JP2001049075A - Curable composition and its usage - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve flexibility, mechanical properties, molding/processing properties and heat resistance by compounding a block copolymer having a block formed from an aliphatic hydrocarbon compound and an isobutylene-based polymer bearing a silyl group bonded to a hydrolyzable or hydroxyl group. SOLUTION: This curable composition comprises (A) 99-1 wt.% of a block copolymer having at least one block formed from an aliphatic hydrocarbon compound and a number-average mol.wt. of 500-1,000,000, and (B) 1-99 wt.% of an isobutylene-based polymer bearing a silyl group bonded to a hydrolyzable or hydroxyl group and having a number-average mol.wt. of 1,000-40,000 and a mol.wt. distribution of 1.5 or less. Desirably, to this curable composition are added 0.01-50 pts.wt. of a silanol condensation catalyst and 0.01-50 pts.wt. of a hydrolyzable group-containing silane compound, both based on 100 pts.wt. of the component B, and 10-1,000 pts.wt. of a plasticizer and 2-1,000 pts.wt. of a tackifier resin, both based on 100 pts.wt. of the total of the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition which can be suitably used as a rubber material, for example, a tire, a sealing material, a gasket, an adhesive, a pressure-sensitive adhesive, a vibration control material, and a method of using the same.

[0002]

2. Description of the Related Art A block copolymer containing a polymer block composed of an aliphatic hydrocarbon-based compound is widely used as a thermoplastic resin which is inexpensive and has excellent workability. A block copolymer composed of a polymer block of an aromatic hydrocarbon-based compound and a styrene-based polymer block is easily melted by heating, so that a gasket, a sealing material, It is used as an adhesive and vibration damping material.

However, a block copolymer containing a polymer block composed of an aliphatic hydrocarbon-based compound, particularly a block copolymer composed of a polymer block composed of an aliphatic hydrocarbon-based compound and a styrene-based polymer block. In the case of coalescence, various properties such as mechanical properties and viscosity upon heating and melting are governed by the ratio of the high Tg segment and the low Tg segment of the thermoplastic elastomer and their respective molecular weights. There has been a problem that the deterioration of physical properties at a high temperature is large.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to improve the deterioration of the properties of a block copolymer having at least one type of block formed from an aliphatic hydrocarbon compound at high temperatures. And

[0005]

The present inventor has studied and found that:
(A) a block copolymer having at least one type of block formed from an aliphatic hydrocarbon-based compound, and
It has been found that a curable composition containing (B) an isobutylene-based polymer having a silicon group bonded to a hydrolyzable group or a hydroxyl group solves the above problem.

The present invention relates to (A) a block copolymer having at least one kind of block formed from an aliphatic hydrocarbon compound, and (B) isobutylene having a silicon group bonded to a hydrolyzable group or a hydroxyl group. And a curable composition containing a polymer. Further, the present invention provides a sealing agent comprising the curable composition, an adhesive comprising the curable composition, a pressure-sensitive adhesive comprising the curable composition, a composition for a gasket comprising the curable composition, and It is also a spacer for a double glazing made of a curable composition.

Further, the present invention provides an application method of applying or molding the above-mentioned curable composition in a state of being dissolved in a solvent, an application method of applying or molding the above-mentioned curable composition under heating conditions, and the above-mentioned curable composition. It is also a usage method in which the condensation reaction of the component (B) with water proceeds after construction or molding of the product. Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer (A) having at least one type of block formed from an aliphatic hydrocarbon compound used in the present invention will be described. The aliphatic hydrocarbon-based compound is not particularly limited as long as it can form a polymer. For example, ethylene, propylene,
-Butene, isobutylene, butadiene, isoprene and the like. These may be used alone or in combination. In addition, these polymers can be used after hydrogenation.

The block formed from the aliphatic hydrocarbon-based compound in the component (A) (hereinafter also referred to as an aliphatic hydrocarbon-based block) is not particularly limited. ) Homopolymerizing a diene-based compound such as butadiene and isoprene; (2) polymerizing the diene-based compound and then hydrogenating it;
(3) Polymerizing an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene or the like as a main monomer. (4) Copolymerizing the olefinic compound with a diene-based compound. Can be used as it is or by hydrogenation. Examples of the relatively rigid aliphatic hydrocarbon-based block include a crystalline block, and specific examples include a polyethylene block and a polyhexene block.

The block other than the aliphatic hydrocarbon-based block in the component (A) is not particularly limited as long as the block can form a block copolymer with the aliphatic hydrocarbon-based block. Blocks of group compounds and nitrile compounds are exemplified, and more specifically, blocks of styrene, α-methylstyrene, and acrylonitrile are exemplified.

