the base was exposed, and the cracking resistance was evaluated by the total weight of the nuts.

(tolerance to salt water for spraying)

A test piece coated on a cation-plated steel plate as a coating film of a given thickness was scribed to the base metal at the center and left in a tank sprayed with brine for 200 hours. When the cellophane tape placed on the cross-hatched surface peeled off, its resistance to sprayed saline was evaluated by the maximum width of the peel.

(vibration resistance)

According to the vibration isolation test method (JASO7006) of the automobile floor coating, the formula d is (f)₂-f₁)/f₀The vibration isolation coefficient (d) defined is evaluated for vibration resistance, where f₀Is the resonance frequency at the second resonance point, and f2 and f1 are sound intensity dropsThe frequencies at the 3dB lower section were all measured at 25 ℃.

(curing speed test)

Tack free time at moderate temperature

The cation-plated steel sheet coated with the composition to a thickness of 10 mm was allowed to stand at 60 ℃ in a dryer. The tack of the coating composition was measured with a finger at given time intervals. Tack free time is defined as the time when the composition is no longer transferred to the fingertips.

(weather resistance test)

The weather resistance was evaluated by conducting an accelerated weather resistance test in accordance with JIS B-7753 under the following conditions:

an analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 250 hours

The test specimen was visually inspected and its weather resistance was evaluated according to the following four grades.

◎ No cracking or melting part was observed at all

○ very slight cracking or melting of parts was observed

△ some degree of cracking or melting of the parts was observed

X: severe cracking or melting of the parts was observed

TABLE X1

		Example X					Reference example X									Comparative example X
																					1	2	3	4	5	1	2	3	4	5	6	7	8	9	1	2	3
		A-1					CA-1			CA-2			CA-3			CA-4
																			Curing conditions	At 140 deg.C for 30 min	○	○	-	-	-	○	○	-	○	○	-	○	○	-	○	○	-
120 ℃ for 20 minutes	-	-	○	-	-	-	-	○	-	-	○	-	-	○	-	-	○
																		120 ℃ for 10 minutes		-	-	-	○	-	-	-	-	-	-	-	-	-	-	-	-	-
100 ℃ for 20 minutes	-	-	-	-	○	-	-	-	-	-	-	-	-	-	-	-	-
																		Thickness of coating film		1.5 mm	○	-	-	-	-	○	-	-	○	-	-	○	-	-	○	-	-
0.5mm	-	○	○	○	○	-	○	○	-	○	○	-	○	○	-	○	○
																			Resistance to cracking		135	98	92	92	81	103	79	74	102	80	79	101	73	77	68	41	9
Vibration resistance (x 10)3)		55	16	15	14	14	45	10	12	42	11	12	42	11	13	8	5	4
																			Tolerance to sprayed salt water (mm)		≤1	≤1	≤1	≤1	≤1	≤1	≤1	1.2	≤1	≤1	1.3	≤1	≤1	1.3	≤1	1.8	3.6
Tack free time		30	30	30	30	30	60	60	60	80	80	80	100	100	100	90	90	90
																			Weather resistance		◎	◎	◎	◎	◎	△	△	△	△	△	△	△	△	△	×	×	×

As shown in Table X1, the coating of the present invention exhibits excellent chipping resistance, vibration resistance, resistance to sprayed salt water and weather resistance for automobiles, and also has a high curing speed even when cured at low temperatures and in a short time and the coating is thin.

<example Y series>

Production example Y1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)]

In a stainless polymerization reactor having a basic capacity of 100 l and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 l/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and hydrogen and VO (OC) as a catalyst were continuously fed at rates of 700 l/hr, 45 mmol/hr and 315 mmol/hr, respectively₂H₅)₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization reaction conducted under the above conditions produces an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in the form of a homogeneous solution.

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thus prepared contained 68 mol% of ethylene, and had an Iodine Value (IV) of 10 (g/100 g), an intrinsic viscosity [ η]of 0.2dl/g and an Mw/Mn of 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of a dimethoxymethylsilyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber.

Example Y1

In production exampleThe silyl group containing copolymer rubber prepared in Y1 was incorporated with the following: paraffin process oil (Idemitsu Kosan, Diana process oil PS-32)^TM) Limestone powder (Maruo Calcium, Snowlite SS)^TM) And Natrii sulfas (Na)₂SO₄·10H₂O), the mixture was well kneaded with a 3-roll coater to make the main component for a sealant. The amounts in parts by weight are shown in Table Y1. With dibutyl tin diacetylacetonate (NITTO KASEI, U-220)^TM) As a curing catalyst.

The main components and the curing catalyst as the sample components were well kneaded to form sheets having a thickness of about 1.5 mm, and cured in an oven at 23 ℃ and 50% RH for 7 days, and then further cured at 50 ℃ and 70% RH for 7 days. The composition is shown in Table Y1.

The cured sheet sample was tested under temperature/humidity conditions B (40 ℃ C. and90% RH) in accordance with JIS Z-0208 (moisture permeability of moisture-proof packaging material).

The moisture permeability of the sample was evaluated on three scales:

○ permeability of 1-25 g/m²24 hours

△ permeability of 25-50 g/m²24 hours

X: permeability: not less than 50 g/m²24 hours

The results are shown in Table Y1.

Reference example Y1

A sample was prepared in the same manner as in example Y1, except that the silyl group containing copolymer rubber prepared in production example Y1 was replaced with an isobutylene polymer having reactive silicon containing groups at both terminals prepared by the method disclosed in Japanese patent laid-open publication No.209539/1999 (paragraph 0044-0053), and the test was conducted in the same manner. The moisture permeability results thereof are shown in Table Y1, in which the isobutylene polymer having a reactive silicon-containing group is listed in the list of component (A).

