JPH02228365A - Two-component hardenable composition with improved storage stability - Google Patents

Abstract

PURPOSE:To improve the storage stability of a two-component hardenable compsn. by compounding component A comprising a specific org. rubber polymer, an epoxy resin hardener, and a silicone compd. with component B comprising an epoxy resin and a hardening catalyst of said org. rubber polymer. CONSTITUTION:Two-component hardenable compsn. comprises: component A consisting of a liq. org. rubber polymer with an MW of 500-50000 which has in its molecule at least one Si-contg. group having a hydroxyl or hydrolyzable group directly attached to Si and capable of forming a siloxane linkage to crosslink, an epoxy resin hardener (e.g. triethylenetetramine), and a silicone compd. having at least three hydrolyzable groups on one Si (e.g. gamma- ureidopropylethoxysilane); and component B consisting of an epoxy resin and a hardener (e.g. tetrabutyl titanate) of said liq. org. rubber polymer.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a two-component curable composition with improved storage stability, particularly a two-component curable composition with improved storage stability using an epoxy resin and a specific rubber-based organic polymer. The present invention relates to an improved two-component curable composition.

[Prior Art] Conventionally, epoxy and rubber-based organic polymers have been used which have a hydroxyl group and/or a hydrolyzable group bonded to a silicon atom, and which have a silicon atom-containing group that can be crosslinked by forming a siloxane bond. Compositions containing resin are known, and are used in adhesives due to their excellent adhesive properties.

[Problems to be Solved by the Invention] However, in order to use this composition as a two-component curable composition, a mixture of the rubber-based organic polymer having a silicon atom-containing nail group and an epoxy resin curing agent is used as a two-component curable composition. If it is used as one liquid of the mold-curing composition, there is a problem that the storage stability is not good, and the viscosity increases or gels during storage. This problem is particularly severe in the case of a liquid mixed with a filler that tends to contain a large amount of water.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems. A rubber-based organic polymer having a silicon atom-containing group that can be crosslinked by forming an epoxy resin curing agent; and ■ a silicon compound having a group in which three or more hydrolyzable groups are bonded to one silicon atom. The present invention relates to a 2-acid type curable composition having improved storage stability, comprising (B) (1) an epoxy resin and (1) a curing catalyst for the rubber-based organic polymer.

[Example] A silicon atom-containing compound that has a hydroxyl group and/or a hydrolyzable group bonded to a silicon atom, which is one of the components of liquid A used in the present invention, and can be crosslinked by forming a siloxane bond. As the polymer forming the skeleton of the rubber-based organic polymer (component (A) (1)) containing groups (hereinafter referred to as reactive silicon groups), for example, polymers formed by polymerization of cyclic ethers such as propylene oxide, ethylene oxide, and tetrahydrofuran are used. Polyether systems obtained by condensation of dibasic acids such as adipic acid with glycol or ring-opening polymerization of lactones; Ethylene-propylene copolymer systems; Copolymer systems of polyisobutylene or isobutylene and isoprene, etc. ;Polychloroprene;Copolymer system of polyisoprene or isoprene and butadiene, styrene, acrylonitrile, etc.;Copolymer system of polybutadiene or butadiene and styrene, acrylonitrile, etc.;Polyisoprene, polybutadiene, or copolymer of isoprene and butadiene with hydrogen Polyolefin system obtained by addition; polyacrylic ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, or copolymer system of the acrylic ester and vinyl acetate, acrylonitrile, styrene, ethylene, etc.; the present invention A graft polymer system obtained by polymerizing a vinyl monomer in a rubber-based polymer used for;
Examples include polymers such as polysulfide. Among these, polypropylene oxide polyethers have a general formula: -R1-0- (wherein R1 has 2 to 4 carbon atoms)
A graft obtained by polymerizing a monomer such as acrylic acid ester, styrene, acrylonitrile, or vinyl acetate in the presence of a polyether such as polyether or polypropylene oxide, which has a repeating unit represented by (representing a divalent alkylene group) Polymers or copolymers such as polyacrylic acid alkyl esters or copolymers of acrylic acid alkyl esters containing 50% or more of acrylic acid alkyl esters and vinyl acetate, acrylonitrile, styrene, ethylene, etc. are reactive. This method is preferable because silicon groups can be easily introduced into the terminals of molecules, and liquid polymers can be easily produced without using a solvent. Polypropylene oxide is particularly preferred because it has good water resistance, is inexpensive, and is easy to handle as a liquid.