In the present invention, the block copolymer of the component (A) is a block composed of a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of an aliphatic hydrocarbon compound. Copolymers are preferred. Here, the “polymer block mainly composed of a certain compound” means that the monomer unit corresponding to the compound accounts for 60% or more, preferably 80% or more of the monomer units constituting the polymer block. That means.

The composition of the component (A) is not limited as long as the properties can be exhibited, but from the viewpoint of availability and fluidity at high temperatures,
A block copolymer comprising a styrene block and a block of butadiene and / or isoprene and / or isobutylene and a hydrogenated product thereof are mentioned. More specific examples include SBS (styrene-butadiene-styrene block copolymer). ), SIS (styrene-isoprene-styrene block copolymer), SEBS (styrene-ethylenebutylene-styrene block copolymer), SEPS
(Styrene-ethylene propylene-styrene block copolymer), SIBS (styrene-isobutylene-styrene block copolymer) and the like.

[0013] In the block copolymer of the component (A),
The content ratio of the aliphatic hydrocarbon-based block and the block other than the aliphatic hydrocarbon-based block is not particularly limited, but is 5/9 by weight based on the balance between fluidity and physical properties.
5-95 / 5 is preferable, and 10 / 90-60 / 40 is more preferable. The structure of the block can be linear or side chain.

The number average molecular weight of the block copolymer of the component (A) is not particularly limited, but is usually from 500 to 10.
About 00000, preferably 1000 to 100
It is about 000.

The isobutylene polymer having a silicon group bonded to a hydrolyzable group or a hydroxyl group, which is the component (B) of the present invention, will be described. In the present invention, a silicon group bonded to a hydrolyzable group or a hydroxyl group means a group having a Si-X bond, for example, where X is a hydrolyzable group or a hydroxyl group. Usually, Si-OH and HX are provided by a hydrolysis reaction of the Si-X bond.

The isobutylene polymer as the component (B) is
Silicon groups are well-known functional groups,
As an example, general formula (1):-(SiR¹ _2-bX_bO)_m-SiR² _3-aX_a (1) [wherein, R¹And R²Are all C 1-20
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
An aralkyl group of 0 or R³ ₃SiO- (R³Is the carbon number
A monovalent hydrocarbon group of 1 to 20;³Is the same
Or may be different).
An organosiloxy group,¹Or R ²Is two or more
When present, they may be the same, different
May be. X is a hydrolyzable group or a hydroxyl group, and two
When they exist, they may be the same or different
It may be. a is an integer selected from 0 to 3,
b is an integer selected from 0 to 2. However, a + mb
Satisfies ≧ 1. In addition, m (SiR¹ _2-bX_bO)
B need not be the same. m is from 0 to 19
An integer to be chosen. And the group represented by
Wear.

The hydrolyzable group in the general formula (1) is not particularly limited, and may be a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, an alkoxy group, and an acyloxy group. , A ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Among these, an alkoxy group is particularly preferred because of its mild hydrolytic property and easy handling.

This hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 groups, and (a + m
b) preferably ranges from 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.
The number of silicon atoms forming the reactive silicon group may be one or two or more. In the case of silicon atoms linked by a siloxane bond or the like, the number of silicon atoms is preferably up to 20. In particular, the general formula ^{_{(2): -SiR 2 3-}} a X a (2) (. ^{Wherein, R} 2, X and a are same as defined above) reactive silicon group represented by is readily available It is preferred.

At least one, preferably 1.1 to 5, reactive silicon groups are present on average per molecule of the isobutylene-based polymer. If the number of reactive silicon groups contained in the molecule is less than one, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior. The reactive silicon group may be present at the terminal of the molecular chain of the isobutylene-based polymer, may be present inside, or may be present at both ends. In particular, when at least one reactive silicon group is present at the end of the molecular chain, the effective network chain amount of the isobutylene-based polymer component contained in the finally formed cured product is increased, so that high strength and high elongation are achieved. It is preferable from the viewpoint that a rubber-like cured product is easily obtained. These isobutylene-based polymers having a reactive silicon group may be used alone or in combination of two or more.

The isobutylene-based polymer in the present invention means a polymer containing an isobutylene unit in an amount of 50% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more. As the monomer other than isobutylene, the above-mentioned aliphatic hydrocarbon-based compound, styrene,
α-methylstyrene, acrylonitrile and the like. The number average molecular weight of the isobutylene polymer is 500 to 1
It is preferably about 00000, particularly 1000 to 4
Those having a molecular weight of about 0000 are preferable from the viewpoint of easy handling. Further, regarding the molecular weight distribution (Mw / Mn),
The narrower the molecular weight distribution is, the lower the viscosity at the same molecular weight is, the better the gel permeation chromatography (GPC) method (mobile phase: tetrahydrofuran,
In terms of styrene, it is preferably 2.0 or less, more preferably 1.5 or less.