TABLE Y1

	Examples	Reference example
			Composition of (Main Components) Component (A2) Silyl group-containing copolymer rubber prepared in production example 1 Isobutylene polymers containing reactive silicon Other additives Operating oil (PS-32) Lime powder (Snowlite SS) Na2SO4·H2O Component (H) Curing agent (U-220)	Y1 100 - 100 460 2 4	Y1 - 100 100 460 2 4
Characteristics of the cured product Moisture permeability (g/m)224 hours) Thickness (millimeter)	0 1.637	0 1.868

Examples Y2-Y5

The silyl group-containing copolymer rubber prepared in production example Y1 was well kneaded with the following additives by a 3-paint roller apparatus to prepare the main components of each of examples Y2 to Y5: anti-aging agents (Ciba-GeigyJapan, Irganox 1010; Sumitomo Chemical, Sumisorb 400^TMAnd Sankyo SanolLS-765^TM) (ii) a Light stabilizers (Sanshin Kagaku Kogyo, Sandant NBC)^TM(ii) a And ACC, CYASORBUV-1084^TM) (ii) a Photocurable resin (TOAGOSEI, Aronix M-400)^TM) (ii) a Thixotropic agent (Kusumoto Kasei, Disparlon # 305)^TM) (ii) a Silane coupling agents (Nippon Unicar, A-1310 and A-187)^TM). The compositions are shown in Table Y2.

The curing agent was prepared by the following method: a curing catalyst (Sankyo organic Chemicals, Ltd., SCAT-27) will be included in the disposable cup^TM) And the mixture of the other components were kneaded by hand and stirred 3 times at 10,000 rpm for 10 minutes each with a homogenizer (nihon seiki Sesakusho co., ltd., Excel autohomogenizer). The compositions are shown in Table Y2.

Specimens were prepared in accordance with JIS A-5758/1992 which specifies the method for preparing the tensile adhesion test specimens; the composition comprising the main component and the curing agent (the composition of which is shown in Table Y2) was, after sufficiently kneading, placed in an H-shaped glass or aluminum substrate frame and cured in an oven at 23 ℃ and 50% RH for 7 days and at 50 ℃ and 70% RH for another 7 days.

Three materials are used for preparing a base material for an H-shaped tensile test; float glass (Koen-sha with a size of 3X 5X 0.5 cm, designated by Japan Serial Industry Association) in accordance with JIS A-5758/1992, pure aluminum (Taiyu Kizai, A1100P with a size of 5X 0.2 cm) in accordance with JIS H-4000, and heat ray reflective glass (KLS) coated with hot-melt TiOX^TM5X 0.6 cm).

Each of these H-shaped substrates was washed with methyl ethyl ketone (Wako-Junyaku Kogyo, Special grade) and wiped with clean cotton cloth, then it was filled with the composition.

The H-shaped test piece thus prepared, in which the test piece was stretched at a stretching speed of 50 mm/min in a constant temperature chamber maintained at 23 ℃ and a relative humidity of 65. + -. 5%, was tested in accordance with the method for testing tensile adhesion of JIS A-5758/1992. The Cohesive Failure (CF)/Thin Coating Failure (TCF)/adhesive failure ratios shown in table Y3 were determined by visual inspection of the cross-section of the tensile specimens.

As shown in Table Y3, all of the compositions prepared in examples Y2-Y5 exhibited good adhesion to the substrate.

Reference examples Y2-Y5

Respective compositions of referential examples Y2 to Y5 were prepared in the same manner as in examples Y2 to Y5, except that the silyl group-containing copolymer rubber prepared in production example Y1 was replaced with the isobutylene polymer having groups of reactive silicon at both terminals, prepared in referential example Y1. The test results are shown in Table Y4.

TABLE Y2

	Examples
						Y2	Y3	Y4	Y5
[ major Components] Polymer prepared in preparation Y1 PS32 EDS-D10A PO320B10 Talc LMR Sandant NBC Aronix M400 Disparlon #306 Sumisorp 400 Sanol LS786 Irganox 1010 A-187 A1310	100 112.5 62.5 22.5 12.5 3 3 5 1 1 1 2 4	100 135 75 270 150 3 3 5 1 1 1 2 4	100 157 87.5 315 175 3 3 5 1 1 1 2 4	100 180 100 360 200 3 3 5 1 1 1 2 4
					[ curing agent] SCAT-27 PS32 CB#30 Na2SO4·10H2O Snowlite SS	4 12.5 2.5 4 25	4 15 2.5 4 30	4 17.5 2.5 4 35	4 2.0 2.5 4 40
Polymer content (%)	14.4	12.4	10.9	9.7

TABLE Y3

Number (C)	Base material		50% tensile stress M50 (kilogram force/cm)2)	Maximum tensile stress Tmax (kilogram force/cm)2)	Elongation at maximum load Emax(％)	Failure (%)
									CF	TCF	AF
						Example Y2	Float glass	1 2 Mean value of				4.46 4.66 4.64	6.17 6.20 6.19	87 86 87	100 100 100	0 0 0	0 0 0
Pure aluminium	1 2 Mean value of	4.39 4.37 4.38	6.21 6.10 6.16	91 87 98	99 100 100				1 0 0	0 0 0
							KLS	1 2 Mean value of			4.67 4.69 4.68	6.22 6.25 6.24	88 93 91	99 100 100	1 0 0	0 0 0
Example Y3	Float glass	1 2 Mean value of	4.69 4.71 4.70	6.26 6.27 6.27	86 84 85				98 98 98	2 2 2							0 0 0
						Pure aluminium	1 2 Mean value of	4 37 4.35 4.36			6.18 6.12 6.15	87 82 85	99 100 100	1 0 0	0 0 0
	KLS	1 2 Mean value of	4.80 4.83 4 82	6.32 6.36 6.34	80 79 80				97 97 97	3 3 3						0 0 0
						Example Y4	Float glass	1 2 Mean value of			4.66 4.69 4.68	6.11 6.02 6.07	72 74 73	98 100 99	2 0 1		0 0 0
Pure aluminium	1 2 Mean value of	4 36 4.33 4.35	6.11 6.08 6.05	79 77 78	92 97 95				7 3 5	0 0 0
							KLS	1 Mean value of			4.67 4.70 4.69	6.13 6.11 6.12	75 72 74	99 99 99	1 1 1	0 0 0
Example Y5	Float glass	1 2 Mean value of	4.33 4 30 4.32	6.27 6.23 6.25	70 73 72				98 99 99	2 1 1							0 0 0
						Pure aluminium	1 2 Mean value of	3.76 3.72 3.74			5.89 5.91 5.90	73 77 75	99 98 98	2 2 2	0 0 0
	KLS	1 2 Mean value of	4.32 4.37 4.35	6.18 6.11 6.15	78 71 75				100 100 100	0 0 0						0 0 0