The reactive silicon group referred to in the present invention is a group that can be crosslinked by a silanol condensation reaction containing a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded. Or a hydrolyzable group, R
2 is a monovalent hydrocarbon group having 1 to 2 carbon atoms or a bow 5t
A triorganosiloxy group represented by -0- (R3 is a monovalent hydrocarbon group having 1 to 2 carbon atoms), a is 0.1.2 or 3, b is 0.1 or 2, and 1≦(a and b),
m is a group represented by 0 or an integer of 1 to 18). When X is a hydrolyzable group, the reactive silicon group is crosslinked by causing a hydrolysis reaction and a silanol condensation reaction with moisture in the presence or absence of a silanol condensation catalyst. When 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.

Specific examples of hydrolyzable groups include commonly used groups such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. can give.

Among these, alkoxy groups are particularly preferred because they are mildly hydrolyzable and easy to handle.

One to three hydrolyzable groups are bonded to one silicon atom.

The number of silicon atoms forming the reactive silicon group may be one or two or more, but in the case of silicon atoms connected by siloxane bonds etc., up to 20 silicon atoms may be used. Can be used.

Among the reactive silicon groups, a group represented by t-Xc (wherein X, R2i; are the same as above, ci, tl, 2 or 3) is preferred for economical reasons.

The reactive silicon group is chemically bonded to the rubber-based organic polymer main chain. In the bond between the reactive silicon group and the main chain of the rubber-based polymer, the presence of a bond such as an s+-o-c6 bond is not desirable because the bond may be cleaved by moisture. In the reactive silicon group, the silicon atom closest to the main chain of the rubber-based polymer is preferably bonded with a '3 s+-c:; bond.

Examples of methods for introducing reactive silicon groups into rubber-based organic polymers include the following methods.

(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, By copolymerizing with polymerizable monomers such as isobutylene, chlorobrene, isoprene, butadiene, and acrylic esters,
- A method of copolymerizing a monomer having a copolymerizable epoxy group and a reactive silicon group in the molecule, such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc., with propylene oxide or ethylene oxide, etc. .

These methods allow the introduction of reactive silicon groups into molecular side chains.

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

(3) Using an azo or peroxide polymerization initiator containing a reactive silicon group such as azobis-2-(6-methyljethoxysilyl-2-cyanohexane) to generate a radically polymerizable monomer. How to polymerize.

('2J, In method (3), a reactive silicon group is introduced at the end of the polymer molecule.

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

Specific reaction examples are shown in the table below, but are not limited thereto.

[White space below] In particular, as the polymers having a Y functional group used as starting materials and intermediate materials in the table, the main chain is essentially -R1- such as polypropylene polyol, polyethylene polyol, polytetramethylene diol, etc. 0
- (in the formula, R1 represents a divalent alkylene group having 2 to 4 carbon atoms) polyether polyols consisting of a repeating unit; condensation of a dibasic acid such as adipic acid with glycol or opening of lactones; Polyester polyols obtained by ring polymerization: Polyols of polyisobutylene or polycarboxylic acids; Polyols or polycarboxylic acids of polybutadiene or copolymers of butadiene and styrene, acrylonitrile, etc.; Polyolefins obtained by hydrogenating polyisoprene or polybutadiene. Polyols; Polymers containing isocyanate functional groups obtained by reacting the polyols or polycarboxylic acids with polyisocyanates; Vinyl-type polymers obtained by reacting the polyols with halogen compounds containing vinyl-type unsaturated groups, etc. The above-mentioned polymers containing unsaturated groups are particularly preferred, and it is more preferred that the Y functional group is located at the terminal of the polymerized molecule.