The isobutylene polymer having a reactive silicon group in the molecule is obtained by adding a vinylsilane or an allylsilane having a reactive silicon group to a monomer mainly containing isobutylene and copolymerizing the monomer. Manufactured by Further, the isobutylene-based polymer having a reactive silicon group at both the inside and the end of the molecule is a single unit constituting the main chain in the polymerization at the time of producing the isobutylene-based polymer having a reactive silicon group at the molecular end. It can be produced by copolymerizing vinyl silanes or allyl silanes having a reactive silicon group other than the monomer, and then introducing a reactive silicon group to the terminal.

Various properties of the composition of the present invention include the component (A),
It is designed and controlled by the molecular structure of the component (B), the ratio of the components (A) / (B), and the characteristics of the other components. There is no limitation on the quantitative ratio of the component (A) and the component (B) of the present invention.
(B) is preferably in the range of 1/99 to 99/1, more preferably 10/90 to 90/10.

In the curable composition of the present invention, a part or all of the hydrolyzable group bonded to the silicon group of the isobutylene polymer as the component (B) is hydrolyzed to form a siloxane bond (silanol bond). By performing a condensation reaction, particularly excellent properties are exhibited.

In order to cure the component (B) by a silanol condensation reaction, it is possible to add a silanol condensation catalyst [component (C)] to the composition of the present invention. Specific examples of silanol condensation catalysts include, for example, tin, aluminum, titanium compounds, or amine compounds or salts of amine compounds with carboxylic acids; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids A reaction product of an excess polyamine and an epoxy compound; a silane coupling agent-based amine compound having an amino group such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; And other known silanol condensation catalysts such as other acidic catalysts and basic catalysts. The silanol condensation catalyst is freely selected according to the conditions of use, but from the viewpoints of storage stability, curing rate, and availability, tin compounds, particularly dibutyltin compounds, are preferred. The silanol condensation catalyst may be used alone,
You may mix and use more than one kind. From the viewpoints of curing rate and storage stability, the silanol condensation catalyst is in the range of 0.01 to 50 parts based on 100 parts (hereinafter referred to as parts by weight) of the isobutylene-based polymer (B) having a reactive silicon group. It is preferable to use them. In particular, 0.1 to 30 parts, and further,
It is preferable to use in the range of 0.1 to 5 parts.

In the composition of the present invention, in addition to the above components (A) and (B),
A hydrolyzable group-containing silane compound [component (D)], a plasticizer [component (E)], and a tackifying resin [component (F)] can be appropriately compounded.

The hydrolyzable group-containing silane compound (component (D)) has effects such as improvement in adhesiveness, adjustment of curability and storage stability, and can be appropriately used according to the required characteristics. The type of the hydrolyzable group-containing silane compound is not particularly limited as long as it can be used, and examples thereof include those having a hydrolyzable group such as a methoxy group, an ethoxy group, a propoxy group, and an oxime group. The functional group other than the silyl group present in the hydrolyzable group-containing silane compound is not particularly limited as long as it can be used, but a vinyl group, a methacryl group, an acryl group, a mercapto group, a hydroxyl group, an isocyanate group, an amino group, Amide groups and glycidyl groups are exemplified. As more specific examples, ethyl silicate, silicate condensate, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane,
3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N -(Β-aminoethyl) aminopropylmethyldimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidylpropyltrimethoxysilane and the like are exemplified.

The silane compound is used in an amount of 0.1 part based on 100 parts of the isobutylene-based polymer (B) having a reactive silicon group.
It is preferably used in the range of from 01 to 50 parts. In particular,
It is preferable to use 0.1 to 30 parts, more preferably 1 to 10 parts.

The above silane compounds may be used alone or in combination of two or more. For example, from the viewpoint of storage stability, silicate, vinyltrimethoxysilane, 3-methacryloxypropyltrisilane may be used. One or more compounds selected from methoxysilane are used, and 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3
-Aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropyl A method of using one or more compounds selected from methyldimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-glycidylpropyltrimethoxysilane is also possible.

The plasticizer (component (E)) is used to adjust the flow characteristics, and can be freely selected from commonly used plasticizers as needed.
Those having good compatibility with the component isobutylene polymer are more preferable, and specific examples thereof include process oil, olefin-based oligomer, polybutene, chlorinated olefin, hydrogenated phthalate ester, ester-based oligomer, and the like. These plasticizers may be used alone or in combination of two or more. In addition, these plasticizers and other plasticizers such as phthalic acid ester and adipic acid ester are used. It is also possible. The amount of the plasticizer to be used is determined according to the other compounding composition and the target properties, and there is no particular limitation in the usable range. It is preferable to use in the range. In particular, it is preferable to use in the range of 10 to 200 parts.