TABLE Y4

Number (C)	Base material		50% tensile stress M50 (kilogram force/cm)2)	Maximum tensile stress Tmax (kilogram force/cm)2)	Elongation at maximum load Emax(％)	Failure (%)
									CF	TCF	AF
						Reference example Y2	Float glass	1 2 Mean value of				4.67 4.76 4.72	6.98 6.87 6.93	98 91 95	100 100 100	0 0 0	0 0 0
Pure aluminium	1 2 Mean value of	4.43 4.38 4.41	6.51 7.01 6.76	91 106 99	100 99 100				0 1 1	0 0 0
							KLS	1 2			4.79 4.66 4.73	7.25 7.43 7.34	99 105 102	98 100 99	2 0 1	0 0 0
Reference example Y3	Float glass	1 2 Mean value of	4.74 4.79 4.77	6.70 7.10 6.90	89 93 91				95 85 90	5 15 10							0 0 0
						Pure aluminium	1 2 Mean value of	4.38 4.43 4.41			6.81 6.53 6.67	94 85 90	100 95 98	0 6 3	0 0 0
	KLS	1 2	4.92 5.03 4.98	6.58 6.86 6.72	81 83 82				90 90 90	10 10 10						0 0 0
						Reference example Y4	Float glass	1 2 Mean value of			4.75 4.79 4.77	6.32 6.48 6.38	77 77 77	98 100 95	2 0 1		0 0 0
Pure aluminium	1 2 Mean value of	4.38 4.53 4.46	6.34 5.94 6.14	86 75 81	85 100 100				16 0 8	0 0 0
							KLS	1 2 Mean value of			4.68 4.83 4.76	6.29 6.17 6.23	81 74 78	99 90 100	1 10 6	0 0 0
Reference example Y5	Float glass	1 2 Mean value of	4.28 4.36 4.32	6.00 5.98 5.99	79 76 78				95 100 98	5 0 3							0 0 0
						Pure aluminium	1 2 Mean value of	3.92 3.99 3.96			5.38 6.13 5.76	79 87 83	95 98 97	5 2 4	0 0 0
	KLS	1 2 Mean value of	4.37 4.83 4.60	6.35 5.86 6.11	85 70 78				100 100 100	0 0 0						0 0 0

The compositions prepared in examples Y1-Y5and reference examples Y1-Y5 were subjected to curing speed and weather resistance tests. The results are shown in Table Y5.

The curing speed and weather resistance of the compositions prepared in examples Y1-Y5 and reference examples Y1-Y5 were measured by the following methods.

1) Speed of curing

The curing speed (film expandability) at room temperature of each composition comprising the main component and the catalyst was measured by curing each composition in a mold (size of 20 × 80 × 5 mm) at 23 ℃ and 50% RH for 24 hours and then taking out from the mold. The thickness of the cured portion was measured with a micrometer having a spring force as weak as 0.1 mm.

<evaluation of curing Rate>

X: the thickness of the cured part is less than 0.5mm

△ the thickness of the cured part is 0.5mm or more but less than 1 mm.

○ the thickness of the cured portion is not less than 1 mm.

2) Weather resistance test

An accelerated weather resistance test was carried out in accordance with JIS B-7753 under the following conditions:

an analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The test piece after the visual inspection was evaluated for weather resistance according to the following three grades:

○ No cracking or melting part observed

△ slight cracking or melting of parts was observed

X: cracks or molten portions were observed

TABLE Y5

	Weather resistance	Speed of curing
			Example Y1 Example Y2 Example Y3 Example Y4 Example Y5	○ ○ ○ ○ ○	○ ○ ○ ○ ○
Reference example Y1 Reference example Y2 Reference example Y3 Reference example Y4 Reference example Y5	△ △ △ △ △	× × × × ×

<example Z series>

Production example Z1

[ production of silyl-containing ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber]

In a stainless polymerization reactor having a basic capacity of 100 liters and equipped with a stirring blade (stirring speed: 250 rpm), hexane, ethylene, propylene and 5-vinyl-2-norbornene were continuously fed from the side of the reactor into the liquid phase at rates of 60 liters/hr, 2.5 kg/hr, 4.0 kg/hr and 380 g/hr, respectively, and at rates of 700 liters/hr, 45 mmol, respectivelyHydrogen and VO (OC) as a catalyst were continuously fed at a rate of 315 mmol/hr and a rate of hydrogen/hr₂H₅)₂Cl and Al (Et)_1.5Cl_1.5The ternary polymerization reaction is continuously carried out.

The copolymerization reaction conducted under the above conditions produces an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in the form of a homogeneous solution.

A small amount of methanol was added to the polymer solution continuously withdrawn from the bottom of the reactor to terminate the polymerization. The polymer was separated from the solvent by stripping the solution and dried under vacuum at 55 ℃ for 48 hours.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thus prepared contained 68 mol% of ethylene, and had an Iodine Value (IV) of 10 (g/100 g), an intrinsic viscosity [ η]of 0.2dl/g and an Mw/Mn of 15.

At 100 g of an ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A)₀-1) A2% solution of chloroplatinic acid in toluene (0.3 g) and 1.5 g methyldimethoxysilane were added and allowed to react with each other at 120 ℃ for 2 hours. The excess methyldimethoxysilane and the solvent (toluene) in the effluent were distilled off. This gave 101.5 g of dimethoxymethylsilyl-containing ethylene/propylene/5-vinyl-2-norborneneA random copolymer rubber.

Examples Z1-Z3, and comparative example Z1

The following were incorporated in 100 parts of the polymer prepared in production example Z1: 30 parts of paraffin process oil (Idemitsu Kosan, Diana process oil PS-32)^TM) 130 parts of butyl hot melt (yokohama rubber, Hamite hot melt M-120), and 6 parts of mirabilite (reagent, Na)₂SO₄·10H₂O), 3 parts of tin octylate (NITTO KASEI, Neostan U-28)^TM) And 0.75 parts laurylamine (Wako Jun-yaku), all parts by weight. The mixture was well kneaded using a 3-roll coater to prepare a sample of example Z1.

Compositions of examples Z2 and Z3 were prepared in the same manner as in example Z1, except that the contents of the butyl-based hot melt were 303.3 parts by weight and 1169 parts by weight, respectively, to prepare samples. A composition of comparative example Z1 was also prepared in the same manner as in example Z1, except that the polymer was incorporated only in the hot melt to prepare a sample. Tensile tests were carried out on these specimens.

