JP2014218584A - Composition comprising polymer having monofunctional silicon group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which provides a cured material having excellent environmental compatibility, good workability before a reaction, a practical reaction rate, and excellent elasticity; or an adhesive composition.SOLUTION: The curable composition comprises a polymer (A) and an amine compound-based silanol condensation catalyst (B), the polymer (A) having a hydrolyzable group on a silicon atom and having, on the carbon atom bonded to the silicon atom, a reactive silicon group having any of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom carbon atom bonded thereto. The polymer (A) comprises one or more organic polymers selected from the group consisting of polyoxyalkylene-based polymers, poly(meth)acrylate-based polymers, and saturated hydrocarbon-based polymers.

Description

  The present invention relates to a composition comprising a polymer having a reactive silicon group in which one hydroxyl group or hydrolyzable group is bonded to silicon.

  Reactive silicon groups have the characteristic of forming siloxane bonds by hydrolysis and condensation reactions. Such a polymer containing a reactive silicon group can be made to have a higher molecular weight by bonding the polymers to each other by utilizing the reaction of the silicon group. Polymers having a dimethoxymethylsilyl group or a trimethoxysilyl group are well known, and many of them are converted into a cured product with a high molecular weight and a cross-linking by reaction.

  Among these organic polymers having a reactive silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid alkyl ester polymer, or a polyisobutylene polymer have already been used. Industrially produced and widely used for applications such as sealing materials, adhesives, paints, and pressure-sensitive adhesives (Patent Documents 1, 2, 3, and 4).

The mechanical properties of a cured product obtained from a curable composition containing a polymer having a reactive silicon group are complicatedly influenced by the main chain skeleton of the polymer, the structure and number of silicon groups, and the like. In general, in a three-dimensional network structure forming a cured product, if the molecular weight between crosslinking points is large, a cured product having a soft and good stretchability tends to be obtained. That is, it is considered that a cured product having good stretchability can be obtained by using a linear and high molecular weight reactive silicon group-containing polymer. However, in general, as the molecular weight of the polymer increases, the viscosity tends to increase and the handling tends to be difficult. Therefore, there is a limit to the method of increasing the molecular weight of the reactive silicon group-containing polymer and improving the stretchability of the resulting cured product. Therefore, a method of increasing the molecular weight between cross-linking points of the cured product using chain extension can be considered. Specifically, there is a method using a polymer having a monofunctional reactive silicon group (for example, methoxydimethylsilyl group) at both ends. The idea is that the monofunctional reactive silicon groups react with each other to obtain only one siloxane bond, which does not serve as a crosslinking point and can extend the molecular chain. As a result, the polymer before curing has a low molecular weight and good workability, and it can be expected that a cured product having a high molecular weight between cross-linking points and high strength and high stretchability can be obtained by the reaction. In addition, it can be expected to be applied to a pressure-sensitive adhesive composition that deliberately reduces cross-linking and utilizes the expression of adhesiveness by increasing the molecular weight of the polymer.
Several examples of techniques related to the curable composition using such an organic polymer having a monofunctional reactive silicon group have been disclosed so far. (Patent Documents 5, 6, 7, 8, 9) However, monofunctional silicon groups are extremely low in reactivity, and it takes time to cure the curable composition, and a curing operation such as heating is necessary. Therefore, there is much room for improvement in practical use. In Patent Document 7, a practical curing time is achieved by using a monofunctional silicon group-containing organic polymer having a limited structure. However, even in this method, there is a concern that storage stability is lowered due to the high activation of the silicon group.
On the other hand, from the viewpoint of environmental impact, it is desired to develop a technology that ensures the target physical properties without including components that adversely affect the environment in the polymer and the composition. Specific examples include limiting the use of an organic tin compound having a carbon-tin bond as a curing catalyst, limiting the use of a halogen-containing component, and limiting the use of an isocyanate compound.

JP-A-52-73998 JP 59-122541 A JP 2000-119527 A JP-A 63-6041 JP 09-095619 A JP 2001-323151 A WO2003 / 059981 JP 2009-120719 A JP 2009-179776 A

  The present invention is a composition excellent in environmental compatibility, (i) using a polymer having a reactive silicon group, good workability before reaction, having a practical curing rate, excellent It is an object of the present invention to provide a curable composition that gives a cured product having excellent stretchability, or (ii) a pressure-sensitive adhesive composition that has good workability before reaction and exhibits adhesiveness in a practical time. To do.

  As a result of intensive studies to solve the above problems, the present inventors have used a composition having a specific functional group on silicon and a polymer having a monofunctional reactive silicon group having one hydrolyzable group. The following invention using a product has been completed.

That is, the present invention
(1) A reactive silicon group having one hydrolyzable group on a silicon atom and any one of a halogen atom, an oxygen atom, a nitrogen atom and a sulfur atom bonded to a carbon atom bonded to the silicon A composition containing a polymer (A) having
(2) The reactive silicon group of the polymer (A) is represented by the general formula (1):
-SiR ¹ _a R ² _2-a X (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and a substituent in which any one of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom is bonded to a carbon atom bonded to a silicon atom. R ² is a hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by R ³ ₃ SiO—. Three R ³ are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and a is 1 or 2)), the composition according to (1),
(3) The composition according to (2), wherein R ¹ in the general formula (1) is a hydrocarbon group in which either an oxygen atom or a nitrogen atom is bonded to a carbon atom bonded to a silicon atom.
(4) The composition according to (3), wherein R ¹ in the general formula (1) is a hydrocarbon group in which an oxygen atom is bonded to a carbon atom bonded to a silicon atom,
(5) The composition according to (4), wherein R ¹ in the general formula (1) is a hydrocarbon group in which a methoxy group is bonded to a carbon atom bonded to a silicon atom.
(6) The composition according to (5), wherein R ¹ in the general formula (1) is a methoxymethyl group,
(7) The composition according to any one of (1) to (6), wherein R ² in the general formula (1) is a triorganosiloxy group represented by R ³ ₃ SiO—.
(8) The polymer (A) is at least one organic polymer selected from the group consisting of a polyoxyalkylene polymer, a poly (meth) acrylate polymer, and a saturated hydrocarbon polymer. (1) to the composition according to any one of (7),
(9) The composition according to (8), wherein the polymer (A) is a polyoxyalkylene polymer,
(10) The composition according to any one of (1) to (9), wherein the main chain of the polymer (A) is a polymer having a branched structure,
(11) The composition according to any one of (1) to (10), wherein the average number of reactive silicon groups is 1.8 to 3.0 per molecule of the polymer (A). object,
(12) A polymer in which the main chain of the polymer (A) has only a linear structure and the average number of reactive silicon groups is 1.7 to 2.0 per molecule of the polymer. The composition according to any one of (1) to (9),
(13) The composition according to any one of (1) to (12), further comprising a silanol condensation catalyst (B), wherein the silanol condensation catalyst is a non-organotin compound.
(14) The composition according to any one of (1) to (12), further comprising a silanol condensation catalyst (B), wherein the silanol condensation catalyst is an amine compound,
(15) A curable composition comprising the composition according to any one of (1) to (14),
(16) A room temperature curable composition comprising the curable composition according to (15),
(17) A pressure-sensitive adhesive composition comprising the composition according to any one of (1) to (14),
(18) A cured product obtained from the composition according to any one of (1) to (14),
About.

  The composition of the present invention is excellent in environmental compatibility, has good workability, has both rapid curability and good stretchability, or has fast tackiness.

  Hereinafter, the present invention will be described in detail.

  The polymer in the present invention conforms to the following definition. A polymer contains all the polymer components obtained by the manufacturing process of the polymer, and includes components having different molecular weight, structure, number of substituents, and the like. For the identification of the polymer, the average molecular weight, the molecular weight distribution, and the amount of substituents introduced on average per molecule (average number and content) are used. In the description of the present invention, representative molecular structures may be described for convenience.

