JPH02145675A - Two-pack type adhesive - Google Patents

Abstract

PURPOSE:To provide the subject adhesive having excellent storage stability and composed of a composition A containing a specific rubber-based organic polymer and an epoxy resin hardener and a composition B containing an epoxy resin, a curing catalyst for the above polymer and a carboxylic acid. CONSTITUTION:The objective adhesive is composed of (A) a composition containing (i) a rubber-based organic polymer (preferably having a number- average molecular weight of 1,000-20,000) having hydroxyl group or hydrolyzable group bonded to silicon atom and at least one Si-containing group crosslinkable by the formation of a siloxane bond and (ii) an epoxy resin hardener (e.g. triethylenetetramine) and (B) a composition containing (iii) an epoxy resin, (iv) a curing catalyst for the component (i) (e.g. tetrabutyl titanate) and (v) a carboxylic acid (preferably a 8-40C higher fatty acid such as caprylic acid).

Description

[Detailed description of the invention] Industrial applications The present invention relates to a two-component adhesive.

Prior art and its problems At least one silicon atom-containing group (hereinafter referred to as a "reactive silicon group") has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond.
A curable resin composition containing a rubber-based organic polymer and an epoxy resin as main components was known prior to the filing of the present application (Japanese Patent Application Laid-open No. 6/1-268720).

However, according to the research of the present inventor, when the above resin composition is used as a two-component adhesive, in other words, the above rubber-based organic polymer is used as one component, and the curing catalyst for the epoxy resin and the rubber-based organic polymer is used. It has been found that when used as a two-component adhesive as the other component, the following drawbacks occur. That is, the latter component has poor storage stability;
Therefore, after leaving the composition for a long period of time, one of the two-component adhesives
It has been found that when used as a component, the curing rate of the adhesive is slowed and the curing reaction cannot proceed quickly.

This tendency is remarkable when the component containing the epoxy resin contains a filler, especially an inorganic filler.

In view of the current situation, the present inventor has developed two materials with excellent storage stability.
We have been conducting extensive research in order to develop a corrugated adhesive. As a result, it has been found that the intended purpose of the present invention can be achieved when a carboxylic acid is blended into the epoxy resin-containing component. The present invention was completed based on this knowledge.

That is, the present invention provides: (A) a composition (hereinafter referred to as "composition A") containing (1) a rubber-based organic polymer having at least one reactive silicon group and (2) an epoxy resin curing agent; (B) A composition containing (1) an epoxy resin, (2) a curing catalyst for the rubber-based organic polymer, and (3) a carboxylic acid (
(hereinafter referred to as "composition B").

In the present invention, composition A contains a rubber-based organic polymer having at least one reactive silicon group and an epoxy resin curing agent.

Examples of polymers forming the skeleton of rubber-based organic polymers having at least one reactive silicon group include polyethers obtained by polymerizing cyclic ethers such as propylene oxide, ethylene oxide, and tetrahydrofuran; dibasic acids such as adipic acid; Polyesters obtained by condensation with glycol or ring-opening polymerization of lactones; ethylene-propylene copolymer systems; copolymer systems of polyisobutylene or isobutylene with isoprene, etc.; polychloroprene; polyisoprene or isoprene with butadiene, styrene, Copolymer systems with acrylonitrile, etc.; copolymer systems of polybutadiene or butadiene with styrene, acrylonitrile, etc.; polyolefin systems obtained by hydrogenating polyisoprene, polybutadiene, or copolymers of isoprene and butadiene; ethyl acrylate, butyl acrylate A polyacrylic ester obtained by radical polymerization of monomers such as or a copolymer system of the acrylic ester and vinyl acetate, acrylonitrile, styrene, ethylene, etc.; a vinyl monomer is polymerized in the rubber-based organic polymer used in the present invention Examples include graft polymer systems obtained by: polysulfide-based polymers, and the like. Among these, polypropylene oxide polyethers have the general formula: [In the formula, R represents a divalent alkylene group having 2 to 4 carbon atoms.

] Polymers or copolymers such as graft polymers obtained by polymerizing vinyl monomers such as acrylic esters, styrene, acrylonitrile, and vinyl acetate in the presence of polyethers such as polyethers and polypropylene oxides having repeating units represented by Polymer, polyacrylic acid alkyl ester or acrylic acid alkyl ester containing 50% by weight or more of acrylic acid alkyl ester and vinyl acetate,
Copolymers with acrylonitrile, styrene, ethylene, etc. are preferred because they facilitate the introduction of reactive silicon groups at the molecular ends and facilitate the production of liquid polymers without using solvents.