The test pieces were prepared in accordance with JIS A-6850/1976 which specifies the method for preparing the test pieces for testing the tensile bond strength of the adhesives. Each composition was spread and pressed onto an aluminum plate (Taiyu Kizai, A-1050P, size 2.5X 10X 0.3 mm, defined by JIS H-4000) as a substrate, which had been washed with methyl ethyl ketone and wiped with a clean cotton cloth in advance. Each composition as a sealing material was cured in an oven at 50 ℃ for 4 days.

The test piece prepared by the above method was stretched at 50 mm/min in a constant temperature chamber maintained at 23 ℃ and RH 65. + -. 5% according to JIS A-6850 of tensile adhesion test method. The results are shown in Table Z1.

Reference examples Z1-Z3

Each of the isobutylene polymers in referential examples Z1-Z3 was prepared in the same manner as in corresponding examples Z1, Z2 or Z3, except that the isobutylene polymer having a reactive silicon-containing group at both terminals thereof prepared according to the method disclosed in Japanese patent laid-open publication No.209540/1999 (paragraph 0041-0053) was used in place of the silyl-containing copolymer rubber prepared in production example Z1, and the test was carried out in the same manner. The results are shown in Table Z1 together with the results of the curing speed and weather resistance tests.

The curing speed and weather resistance were measured by the following methods.

1) Speed of curing

The curing speed (film expandability) at room temperature of each of the above compositions comprising the main components and the catalyst was measured by the following method:

each composition was cured in a mold (dimensions 20X 80X 5 mm) at 23 ℃ and 50% RH for 24 hours and then removed from the mold. The thickness of the cured portion was measured with a micrometer having a spring force as weak as 0.1 mm.

<evaluation of curing Rate>

X: the thickness of the cured part is less than 1mm

○ the thickness of the cured part is not less than 1 mm.

2) Weather resistance test

An accelerated weather resistance test was carried out in accordance with JIS B-7753 under the following conditions:

an analyzer: sun Carbon Arc aging tester

Light/rain cycle: illumination 120 min/rainfall 18 min

Black plate temperature (Black panel temperature): 63 + -2 deg.C

Temperature in the tank: 40 +/-2 DEG C

Total illumination time: 500 hours

The test piece after the visual inspection was evaluated for weather resistance according to the following three grades:

○ No cracking or melting part observed

△ slight cracking or melting of parts was observed

X: cracks or molten portions were observed

TABLE Z1

		Maximum tensile stress Tmax (kilogram force- Centimeter2)	At maximum load Elongation percentage Emax(％)	Speed of curing	Weather resistance
						Example Z1	1 2	2.1 1.9	90 100	○	○
Mean value of	2.0	95
			Example Z2	1 2	2.0 1.8		76 84	○	○
Mean value of	1.9	80
				Example Z3	1 2	1.8 1.6	55 65			-	-
Mean value of	1.7	60
			Comparative example Z1		1 2	1.2 1.4	45 35	×	△
Mean value of	1.3	40
				Reference example Z1	1 2	2.1 2.1	32 28			×	△
Mean value of	2.1	30
			Reference example Z2		1 2	1.5 1.7	12 8	×	△
Mean value of	1.6	1 0
				Reference example Z3	1 2	1.6 1.6	18 22			-	-
Mean value of	1.6	20

Example Z4 and reference example Z4

Cured sheets having a thickness of about 2 mm were prepared using the compositions prepared in each of example Z1 and reference Z1. The cured sheet was die-cut into a dumbbell No. 3 according to JIS K-6301. The results of the tensile tests are shown in Table Z2 (example Z4) and Table Z3 (reference Z4), respectively. The test specimens were cured at 23 ℃ for 7 days and at 50 ℃ for another 7 days and then removed and their H-shaped mechanical properties measured.

The test was carried out at a tensile rate of 200 mm/min in a thermostat maintained at 23, 50 and 70 ℃ in accordance with the tensile test method prescribed in JIS K-6301.

TABLE Z2

Example Z4		50% tensile stress M50 (kilogram force/cm)2)	100% tensile stress M100 (kilogram force/cm)2)	Maximum tensile stress Tmax (kilogram force/cm)2)	At maximum negative Stretching when loaded Length of growth Emax(％)
						23 (℃)	1 2 3	1.1 0.9 1.0	1.6 1.5 1.7	10.0 10.5 9.5	560 480 520
Mean value of	1.0	1.6	10.0	520
					50 (℃)		1 2 3	0.9 0.7 0.8	1.5 1.5 1.2	4.5 5.5 5.0	390 370 380
Mean value of	0.8	1.4	5.0	380
						70 (℃)	1 2 3	0.8 0.8 0.7	1.5 1.5 1.4	4.1 4.0 3.9	340 340 320
Mean value of	0.8	1.5	4.0	330

TABLE Z3

Reference example Z4		50% tensile stress M50 (kilogram force/cm)2)	100% tensile stress M100 (kilogram force/cm)2)	Maximum tensile stress Tmax (kilogram force/cm)2)	At maximum negative Stretching when loaded Length of growth Emax(％)
						23 (℃)	1 2 3	1.0 1.1 1.2	1.7 1.7 1.9	9.2 11.0 11.7	410 480 470
Mean value of	1.1	1.8	10.6	450
					50 (℃)		1 2 3	0.9 0.8 1.0	1.5 1.5 1.7	4.4 5.1 5.8	310 320 330
Mean value of	0.9	1.5	5.1	320
						70 (℃)	1 2 3	1.0 0.9 0.9	1.7 1.6 1.5	5.0 4.4 3.5	330 300 260
Mean value of	0.9	1.6	4.3	300

Claims (94)

1. A curable composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a compound (B) having a hydroxyl group and/or a hydrolyzable group other than the rubber (A1).

2. The curable composition according to claim 1, wherein the compound (B) having a hydroxyl group and/or a hydrolyzable group contains silicon.

3. A curable elastomeric composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a copolymer derived fromAs a nonconjugated polyene, the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]Hydrolyzable methyl of the formulaThe silane groups, which are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a compound having a silanol group (B1) and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule.