  In the present invention, as the component (A), any one of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom is present on the carbon atom having one hydrolyzable group on the silicon atom and bonded to the silicon. A polymer (A) having a reactive silicon group to which is bonded is used. Substituents on carbon atoms bonded to silicon tend to affect the reactivity of hydrolyzable groups on silicon. Among them, halogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms have non-conjugated electron pairs, which tend to interact with silicon and hydrolyzable groups, and to increase hydrolyzability by inducing effects through covalent bonds. There is.

Such a silicon group can be represented by the following general formula (1) or (2).
General formula (1):
-SiR ¹ _a R ² _2-a X (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and a substituent in which any one of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom is bonded to a carbon atom bonded to a silicon atom. R ² is a hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by R ³ ₃ SiO—. Three R ³ are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and a is 1 or 2).
General formula (2):
—W—CH ₂ —SiR ² ₂ X (2)
(Wherein R ² and X are the same as above. W is an oxygen atom, —NH—, —NR ⁴ — (R ⁴ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), a sulfur atom. Represents any selected linking group.)
When the polymer (A) has a silicon group of the general formula (2), the polymer main chain and the silicon group are bonded by a urethane bond, a urea bond, a thiourea bond, or the like. These bonds may be cleaved due to the presence of the catalyst component or heat, and as a result, the heat resistance strength or the restoring property of the cured product may not be obtained. Therefore, the polymer (A) of the present invention is preferably one containing a silicon group of the general formula (1).

The atom on the carbon atom bonded to the silicon atom of the polymer (A) is preferably an oxygen atom or a nitrogen atom, more preferably an oxygen atom from the viewpoint of environmental compatibility. Examples of the substituent on the carbon atom bonded to the silicon atom of the substituent R ¹ in the silicon group represented by the general formula (1) include a fluoro group, a chloro group, a bromo group, a halogen atom of an iodo group, a hydroxy group, Oxygen substituents such as alkoxy groups, aryloxy groups and acyloxy groups, substituted or unsubstituted amino groups, imino groups, urethane bonds, urea bonds, isocyanate groups, ureido groups and other nitrogen substituents, mercapto groups, alkylthio groups, thios Specific examples include sulfur substituents such as urethane bonds.

Specific examples of R ¹ in the general formula (1) include a fluoromethyl group, a chloromethyl group, a methoxymethyl group, an ethoxymethyl group, a phenoxymethyl group, a 1-methoxyethyl group, an acetoxymethyl group, an amino group, and the like. Examples include methyl group, N-methylaminomethyl group, N, N-dimethylaminomethyl group, N-ethylaminomethyl group, N, N-diethylaminomethyl group, N-piperidinomethyl group, methylcarbamatemethyl group, isocyanatemethyl group It is done. In these, a chloromethyl group and a methoxymethyl group are more preferable from the point of availability and activity. The methoxymethyl group is also preferable from the point of not containing a halogen atom.

  X in the general formula (1) represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include known hydrolyzable groups. Specific examples thereof include hydrogen, halogen, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, ketoximate group, amino group, and amide group. , Acid amide group, aminooxy group, mercapto group and the like. Among these, halogen, alkoxy group, alkenyloxy group, and acyloxy group are preferable because of high activity, and hydrolyzability is gentle and easy to handle. Therefore, alkoxy groups such as methoxy group and ethoxy group are more preferable, methoxy group, An ethoxy group is particularly preferred. In addition, the ethoxy group and the isopropenoxy group are preferably removed from the reaction by ethanol and acetone, respectively, from the viewpoint of safety.

Specific examples of R ² in the general formula (1) include an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; In addition, R ³ ₃ SiO— (three R ³ are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different.) And a triorganosiloxy group represented by: Among these, a methyl group and a trimethylsiloxy group are particularly preferable. A methyl group is preferred because of its ease of introduction. A trimethylsiloxy group is preferable from the viewpoint of reaction activity of the reactive silicon group.

  Specific examples of the reactive silicon group represented by the general formula (1) include (chloromethyl) methoxymethylsilyl group, bis (chloromethyl) methoxysilyl group, and (chloromethyl) (methoxy) (trimethylsiloxy) silyl. Group, (methoxymethyl) (methoxy) methylsilyl group, (methoxymethyl) (ethoxy) methylsilyl group, (methoxymethyl) (acetoxy) methylsilyl group, (methoxymethyl) (isopropenyloxy) methylsilyl group, (methoxymethyl) (dimethoxy) Ketoximate) methylsilyl group, (methoxymethyl) (ethylmethylketoxime) methylsilyl group, (methoxymethyl) (methoxy) (trimethylsiloxy) silyl group, bis (methoxymethyl) methoxysilyl group, (aminomethyl) (methoxy) Methylsilyl group, ( , N- dimethylaminomethyl) (methoxy) methylsilyl group, (N, N- diethylaminomethyl) (methoxy) methylsilyl group, (acetoxymethyl) (methoxy) methylsilyl group, but and the like, without limitation. Among these, a (chloromethyl) methoxymethylsilyl group and a (methoxymethyl) (methoxy) methylsilyl group are preferable because they exhibit high activity and provide a cured product having good mechanical properties. From the viewpoint of introducing a functional group, a (methoxymethyl) (methoxy) (trimethylsiloxy) silyl group is particularly preferable.

  The method for introducing the reactive silicon group is not particularly limited, and a known method can be used. The introduction method is illustrated below.

  (I) Hydrosilylation: First, an unsaturated bond is introduced into a polymer (also referred to as a precursor polymer) that is a raw material of the polymer (A), and a hydrosilane compound is hydrosilylated with respect to the unsaturated bond. It is the method of adding by. Any method can be used for introducing the unsaturated bond. For example, a precursor polymer having a functional group such as a hydroxyl group is allowed to react with a compound having reactivity with this functional group and a compound having an unsaturated group. There are a method for obtaining an unsaturated group-containing polymer and a method for copolymerizing a polymerizable monomer having an unsaturated bond.

  (Ii) Reaction of a reactive group-containing polymer (precursor polymer) with a silane coupling agent: reacting with the precursor polymer having a reactive group such as a hydroxyl group, an amino group, or an unsaturated bond, and the reactive group. And a compound having both a group capable of forming a bond and a reactive silicon group (also called a silane coupling agent). As a combination of the reactive group of the precursor polymer and the reactive group of the silane coupling agent, a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, Examples include, but are not limited to, Michael addition of amino group and acrylic structure, carboxylic acid group and epoxy group, unsaturated bond and mercapto group.

  The method (i) is preferable because the reaction is simple, the adjustment of the amount of reactive silicon groups introduced, and the physical properties of the resulting reactive silicon group-containing polymer are stable. The method (ii) has many reaction options, and it is easy and preferable to increase the rate of introduction of reactive silicon groups.

  A part of hydrosilane compound used by the method of (i) is illustrated. (Chloromethyl) methoxymethylsilane, bis (chloromethyl) methoxysilane, (chloromethyl) (methoxy) (trimethylsiloxy) silane, (methoxymethyl) (methoxy) methylsilane, (methoxymethyl) (ethoxy) methylsilane, (methoxy Methyl) (methoxy) (trimethylsiloxy) silane, bis (methoxymethyl) methoxysilane, (aminomethyl) (methoxy) methylsilane, (N, N-dimethylaminomethyl) (methoxy) methylsilane, (N, N-diethylaminomethyl) Alkoxysilanes such as (methoxy) methylsilane, (acetoxymethyl) (methoxy) methylsilane; (acetoxy) (methoxymethyl) methylsilane, (acetoxy) (methoxymethyl) (trimethylsiloxy) silane, and the like Xysilanes; ketoximate silanes such as (methoxymethyl) methyl (dimethyl ketoximate) silane, isopropenyloxy silanes (deacetone type) such as (isopropenyloxy) (methoxymethyl) methyl silane, etc. .