As the silicon compound having the Y' functional group, γ-(
Amino group-containing silanes such as 2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, Mercapto-tasting silanes such as γ-mercaptopropylmethyldimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Vinyl-type unsaturated group-containing silanes such as vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, etc.; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane, etc. Silanes;
γ-Isocyanatepropyltriethoxysilane, γ-
Specific examples include isocyanate-containing silanes such as isocyanate propylmethyldimethoxysilane; hydrosilanes such as methyldimethoxysilane, trimethoxysilane, methyljethoxysilane, etc., but are not limited to these. do not have.

In the combination of a polymer containing a Y functional group and a silicon compound containing a Y functional group, in particular (1) the polymer having an incyanate group and the amino base are combined with silanes or mercapto group-containing silanes. and (II) a combination of a vinyl-type unsaturated group-containing polymer and a hydrosilane. Furthermore, in (II), a combination of polypropylene oxide having an allyl ether group at the molecular end and hydrosilanes is particularly preferred. (11
), a platinum-based compound or the like is used as a catalyst to carry out a hydrosilylation reaction, whereby a vinyl group and a hydrosilyl group are reacted, and a silyl group can be introduced into the polymer.

The molecular weight of the rubber-based polymer (component (A) (1)) having at least 1, preferably 1.2 to 6 reactive silicon groups in the molecule used as a component of liquid A in the present invention. is about 500 to 50,000, especially 1,000
A liquid material of about 20,000 to 20,000 is preferred from the viewpoint of ease of handling. When the number of reactive silicon groups contained in the molecule is less than one, the crosslinking density of the cured product decreases, the rubber elasticity becomes insufficient, and the modification effect is not clear.

A reactive silicon group-containing polymer having silicon atoms attached with a hydroxyl group can also be obtained by hydrolyzing a reactive silicon-based polymer having silicon atoms attached with a hydrolyzable group.

In the rubber-based organic polymer having at least one reactive silicon group in the molecule used in the present invention (component (A) (1)), the reactive silicon group is preferably present at the end of the molecule. When a reactive silicon group is present at the end of the molecule, the length of the molecular chain between crosslinking points becomes longer in the cured product that is formed, making it easier to effectively exhibit rubber elastic properties, thus reducing the brittleness of the epoxy resin. This makes it easier to improve and replace with high-strength products.

Specific examples of rubber-based organic polymers having reactive silicon groups as described above include, for example, Japanese Patent Publications Nos. 45-36319, 4G-12154, 49-32673, 50-158599, 51 -73561, same 5
No. 4-609fi, No. 55-13787, No. 54-1
No. 37H, No. 55-82123, No. 55-12382
No. 0, No. 55-125121, No. 55-131021
No. 55-131022, No. 55-135135, No. 55-137129, No. 57-179210,
No. 58-191703, No. 59-78220, No. 5
No. 9-78221, No. 59-78222, No. 59-7
Examples include those disclosed in publications such as No. 8223 and No. 59-168014, and these are effectively used, but are not limited thereto.

As the epoxy resin curing agent (component (A) (ii)), which is another component of liquid A used in the present invention, commonly used curing agents for epoxy resins can be used. Examples of such curing agents include triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, -xylylenediamine, -fluorinated diamine, diaminodiphenylmethane, diaminodiphenylsulfone, and Amines such as phorondiamine, 2.4.8-)lis(dimethylaminomethyl)phenol; tertiary amine salts; polyamide resins; imidazoles; ketimines; dicyandiamides; boron trifluoride complex compounds; anhydrous Phthalic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride,
Examples include, but are not limited to, carboxylic acid anhydrides such as endomethylenetetrahydrophthalic anhydride, dodecynylsuccinic anhydride, pyromellitic anhydride, chlorenic anhydride; alcohols; phenols; carboxylic acids, etc. It's not something.