4. A vulcanizable rubber composition characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

a tetravalent tin compound (C), and

a silicon compound (B2) represented by the following general formula [ V]:

R⁴ _aSi(OR⁵)_4-a[V]in the formula, R⁴And R⁵Each is a substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, "a" is 0, 1, 2 or 3.

5. A curable composition, characterized in that the composition comprises:

(a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,Wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule (B3).

6. A curable composition, characterized in that the composition comprises:

(a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]The junction of the norbornene compound having at least one special vinyl end group is shownStructural unit and containing the following general formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) an organosilicon compound (B4) represented by the following general formula [ VI]:

(R²(CH₃)₂SiO)_nR¹[VI]in the formula, R¹Is an alcohol residue or a weak acid residue, R²Is methyl or vinyl and "n" is a positive integer.

7. A room temperature curable rubber composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a silane compound (B5) represented by the following general formula [ VII-1]To [ VII-6]One of them represents:

in the formula, R⁴Is a monovalent hydrocarbon group of 1 to 10 carbon atoms selected from the group consisting of alkyl, aralkyl and aryl groups;

x is a group selected from the group consisting of halogen, hydroxy, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoxime salt, mercapto and alkenyloxy;

R⁵is alkylene or arylene of 8 to 200 carbon atoms; r⁶Is a monovalent alkyl group of 8 to 200 carbon atoms; "n" is an integer of 0 to 2.

8. A curable rubber composition, characterized in that it comprises, as an active ingredient

A silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, hydroxy, amino,Mercapto, alkenyloxy, thioalkoxy, and amino; "a" is an integer of 0 to 2,

an amine (D) selected from the group consisting of aliphatic amines, cycloaliphatic amines, modified cycloaliphatic polyamines and ethanolamine,

from the general formula Y³A silane coupling agent (B6) represented by (Si) Z, wherein Y is an alkoxy group; z is an alkyl group containing a functional group selected from the group consisting of an amino group which may be substituted or unsubstituted with an aminoalkyl group and a mercapto group, and

the resin (E) is composed of a clear coat base paint, an acrylic resin base paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy base paint or organopolysiloxane.

9. A curable composition, characterized in that the composition comprises:

(a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) a silyl compound substituted with an amino group (B7).

10. A curable composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2,

a filler (F), a plasticizer (G), a curing catalyst (H), and an organic carboxylate compound (B8).

11. A vulcanizable rubber composition characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is 1 to 12 carbon atomsA monovalent hydrocarbon group of the group; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

an alcohol (B9), and/or a hydrolyzable ester compound (I) other than the hydrolyzable organosilicon compound (B10), and

a hydrolyzable organosilicon compound (B10).

12. A two-liquid or multi-liquid type vulcanizable rubber composition comprising at least two liquids, characterized in that it comprises:

a main component (I) containing a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1), the copolymer rubber (A1) having a structure derived from a copolymer rubber of the following general formula [ I]as a nonconjugated polyene]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a curing agent (II) comprising a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11).

13. A vulcanizable rubber composition, comprising:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2, and

a polymer compound (K) other than the rubber (A2) and/or an inorganic filler (L).

14.A rubber composition comprising:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2, and

silicone polymer (K1).

15. A rubber composition comprising:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an organic rubber (K2), and

a crosslinking agent (M) for an organic rubber (K2).

16. A rubber composition comprising:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an epoxy resin (K3) is used,

a silane coupling agent (N),

a silanol condensing catalyst (O), and

a curing agent (P) for the epoxy resin.

17. A rubber composition comprising:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an epoxy resin (K3) is used,

a silicon compound (Q) having in the molecule a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group, and

a silicon compound (R) having at least two hydroxyl groups bonded to silicon atoms in the molecule.

18. A rubber composition comprising:

silyl-containing ethylene/α -olefin/nonconjugated polyeneA regular copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

calcium carbonate (L1), and

talc (L2).

19. The rubber composition according to any one of claims 14 to 18, wherein the silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) has at least one silyl-containing unit represented by the following general formula (2) or (3):

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; r³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2 and "n" is an integer of 0 to 10.

20. The rubber composition as described in any one of claims 14 to 19, wherein said silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (a2) is obtained by reacting a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber with a silicon compound, and adding SiH groups in the silicon compound to double bonds of the copolymer rubber, said copolymer rubber containing, as a nonconjugated polyene, a norbornene compound having at least one vinyl terminal group represented by the following general formulae (4) and/or (5):in the formula, R¹Is a hydrogen atom orAlkyl of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; r³Is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms; "n" is an integer of 0 to 10,

the silicon compound is represented by the following general formula (6):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2.

21. A curable composition, characterized in that the composition comprises:

(a) a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2,

(b) a light stabilizer (S) containing nickel, and

(c) a silane coupling agent (T).

22. A vulcanizable rubber composition characterized in that the composition comprises:

containing silyl groupsAn ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a rubber obtained by copolymerizing an ethylene/α -olefin/nonconjugated polyene having the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a sulfur-based aging inhibitor (U).

23. A curable composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, carboxyl, amino,ketoxime salts, amides, acid amides, aminoxy groups, thioalkoxy groups, and amino groups; "a" is an integer of 0 to 2, and

a compound (V) containing an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air and/or a photopolymerizable material in the molecule.

24. An adhesive composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein Ris a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

a tackiness-imparting resin (W), and

a curing catalyst (H) comprising the following general formula [ VIII]An organozirconium compound represented by the formula (H1) or the following general formula [ IX []]Organoaluminum compound (H2) represented:

wherein "n" is an integer of 04,

r is a monovalent hydrocarbon group of 1 to 20 carbon atoms,

y is selected from the group consisting of hydrocarbyl, halogenated hydrocarbyl, cyanoalkyl, alkoxy, halogenated alkoxy, cyano, having 1 to 8 carbon atomsAlkoxy and amino groups, which may be identical or different, andwherein "p" is an integer of 0 to 3,

r is a monovalent hydrocarbon group of 1 to 20 carbon atoms,

y is a group selected from the group consisting of a hydrocarbon group of 1 to 8 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, a cyanoalkoxy group and an amino group, which may be the same or different.

25. A rubber composition having improved pot life, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

the curing catalyst (H) includes a mercaptide-type organotin compound having Sn — S bond (H3), a sulfide-type organotin compound having Sn ═ S bond (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds and a carboxylic acid-type organotin compound (H7).