  Examples of the silane coupling agent that can be used in the method (ii) include the following compounds. Mercaptosilanes such as 3-mercaptopropyl (methoxymethyl) (methoxy) methylsilane that react with unsaturated bonds; Isocyanatosilanes such as 3-isocyanatopropyl (methoxymethyl) (methoxy) methylsilane that react with hydroxyl groups; Epoxysilanes such as 3-glycidoxypropyl (methoxymethyl) (methoxy) methylsilane that react with amino groups and carboxylic acid groups; 3-aminopropyl (methoxymethyl) (methoxy) that reacts with isocyanate groups and thioisocyanate groups ) Aminosilanes such as methylsilane; hydroxyalkylsilanes and the like. The above silane coupling agent is an example, and a silyl group can be introduced by utilizing or applying a similar reaction.

  In addition, for silyl groups with trialkylsiloxy groups such as (methoxymethyl) (methoxy) (trimethylsiloxy) silyl groups, the corresponding bifunctional reactive silicon groups such as (methoxymethyl) dimethoxysilyl groups are once introduced. In addition, it can be introduced by a method in which one of the hydrolyzable groups is substituted with a trialkylsiloxy group. As the substitution reaction, a substitution reaction with silanol such as trimethylsilanol or an ester exchange reaction with methoxytrimethylsilane can be used. This method is preferable because a bifunctional silane that is easier to synthesize can be used.

  The number of reactive silicon groups in the polymer (A) is averaged per molecule, the lower limit is preferably 1.1 or more, and the upper limit is preferably 5 or less. In the case where the polymer has a branched structure, the lower limit of the number of reactive silicon groups is preferably 1.8 or more, and more preferably 2.0 or more. The upper limit is more preferably 3 or less. If the number of reactive silicon groups is too small, sufficient bonding between the polymers does not occur, and it becomes difficult to obtain the properties of the resulting cured product or adhesive. On the other hand, when there are too many reactive silicon groups, stretchability may be reduced, which is disadvantageous economically. When the polymer has only a linear structure, the lower limit of the number of reactive silicon groups is preferably 1.8 or more, and more preferably 2.0 or more.

The average number of reactive silicon groups in the polymer (A) is determined by a method in which protons on carbon to which reactive silicon groups are directly bonded are quantified by a high resolution ¹ H-NMR measurement method.

  The number average molecular weight of the polymer (A) is about 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene in GPC. When the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced is increased, which may be inconvenient in terms of production cost. When the number average molecular weight exceeds 100,000, the viscosity becomes high and the workability is increased. Tend to be inconvenient.

  The molecular weight distribution (Mw / Mn) of the organic polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less. 4 or less is particularly preferable.

  The main chain skeleton of the polymer (A) is not particularly limited, and those having various main chain skeletons can be used. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, Polyoxyalkylene polymers such as polyoxyethylene-polyoxypropylene copolymers and polyoxypropylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc. , Polychloroprene, polyisoprene, isoprene or copolymers of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or copolymers of butadiene and acrylonitrile and styrene, and hydrogenating these polyolefin polymers Hydrocarbon polymers such as hydrogenated polyolefin polymers; polyester polymers obtained by condensation of dibasic acids such as adipic acid and glycols or ring-opening polymerization of lactones; ethyl (meth) acrylate, (Meth) acrylate polymer obtained by radical polymerization of monomers such as butyl (meth) acrylate; obtained by radical polymerization of monomers such as (meth) acrylate monomer, vinyl acetate, acrylonitrile, styrene Vinyl polymer; Graft polymer obtained by polymerizing vinyl monomer in the polymer; Polysulfide polymer; Polyamide 6 by ring-opening polymerization of ε-caprolactam, Polyamide by condensation polymerization of hexamethylenediamine and adipic acid 6.6, condensation of hexamethylenediamine and sebacic acid Polyamides such as polyamide 6 · 10 by polymerization, polyamide 11 by condensation polymerization of ε-aminoundecanoic acid, polyamide 12 by ring-opening polymerization of ε-aminolaurolactam, and a copolymerized polyamide having two or more components among the above polyamides Examples thereof include organic polymers such as polycarbonate polymers and diallyl phthalate polymers produced by condensation polymerization from bisphenol A and carbonyl chloride. Of these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylate polymers have relatively low glass transition temperatures. The resulting cured product is preferable because it is excellent in cold resistance.

  The glass transition temperature of the organic polymer (A) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably −20 ° C. or lower. When the glass transition temperature is higher than 20 ° C., the viscosity in winter or in a cold region may be increased, which may make it difficult to handle, and the flexibility of the cured product may be decreased, and the elongation may be decreased. The glass transition temperature can be determined by DSC measurement according to the measurement method specified in JISK7121.

  Organic polymers such as saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth) acrylic ester polymers are used as adhesive groups for low molecular weight components when used as a base polymer for adhesives and sealants. It is preferable because there is little contamination due to transfer to materials.

  Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are preferred because they have high moisture permeability and are excellent in deep part curability and further in adhesion when made into one-component compositions. An oxyalkylene polymer is particularly preferable.

The polyoxyalkylene polymer is a polymer having a repeating unit represented by —R ⁵ —O— (wherein R ⁵ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁵ is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by —R ⁵ —O— include —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H _{5) O -, - CH 2} C (CH 3) (CH 3) O -, - CH 2 CH 2 CH 2 CH 2 O- and the like. The main chain structure of the polyoxyalkylene polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units. In particular, when used in sealants, adhesives, etc., those composed of a polyoxypropylene-based polymer having a repeating unit of oxypropylene of 50% by weight or more, preferably 80% by weight or more of the polymer main chain structure, It is preferable from the point of being crystalline and having a relatively low viscosity.

  The method for synthesizing the polyoxyalkylene polymer is not particularly limited. For example, a polymerization method using an alkali catalyst such as KOH, an organoaluminum compound and a porphyrin disclosed in JP-A-61-215623 can be used. Polymerization method using transition metal compound-porphyrin complex catalyst such as complex obtained by reaction, JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Polymerization method using double metal cyanide complex catalyst shown in each publication such as Japanese Patent No. 3427256, US Pat. No. 3,427,334, US Pat. No. 3,427,335, and polymerization method using a catalyst comprising a polyphosphazene salt shown in JP-A-10-273512 , Japanese Patent Laid-Open No. 11060722 A polymerization method using a catalyst comprising a phosphazene compound and the like.

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. (2) A homopolymerization of a diene compound such as butadiene or isoprene, or a copolymerization with the olefin compound. Thereafter, it can be obtained by a method of hydrogenation. Among these, isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferable because it is easy to introduce a functional group at the end, easy to control the molecular weight, and can increase the number of terminal functional groups. An isobutylene polymer is more preferable.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the repeating units may be formed from isobutylene units, or may be a copolymer with other repeating units (monomers). However, from the viewpoint of rubber properties, the repeating units are derived from isobutylene. What has 50 weight% or more of a unit is preferable, What has 80 weight% or more is more preferable, What has 90 to 99 weight% is especially preferable.

  The method for synthesizing the saturated hydrocarbon polymer is not particularly limited, and various conventionally reported polymerization methods can be mentioned, but the living polymerization method that has been reported in many recent years is particularly preferable. Among these, in the case of saturated hydrocarbon polymers, particularly isobutylene polymers, inifer polymerization discovered by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1977, 15, 2869) can be easily produced, a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends. It has been.

  It does not specifically limit as a (meth) acrylic acid ester type monomer which comprises the principal chain of a (meth) acrylic acid ester type (co) polymer, Various things can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , Tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylate n -Octyl, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) Benzyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ( T) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (3-trimethoxysilyl) propyl (meth) acrylate, (meth) (3-dimethoxymethylsilyl) propyl acrylate, (2-trimethoxysilyl) ethyl (meth) acrylate, (2-dimethoxymethylsilyl) ethyl (meth) acrylate, trimethoxysilylmethyl (meth) acrylate, ( (Meth) acrylic acid (dimethoxymethylsilyl) methyl, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic acid 2 -Perfluoroethylethyl, 2- (meth) acrylic acid Fluoroethyl-2-perfluorobutylethyl, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoro (meth) acrylate (Meth) such as methyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Examples include acrylic acid monomers.