The amount of the curing agent used varies depending on the type of epoxy resin and curing agent, but the curing agent is used as appropriate depending on the purpose in the range of 0.1 to 300 parts per 100 parts (parts by weight, same hereinafter) of the epoxy resin. do it.

Liquid A used in the present invention contains one silicon atom in addition to the rubber-based organic polymer having reactive silicon groups (component (A) (1)) and the epoxy resin curing agent (component (A) ■). to 3
Contains a silicon compound (component (A) (ii)) having a group to which two or more hydrolyzable groups are bonded.

When the mixture of components (A) (1) and (A) This is a component used to solve the problem of depletion. When the silicon compound is used, the hydrolyzable group bonded to one silicon atom, which is a group exhibiting reactivity equal to or higher than that of the reactive silicon group present in component (A) (1), is Since there are more than 1 groups, (A) (1
) The storage stability of Solution A is improved because it preferentially reacts with moisture in the system, which reduces storage stability by reacting with components such as thickening or gelling. This effect is particularly significant when a filler that tends to contain a large amount of water is mixed.

As such component (A), a hydrolyzable group such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, or an alkenyloxy group is used. Examples include silicon compounds having three or more groups bonded to one silicon atom, such as CH3Si
(OCH3) 3 81 (QC2H5) 4, Cs Hs 81 (OCRl)
s, CH2=CH9l(OCOCH3)3, CH35
I(ON -C(CH3) (C2Hs) )3,C)
(381(N(C)Is)2)s, CH391(O
N(CHx) (C2Hs) )3, CHs 31(N
(CH3) (OCCH3) )3, CH391(QC(
CHx) -CH2) s, 82 NG) (2CH2C
H2Sl (OCh) 3. 82 NC) 12 CH
2C82S I (OC2Is)3, H2NCH2C
H2NHCH2CH2CH25t(OCHris, 8
2 NC82CH2N)ICH2C)12 CH281
(OC2H5)3,C)+2- C(CH3) C00
C82C)+2c 82 Sl (OCH3) s
, γ-ureidopropyltriethoxysilane, N-β-
(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, H3CH2CH2CH281(OCH3) s, H3C
Examples include H2CH2CH2St (OC2H5)3, β-carboxyethyltriethoxysilane, N-β-(N-carboxymethylaminoethyl)-γ-aminopropyltrimethoxysilane, and the like.

When a silicon compound having a functional group that reacts with an epoxy group (for example, a primary, secondary, or tertiary amino group, mercapto group, epoxy group, carboxyl group, etc.) is used as the silicon compound, (^) (1 The miscibility of the rubber-based organic polymer which is component ) with the epoxy resin which is component (B) (1) described below is improved, and a homogeneous cured product is obtained.
This is preferable because the properties of the cured product can be improved.

The amount of the silicon compound to be used varies depending on whether the A liquid contains a filler or not, but it is usually preferably contained in about 0.1 to 20 parts in 100 parts of A liquid.
．． More preferably, the amount is about 5 to 10 parts. Also,(
A) 0.06 to 100 parts of the total amount of the rubber-based organic polymer as the component (1) and the epoxy resin as the component (B) (1)
It is preferably about 12 parts, more preferably about 0.3 to 6 parts.

Examples of the epoxy resin (B) (component (1)) used in the present invention, which is one of the components of (B) G, include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, and tetrabromobisphenol A. Flame-retardant epoxy resins such as glycidyl ether of -Aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N
-diglycidylaniline, N,N-diglycidyl-o
- glycidyl ethers of polyhydric alcohols such as toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin, etc.
Examples include hydantoin type epoxy resins and epoxidized products of unsaturated polymers such as petroleum resins, but are not limited thereto, and commonly used epoxy resins may be used. Among these epoxy resins, those containing at least two epoxy groups represented by the formula: % formula % in the molecule have high reactivity during curing, and the cured product tends to form a three-dimensional network. Preferable from this point of view. More preferred are bisphenol A type epoxy resins and novolac type epoxy resins.