26. A curable composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

the compound (H8) as the curing catalyst (H) is represented by the general formula Q₂Sn(OZ)₂Or [ Q]₂Sn(OZ)]₂O represents a group represented by the formula, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn in the molecule.

27. A vulcanizable rubber composition characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,

in the formula, R³Is a hydrogen atom or an alkyl group of 1to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

titanate (Y).

28. A crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a compound (B) containing a hydroxyl group and/or a hydrolyzable group;

the curable elastic composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

29. The curable composition according to claim 28 wherein the compound (B) containing hydroxyl and/or hydrolysable groups comprises silicon.

30. A crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x isA hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

a compound having a silanol group and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule (B1),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

31. A crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

a tetravalent tin compound (C), and

a silicon compound (B2) represented by the following general formula [ V]:

R⁴ _aSi(OR⁵)_4-a[V]in the formula, R⁴And R⁵Each is a substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, "a" is 0, 1, 2 or3，

The composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

32. A curable composition, comprising:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) a silicon compound (B3) having at least one amino group and at least one trialkylsiloxy group in the molecule;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

33. A curable composition, comprising:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) an organosilicon compound (B4) represented by the following general formula [ VI]:

(R²(CH₃)₂SiO)_nR¹[VI]in the formula, R¹Is an alcohol residue or a weak acid residue, R²Is methyl or vinyl, "n" is a positive integer;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

34. A crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a silane compound (B5) represented by the following general formula [ VII-1]To [ VII-6]One of them represents: in the formula, R⁴Is a hydrocarbon group of 1 to 10 carbon atoms selected from the group consisting of alkyl, aralkyl and aryl groups; x is a group selected from the group consisting of halogen, hydroxy, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoxime salt, mercapto and alkenyloxy; r⁵Is alkylene or arylene of 8 to 200 carbon atoms; r⁶Is a monovalent alkyl group of 8 to 200 carbon atoms; "n" is an integer from 0 to 2;

the composition is curable at ordinary temperature and is useful for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

35. A crosslinkable rubber composition comprising, as an active ingredient

An organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

an amine (D) selected from the group consisting of aliphatic amines, cycloaliphatic amines, modified cycloaliphatic polyamines and ethanolamine,

silane coupling agent (B6) represented by the general formula Y₃(Si) Z, wherein Y is alkoxy; z is an alkyl group containing a functional group selected from the group consisting of an amino group which may be substituted or not by an aminoalkyl group and a mercapto groupSubstituted, and

a resin (E) composed of a clear coat base paint, an acrylic resin base paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy base paint or organopolysiloxane;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

36. A curable composition, comprising:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) a silyl compound substituted with an amino group (B7),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

37. A curable composition, comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2,

a filler (F), a plasticizer (G), a curing catalyst (H), and an organic carboxylate compound (B8);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

38. A crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula, andessentially no unsaturated double bonds in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

an alcohol (B9), and/or a hydrolyzable ester compound (I) other than the hydrolyzable organosilicon compound (B10), and

a hydrolyzable organosilicon compound (B10);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

39. A cross-linkable rubber composition of the two-liquid or multi-liquid type, comprising at least two liquids, characterized in that it comprises:

a main component (I) comprising an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a curing agent (II) comprising a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

40. A crosslinkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula(1) and having substantially no unsaturated double bond in its main chain,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2, and

a high-molecular compound (K) other than the organic polymer (Z1) and/or an inorganic filler (L),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

41. A crosslinkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2, and

silicone polymer (K1);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

42. A crosslinkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

a crosslinking agent (M) for an organic rubber (K2),

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

43. A crosslinkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an epoxy resin (K3) is used,

a silane coupling agent (N),

a silanol condensing catalyst (O), and

a curing agent (P) for the epoxy resin;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

44. A crosslinkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxyA group, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an epoxy resin (K3) is used,

a silicon compound (Q) having in the molecule a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group, and

a silicon compound (R) having at least two hydroxyl groups bonded to silicon atoms in the molecule;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

45. A crosslinkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

calcium carbonate (L1), and

talc (L2);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

46. A curable composition, characterized in that the composition comprises:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2,

(b) a light stabilizer (S) containing nickel, and

(c) a silane coupling agent (T);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

47. A crosslinkable rubber composition, characterized in that it comprises:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

sulfur-based aging inhibitors (U);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

48. A curable composition, characterized in that the composition comprises:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

a compound (V) containing an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air and/or a photopolymerizable material in a molecule;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

49. An adhesive composition, characterized in that the crosslinkable rubber composition comprises:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

a tackiness-imparting resin (W), and

a curing catalyst (H) comprising the following general formula [ VIII]An organozirconium compound represented by the formula (H1) or the following general formula [ IX []]Organoaluminum compound (H2) represented:

wherein "n" is an integer of 0 to 4,

r is a monovalent hydrocarbon group of 1 to 20 carbon atoms,

y is a group selected from the group consisting of a hydrocarbon group of 1 to 8 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, a cyanoalkoxy group and an amino group, which may be the same or different, and

wherein "p" is an integer of 0 to 3,

r is a monovalent hydrocarbon group of 1 to 20 carbon atoms,

y is a group selected from the group consisting of a hydrocarbon group of 1 to 8 carbon atoms, a halogenated hydrocarbon group, a cyanoalkyl group, an alkoxy group, a halogenated alkoxy group, a cyanoalkoxy group and an amino group, which may be the same or different;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

50. A crosslinkable rubber composition, characterized in that it comprises:

an organic polymer (Z) containing the following general formula [ III]Hydrolyzable silyl of the formulaAnd substantially no unsaturated double bonds in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen,Alkoxy, acyloxy, ketoxime, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

a curing catalyst (H) comprising a mercaptide-type organotincompound having Sn — S bonds (H3), a sulfide-type organotin compound having Sn ═ S bonds (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds and a carboxylic acid-type organotin compound (H7);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

51. A curable composition, characterized in that the composition comprises:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

the compound (H8) as the curing catalyst (H) is represented by the general formula Q₂Sn(OZ)₂Or [ Q]₂Sn(OZ)]₂O represents a group represented by the formula, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn in the molecule;

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

52. A vulcanizable rubber composition characterized in that the composition comprises:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

titanate (Y);

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

53. A curable composition, characterized in that the composition comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from a nonconjugated polyene represented by the following general formula [ I]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy,acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

the composition is used for electric/electronic device members, transportation machines, and civil engineering/construction, medical and leisure areas.