  Examples of other monomer units include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as N-methylolacrylamide and N-methylolmethacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and diethylaminoethyl acrylate. And monomers containing a nitrogen-containing group such as diethylaminoethyl methacrylate.

  As the (meth) acrylic acid ester polymer, a polymer obtained by copolymerizing a (meth) acrylic acid ester monomer and a vinyl monomer copolymerizable therewith can also be used. The vinyl monomer is not particularly limited, and examples thereof include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, and the like. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid And dialkyl esters; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenol Maleimide monomers such as lumaleimide and cyclohexylmaleimide; Vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; Vinyl monomers containing amide groups such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid Vinyl ester monomers such as vinyl and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. It is also possible to use a plurality as copolymerization components.

  Among the (meth) acrylic acid ester polymers obtained from the above monomers, a copolymer composed of a styrene monomer and a (meth) acrylic acid monomer is preferable because of its excellent physical properties. A (meth) acrylic acid ester polymer composed of an acid ester monomer is more preferred, and an acrylic acid ester polymer composed of an acrylic acid ester monomer is particularly preferred.

  In particular, when the organic polymer (A) is used for applications such as general construction, butyl acrylate is required because physical properties such as low viscosity of the compound, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. A butyl acrylate polymer composed of a monomer is preferred. Moreover, when using for the use as which oil resistance etc. are requested | required, such as a motor vehicle use, the copolymer which has ethyl acrylate as a main component is preferable. Polymers made of ethyl acrylate are excellent in oil resistance but may be slightly inferior in low-temperature properties (cold resistance). To improve low-temperature properties, it is possible to replace a part of ethyl acrylate with butyl acrylate. Is possible. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. It is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics without impairing oil resistance.

  However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain a suitable polymer by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although it is not limited, examples of excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (by weight ratio of 40-50 / 20- 30/30 to 20). In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. .

  As will be described later, the reactive silicon group-containing polymer used in the present invention can be used by mixing polymers having different main chain skeletons. For example, when a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth) acrylic acid ester polymer are mixed, the (meth) acrylic acid ester having an alkyl group having 1 to 8 carbon atoms By using a copolymer composed of a monomer and a (meth) acrylic acid ester monomer having an alkyl group having 10 or more carbon atoms, the mixing property is improved.

  The method for synthesizing the (meth) acrylic acid ester-based polymer is not particularly limited, and examples thereof include known methods. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a living radical polymerization method.

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” in which a (meth) acrylate monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, In addition to the characteristics of the “Living Radical Polymerization Method”, it has a specific functional group because it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts. The method for producing a (meth) acrylic acid ester polymer is more preferable. Examples of the atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  On the other hand, the main chain skeleton of the organic polymer may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

Although it does not specifically limit as said urethane bond component, The group (henceforth an amide segment) produced | generated by reaction of an isocyanate group and an active hydrogen group can be mention | raise | lifted. The amide segment is a group represented by —NR ⁶ (C═O) — (R ⁶ represents a hydrogen atom or a substituted or unsubstituted organic group). The amide segment is not particularly limited, and for example, a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between an isocyanate group and an amino group; a group formed by a reaction between an isocyanate group and a mercapto group Examples thereof include a functional group having an amide bond such as a thiourethane group, and a group formed by further reacting an active hydrogen in the urethane group, urea group and thiourethane group with an isocyanate group.

  A cured product obtained by curing a curable composition comprising a polymer containing a urethane bond or an ester bond in the main chain may cleave the main chain at the urethane bond or ester bond part due to heat, etc., and the strength of the cured product May be significantly reduced.

  When there are many amide segments in the main chain skeleton of the polymer (A) of the present invention, the viscosity of the polymer tends to increase. Moreover, a viscosity may rise after storage, and workability | operativity of the composition obtained may fall. Furthermore, as described above, the amide segment may be cleaved by heat or the like. Therefore, in order to obtain a composition having excellent storage stability and workability, it is preferable that the amide segment is not substantially contained. On the other hand, curability tends to be improved by the amide segment in the main chain skeleton of the polymer (A). Therefore, when the main chain skeleton of the polymer (A) contains an amide segment, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 5, and 2 to 3 Particularly preferred. When the number is less than 1, the curability may not be sufficient. When the number is more than 10, the polymer may have a high viscosity and may be difficult to handle.

  The main chain structure of the organic polymer (A) may be linear or may have a branched chain. Since fast curability is easy to obtain, it is preferable to have a branched chain. The number of branched chains is more preferably 1 to 4 and the number of branched chains is most preferably 1 from the viewpoint of obtaining a cured product exhibiting good elongation properties.

  The organic polymer (A) used in the present invention may have any one main chain skeleton among the various main chain skeletons described above, and is a mixture of polymers having different main chain skeletons. May be. Moreover, about a mixture, what manufactured each polymer separately may be mixed, and you may manufacture simultaneously so that it may become arbitrary mixed compositions.

The composition of the present invention contains the organic polymer (A) as an essential component, but if necessary, in addition to the polymer (A), the general formula (3):
—CR ⁷ ₂ CR ⁷ ₂ —SiR ² _3-b X _b (3)
(In the formula, R ² and X are the same as above. R ⁷ is independently hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. B is any of 1, 2, and 3) A polymer (C) having an average of 0.5 or more reactive silicon-containing groups described in 1 molecule may be included.

  The reactive silicon group described in the general formula (3) is not particularly limited, and examples thereof include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triisopropenoxy group, a dimethoxymethylsilyl group, a dimethoxymethyl group, and a dimethoxymethylsilyl group. Examples thereof include ethoxymethylsilyl group, diisopropoxymethylsilyl group, methoxydimethylsilyl group and ethoxydimethylsilyl group. Among them, a methoxydimethylsilyl group and a trimethoxysilyl group are preferable from the viewpoints of curability and mechanical properties of the obtained cured product.

  The main chain skeleton of the polymer (C) and the synthesis method thereof can be explained in the same manner as the polymer (A).

  Moreover, the polymer (A) of this invention may contain the reactive silicon containing group represented by General formula (3) in a molecule | numerator.

  The polymer (A) and the polymer (C) can be mixed and used at an arbitrary ratio, and the ratio of the mixture can be selected from the viewpoints of curing speed, stability, cost, and the like. . The upper limit of the mixing ratio of the polymer (C) (the blending amount of the polymer (C) / the total amount of the polymer (A) and the polymer (C)) is preferably 90% or less, and 80% or less. More preferably. The polymer (A) and the polymer (C) may be of the same type or different types with respect to the main chain skeleton, but are preferably compatible with each other.

  In the present invention, the silanol condensation catalyst (B) is used for the purpose of accelerating the reaction of hydrolyzing and condensing the reactive silicon group of the polymer (A) and extending or crosslinking the polymer.

  As a silanol condensation catalyst for a reactive silicon group-containing polymer, it has already been known that a large number of catalysts can be used. For example, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc. In the past, organotin compounds, particularly dibutyltin compounds, have been widely used. However, as described above, since an organic tin compound has a concern about the influence on the environment, it is preferable to use a non-organic tin-based compound, particularly a non-butyl tin-based compound as the silanol condensation catalyst.

  In the present invention, an amine compound can be suitably used as the silanol condensation catalyst (B).