The tackifying resin [component (F)] has tackiness,
It is used for adjusting adhesiveness, resin compatibility, viscosity control, etc., and can be freely selected from commonly used ones according to the purpose, for example, petroleum resin, hydrogenated petroleum, phenol System, terpene system, rosin ester system, modified terpene system, hydrogenated terpene system, pinene system, coumarone indene system, styrene system and the like. The amount of the tackifying resin used is determined according to the other compounding composition and target properties, and is not particularly limited in the usable range, but is 2 to 1000 parts with respect to 100 parts in total of the components (A) and (B). It is preferable to use it in the range. In particular, it is preferable to use in the range of 10 to 100 parts.

In the composition of the present invention, in addition to the above components, a thermoplastic resin, a wax, a filler, a hindered phenol-based or a hindered amine-based oxidizing agent may be used, if necessary, in addition to the above-mentioned components. An inhibitor, an ultraviolet absorber, a light stabilizer, a pigment, a surfactant, a foaming agent, an adhesion-imparting agent, and the like can be appropriately compounded.

The thermoplastic resin used in the present invention is used for the purpose of imparting properties such as hardness, strength and elongation, reducing costs, adjusting moldability, etc., and is selected from plastics, rubber, etc. according to the purpose. However, for example, polyethylene, polypropylene, α-olefin copolymer,
EPDM, butyl rubber, polyisobutylene, polystyrene, polyvinyl chloride and the like are exemplified.

The filler used in the present invention is used for the purpose of imparting properties such as hardness, strength and stretchability, and for reducing costs, and calcium carbonate, clay, talc, silica, alumina and the like can be used. Further, a flame-retardant filler such as aluminum hydroxide, magnesium hydroxide and ammonium phosphate can be used for imparting flame retardancy. Further, for the purpose of imparting hygroscopicity, a hygroscopic filler such as zeolite, silica gel, and molecular sieve can be used.

The method for producing the composition of the present invention is not particularly limited. For example, the components (A) and (B) and the above components are kneaded using a mixer, a roll, a kneader, a molding machine or the like. And a method in which the components are dissolved in an appropriate amount of a solvent and mixed.

The method for molding the composition of the present invention includes:
Normal methods can be used, for example, extrusion molding, injection molding,
Various molding methods such as compression molding are exemplified. Further, as a method of applying the composition of the present invention, a normal method can be used, for example, an application method using a hot melt applicator, after applying a solvent diluted at room temperature or under heating,
A method of evaporating the solvent at room temperature or under heating is exemplified.

The composition of the present invention exhibits particularly excellent characteristics by curing the component (B) by a silanol condensation reaction. The supply of water is effective for the silanol condensation reaction, and the method of supplying water in the present invention is not particularly limited. For example, (1) a method of supplying water at the time of kneading the composition, and (2) a method of kneading Immediately before molding into the composition,
A method of supplying water, (3) a method of supplying water after molding the kneaded composition, and the like are preferable.

Water or metal as a necessary water supply source
It is also possible to use hydrates of the salts. Hydration of metal salts
It is possible to use widely available products
For example, hydrates of alkaline earth metal salts, other metals
And hydrates of salts. Among these, alkali
Metal salt hydrates and alkaline earth metal salt hydrates are preferred.
Specifically, MgSO₄・ 7H₂O, Na₂CO₃
・ 10H₂O, Na₂SO ₄・ 10H₂O, Na₂S₂
O₃・ 5H₂O, Na₃PO₄・ 12H₂O, Na ₂B
₄O₇・ 10H₂O and the like. Metal salt hydrate
Is an isobutylene polymer having a reactive silicon group
(B) Used in the range of 0.01 to 50 parts per 100 parts.
Is preferred. In particular, 0.1 to 30 parts, and further,
1 to 20 parts, and more preferably 2 to 10 parts
Is preferred. Use only one type of hydrate of the above metal salt
Or two or more of them may be used in combination.

The curable composition of the present invention is particularly suitably used as a rubber-based material, for example, a tire, a sealing material, a gasket, an adhesive, and a pressure-sensitive adhesive. Sports equipment use, stationery use,
Civil engineering for automobile interior and exterior applications, civil engineering sheets, waterproof sheets, etc.
For architectural use, AV / home appliance use, OA / office equipment use,
Anti-vibration, such as clothing and footwear applications, textile applications, medical applications such as various catheters, containers, and caps, sanitary products such as disposable diapers and sanitary products, packaging and transport materials, and wire applications such as wire coating, cables, connectors, and plugs. It can be used for vibration control materials such as vibration isolation and vibration suppression, asphalt modifiers, resin modifiers, and the like.

The method of use in specific applications will be described below, but the present invention is not limited to these examples. The component (A), in particular, a styrene-based block polymer, has been widely used as a main component of pressure-sensitive adhesives and adhesives, and the curable composition of the present invention can be effectively used in those applications. It is.