In the present invention, the reactive silicon group is not particularly limited, but representative examples include, for example, general formula (1) [wherein R1 and R2 both have 1 to 20 carbon atoms] Hydrocarbon group or (R')3SiO- (R' has 1 to 2 carbon atoms
0 monovalent hydrocarbon group, and the three R's may be the same or different), and when two or more R1 or R2 are present; , they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X's are present, they may be the same or different. a represents 0, 1.2 or 3, and b represents 0.1 or 2, respectively. Moreover, b in m pieces of -5i-0- b does not need to be the same. m is O or 1-1
Indicates an integer of 9. However, it is assumed that a+(sum of b)≧1 is satisfied. ] Groups represented by these can be mentioned.

When the above X is a hydroxyl group, the reactive silicon group undergoes a silanol condensation reaction in the presence or absence of a silanol condensation catalyst and is crosslinked. Further, when X is a hydrolyzable group, the reactive silicon group undergoes a hydrolysis reaction and a silanol condensation reaction with moisture in the presence or absence of a silanol condensation catalyst and is crosslinked.

The hydrolyzable group represented by X above is not particularly limited, and includes conventionally known hydrolyzable groups, specifically,
Examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups,
An amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferred, and an alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in a range of 1 to 3, and (sum of a plus sum) is preferably in a range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to a reactive silicon group, they may be the same or different.

The number of silicon atoms forming the reactive silicon group may be one,
The number may be two or more, but in the case of silicon atoms connected by siloxane bonds or the like, the number may be up to about 20. In particular, general formula (2) [wherein R2, X and a are the same as above. A reactive silicon group represented by the following is preferred from the viewpoint of easy availability.

In addition, as the monovalent hydrocarbon group having 1 to 20 carbon atoms for R1 and R2 in the above general formula (1), the monovalent hydrocarbon group having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 carbon atoms
-20 aralkyl groups can be exemplified, and more specific examples include alkyl groups such as methyl groups and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. . Further, as a triorganosiloxy group, specifically R' is a methyl group,
Examples include a triorganosiloxy group represented by (R')3sio- such as a phenyl group.

Among these, methyl group is particularly preferred.

The reactive silicon group is chemically bonded to the main chain of the rubber-based organic polymer. In the bond between the reactive silicon group and the main chain of the rubber-based polymer, the presence of a bond such as the ;5t-o-c bond is undesirable because the bond may be cleaved by moisture. Among them, the silicon atom closest to the main chain of the rubber-based organic polymer is preferably bonded with a ;5i-C% bond.

At least one reactive silicon group, preferably 1.2 to 6 reactive silicon groups, should be present in one molecule of the rubber-based organic polymer. When the number of reactive silicon groups contained in the molecule is less than 1, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior.

The reactive silicon group may be present at the end of the rubber-based organic polymer molecular chain, may be present inside, or may be present on both sides. In particular, when a reactive silicon group is present at the end of the molecular chain, the length of the molecular chain between the mulberry bridge points becomes longer in the cured product that is formed, making it easier to effectively exhibit rubber elastic properties. This is preferable because the brittleness of the epoxy resin blended into the agent can be easily improved, and on the other hand, in the case of a rubber cured product mainly composed of a rubber-based organic polymer, high strength can be easily obtained.

The reactive silicon group may be introduced into the rubber-based organic polymer by any known method, such as the following methods (1) to (4).

(1) A monomer having a copolymerizable unsaturated group and a reactive silicon group in the molecule, such as vinyltrialkoxysilane, methacryloyloxypropylmethyldialkoxysilane, methacryloyloxypropyltrialkoxysilane, etc., in ethylene, propylene, It can be copolymerized with polymerizable monomers such as isobutylene, chloroprene, isoprene, butadiene, and acrylic esters, or copolymerizable with γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc. A method in which a monomer having an epoxy group and a reactive silicon group in its molecule is copolymerized with propylene oxide or ethylene oxide.

By this method, reactive silicon groups can be introduced into the side chains of the molecules.

(2) A chain transfer agent is a compound having a mercapto group, a disulfide group, etc. and a reactive silicon group in its molecule, such as mercaptopropyltrialkoxysilane, mercaptopropylmethyldialkoxysilane, etc., which can cause a chain transfer reaction in radical polymerization. A method of polymerizing radically polymerizable monomers using

(3) Azobis-2-(8-methyljethoxysilyl-
A method of polymerizing radically polymerizable monomers using an azo or peroxide polymerization initiator containing a reactive silicon group such as 2-cyanohexane).