  Examples of amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexyl. Aliphatic primary amines such as amines; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, Aliphatic secondary amines such as distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; Aliphatic tertiary amines such as amylamine, trihexylamine and trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatic amines such as aniline, laurylaniline, stearylaniline and triphenylamine; Pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylaminopyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2- Piperidinemethanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 6- (Dibutylamino) -1,8 Diazabicyclo [5,4,0] undecene-7 (DBA-DBU), 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4,0] undec-7-ene (OH-DBU), OH -Compounds in which the hydroxyl group of DBU is modified by urethanation, etc., 1,5-diazabicyclo [4,3,0] nonene-5 (DBN), 1,4-diazabicyclo [2,2,2] octane (DABCO), aziridine Nitrogen-containing heterocyclic compounds such as: DBU phenol salt (specifically, trade name: U-CAT SA1 (manufactured by San Apro)), DBU octylate (specifically, trade name: U-CAT SA102) (Product of San Apro)), DBU p-toluenesulfonate (specifically, trade name: U-CAT SA506 (product of San Apro)), DBN octylate (specifically , Trade name: U-CAT 1102 (manufactured by San-Apro)) and other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine , Ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2- (2-aminoethylamino) Ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2- ( -Piperazinyl) amines such as ethylamine, xylylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol; guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1 -Biguanides such as phenyl biguanide, and the like.

  Among these, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU and DBN; guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1 Biguanides such as -o-tolyl biguanide and 1-phenyl biguanide are preferable because they exhibit high activity, and aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness. preferable.

  Further, the amine compound is basic, but an amine compound having a pKa value of the conjugate acid of 11 or more is preferably high in catalytic activity, and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN and the like are particularly preferable because the pKa value of the conjugate acid is 12 or more and high catalytic activity is exhibited.

  In the present invention, an amino group-containing silane coupling agent (sometimes referred to as aminosilane) can be used as the amine compound used in the silanol condensation catalyst. As the hydrolyzable group of aminosilane used as the silanol condensation catalyst of the present invention, an alkoxy group such as a methoxy group and an ethoxy group is more preferred because of its mild hydrolyzability and easy handling, and a methoxy group and an ethoxy group are particularly preferred. In addition, the ethoxy group and the isopropenoxy group are preferably removed from the reaction by ethanol and acetone, respectively, from the viewpoint of safety. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more from the viewpoint of catalytic activity.

  The aminosilane used as the silanol condensation catalyst is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltris (2-propoxy) silane, and γ-aminopropylmethyldimethoxy. Silane, γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ- Aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltriisopropoxysilane, N-β- (β-aminoethyl) aminoethyl -Γ-aminopropyltrimethoxysilane N-6-aminohexyl-γ-aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N- Phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldi Examples thereof include ethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.

Among the aminosilanes, aminosilanes having an amino group (—NH ₂ ) are preferable from the viewpoint of curability. Dimethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane are preferred.

  A ketimine compound that generates the amine compound by hydrolysis can also be used as a silanol condensation catalyst.

Examples of the silanol condensation catalyst (B) other than the amine compound include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, etc. Carboxylic acid; derivatives of the above carboxylic acids (carboxylic anhydride, ester, amide, nitrile, acyl chloride); tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, carboxyl Titanium oxide, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, potassium Carboxylic acid metal salts such as manganese borate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diiso Titanium compounds such as propoxy titanium and diisopropoxy titanium bis (ethylacetocetate); dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis ( Methyl maleate), dibutyl tin bis (ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis Benzyl maleate), dibutyltin diacetate, dioctyltin bis (ethyl maleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyl Organotin compounds such as tin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester; aluminum tris (acetyl) Acetonate), aluminum tris (ethyl acetoacetate), aluminum compounds such as diisopropoxyaluminum ethyl acetoacetate; zirconi such as zirconium tetrakis (acetylacetonate) Various metal alkoxides such as tetrabutoxyhafnium; organic acidic phosphates; organic sulfonic acids such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid; boron trifluoride, trifluoride Boron trifluoride complexes such as boron fluoride diethyl ether complex and boron trifluoride ethylamine complex; ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium hydrogen fluoride, 1,1,2,3 , 3,3-hexafluoro-1-diethylaminopropane (MEC81, commonly known as Ishikawa reagent), potassium hexafluorophosphate, Na ₂ SiF ₆ , K ₂ SiF ₆ , (NH ₄ ) ₂ SiF _6, etc. can give. However, for the reasons described above, the amount of the organic tin compound used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and 0.05 parts by weight with respect to 100 parts by weight of the polymer (A). The following are more preferred, particularly not substantially contained, most preferably not contained. In the present invention, “substantially no organotin catalyst” means that the content of the organotin compound used as the silanol condensation catalyst (B) is 0 with respect to 100 parts by weight of the polymer (A). .01 parts by weight or less.

  The silanol condensation catalyst (B) may be used in combination of two or more different types of catalysts. For example, the combined use of the amine compound and carboxylic acid may improve the reactivity. There is sex.

  As a usage-amount of a silanol condensation catalyst (B), 0.001-20 weight part is preferable with respect to 100 weight part of polymers (A), Furthermore, 0.01-15 weight part is more preferable, 0.01 10 parts by weight is particularly preferred. If the amount of the silanol condensation catalyst (B) is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, when the blending amount of the silanol condensation catalyst (B) exceeds 20 parts by weight, the reaction rate is too high, and the workable time tends to deteriorate due to the shortened time in which the composition can be used, and the storage stability tends to deteriorate. There is. Furthermore, in the silanol condensation catalyst (B), after the curable composition is cured, it may ooze out on the surface of the cured product or contaminate the cured product surface. However, since the polymer (A) of the present invention can exhibit sufficient reactivity even with a small amount of silanol condensation catalyst, the amount of the silanol condensation catalyst (B) used is 0.01 to 2 in such a case. By setting the content to 0.0 parts by weight, the surface state of the cured product can be maintained well while ensuring curability.

  A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity, slump property of the composition, and mechanical properties such as hardness, tensile strength, and elongation of the cured product obtained by curing the curable composition can be adjusted. Specific examples of the plasticizer include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, and the like; bis (2-ethylhexyl) ) Terephthalic acid ester compounds such as 1,4-benzenedicarboxylate (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester ( Specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributy acetyl citrate Aliphatic polycarboxylic acid ester compounds such as butyl; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl ester (specifically, trade name: Mesamol (manufactured by LANXESS)); Phosphate ester compounds such as cresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil and epoxybenzyl stearate And epoxy plasticizers.

  Moreover, a polymeric plasticizer can be used. When a high molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low molecular plasticizer is used. Furthermore, the drying property (paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; number average molecular weight of 500 or more Furthermore, more than 1,000 polyether polyols such as polyethylene glycol polypropylene glycol and polytetramethylene glycol, or the hydroxy group of these polyether polyols are esterified Polyethers such as derivatives converted to ether groups; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. It is not something.

  Among these polymer plasticizers, those compatible with the polymer (A) are preferable. From this point, a polyether polymer is preferable. Further, when a polyether polymer is used as a plasticizer, it is preferable because surface curability and deep part curability are improved and curing delay after storage does not occur, and polypropylene glycol is more preferable. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers such as poly (meth) acrylic acid alkyl esters are particularly preferred. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of a (meth) acrylic acid alkyl ester monomer described in JP-A No. 2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000. 5,000. Most preferred is 1,000 to 3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, and the initial physical properties cannot be maintained over a long period of time. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight of the polymer plasticizer is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

  The polymer plasticizer may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. When it has a reactive silicon group, it is preferably 1 or less, more preferably 0.8 or less on average per molecule. When using a plasticizer having a reactive silicon group, particularly a polyether polymer having a reactive silicon group, the number average molecular weight must be lower than that of the reactive silicon group-containing polyoxyalkylene polymer (A). It is.

  The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer (A). If it is less than 5 parts by weight, the effect as a plasticizer is not expressed, and if it exceeds 150 parts by weight, the mechanical strength of the cured product is insufficient. A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

  A solvent or diluent can be added to the composition of the present invention. Although it does not specifically limit as a solvent and a diluent, Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. . The said solvent or diluent may be used independently and may be used together 2 or more types.

  In the composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter.