For example, when used as a pressure-sensitive adhesive or an adhesive, a composition containing a styrene-based block polymer [component (A)] as a main component has excellent characteristics at room temperature, but has an excellent environmental temperature. However, there is a problem that the fluid flows when the pressure is high. When the curable composition of the present invention is used, since the isobutylene-based polymer as the component (B) is crosslinked by a silanol condensation reaction, the properties of the styrene-based block polymer [component (A)] are significantly reduced. And the flow can be suppressed at a high temperature.

The method of using the above-mentioned pressure-sensitive adhesive or adhesive is not particularly limited as long as it can be generally used. For example, a curable composition applied by heating and dissolving (hot-melt) or diluting with a solvent on a substrate is treated with water And a method of adding water before coating. In the case of using the former method, the supply of water vapor and moisture can be performed by using water in the air, steam or a humidification step, immersion in water, and the like, and the thickness of the curable composition is relatively thin. Preferably, by setting the thickness to 10 mm or less, more efficient production is possible.

The specific application of the above-mentioned pressure-sensitive adhesive or adhesive is not particularly limited, but it can be used as a pressure-sensitive adhesive tape or hot-melt adhesive, and has good weather resistance and heat resistance. Used in the fields of electric, electric and automobile.

The component (A), in particular, a styrene-based block polymer is also widely used as a main component of a gasket, a sealing agent, and a molded article, and the curable composition of the present invention can be effectively used in those applications. Can be used for

In this application, conventionally, the moldability (fluidity at high temperature) and the physical properties during use are determined by the molecular structure of the component (A). For example, in the case of a styrene-based block polymer, an aliphatic hydrocarbon-based block is used. It is controlled by the molecular weight, ratio, structure and low viscosity additive of styrene and styrenic blocks, and those with good moldability (fluidity at high temperature) have the problem that the strength and physical properties at high temperature are reduced. . In the curable composition of the present invention, by appropriately selecting the structure of the isobutylene-based polymer as the component (B), the composition can be molded without significantly lowering the properties of the styrene-based block polymer [component (A)]. The properties are good, and a decrease in physical properties can be suppressed.

The method for producing the above gasket, sealing agent and molded product is not limited as long as it can be generally used, but in order to obtain good moldability, control of the silanol condensation reaction is effective. Alternatively, there may be mentioned a method of supplying water to the curable composition discharged from the applicator in a heated and dissolved state to promote a silanol condensation reaction, and a method of adding water before discharging.

In the case of using a method in which the silanol condensation reaction is carried out by supplying water, the supply of water can be performed by using water in the air, a steam or humidification step, immersion in water, or the like.

In the case of adding water before discharging, various adding methods can be selected. For example, (1) water and / or a silanol condensation catalyst which is the component (C) is mixed with a mixer or static before discharging. Or a method of mixing with a mechanical mixer, (2) a method of adding a silanol catalyst having high temperature dependency and controlling the reaction by a temperature change,
(3) A method of adding a compound to which water is adsorbed and controlling the reaction by a change in temperature is exemplified.

The specific use of the gasket, sealing agent, and molded article is not particularly limited, and examples thereof include a hot-melt sealing material, a building gasket material, an automobile molded article, and a vibration control material. In these applications, a manufacturing method such as molding and using as a molded article, or coating on a substrate and applying the molded article is employed. From the viewpoint of productivity, a molding method by heating and melting is effective.

The curable composition of the present invention is effective as a spacer for a double glazing and / or a sealing material for a double glazing. Conventionally, butyl hot-melt sealing materials have been known as resins used for double-glazing because of their low moisture permeability and weather resistance.However, the balance between hardness at room temperature, strength and fluidity at high temperatures is known. Although it is difficult to secure them, improvements such as the combined use of α-olefins and the use of metal plates have been made, but they do not have sufficient properties such as deterioration in physical properties at high temperatures. By using the curable composition of the present invention, it is possible to improve the decrease in physical properties at high temperatures. In this application, from the viewpoint of weather resistance, SEBS, S
It is preferable to use EPS and SIBS, and particularly preferable from the viewpoint of low moisture permeability. In addition to the components of the present invention, polyethylene, polypropylene, α-olefin copolymer, EPDM, butyl rubber,
It is effective to add a thermoplastic resin such as polyisobutylene or a hygroscopic compound such as zeolite.