The amount of epoxy resin used is 1/100 to 10011, especially 10/100 to 1 in weight ratio of rubber-based organic polymer with reactive silicon groups/epoxy resin, which is one component of liquid A.
Preferably there is a range of 0.00710.

Curing catalyst ((B) which is another component of liquid B used in the present invention)
Component (1) is a catalyst that promotes the silanol condensation reaction when the rubber-based organic polymer is cured.

Specific examples of the curing catalyst 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 phthalate ester; dibutyltin diacetylacetonate; organoaluminium compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate Chelate compounds such as lead octylate, nibutylamine, 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)undecene-7(D
Amine compounds such as BU) or their salts with carboxylic acids; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products between excess polyamines and epoxy compounds; silanes having amino groups Coupling agents, such as silanol condensation catalysts such as γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts. can be given. These catalysts may be used alone or in combination of two or more. The amount of curing catalyst used is 0 parts per 100 parts of the rubber-based organic polymer (A) (1) component and the silicon compound (A) (2) component.
．． 1 to 20 parts is preferable, and 1 to 10 parts is more preferable.

In the present invention, other additives may be added to liquid A and/or liquid B. Examples of preferable additives include a functional group capable of reacting with an epoxy group that improves the miscibility of the rubber polymer and the epoxy resin, and one or two hydrolyzable groups bonded to one silicon atom. Examples include silicon compounds containing a group in the molecule.

The functional groups that can react with the epoxy group in the silicon compound include the groups as explained in the component part (A), specifically, primary, secondary, and tertiary amino groups: mercabuto groups; epoxy groups. : Examples include carboxyl group. In addition, as a group in which 1 to 2 hydrolyzable groups are bonded to one silicon atom, one silicon atom is bonded to one silicon atom among the reactive silicon groups present in the rubber-based organic polymer used for the liquid A. Although a group in which ~2 hydrolyzable groups are bonded may be used, an alkoxysilyl group is particularly preferred from the viewpoint of ease of handling.

Specific examples of such silicon compounds include γ-aminopropylmethyldimethoxysilane, γ-(2
Silanes containing amino groups such as -aminoethyl)aminopropylmethyldimethoxysilane; Silanes containing mercapto groups such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyljethoxysilane; γ-glycidoxypropylmethyldimethoxy Epoxy bond-containing silanes such as silane; carboxysilanes such as β-carboxyethyl phenylbis(2-methoxyethoxy)silane; and the like. These silicon compounds may be used alone or in combination of two or more.

When such a silicon compound is used, the amount used is 1 to 20 parts, especially 0 parts, based on the total of the rubber-based organic polymer and epoxy resin that are components (A) and (1). A range of .2 to 10 parts is preferred.

Although such a silicon compound may be added to the A liquid or the B liquid, it is preferable to add it to the A liquid. In addition(
A) If a compound having a functional group capable of reacting with an epoxy group is used as the component (2), less than 9 can be used.

As other additives, inorganic fillers, fillers other than inorganic fillers, anti-aging agents, ultraviolet absorbers, lubricants, pigments, blowing agents, carboxylic acids, solvents, etc. may be added as necessary.

Specific examples of the inorganic filler include asbestos, glass fiber, carbon fiber, mica, graphite, diatomaceous earth, clay, hume silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, and clay.
Talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, zinc powder, etc. can be used. These fillers may be used alone or in combination of two or more.

The inorganic filler may be mixed with the A liquid, the B liquid, or the A liquid and the B liquid separately. In addition, when a filler is contained in liquid A, storage stability is reduced due to water adhering to the filler, so the effect of improving storage stability by using component (A) (2) becomes significant.