  Specific examples of the silane coupling agent include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and α-isocyanatemethyltrimethoxysilane. Isocyanate group-containing silanes such as α-isocyanatomethyldimethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N -Β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropy Triethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxy Silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, (aminomethyl) dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (phenylaminomethyl) dimethoxymethylsilane, (phenylaminomethyl) trimethoxysilane, bis Amino group-containing silanes such as (3-trimethoxysilylpropyl) amine; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopro Mercapto group-containing silanes such as rumethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4- Epoxy group-containing silanes such as epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) Carboxysilanes such as silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyl Vinyl-type unsaturated group-containing silanes such as oxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; methyl (N- Carbamate silanes such as dimethoxymethylsilylmethyl) carbamate, methyl (N-trimethoxysilylmethyl) carbamate, methyl (N-dimethoxymethylsilylpropyl) carbamate, methyl (N-trimethoxysilylpropyl) carbamate; (methoxymethyl) dimethoxy Alkoxy group-containing silanes such as methylsilane, (methoxymethyl) trimethoxysilane, (ethoxymethyl) trimethoxysilane, and (phenoxymethyl) trimethoxysilane; Pills succinic anhydride, 3-may be mentioned acid anhydride-containing silanes such as (triethoxysilyl) propyl succinic anhydride and the like. In addition, these partial condensates and derivatives thereof, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc. It can be used as a ring agent. These silane coupling agents may be used alone or in combination. As the reaction product of the silane coupling agent, a reaction product of isocyanate silane and a hydroxyl group-containing compound, an amino group-containing compound; a Michael addition reaction product of aminosilane; a reaction product of an aminosilane and an epoxy group-containing compound, an epoxy silane and a carboxylic acid group Examples thereof include a reaction product with a containing compound and an amino group-containing compound.

  0.1-20 weight part is preferable with respect to 100 weight part of polymers (A), and, as for the usage-amount of a silane coupling agent, 0.5-10 weight part is especially preferable.

  Specific examples of the adhesion-imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

  Moreover, a silicate can be added to the composition of this invention. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product obtained from the curable composition of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane and alkylalkoxysilane or partial hydrolysis condensates thereof can be used.

  Specific examples of the silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

  The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance improvement effect of the present invention are greater than those of tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

  When using a silicate, the usage-amount is 0.1-20 weight part with respect to 100 weight part of polymers (A), Preferably it is 0.5-10 weight part.

  Various fillers can be mix | blended with the composition of this invention. Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, Resin powder such as magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, PVC powder, PMMA powder And fillers such as asbestos, glass fibers and filaments.

  As described in Japanese Patent Application Laid-Open No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, and then sealed in a bag made of an airtight material and left for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, storage stability can be improved particularly when a one-component composition is used.

  Further, when obtaining a highly transparent composition, as described in JP-A-11-302527, polymer powder made from a polymer such as methyl methacrylate or amorphous silica is used. Etc. can be used as fillers. Further, as described in JP-A-2000-38560, a composition having high transparency can be obtained by using hydrophobic silica or the like, which is a fine powder of silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler. Can be obtained. The surface of silicon dioxide fine powder is generally a silanol group (-SiOH), and (-SiO-hydrophobic group) is generated by reacting organosilanide or alcohol with this silanol group. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane and the like are reactively bonded to the silanol group present on the surface of the silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.

  When you want to obtain a hardened material with high strength by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment A filler selected from fine calcium carbonate, calcined clay, clay and activated zinc white is preferred, and the amount used is preferably 1 to 200 parts by weight per 100 parts by weight of the polymer (A).

  In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the polymer (A), preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. When calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used. Surface treatment agents for producing surface-treated calcium carbonate powder include palmitic acid, caprylic acid, capric acid, lauric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, etc. Carboxylic acids such as fatty acids and unsaturated fatty acids, rosin acid compounds and esters thereof, silane compounds such as hexamethyldisilazane, chlorosilane, and aminosilane, paraffin compounds, and the like. I don't mean. Especially, when a surface treating agent is carboxylic acid, when it is set as a curable silicone type resin composition, since it becomes difficult to produce hardening delay further, it is preferable. Further, among the carboxylic acids, saturated fatty acids or unsaturated fatty acids are particularly preferred because they are much less likely to cause curing delay. Of course, these fillers may be used alone or in combination of two or more. Fatty acid surface-treated colloidal calcium carbonate and heavy calcium carbonate that has not been surface-treated such as calcium carbonate having a particle size of 1 μm or more can be used in combination.

  The amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of the total amount of the polymer (A).

  In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  The composition of the present invention is an adhesive for exterior wall joints, exterior wall tiles, and exterior wall tiles, such as sizing boards, especially ceramic sizing boards, because the cured product has good chemical resistance. However, it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, high-quality outer walls are used as outer walls due to the mixture of spatter coating, colored aggregates, and the like. When a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, is blended in the composition of the present invention, the cured product is in harmony with such a high-quality outer wall. However, since the chemical resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time. When a granular material is used, the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.

  As described in JP-A-9-53063, preferable diameters, blending amounts, materials, and the like of the scaly or granular substance are as follows.

  The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and a material having an appropriate size is used according to the material and pattern of the outer wall. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.

  The scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

  As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall.

  A preferable finishing method and the like are described in JP-A-9-53063.

  Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface becomes sandy or sandstone-like, and the weight can be reduced. The preferred diameter, blending amount, material and the like of the balloon are as described in JP-A-10-251618.

  The balloon is a spherical filler with a hollow inside. The balloon can be added for the purpose of reducing the weight (lowering the specific gravity) of the composition. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. In addition, an inorganic material and an organic material can be combined, or a plurality of layers can be formed by stacking. An inorganic or organic balloon or a combination of these can be used. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide, or the like, or an inorganic balloon may be surface treated with a silane coupling agent.

  The balloon preferably has a particle size of 0.1 mm or more in order to obtain a surface having a sandy or sandstone texture. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and the rough feeling may not be exhibited. The blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in terms of volume concentration in the composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when it exceeds 25 vol%, the viscosity of the sealing material and the adhesive becomes high, the workability is poor, the modulus of the cured product is also high, and the sealing material and bonding The basic performance of the agent tends to be impaired. The volume concentration with a particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.

  When using a balloon, the anti-slip agent as described in JP-A-2000-154368 and the surface of a cured product as described in JP-A-2001-164237 are matted to give an uneven state. An amine compound for obtaining a state, particularly a primary and / or secondary amine having a melting point of 35 ° C. or higher can be added.

  Specific examples of the balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, JP-A-9-53063, JP-A-10-10. -251618, JP-A 2000-154368, JP-A 2001-164237, WO 97/05201, and the like.

  Moreover, the thermally expansible fine particle hollow body as described in Unexamined-Japanese-Patent No. 2004-51701, 2004-66749, etc. can be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylindene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape. By heating the bonding part using this composition, the gas pressure in the shell of the thermally expandable fine hollow body increases, and the volume of the polymer outer shell material softens, so that the volume expands dramatically and the bonding interface is Plays the role of peeling. By adding the thermally expandable fine hollow body, it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.

  Even when the composition of the present invention contains particles of cured sealant, the cured product can form irregularities on the surface and improve the design. Preferred diameters, blending amounts, materials, and the like of the cured sealant particles are as follows as described in JP-A No. 2001-115142. The diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.

  An anti-sagging agent may be added to the composition of the present invention as needed to prevent sagging and improve workability. The sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These anti-sagging agents may be used alone or in combination of two or more.

  The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer (A).

  An antioxidant (antiaging agent) can be used in the composition of the present invention. If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by Ciba Japan Co., Ltd.); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 (and above) All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.) Hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

  0.1-10 weight part is preferable with respect to 100 weight part of polymers (A), and, as for the usage-amount of antioxidant, 0.2-5 weight part is especially preferable.

  A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred.

  0.1-10 weight part is preferable with respect to 100 weight part of polymers (A), and, as for the usage-amount of a light stabilizer, 0.2-5 weight part is especially preferable.