54. The composition according to any one of claims 28 to 53, wherein the electric/electronic parts in the field using the composition are compositions for heavy electrical parts, electronic devices, sealing materials for electric/electronic device circuits and substrates, encapsulating materials, coating materials and adhesives; a repair material for covering electric wires, an insulating sealing material for electric wire connection parts, a roller for office automation equipment, a vibration damping material, and a sealing material for gel and capacitor.

55. The composition of claim 54, wherein the sealant material is used in refrigerators, freezers, washing machines, gas meters, microwave ovens, steam irons, and electrical leakage breakers.

56. The composition of claim 54, wherein the encapsulant is used in high voltage transformer circuits, printed wiring boards, high voltage transformers with variable resistance, electrical insulation devices, semiconductor devices, electrical conducting devices, solar cells, and flyback transformers for televisions.

57. The composition of claim 54, wherein the coating material is used for coating thick film resistors for high voltage devices and circuit elements for hybrid integrated circuits; HIC; an electrically insulating member; a semiconductor component, a conductive member; a module; printing a circuit; a ceramic substrate;a buffer material for a diode, a transistor, and a connection line; a semiconductor device; and an optical fiber for optical communication.

58. The composition of claim 54, wherein said adhesive is used for bonding high voltage wedges or necks of Cathode Ray Tubes (CRTs), electrically insulating parts, semiconductor parts, and conductive parts.

59. The composition according to any one of claims 28 to 53, wherein the transport means of the field in which the composition is used comprise automobiles, ships, airplanes and railway vehicles.

60. The composition of claim 59, wherein the composition is used in the field of vehicles as a sealing material for engine gaskets, electrical components, and fuel filters; packaging materials for igniter HIC and hybrid integrated circuits; coating materials for vehicle bodies, window glasses, and engine control substrates; and adhesives for oil pan gaskets, timing belt cover gaskets, braids, headlight lenses, sunroof seals, and rearview mirrors.

61. The composition of claim 59, wherein said application in a ship is in the field of wire-connecting/distribution boxes, electrical system components, and wire-sealing materials; and adhesives for electrical wires and glass.

62. Composition according to any one of claims 28 to 53, characterized in that the civil engineering/construction field in which it is used is as sealant material for construction materials for joints: butt joints in commercial architectural glass curtain wall methods, glass edge joints with window frames, interior joints in sanitary fixtures, toilets and showcases, joints around bath tubs, joints in exterior flexible joints and siding for prefabricated houses; a sealing material for laminated glass; sealing materials for civil engineering for road repair; coatings/adhesives for metals, glass, stone, slate, concrete and tile; an adhesive sheet, a waterproof sheet, and a vibration-proof sheet.

63. The composition according to any one of claims 28 to 53, wherein the medical field is the sealing material of rubber stoppers for medical use, syringe gaskets and rubber stoppers for hypotensor.

64. A composition according to any one of claims 28 to 53, wherein the leisure area is swimming caps, diving masks and earplugs for swimming; gel cushioning materials for athletic shoes and baseball gloves.

65. A sealant, potting agent, coating material or adhesive, characterized in that it consists of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a compound (B) containing a hydroxyl group and/or a hydrolyzable group.

66. The sealant, encapsulant, coating material or adhesive according to claim 65, wherein the compound (B) containing a hydroxyl group and/or a hydrolysable group contains silicon.

67. A sealant, potting agent, coating material or adhesive, characterized by being composed of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

a compound having a silanol group (B1) and/or a compound capable of reacting with moisture to form a compound having a silanol group in the molecule.

68. A sealant, potting agent, coating material or adhesive, characterized in that it consists of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxyA group and an amino group; "a" is an integer of 0 to 2,

a tetravalent tin compound (C), and

a silicon compound (B2) represented by the following general formula [ V]:

R⁴ _aSi(OR⁵)_4-a[V]in the formula, R⁴And R⁵Each is a substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, "a" is 0, 1, 2 or 3.

69. A sealant, encapsulant, coating material or adhesive, characterized in that it consists of a curable composition comprising:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule (B3).

70. A sealant, encapsulant, coating material or adhesive, characterized in that it consists of a curable composition comprising:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2,

(b) an organosilicon compound (B4) represented by the following general formula [ VI]:

(R²(CH₃)₂SiO)_nR¹[VI]in the formula, R¹Is an alcohol residue or a weak acid residue, R²Is methyl or vinyl and "n" is a positive integer.

71. A sealant, potting agent, coating material or adhesive, characterized by being composed of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

a silane compound (B5) represented by the following general formula [ VII-1]To [ VII-6]One of them represents:

in the formula, R⁴Is a hydrocarbon group of 1 to 10 carbon atoms selected from the group consisting of alkyl, aralkyl and aryl groups;

x is a group selected from the group consisting of halogen, hydroxy, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoxime salt, mercapto and alkenyloxy;

R⁵is alkylene or arylene of 8 to 200 carbon atoms; r⁶Is a monovalent alkyl group of 8 to 200 carbon atoms; "n" is an integer of 0 to 2.

72. A sealant, a potting agent, a coating material or an adhesive, characterized by being composed of a crosslinkable rubber composition containing, as an active ingredient

An organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

an amine (D) selected from the group consisting of aliphatic amines, cycloaliphatic amines, modified cycloaliphatic polyamines and ethanolamine,

silane coupling agent (B6) represented by the general formula Y₃(Si) Z, wherein Y is alkoxy; z is an alkyl group containing a functional group selected from the group consisting of an amino group which may be substituted or not by an aminoalkyl group and a mercapto groupSubstituted, and

the resin (E) is composed of a clear coat base paint, an acrylic resin base paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy base paint or organopolysiloxane.

73. A sealant, encapsulant, coating material or adhesive, characterized by consisting of a curable composition comprising:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is 1-A monovalent hydrocarbon group of 12 carbon atoms; x is a hydrolyzable groupselected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) a silyl compound substituted with an amino group (B7).

74. A sealant, encapsulant, coating material or adhesive, characterized by consisting of a curable composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2,

a filler (F), a plasticizer (G), a curing catalyst (H), and an organic carboxylate compound (B8).