The total amount of the inorganic filler used is usually 1 to 500 parts, particularly 10 to 300 parts, based on 100 parts of the total amount of the rubber-based organic polymer and epoxy resin that are components (A) and (1). .

The curable composition of the present invention can be used for various purposes. For example, molded products with improved impact resistance, flexibility, toughness, etc. are molded using commonly used epoxy resin molding methods such as compression molding, transfer molding, and injection molding. Laminated molded products such as copper-clad laminates and reinforced water can be replaced. Also adhesives with improved peel strength, foam materials with improved flexibility, binders for fiberboard or particleboard, paints, binders for shell molds, binders for brake linings, binders for grinding wheels, It can also be suitably used as a composite material made of a combination with glass fiber or carbon fiber. Furthermore, it can be molded by methods commonly used for molding solid rubber such as natural rubber or rubber-based liquid polymers such as polyurethane, to produce rubber molded products and rubber-like foams with improved strength.

It can also be suitably used as a sealant, adhesive, etc.

Among these, it can be particularly preferably used as an adhesive or a binder.

Next, the composition of the present invention will be explained based on Examples.

Production example 1 Polypropylene glycol (number average molecular weight 2500) 9
0 parts and polypropylene triol (number average molecule ffl
3000) Using 10 parts as a starting material, perform 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. 800 g of polypropylene oxide having a molecular weight of 500 was placed in a pressure-resistant reaction vessel equipped with a stirrer, and 20 g of methyldimethoxysilane was added thereto. Then, a chloroplatinic acid catalyst solution (82PtC1a6
8.9g of 1120 and 18ml of isopropyl alcohol
After adding 0.40 ml of a solution dissolved in 160 ml of tetrahydrofuran, the mixture was reacted 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, it was found that the polypropylene oxide had approximately 1.75 C)+3 (C)+30 )2 SI CH2CH2CH2CH20- groups per molecule at the molecular terminals.

Production Example 2 Using polypropylene glycol (number average molecular weight 2000) as a starting material, the molecule undergoes a jump reaction using methylene chloride, and then the allyl ether group obtained by capping the molecular chain ends with allyl chloride 500 g of polypropylene oxide having a number average molecular weight ffl 5000 which had been introduced at 95% was placed in a pressure-resistant reaction vessel equipped with a stirrer, and 32 g of triethoxysilane was added thereto. Next, 0.40ml of chloroplatinic acid catalyst solution (same composition as Production Example 1)
was added, and then 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 (CH3CI+20)3 was present at the molecular end.
SI C)12 Polypropylene oxide having about 1.8 C82CH20- groups per molecule was converted.

Production Example 3 300 g of polypropylene glycol with a number average molecular ffi of 300 G was charged into a flask equipped with a stirrer, and then 28 g of tolylene diisocyanate and 0.2 g of dibutyltin dilaurate were added, and the mixture was stirred at 100° C. for 5 hours under a nitrogen gas flow. Made it react.

Then γ-aminopropyltriethoxysilane 22.
1 g of the solution was added and reacted with stirring at 100° C. for 3 hours to obtain a polyether having an average molecular weight of about 6,600, a triethoxysilyl group at the end, and about 2 reactive silicon groups in the molecule.

Production Example 4 Butyl acrylate) 80g, stearyl methacrylate)
20g of γ-methacryloyloxypropylmethyldimethoxysilane, 1.8g of γ-mercaptopropylmethyldimethoxysilane, and 0.5g of 2.2゛-azobisisobutyronitrile were mixed and stirred to uniformly dissolve them. Ta. 25 g of the mixture was placed in four 200 ml flasks equipped with a stirrer and a chilled bone, 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. After completion of the dropwise addition, 0.15 g of AIBN was added 15 minutes and 30 minutes later, respectively. 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.