  When a photocurable substance is blended in the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB119FL (all are manufactured by Ciba Japan Co., Ltd.); Adeka Stub LA-57, LA-62, LA-67, LA-63 (all above) Light stabilizers such as SANOL LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

  An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of UV absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, but benzotriazole is particularly preferable, and commercially available names are Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (manufactured by Ciba Japan Co., Ltd.) can be mentioned. 2- (2H-1,2,3-benzotriazol-2-yl) -phenolic compounds are particularly preferred. Furthermore, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber in combination.

  0.1-10 weight part is preferable with respect to 100 weight part of polymers (A), and, as for the usage-amount of a ultraviolet absorber, 0.2-5 weight part is especially preferable.

  You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property modifier, For example, alkyl alkoxysilanes, such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane Arylalkoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, and other alkylisopropenoxysilanes; tris (trimethylsilyl) borate, tris (triethyl) And trialkylsilyl borates such as silyl) borate; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and break elongation. The said physical property modifier may be used independently and may be used together 2 or more types.

  In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mention | raise | lifted. Further, a derivative of an alkyl alcohol such as hexanol, octanol or decanol which produces a silicon compound which produces a silane monool such as trimethylsilanol by hydrolysis, or trimethylol described in JP-A-11-241029 A compound that is a derivative of a polyhydric alcohol having 3 or more hydroxyl groups, such as propane, glycerin, pentaerythritol, or sorbitol, that generates a silicon compound that generates a silane monool by hydrolysis.

  Moreover, the compound which produces | generates the silicon compound which is a derivative | guide_body of an oxypropylene polymer as described in Unexamined-Japanese-Patent No. 7-258534, and produces | generates a silane monool by hydrolysis can be mentioned. Furthermore, an organic polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis described in JP-A-6-279893 can also be used.

  Trialkylsilyl borates such as tris (trimethylsilyl) borate and tris (triethylsilyl) borate can also be used as the compound having an action of reducing the modulus of the cured product.

In the present invention, a tackifying resin can be added for the purpose of enhancing the adhesion and adhesion to the substrate, or as necessary. The tackifying resin is not particularly limited, and those that are usually used can be used.
Specific examples include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation thereof, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene-phenols. Resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon) Resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.

  The styrenic block copolymer and its hydrogenated product are not particularly limited. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene. Examples include butylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS).

  Among these, a terpene-phenol resin is preferable because of high compatibility with the polymer (A) and high adhesion effect. On the other hand, when the color tone is important, a hydrocarbon resin is preferable.

  The amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, even more preferably 5 to 30 parts by weight based on 100 parts by weight of the polymer (A). When the amount is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and when the amount exceeds 100 parts by weight, the viscosity of the composition may be too high and handling may be difficult.

  In the composition of the present invention, a compound containing an epoxy group can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polymer (A).

  A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M305 , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, Aronix M-400 (polyfunctional), etc. In addition, a compound containing an average of 3 or more functional groups per molecule is preferable. (All Aronix is a product of Toa Gosei Chemical Co., Ltd.)

  Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect. The photocurable material is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A). There is no effect of improving the properties, and if it is 20 parts by weight or more, the cured product tends to be too hard and cracks tend to occur.

  An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resin; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds. The amount of the oxygen curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymer (A). If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

  An epoxy resin can be added to the composition of the present invention. A composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Epoxy hydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these, and generally used epoxies Resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolac type epoxy resins. The use ratio of these epoxy resin and polymer (A) is in the range of (A) / epoxy resin = 100/1 to 1/100 in weight ratio. When the ratio of (A) / epoxy resin is less than 1/100, it is difficult to obtain an effect of improving the impact strength and toughness of the cured epoxy resin, and the ratio of (A) / epoxy resin exceeds 100/1. And the intensity | strength of a polymer hardened | cured material will become inadequate. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The component (A) is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the intensity | strength of hardened | cured material, it is good to use 1-200 weight part of epoxy resins with respect to 100 weight part of (A) component, More preferably, it is 5-100 weight part.

  When an epoxy resin is added, the composition of the present invention can naturally be used in combination with a curing agent that cures the epoxy resin. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.

  When the epoxy resin curing agent is used, the amount used is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Ketimine can be used as a curing agent for the epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. When ketimine is used, a one-component composition can be obtained. Such a ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

  For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino Polyvalent amines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyltri Tokishishiran, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, aminosilanes such as N-(beta-aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane; and it may be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane And the like can be used.

  When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like. These ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

  To the curable composition of the present invention, a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, a flame retardant such as aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added. The said flame retardant may be used independently and may be used together 2 or more types.

  The flame retardant is used in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the polymer (A).

  Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, fungicides. Etc. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

  The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the organic polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is of a two-component type, it is not necessary to add a silanol condensation catalyst to the main agent containing an organic polymer having a reactive silicon group, so even if some moisture is contained in the compounding agent. Although there is little concern about the viscosity increase or gelation of the blend, it is preferable to perform dehydration drying when long-term storage stability is required. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 100 parts by weight of organic polymer (A) having a reactive silicon group, preferably A range of 0.5 to 10 parts by weight is preferred.

  The method for preparing the composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader, or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing can be employed.

  The composition of the present invention is suitable for use as a curable composition or a pressure-sensitive adhesive composition, and is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, and a vibration isolating material. Can be used for damping materials, soundproofing materials, foam materials, paints, spraying materials, etc. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among these, it is more preferable to use it as a sealing material or an adhesive.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.

(Synthesis Example 1)
A polyoxypropylene diol having a number average molecular weight of about 2,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, a number average molecular weight of 14,500 having a terminal hydroxyl group, and a molecular weight distribution. A polyoxypropylene of 2 (Tosoh HLC-8120GPC was used as the liquid feeding system, the column was Tosoh TSK-GEL H type, and the solvent was polystyrene-equivalent molecular weight measured using THF) was obtained. Subsequently, 1.2 molar equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene, and the methanol was distilled off to make the polymer terminal hydroxyl group an alkoxy anion. Further, 1.2 mole equivalent of allyl chloride was added to the added sodium methoxide to introduce an allyl group at the end of the polymer. By-product salt was removed together with water using hexane and water, and hexane was removed by devolatilization under reduced pressure. As a result, a bifunctional polyoxypropylene (P-1) having a number average molecular weight of about 14,500 having an allyl group at the end was obtained.

(Synthesis Example 2)
50 parts by weight of platinum divinyldisiloxane complex solution (3-wt% 2-propanol solution in terms of platinum metal) is added to 100 parts by weight of allyl-terminated polyoxypropylene (P-1) and (methoxymethyl) dimethoxysilane 2 with stirring. .27 parts by weight were slowly added dropwise. After reacting at 90 ° C. for 2 hours, volatile components were removed by vacuum devolatilization. As a result, polyoxypropylene (P-2) having a (methoxymethyl) dimethoxysilyl group at the terminal was obtained. The average amount of silicon groups introduced was 1.5 per polymer molecule. The obtained polymer was stored in an anhydrous state.

(Synthesis Example 3)
100 parts by weight of the polymer (P-2) was heated and stirred at 90 ° C., and 0.5 part by weight of 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) was added. Further, 1.48 parts by weight of trimethylsilanol was added dropwise. After reacting at 90 ° C. for 5 hours, volatile components were removed by vacuum devolatilization. This confirmed that polyoxypropylene (A-1) having a (methoxymethyl) (methoxy) (trimethylsiloxy) silyl group which is a monofunctional silicon group at the terminal was obtained. ^The average amount of monofunctional silicon groups introduced by ¹ HNMR was 1.2 per molecule. The obtained polymer was stored in an anhydrous state.

(Synthesis Example 4)
A polyoxypropylene triol having a number average molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, a number average molecular weight of 26,200 having a terminal hydroxyl group, and a molecular weight distribution. 3 polypropylene oxide was obtained. Subsequently, 1.2 molar equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene, and the methanol was distilled off to make the polymer terminal hydroxyl group an alkoxy anion. Further, 1.2 mole equivalent of allyl chloride was added to the added sodium methoxide to introduce an allyl group at the end of the polymer. By-product salt was removed together with water using hexane and water, and hexane was removed by devolatilization under reduced pressure. As a result, polyoxypropylene (P-3) having a number average molecular weight of about 26,200 having an allyl group at the end was obtained.