[0050]

The present invention will be described more specifically with reference to the following examples. It should be noted that the present invention is not limited in any way by these embodiments, and can be appropriately changed and implemented without changing the gist thereof. (Example 1) Kraton D-1107 which is the component (A)
100 parts by weight (manufactured by Shell Japan), an isobutylene polymer containing a methyldimethoxy group at the molecular terminal as the component (B) [number average molecular weight 10400, molecular weight distribution (GPC
Method) 1.2 Amount of silicon group per molecule ( ¹ H-NMR
Method) 1.5 to 1.9] 77 parts by weight, 2 parts by weight of Neostan U-220 (manufactured by Nitto Kasei) which is a silanol condensation catalyst as a component (C), and a silane coupling agent A- as a component (D) 174 (manufactured by Nippon Unicar) 3 parts by weight, paraffin-based process oil PS-32 (manufactured by Idemitsu Kosan) as a component (E) 148 parts by weight, terpene-based tackifying resin Px-800 (Yasuhara Chemical) 86 as a component (F) 86 Parts by weight and 57 parts of paraffin wax 135F (manufactured by Japan Brazing Co.) were mixed at 160 ° C. to 120 ° C. under a dry nitrogen flow to obtain a uniform composition. This composition was applied to a PET film with a thickness of 0.5 mm using a hot melt applicator under melting at 120 ° C., and after cooling, an adhesive was obtained. This adhesive was placed at 23 ° C. and 55% RH for 3 days.
It was left at 50 ° C. and 80% RH for 15 hours. This adhesive is S
It was stuck on a US plate and left at 120 ° C. for 2 hours, but no dissolution of the pressure-sensitive adhesive was observed.

(Example 2) 100 parts by weight of Kraton D-1107 (manufactured by Shell Japan) as the component (A),
Isobutylene polymers containing the molecular end as the component (B) methyldimethoxysilane group [number-average molecular weight 10400, molecular weight distribution (GPC method) 1.2,1 silicon group per molecule ⁽¹ H-NMR method) 1. 5 to 1.9] 77 parts by weight,
2 parts by weight of Neostan U-220 (manufactured by Nitto Kasei) which is a silanol condensation catalyst as a component (C), and silane coupling agent A-174 (manufactured by Nippon Unicar) 3 as a component (D)
Parts by weight: 148 parts by weight of paraffin-based process oil PS-32 (manufactured by Idemitsu Kosan) as component (E), and 86 parts by weight of terpene-based tackifying resin Px-800 (Yasuhara Chemical) as component (F) to a concentration of 50%. 80 ℃ ~
After dissolving in toluene at 100 ° C, a coating thickness of 5
0 μm using a bar coder and apply
It was left open at 0 ° C. for 10 minutes to obtain an adhesive. After curing this adhesive at 50 ° C. and 80% RH for 5 days,
It was stuck on a plate and left at 120 ° C. for 2 hours, but no dissolution of the pressure-sensitive adhesive was observed.

(Comparative Example 1) 100 parts by weight of Clayton D-1107 (manufactured by Shell Japan) as the component (A),
Paraffin-based process oil PS-3 as component (E)
2 (manufactured by Idemitsu Kosan) 125 parts by weight, terpene-based tackifying resin Px-800 (Yasuhara Chemical) as component (F)
86 parts by weight and 57 parts of paraffin wax 135F (manufactured by Japan Brazing Co.) were obtained in the same manner as in Example 1 to obtain an adhesive.
This adhesive is placed at 23 ° C. and 55% RH for 3 days at 50 ° C. and 80% RH.
% RH for 15 hours. This adhesive is applied to a SUS plate, and the adhesive is dissolved at 120 ° C within 30 minutes,
It protruded around the T film.

(Comparative Example 2) 100 parts by weight of Clayton D-1107 (manufactured by Shell Japan) as the component (A)
Paraffin-based process oil PS-3 as component (E)
2 (manufactured by Idemitsu Kosan) 125 parts by weight, terpene-based tackifying resin Px-800 (Yasuhara Chemical) as component (F)
86 parts by weight of the adhesive were obtained in the same manner as in Example 2.
After curing this adhesive at 50 ° C. and 80% RH for 5 days,
The adhesive was dissolved on a SUS plate at 120 ° C. for about 1 hour.

(Example 3) 100 parts by weight of Tuftec 1031 (Asahi Kasei) as the component (A), isobutylene polymer having a methyldimethoxy group at the molecular terminal as the component (B) [number average molecular weight 10400, molecular weight distribution (GPC
Method) 1.2 Amount of silicon group per molecule ( ¹ H-NMR
Method) 1.5 to 1.9] 77 parts by weight, 2 parts by weight of Scat-27 (manufactured by Sankyoki Chemical Co., Ltd.) as a silanol condensation catalyst as component (C), and paraffin-based process oil PS as component (E) -32 (Idemitsu Kosan) 27 parts by weight
Using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set to ° C., a uniform composition was obtained. As a result of measuring the melt viscosity of this composition using a capillary rheometer (manufactured by Shimadzu Corporation), it was 930 Pa · s at 100 ° C. While dissolving and kneading the composition at 140 ° C., water was kneaded immediately before discharging, followed by discharging to obtain a transparent molded body.
The JIS-A hardness at 23 ° C. of this molded product was 48. When this molded body was left at 100 ° C. for one week, no change in shape was observed.