75. A sealant, potting agent, coating material or adhesive, characterized by being composed of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

analcohol (B9), and/or a hydrolyzable ester compound (I) other than the hydrolyzable organosilicon compound (B10), and

a hydrolyzable organosilicon compound (B10).

76. A sealant, a potting agent, a coating material or an adhesive, characterized by being composed of a two-liquid-component or multi-liquid-component type crosslinkable rubber composition comprising at least two liquids:

a main component (I) comprising an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a curing agent (II) comprising a silanol condensing catalyst (J) and water or a hydrate of a metallic salt (B11).

77. A sealant, encapsulant, coating material or adhesive comprising a cross-linkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercaptoAnd an alkenyloxy group; "m" is an integer of 0 to 2,

a high-molecular compound (K) other than the organic polymer (Z1) and/or an inorganic filler (L).

78. A sealant, encapsulant, coating material or adhesive comprising a cross-linkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable methyl group represented by the following general formula (1)A silane group and substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

silicone polymer (K1).

79. A sealant, encapsulant, coating material or adhesive comprising a cross-linkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an organic rubber (K2), and

a crosslinking agent (M) for the organic rubber (K2).

80. A sealant, encapsulant, coating material or adhesive comprising a cross-linkable rubber composition comprising:

an organic polymer (Z1) containinga hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an epoxy resin (K3) is used,

a silane coupling agent (N),

a silanol condensing catalyst (O), and

a curing agent (P) for the epoxy resin.

81. A sealant, encapsulant, coating material or adhesive comprising a curable composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula (1) and having substantially no unsaturated double bond in its main chain,wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

an epoxy resin (K3) is used,

a silicon compound (Q) having in the molecule a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group, and

a silicon compound (R) having at least two hydroxyl groups bonded to silicon atoms in the molecule.

82. A sealant, encapsulant, coating material or adhesive comprising a cross-linkable rubber composition comprising:

an organic polymer (Z1) containing a hydrolyzable silyl group represented by the following general formula and having substantially no unsaturated double bond in its main chain,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

calcium carbonate (L1), and

talc (L2).

83. A sealant, encapsulant, coating material or adhesive, characterized by consisting of a curable composition comprising:

(a) an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

(b) a light stabilizer (S) containing nickel, and

(c) a silane coupling agent (T).

84. A sealant, potting agent, coating material or adhesive, characterized by being composed of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a sulfur-based aging inhibitor (U).

85. A sealant, encapsulant, coating material or adhesive, characterized by consisting of a curable composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula, andessentially no unsaturated double bonds in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, mercapto, alkenyloxyRadicals, alkoxy, acyloxy, ketoxime salts, amides, acid amides, aminoxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

a compound (V) containing an unsaturated group capable of causing a polymerization reaction by reacting with oxygen in the air and/or a photopolymerizable material in the molecule.

86. A sealant, potting agent, coating material or adhesive, characterized by being composed of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable groupselected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2,

the curing catalyst (H) includes a mercaptide-type organotin compound having Sn — S bond (H3), a sulfide-type organotin compound having Sn ═ S bond (H4), an organic carboxylic acid (H5), an organic carboxylic acid anhydride (H6), or a mixture of one of the above compounds and a carboxylic acid-type organotin compound (H7).

87. A sealant, encapsulant, coating material or adhesive, characterized by consisting of a curable composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2, and

the compound (H8) as the curing catalyst (H) is represented by the general formula Q₂Sn(OZ)₂Or [ Q]₂Sn(OZ)]₂O represents a group represented by the formula, wherein Q is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and Z is a monovalent hydrocarbon group of 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordinate bond with Sn in the molecule.

88. A sealant, potting agent, coating material or adhesive, characterized by being composed of a crosslinkable rubber composition comprising:

an organic polymer (Z) containing the following general formula [ III]A hydrolyzable silyl group represented by the formula (I) and having substantially no unsaturated double bond in its main chain:wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, mercapto, alkenyloxy, thioalkoxy and amino; "a" is an integer of 0 to 2, and

titanate (Y).

89. A coating material for vehicles, characterized in that it is composed of a curable composition containing a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from [ I]as a nonconjugated polyene]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,

wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group which is a hydrolyzable group,selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime, amide, acid amide, aminoxy, thioalkoxy, and amino; "a" is an integer of 0 to 2.

90. A sealant, a potting agent, a coating material for vehicles or an adhesive, characterized in that it is composed of a curable composition containing a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A1) having a structure derived from [ I]as a nonconjugated polyene]Or [ II]Structural unit of norbornene compound having at least one specific vinyl terminal group and containing the following formula [ III]The hydrolyzable silyl groups represented by (A) are,wherein "n" is an integer of 0 to 10; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms,in the formula, R³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms,

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from the group consisting of hydride, halogen, mercapto, alkenyloxy, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminooxy, thioalkoxy, and amino; "a" is an integer of 0 to 2.

91. A sealant for laminated glass, characterized in that the sealant comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):

wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

a curing catalyst (H), and

water or hydrate of metallic salt (B11).

92. A sealant for laminated glass, characterized in that the sealant comprises:

a silyl-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) containing a hydrolyzable silyl group, represented by the following general formula (1):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2,

a hot-melt resin (X),

a curing catalyst (H), and

water or hydrate of metallic salt (B11).

93. The sealant for laminated glass according to claim 91 or 92, wherein said sealant comprisesThe silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) has at least one silyl group-containing unit represented by the following general formula (2) or (3):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; r¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; r³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2 and "n" is an integer of 0 to 10.

94. The sealing material for laminated glass according to any one of claims 91 to 93, wherein the sealing material is prepared by reacting a silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber with a silicon compound,the silyl group-containing ethylene/α -olefin/nonconjugated polyene random copolymer rubber (A2) is obtained by adding the SiH group in the silicon compound to the double bond of a copolymer rubber containing a norbornene compound having at least one vinyl terminal group as a nonconjugated polyene, represented by the following general formula (4) and/or (5):in the formula, R¹Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; r²Is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; r³Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; "n" is an integer of 0 to 10,

the silicon compound is represented by the following general formula (6):wherein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; x is a hydrolyzable group selected from hydride, halogen, alkoxy, acyloxy, ketoxime salt, amide, acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy; "m" is an integer of 0 to 2.