(Synthesis Example 5)
50 parts by weight of platinum divinyldisiloxane complex solution (3-wt% 2-propanol solution in terms of platinum metal) is added to 100 parts by weight of allyl-terminated polyoxypropylene (P-3) and (methoxymethyl) dimethoxysilane 1 with stirring. .73 parts by weight were slowly added dropwise. After reacting at 90 ° C. for 2 hours, volatile components were removed by vacuum devolatilization. As a result, polyoxypropylene (P-4) having a (methoxymethyl) dimethoxysilyl group at the terminal was obtained. The average amount of silicon groups introduced was 2.3 per molecule of polymer. The obtained polymer was stored in an anhydrous state.

(Synthesis Example 6)
100 parts by weight of the polymer (P-4) was heated and stirred at 90 ° C., and 0.5 part by weight of DBU was added. Further, 1.12 parts by weight of trimethylsilanol was added dropwise. After reacting at 90 ° C. for 5 hours, volatile components were removed by vacuum devolatilization. This confirmed that polyoxypropylene (A-2) having a (methoxymethyl) (methoxy) (trimethylsiloxy) silyl group which is a monofunctional silicon group at the terminal was obtained. ^The average amount of monofunctional silicon groups introduced by ¹ HNMR was 1.8 per molecule. The obtained polymer was stored in an anhydrous state.

(Synthesis Example 7)
A polyoxypropylene having a number average molecular weight of 26,200 having a dimethoxymethylsilyl group at the terminal is the same as in Synthesis Example 5 except that 1.28 parts by weight of dimethoxymethylsilane is used instead of (methoxymethyl) dimethoxysilane. P-5) was obtained. The average number of silicon groups introduced was 2.3 per molecule of polymer. The obtained polymer was stored in an anhydrous state.

(Synthesis Example 8)
100 parts by weight of the polymer (P-5) was heated and stirred at 90 ° C., and 0.5 part by weight of DBU was added. Further, 1.12 parts by weight of trimethylsilanol was added dropwise. After reacting at 90 ° C. for 5 hours, volatile components were removed by vacuum devolatilization. This confirmed that polyoxypropylene (P-6) having a (methoxy) (methyl) (trimethylsiloxy) silyl group which is a monofunctional silicon group at the terminal was obtained. ^The amount of monofunctional silicon groups introduced by ¹ HNMR averaged 1.0 per molecule. The obtained polymer was stored in an anhydrous state.

Example 1
The polymer (A-1) was poured into a sheet-like mold having a thickness of 3 mm and allowed to stand in a room having a constant temperature and humidity at a room temperature of 23 ° C. and a humidity of 50%. Thereafter, it was cured at 23 ° C. and 50% for 3 days and then in an oven at 50 ° C. for 4 days to obtain a sheet-like cured product. In addition, the polymer surface was hardened 1 hour after pouring. The obtained sheet-like cured product was punched into a No. 3 dumbbell mold and subjected to a tensile test at a pulling speed of 200 mm / min. Stress at 50% elongation (M50), stress at 100% elongation (M100), and cured product fracture The elongation in time (EB) was measured. The results are shown in Table 1.

(Comparative Example 1)
100 g of the polymer (P-2) was weighed into a cup, 0.5 g of DBU was added, and the mixture was lightly stirred, and then the cup was capped. Using a rotation / revolution mixer, the polymer and DBU were uniformly mixed and defoamed. The mixture was poured into a sheet-like mold having a thickness of 3 mm and allowed to stand in a room having a constant temperature and humidity at a room temperature of 23 ° C. and a humidity of 50%. Thereafter, it was cured at 23 ° C. and 50% for 3 days and then in an oven at 50 ° C. for 4 days to obtain a sheet-like cured product. In addition, the polymer surface was hardened 1 hour after pouring. The obtained sheet-like cured product was punched into a No. 3 dumbbell mold and subjected to a tensile test at a pulling speed of 200 mm / min. Stress at 50% elongation (M50), stress at 100% elongation (M100), and cured product fracture The elongation in time (EB) was measured. The results are shown in Table 1.

(Example 2)
M50, M100, and EB were measured in the same manner as in Example 1 except that the polymer (A-2) was used instead of the polymer (A-1). The results are shown in Table 1. In addition, the polymer surface was hardened 1 hour after pouring.

(Comparative Example 2)
M50, M100, and EB were measured in the same manner as in Comparative Example 1 except that the polymer (P-4) was used instead of the polymer (P-2). The results are shown in Table 1. In addition, the polymer surface was hardened 1 hour after pouring.

(Comparative Example 3)
M50, M100, and EB were measured in the same manner as in Comparative Example 1 except that the polymer (P-6) was used instead of the polymer (P-2), and the DBU addition amount was 1.5 g. The results are shown in Table 1. In addition, the polymer surface was not hardened | cured 6 hours after pouring.

  From the comparison between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, it is possible to achieve both high reactivity and good stretchability after curing by using the polymer having a monofunctional silicon group of the present invention. I understood. Moreover, when a polymer having a monofunctional silicon group not having a methoxy group on carbon bonded to silicon as in Comparative Example 3, it is difficult to obtain practical reactivity. I understood.

Claims (18)

  A heavy silicon atom having one hydrolyzable group on a silicon atom and a reactive silicon group having a halogen atom, an oxygen atom, a nitrogen atom or a sulfur atom bonded to a carbon atom bonded to the silicon. A composition containing the coalescence (A). The reactive silicon group of the polymer (A) is represented by the general formula (1):
-SiR ¹ _a R ² _2-a X (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and a substituent in which any one of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom is bonded to a carbon atom bonded to a silicon atom. R ² is a hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by R ³ ₃ SiO—. Three R ³ are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and a is 1 or 2. The composition according to claim 1, which is 2.). The composition according to claim 2, wherein R ¹ in the general formula (1) is a hydrocarbon group in which either an oxygen atom or a nitrogen atom is bonded to a carbon atom bonded to a silicon atom. The composition according to claim 3, wherein R ¹ in the general formula (1) is a hydrocarbon group in which an oxygen atom is bonded to a carbon atom bonded to a silicon atom. The composition according to claim 4, wherein R ¹ in the general formula (1) is a hydrocarbon group in which a methoxy group is bonded to a carbon atom bonded to a silicon atom. The composition according to claim 5, wherein R ¹ in the general formula (1) is a methoxymethyl group. The composition according to any one of claims 1 to 6, wherein R ² in the general formula (1) is a triorganosiloxy group represented by R ³ ₃ SiO-.   The polymer (A) is at least one organic polymer selected from the group consisting of a polyoxyalkylene polymer, a poly (meth) acrylate polymer, and a saturated hydrocarbon polymer. 8. The composition according to any one of 7 to 7.   The composition according to claim 8, wherein the polymer (A) is a polyoxyalkylene polymer.   The composition according to any one of claims 1 to 9, wherein the main chain of the polymer (A) is a polymer having a branched structure.   The composition according to any one of claims 1 to 10, which is a polymer having an average number of reactive silicon groups of 1.8 to 3.0 per molecule of the polymer (A).   The main chain of the polymer (A) is a polymer having only a linear structure, and the average number of reactive silicon groups is 1.7 to 2.0 per molecule of the polymer. Item 10. The composition according to any one of Items 1 to 9.   The composition according to any one of claims 1 to 12, further comprising a silanol condensation catalyst (B), wherein the silanol condensation catalyst is a non-organotin compound.   The composition according to any one of claims 1 to 12, further comprising a silanol condensation catalyst (B), wherein the silanol condensation catalyst is an amine compound.   A curable composition comprising the composition according to claim 1.   A room temperature curable composition comprising the curable composition according to claim 15.   A pressure-sensitive adhesive composition comprising the composition according to claim 1. Hardened | cured material obtained from the composition in any one of Claim 1 to 14.