Example 4 400 parts by weight of Tuftec 1031 (Asahi Kasei) as the component (A), isobutylene polymer having a methyldimethoxy group at the molecular terminal as the component (B) [number average molecular weight 10400, molecular weight distribution (GPC
Method) 1.2 Amount of silicon group per molecule ( ¹ H-NMR
Method) 1.5 to 1.9] 77 parts by weight and paraffin-based process oil PS-32 (manufactured by Idemitsu Kosan) as component (E) 2
160 parts by weight of 3 parts by weight of Scat-27 (manufactured by Sankyoki Chemical Co., Ltd.)
Using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set to ° C., a uniform composition was obtained. As a result of measuring the melt viscosity of this composition using a capillary rheometer (manufactured by Shimadzu Corporation), it was 1300 Pa · s at 140 ° C.
While dissolving and kneading the composition at 140 ° C., water was kneaded immediately before discharging, followed by discharging to obtain a transparent molded body. The JIS-A hardness at 23 ° C. of this molded product was 72. When this molded body was left at 120 ° C. for one week, no change in shape was observed.

(Comparative Example 3) 100 parts by weight of Tuftec 1031 (Asahi Kasei) as the component (A), an isobutylene polymer having an allyl group at the molecular terminal [number-average molecular weight of 102
00, molecular weight distribution (GPC method) 1.2] 77 parts by weight and paraffin-based process oil PS-3 as component (E)
2 (manufactured by Idemitsu Kosan) 23 parts by weight, Scat-27 (manufactured by Sankyoki Chemical Co., Ltd.) which is a silanol condensation catalyst as the component (C)
Two parts by weight were mixed using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set at 160 ° C. to obtain a uniform composition. The melt viscosity of this composition was measured using a capillary rheometer (manufactured by Shimadzu Corporation).
-It was s. The composition was discharged while being melted and kneaded at 140 ° C. As a result, a transparent molded body was obtained. This molded product has a larger tack compared to Example 3, and the JIS at 23 ° C.
-A hardness was 28, which was lower than that of Example 3. As a result of leaving this molded body at 100 ° C. for one week, melting was observed and the sample was deformed.

(Comparative Example 4) 400 parts by weight of Tuftec 1031 (manufactured by Asahi Kasei) as the component (A), an isobutylene polymer having an allyl group at the molecular terminal [number-average molecular weight of 102
00, molecular weight distribution (GPC method) 1.2] 77 parts by weight and paraffin-based process oil PS-3 as component (E)
2 (manufactured by Idemitsu Kosan) 23 parts by weight, Scat-27 (manufactured by Sankyoki Chemical Co., Ltd.) which is a silanol condensation catalyst as the component (C)
Two parts by weight were mixed using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set at 160 ° C. to obtain a uniform composition. The melt viscosity of this composition was measured using a capillary rheometer (manufactured by Shimadzu Corporation).
a · s. The composition was discharged while being melted and kneaded at 140 ° C. As a result, a transparent molded body was obtained. The JIS-A hardness at 23 ° C. of this molded product was 60, which was lower than that of Example 4. As a result of leaving this molded body at 120 ° C. for one week, melting was observed in a part of the sample.

(Comparative Example 5) As a result of measuring the melt viscosity of Tuftec 1031 (manufactured by Asahi Kasei) as the component (A) using a capillary rheometer (manufactured by Shimadzu Corporation), the result was 160.
It was 1100 Pa · s at ° C. In this composition, 140
Attempted to dissolve at ℃, but could not be ejected due to high viscosity.

Example 5 Styrene as Component (A)
Isobutylene-styrene block copolymer (hereinafter SIB)
Abbreviated as S: number-average molecular weight is 89,000, molecular weight distribution is 1.18) 100 parts by weight, isobutylene polymer having a methyldimethoxy group at a molecular terminal as component (B) [number-average molecular weight is 5,600, molecular weight distribution ( GPC method) 1.3,
1 silicon group per molecule ⁽¹ H-NMR method) 1.5
1.9], 0.5 parts by weight of Irganox 1010 (manufactured by Ciba-Geigy), tin octylate (manufactured by Nitto Kasei Co., Ltd.)
1.75 parts by weight of 1.55 parts by weight of Neostan U-28) and 0.25 part by weight of laurylamine (Kao Farmin 20D) were previously mixed at room temperature, and the temperature was set to 170 ° C. The rubber composition was manufactured by kneading with a Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) for 15 minutes. The gel fraction of the obtained rubber composition was 30% or more. The rubber composition was compression molded at 170 ° C. to produce a sheet.