In methods (2) and (3), reactive silicon groups are introduced at the ends of polymer molecules.

(4) Using a polymer having a functional group such as a hydroxyl group, a carboxyl group, a mercapto group, an epoxy group, or an isocyanate group (hereinafter referred to as "Y functional group") in the side chain and/or end of the polymer, the Y functional group is used. A method of reacting a compound which contains a functional group capable of reacting with the group in its molecule and has a reactive silicon group with the Y functional group.

Specific examples of the rubber-based organic polymer used in the present invention include, for example, Japanese Patent Publication No. 12154, Japanese Patent Publication No. 45-36319, Japanese Patent Publication No. 49-32673, Japanese Patent Publication No. 46-156599, No. 51-73561, No. 54-6098, No. 55-13767, No. 54-13768, No. 55-82123, No. 55-123820, No. 55-12512
Publication No. 1, Publication No. 55-131021, Publication No. 55-13
No. 1022, No. 55-135135, No. 55
-137129 publication, 57-179210 publication,
No. 58-191703, No. 59-78220, No. 59-78221, No. 59-78222, No. 59-78223, No. 59-16801
Examples include those disclosed in Publication No. 4 and the like.

The number average molecular weight of the rubber-based organic polymer having reactive silicon groups is preferably about 500 to 50,000,
About 1,000 to 20,000 is particularly preferable. In the present invention, such rubber-based organic polymers may be used alone or in combination of two or more.

As the epoxy resin curing agent blended into the composition A in the present invention, a wide variety of commonly used epoxy resin curing agents can be used. Specifically, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2. 4. Amines such as 6-tris(dimethylaminomethyl)phenol; tertiary amine salts; polyamide resins; imidazoles; dicyandiamides;
Boron trifluoride complex compounds; Carboxylic acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynylsuccinic anhydride, pyromellitic anhydride, and chlorenic anhydride; Alcohols ; Phenols; Carboxylic acids, etc. can be exemplified. In the present invention, such a curing agent comprises 1
The species can be used alone or in combination of two or more species.

In the present invention, the ratio of the rubber-based organic polymer and the epoxy resin curing agent blended into the composition A is not particularly limited, but the epoxy resin curing agent is mixed from the composition B. Usually about 0.1 to 300 parts by weight, preferably 0.5 to 300 parts by weight, per 100 parts by weight of the epoxy resin.
It is preferable to mix it so that the weight is about 100 parts by weight.

In the present invention, composition B contains an epoxy resin, a curing catalyst for the rubber-based organic polymer, and a carboxylic acid.

As the epoxy resin blended in composition B, a wide variety of conventionally known epoxy resins can be used, such as epichlorohydrin.
Bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl bisphenol A propylene oxide adduct. Ether type epoxy resin, 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-)luidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol such as glycerin, hydantoin type epoxy resin, epoxidized product of unsaturated polymer such as petroleum resin. etc. Among these, those containing two formulas in the molecule are particularly preferred from the viewpoints of high reactivity during curing and easy formation of a three-dimensional network in the cured product. In the present invention, bisphenol A type epoxy resins and novolac type epoxy resins are most preferred. In the present invention, such epoxy resins may be used alone or in combination of two or more.

As the curing catalyst to be incorporated into composition B, a wide variety of conventionally known silanol condensation catalysts can be used. Specific examples include titanate esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; dibutyltin oxide and phthalic acid. Reactants with esters; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate, etc. Chelate compounds; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine,
Jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2
．． 4; 6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(
5,4,0) Amine compounds such as undecene-7 (DBU), or salts of these with carboxylic acids, etc.; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess polyamines and epoxy compounds reaction product; silane coupling agent having an amino group, such as γ-
Examples include silanol condensation catalysts such as aminopropyltrimethoxysilane and N-(β-aminoethyl)aminopropylmethyldimethoxysilane, as well as other known silanol condensation catalysts such as acidic catalysts and basic catalysts.

These catalysts may be used alone or in combination of two or more.

As the carboxylic acid to be blended in composition B, a wide variety of conventionally known carboxylic acids can be used as long as the carboxylic acid has a total number of carbon atoms of 1 to 40. Among such carboxylic acids, linear or branched saturated or unsaturated fatty acids are preferred, and higher fatty acids having a total number of carbon atoms of 8 to 40 are particularly preferred. Specific examples of such higher fatty acids include caprylic acid,
Saturated fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, Examples include unsaturated fatty acids such as lylunic acid, eicosenoic acid, and arachidonic acid. These carboxylic acids may be used alone or in combination of two or more.