Examples 1 to 2 and Comparative Examples 1 to 2 (Preparation of Liquid A) 100 parts of the polymer obtained in Production Example 1, 1 part of 2,2'-methylene-bis-(4-methyl-6-1-butylphenol) , N-β-(aminoethyl)-7-aminopropyltrimethoxysilane (NBAEγAPTMS) 1 part, vinyltrimethoxysilane (VTMS) 3 parts, heavy calcium carbonate 50 parts, 2.4.8-)Lis-( 5 parts of (dimethylaminomethyl)phenol were mixed well using a three-roll Paint Z roll to obtain a formulation.

(Preparation of Solution B) 50 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy ■), 25 parts of heavy calcium carbonate, 1 part of #5B-85 (organotin compound manufactured by Sankyoki Kagaku ■) , 1 part of lauric acid was mixed well with three paint rolls to obtain a formulation.

Put liquid A and liquid B into sealed glass containers,
The viscosity of liquid A after being stored at 50°C for one month was measured using a BM type viscometer manufactured by Tokyo Keiki at a constant temperature of 23°C.

In addition, in Example 2, the silicon compound in liquid A was N-β.
1 part of -(aminoethyl)-γ-aminopropyltrimethoxysilane (NBAEγAPTMS) and 2 parts of vinyltrimethoxysilane (VTMS). Comparative Example 1 is a case in which no silicon compound is added, and Comparative Example 2 is a case in which 4 parts of dimethyldimethoxysilane (DMDNS) is used in place of NBAEγ^PTMS and VTMS. The results are shown in Table 1.

[Margins below] The tensile speed was 5 ms/ml in the case of tensile shear, and 200 aa+/ml in the case of T-shaped peeling, but the tensile shear strength was 51 kg/c in the A/B mixture system before storage.
jST-shaped peel strength is 4.7kg/25as, 50
After storage for one month at °C, the A/B mixed system has a tensile shear strength of 45 kg/cd and a T-peel strength of 4.5 kg/25a.
+a, and there was no difference in adhesive properties before and after storage.

Examples 4 to 10 Same as Example 1 except that the polymers of Production Examples 1 to 4 were used as the polymer in Liquid A, and 4 to IO parts of various silicon compounds were used instead of NBAEγAPTMS and VTMS in Liquid A. A liquid A was prepared and its viscosity was measured. The results are shown in Table 2 [blank below] From Table 1, it can be seen that AM containing component (A) (2) has excellent storage stability.

Example 3 Using the mixture of 40 g of liquid A and 20 g of liquid B prepared in Example 1, JIS K 0850 and Moon SK were used.
Evaluation as an adhesive was conducted according to 8854.

For tensile shear strength measurement, an aluminum plate A-1050P (100 mm x 25 m I+
A test sample was prepared by applying the above mixture using a spatula, pasting the mixture together, and pressing it together by hand.

The T-peel adhesive strength is JIS I+ 4000 aluminum plate A-1050P (200avX 25m+n
Using a 5kg hand roller, apply the mixture to a thickness of about 0.5aa+ using a spatula, and then roll it back and forth in the length direction using a 5kg hand roller.
A test sample was prepared by crimping twice.

These adhesion test samples were heated at 23°C for 20 minutes and then for 50 minutes.
It was cured for 3 days at ℃ and then subjected to a tensile test.

[Effects of the Invention] The two-component curable composition of the present invention is a composition with excellent long-term storage stability, and is a molding material with improved impact resistance, flexibility, toughness, etc. It is useful as an adhesive, a binder, etc. with improved adhesive strength.

Special permission Out wish Man Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1 (A) (1) A hydroxyl group bonded to a silicon atom and (
or) a rubber-based organic polymer having a hydrolyzable group and a silicon atom-containing group that can be crosslinked by forming a siloxane bond, (2) an epoxy resin curing agent, and (3) three silicon atoms per silicon atom. A storage-stable solution consisting of a solution A containing a silicon compound having a group to which the above hydrolyzable group is bonded, and a solution B containing (1) an epoxy resin and (2) a curing catalyst for the rubber-based organic polymer. Improved two-part curable composition.