(Comparative Example 6) A butyl rubber having a number average molecular weight of 206,000 (butyl 365, 100 parts by weight of SIBS)
A rubber composition was produced by kneading 50 parts by weight of JSR (product of JSR) and 0.5 part of Irganox 1010 (product of Ciba Geigy) for 15 minutes using a Labo Plastmill (manufactured by Toyo Seiki) set at 170 ° C. The gel fraction of the obtained rubber composition was less than 1%. The rubber composition was similarly compression molded at 170 ° C. to produce a sheet. As a result of storing the sheet produced by the above method at 120 ° C. for 10 days, the sheet of Comparative Example 6 was melted and retained its original shape, while the sheet of Example 5 maintained its original shape. I didn't. Therefore, it was confirmed that the heat resistance of the resin composition of the present invention was improved.

[0061]

The rubber composition of the present invention is excellent in balance between flexibility, mechanical properties, moldability and processability, and has good heat resistance. For this reason, rubber materials, for example, tires, sealing materials, gaskets, adhesives, and adhesives, are particularly suitably used as well as food applications, daily necessities, toys / exercise tools, stationery applications, and automobile interiors. Exterior use, civil and architectural use such as civil engineering sheets and waterproof sheets, AV and home appliance use, OA and office equipment use, clothing and footwear use, textile use, medical use such as various catheters, containers and caps, paper diapers and physiology It can be used for anti-vibration materials such as anti-vibration, anti-vibration, vibration control, etc.

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Claims (20)

[Claims] 1. A block copolymer having at least one type of block formed from an aliphatic hydrocarbon-based compound, and (B) an isobutylene-based polymer having a silicon group bonded to a hydrolyzable group or a hydroxyl group. A curable composition comprising: 2. An isobutylene polymer as the component (B)
In the above, a silicon group bonded to a hydrolyzable group or a hydroxyl group
Has the general formula (1):-(SiR¹ _2-bX_bO)_m-SiR² _3-aX_a (1) [wherein, R¹And R²Are all C 1-20
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
An aralkyl group of 0 or R³ ₃SiO- (R³Is the carbon number
A monovalent hydrocarbon group of 1 to 20;³Is the same
Or may be different).
An organosiloxy group,¹Or R ²Is two or more
When present, they may be the same, different
May be. X is a hydrolyzable group or a hydroxyl group, and two
When they exist, they may be the same or different
It may be. a is an integer selected from 0 to 3,
b is an integer selected from 0 to 2. However, a + mb
Satisfies ≧ 1. In addition, m (SiR¹ _2-bX_bO)
B need not be the same. m is from 0 to 19
An integer to be chosen. 2. The group according to claim 1,
Curable composition described above. 3. A block copolymer wherein the block copolymer of component (A) comprises a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of an aliphatic hydrocarbon compound. Claim 1 or 2 which is
The curable composition according to the above. 4. The curable composition according to claim 1, further comprising a silanol condensation catalyst as the component (C). 5. The curable composition according to claim 1, further comprising a hydrolyzable group-containing silane compound as the component (D). 6. The curable composition according to claim 1, further comprising a plasticizer as the component (E). 7. The curable composition according to claim 1, further comprising a tackifier resin as the component (F). 8. The curing method according to claim 1, wherein the isobutylene-based polymer as the component (B) has at least one silicon group bonded to a hydrolyzable group or a hydroxyl group per molecule on average. Composition. 9. The isobutylene-based polymer as the component (B) has at least one silicon group bonded to a hydrolyzable group or a hydroxyl group at a terminal of the polymer.
A curable composition according to any one of claims 1 to 8. 10. The curable composition according to claim 1, wherein the component (B) has a number average molecular weight of 1,000 to 40,000. 11. The curable composition according to claim 1, wherein the isobutylene-based polymer (B) has a molecular weight distribution (Mw / Mn) of 1.5 or less. 12. The block copolymer as the component (A) is composed of SBS, SIS, SEBS, SEPS and SIBS.
The curable composition according to any one of claims 1 to 11, wherein the curable composition is at least one selected from the group consisting of: 13. A sealing agent comprising the curable composition according to claim 1. 14. An adhesive comprising the curable composition according to claim 1. 15. An adhesive comprising the curable composition according to claim 1. 16. A gasket composition comprising the curable composition according to claim 1. Description: 17. A spacer for a double glazing comprising the curable composition according to claim 1. Description: 18. A method for applying or curing the curable composition according to claim 1, wherein the curable composition is applied or molded under heating conditions. 19. A method for applying or curing the curable composition according to claim 1, wherein the curable composition is applied or molded in a state of being dissolved in a solvent. Method. 20. The method of using the curable composition according to claim 1, wherein the condensation reaction of the component (B) with water proceeds after the curable composition is applied or molded. And how to use it.