In the present invention, there are no particular restrictions on the proportions of the epoxy resin, curing catalyst, and carboxylic acid that are blended into composition B. However, for epoxy resins, the weight ratio of rubber organic polymer/epoxy resin used in composition A is usually about 1/100 to 100/1, particularly 10/1.
It is preferable that the ratio is 00 to 100/10.

If the amount of epoxy resin blended is too small, the mechanical strength such as the elastic modulus of the resulting cured product will be insufficient, and conversely, if the amount of epoxy resin blended is too large, the resulting cured product will become brittle and eventually I also don't like it.

The curing catalyst is usually blended in an amount of about 0.1 to 20 parts by weight, preferably about 0.5 to 10 parts by weight, based on the rubber organic polymer mixed in from composition A. good. Furthermore, the carboxylic acid is usually 0.05 to 2
It is preferable that the amount is about 0% by weight, preferably about 0.1 to 10% by weight. If the amount of carboxylic acid blended is too small, the effect of improving storage stability will be small, and if the amount of carboxylic acid blended is too large, there will be a tendency to have the disadvantage of affecting the physical properties of the obtained cured product.
Neither is preferable.

A filler can be added to the composition A and the composition B of the present invention. Examples of fillers include wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, graphite, carbon black, calcium carbonate, talc, magnesium carbonate, quartz, fine aluminum powder, flint powder, Examples include zinc powder.

When composition B of the present invention contains these fillers, especially inorganic fillers, the effects of the present invention are remarkable. The amount of filler used is usually about 1 to 500 parts by weight, especially 10 to 30 parts by weight, based on the total 100 parts by weight of the rubber organic polymer and epoxy resin.
A range of approximately 0 parts by weight is preferred.

The compositions A and B of the present invention may contain various additives such as anti-aging agents, ultraviolet absorbers, lubricants, pigments, foaming agents, etc., as required.

There are no particular restrictions on the use of the two-component adhesive of the present invention, and it can be used in the same manner as conventional two-component adhesives.

Effects of the Invention According to the present invention, a two-component adhesive having excellent storage stability can be obtained even when a filler is added to a composition containing an epoxy resin and a curing catalyst.

EXAMPLES In order to further clarify the present invention, examples are given below. In addition, the term "part" hereinafter simply refers to "polymerization part" and "part".
%” means “weight n%”.

Production example 1 Polypropylene glycol (number average molecular weight 2500) 9
0 parts and polypropylene triol (number average molecule ff1
3000) as a starting material, carry out a molecular weight jump reaction using methylene chloride, and then cap the molecular chain ends with allyl chloride. Allyl ether groups are introduced into 99% of all ends. molecule ff1
800g of polypropylene oxide of 8000 was placed in a pressure-resistant reaction vessel equipped with a stirrer, and 20g of methyldimethoxysilane was added thereto. Then, 8.9 g of chloroplatinic acid catalyst solution (H2P t CQ s .6H20 was removed with isopropyl alcohol for 18 hours and tetrahydrofuran for 16 hours).
After adding 0.40 mQ (solution dissolved in 0 mQ),
The reaction was carried out at 80°C for 6 hours.

When the amount of silicon hydride groups remaining in the reaction solution was determined by IR spectroscopy, it was found that almost no silicon hydride groups remained. Further, when silicon groups were quantified by NMR method, a polypropylene oxide having about 1.75 CH3 (CH30)2 Si CH2CH2CH2CH20- groups per molecule at the molecular terminal was obtained.

Production Example 2 Using polypropylene glycol (number average molecular weight 2000) as a starting material, after carrying out a molecular weight jump reaction using methylene chloride, the allyl ether group obtained by capping the molecular chain ends with allyl chloride
500 g of polypropylene oxide with a number average molecular weight of 15,000 introduced at 5% concentration was placed in a pressure-resistant reaction vessel equipped with a stirrer, and 32 g of triethoxysilane was added thereto. Next, 0.40 mG of a chloroplatinic acid catalyst solution (same composition as in Production Example 1) was added, and the mixture was reacted at 90°C for 3 hours. After removing excess silane under reduced pressure, silicon was quantified by NMR method, and it was found that (CH3CH20)35iC1h C)12 CH20 was present at the molecular end.
A polypropylene oxide having about 1.8 - groups per molecule was obtained.

Production Example 3 300 g of polypropylene glycol with a number average molecular weight of 13,000 was charged into a flask with a stirrer, and then 26 g of tolylene diisocyanate and 0 dibutyltin dilaurate were added.
．． 2 g was added thereto, and the mixture was reacted at 100° C. for 5 hours with stirring under a nitrogen gas flow. Thereafter, 22.1 g of γ-aminopropyltriethoxysilane was added and reacted at 100°C for 3 hours with stirring. A polyether having silicon groups was obtained.

Production Example 4 Mix 80 g of butyl acrylate, 20 g of stearyl methacrylate, 2.2 g of γ-methacryloyloxypropylmethyldimethoxysilane, 1.8 g of γ-mercaptopropylmethyldimethoxysilane, and 0.5 g of 2,2'-azobisisobutyronitrile. Stir to ensure uniform dissolution. 25g of the mixture was placed in a stirrer and cooled for 200m.
The mixture was placed in a fourth flask and heated to 80°C in an oil bath under nitrogen gas. After several minutes, polymerization started and generated heat, but after the heat generation became mild, the remaining mixed solution was gradually added dropwise using a dropping funnel over a period of 3 hours to cause polymerization. AIBN after 15 minutes and 30 minutes after completion of dripping, respectively.
O, 15g each was added. After the addition was completed, stirring was continued for 30 minutes to complete the polymerization reaction.

When the obtained liquid polymer was analyzed by gel permeation chromatography (GPC), the number average molecular weight was about 10,000.

Example 1 and Comparative Example 1 Preparation of Solution A 100 parts of the polymer obtained in Production Example 1, 1 part of 2゜2'-methylene-bis-(4-methyl-6-t-butylphenol), N-β-( 1 part of aminoethyl)-γ-aminopropyltrimethoxysilane, 3 parts of vinyltrimethoxysilane, 48 parts of heavy calcium carbonate, and 5 parts of 2,4.6-dolisu(dimethylaminomethyl)phenol using three paint rolls. Mix well to obtain the formulation.

Preparation of Solution B Epicor) 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy ■) 50 parts, heavy calcium carbonate 25 parts, #918 (organotin compound, trivalent compound synthesis ■
) and 3 parts of stearic acid are mixed well with three paint rolls to obtain a formulation.

Put liquid A and liquid B into sealed glass containers, and add 5
After being stored at 0° C. for one month, 20 g of liquid A and 10 g of liquid B were mixed and cured at 23° C. and 50% RH, and the surface curing time (tack-free time on contact) was measured.

Furthermore, the tack-free time was measured in exactly the same manner except that stearic acid was not used in the B solution, and the results are shown in Table 1 as Comparative Example 1. From Table 1, it can be seen that the addition of stearic acid significantly improves the storage stability.

In Example 1, a mixture of 40 g of liquid A and 20 g of liquid B was used, and JIS K 6850 and JIS K
Evaluation as an adhesive was conducted according to 6854. For tensile shear strength measurement, a JIS H4000 aluminum plate A-1050P (100 x 25 x 2 mm test piece) was used, and the above mixture was applied with a spatula, bonded together, and pressed by hand to prepare a test sample. T-peel adhesive strength is
JISH4000 aluminum plate A1050P (20
Using a spatula, apply the above mixture to a thickness of about 0.5 cm using a 0x25xO, 1aon test piece) and stick it together.
A test sample was prepared by crimping twice. These adhesive test samples were cured at 23° C. for 2 days and then at 50° C. for 3 days, and then subjected to a tensile test. The tensile speed is 50 for tensile shear.
The peeling rate was 200 mm/min in the case of T-shaped peeling. The adhesive strength of the adhesive test samples made using Liquid A and Liquid B after storage at 50°C for one month is shown in Table 1, whereas Comparative Example 1 has a decrease in strength. , Example 1 has the same strength as before storage.

Examples 2 to 7 The results obtained in the same manner as in Example 1 except that various carboxylic acids were used instead of 3 parts of stearic acid in Solution B of Example 1 are shown in Table 2 as Examples 2 to 7. .

Examples 8 to 10 Tack-free was measured in the same manner as in Example 1, except that the polymers of Production Examples 2 to 4 were used instead of the polymer obtained in Production Example 1 in Solution A of Example 1. The results are shown in Table 3 as Examples 8 to 10.

Table 3 (that's all)

Claims (1)

[Scope of Claims] [1] (A) (1) A rubber having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon atom-containing group that can be crosslinked by forming a siloxane bond. A composition containing a rubber-based organic polymer and (2) an epoxy resin curing agent, and (B) a composition containing (1) an epoxy resin, (2) a curing catalyst for the rubber-based organic polymer, and (3) a carboxylic acid. A two-component adhesive made of materials.