JP2001049122A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition giving cured product having excellent physical properties such as water-resistance, solvent resistance and adhesion to inorganic material and stably storable in an aqueous dispersion system by including a specific alkoxysilane compound. SOLUTION: The objective composition contains an alkoxysilane compound of the formula (R1 a 1-4C alkyl; R2 is a 1-4C alkylene; R3 is a 1-8C alkyl or an aryl). The composition is preferably further incorporated with a curing agent having two or more amino groups containing active hydrogen (preferably a curing agent having a molecular weight of 50-500, concretely, dicarboxylic acid dihydrazide, m-xylenediamine, isophoronediamine, etc.). The compound of formula can be produced e.g. by adding an aminoalkyltrialkoxysilane to a compound having an acylacetate group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and more particularly, to a curable composition having excellent film-forming properties and capable of providing a film having excellent film properties. .

[0002]

2. Description of the Related Art
Synthetic resin-based paints and adhesives are generally solvent-type ones in which a synthetic resin is dissolved in various low-boiling solvents, which have excellent paint stability and quick-drying properties. The use of low-boiling solvents has been restricted due to problems such as toxicity, harm to the human body, and adverse effects on the global environment.
Aqueous synthetic resin paints and adhesives, etc., in which various types of synthetic resins are modified to impart water solubility or emulsifiability, or dispersed in water using an emulsifier, have been developed and put into practical use.

[0003] On the other hand, solvent-based epoxy coating compositions have excellent properties applicable to various paints, and development studies of aqueous curable compositions derived from epoxy resins have been conducted.

However, water-based curable compositions derived from these epoxy resins have not yet been obtained with satisfactory properties such as water resistance and solvent resistance.
In recent years, many attempts have been made to use an epoxy emulsion with an aqueous curable composition obtained by mixing it with another aqueous resin (for example, an acrylic emulsion), but in that case, the stability of the emulsion becomes a problem. There were many cases. In addition to this, there is a problem that the adhesion to the surface of inorganic materials such as mortar and light calcium plate is insufficient.

[0005] To compensate for these drawbacks, attempts have been made to introduce an alkoxysilyl group into an epoxy resin and to cure the epoxy resin. For example, Tokiko 1-288
No. 32 proposes a metal rust preventive composition comprising an organosilicon compound having an aminoalkyl group and an alkoxy group and a compound having an oxirane ring, and JP-A-1-197568 discloses a polyepoxy compound. A primer containing a reaction product of a compound and a silicone compound has been proposed. JP-A-3-121171 discloses an organosilicon compound having an aminoalkyl group and an alkoxysilyl group, an epoxy resin having two or more hydroxyl groups, A metal rust preventive composition comprising a pigment and a monoalkyl ether of a dihydric alcohol has been proposed.
No. 8 proposes cationic electrodeposited gelled fine particles obtained by dispersing in water water an epoxy resin amine adduct having a hydrolyzable alkoxysilane group and cross-linking within the particles. The adhesion to the surface is insufficient, and there is a problem in using it as a paint.

[0006] Various modifications of the epoxy resin have been attempted, for example, as described in JP-A-48-25099.
In Japanese Patent Application Laid-Open Publication No. H11-157, an epoxy resin modified with an acetoacetic ester group is proposed, but this modified epoxy resin also has the same problems as described above.

Accordingly, an object of the present invention is to provide a curable composition having excellent cured physical properties such as water resistance, solvent resistance, and adhesion to inorganic materials, and having excellent storage stability in an aqueous dispersion. It is in.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a curable composition containing a specific alkoxysilane compound can achieve the above object.

The present invention has been made based on the above findings, and comprises an alkoxysilane compound having a group represented by the following general formula (I) of the following [formula 3] (same as the above [formula 1]). It is intended to provide a curable composition characterized by the above.

[0010]

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[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the curable composition of the present invention will be described in detail.

In the alkoxysilane compound used in the curable composition of the present invention, R _{1 in the} general formula (I)
Examples of the alkyl group having 1 to 4 carbon atoms represented by are linear or branched groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. 1 to 4 carbon atoms represented by ₂
Examples of the alkylene group include linear or branched groups such as methylene, ethylene, propylene, isopropylene, butylene, and isobutylene.Examples of the alkyl group having 1 to 8 carbon atoms represented by R ₃ include: For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl,
Examples thereof include straight-chain or branched groups such as tertiary amyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, and 2-ethylhexyl. Examples of the aryl group include a phenyl group.

Among the above alkoxysilane compounds used in the present invention, an alkoxysilane compound represented by the following general formula (II) of the following [Chemical Formula 4] (the same as the above [Chemical Formula 2]) is particularly preferable.

[0014]

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In the general formula (II), examples of the alkyl group having 1 to 8 carbon atoms represented by R ₃ include methyl,
A linear or branched group such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, etc. The aryl group includes, for example, a phenyl group, and has 2 to 4 carbon atoms represented by A.
Examples of the alkylene group include linear or branched groups such as ethylene, propylene, isopropylene, butylene, and isobutylene, and have 1 to 1 carbon atoms represented by D.
As alkanetriyl of No. 8, methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl,
Straight-chain or branched groups such as octanetriyl;
The alkylene group having 1 to 4 carbon atoms represented by ₁ and D _2, for example, methylene, ethylene, propylene,
Examples thereof include linear or branched groups such as isopropylene, butylene, and isobutylene. Examples of the alkylidene group represented by Z include methylidene, ethylidene, propylidene, isopropylidene, butylidene, and isobutylidene.

Among the compounds represented by the general formula (II), preferred compounds include (1) a compound in which at least one of X ₁ , Y, Y ₁ and Y ₂ is —COCH ₂ COR ₃ ; 2) a compound wherein B ₁ is a group represented by the formula (a-1), and m, n, p and q are 0, (3) B
₁ is a group represented by the formula (a-2), and m, n, p
And (4) a compound in which B ₁ is a direct bond, m and q are 0, and r is 0.

The above-mentioned alkoxysilane compound used in the present invention can be easily produced by adding an aminoalkyl trialkoxysilane to a compound having an acyl acetate group.

More specifically, the method for producing the alkoxysilane compound represented by the general formula (II), which is preferably used as the alkoxysilane compound, is not particularly limited. After the acyl acetate compound represented by the formula (III) is produced, it can be easily produced by reacting a part of the acyl acetate group with an aminoalkoxysilane compound having a reactive group therewith. .

[0019]

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Here, the acylacetate compound represented by the general formula (III) is classified according to its production method.
For example, (a) a compound obtained by directly adding acylacetic acid to a glycidyl group of a polyglycidyl ether of a bisphenol compound, and (b) a dihydroxycarboxylic acid or dialkanolamine added to a glycidyl group of a polyglycidyl ether of a bisphenol compound. Compounds obtained by a method of introducing an acyl acetate group into a hydroxy group of the obtained polyhydroxy compound, (c) compounds obtained by a method of introducing an acyl acetate group into a hydroxyl group of an alkylene oxide adduct of a bisphenol compound, and the like. No.

Here, as the bisphenol compound,
Examples include methylidene bisphenol (bisphenol F), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), and butylidene bisphenol.

In the compound (a), the method for adding acyl acetic acid to the glycidyl ether of the bisphenol compound is not particularly limited, but is, for example, 100 to 100% using an esterification catalyst such as ethyltriphenylphosphonium bromide. It can be easily carried out by reacting at 200 ° C. for several hours.

In the compound (b), the dihydroxycarboxylic acid includes, for example, dimethylolpropionic acid, diethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid and the like, and the dialkanolamine includes, for example, Examples include dimethanolamine and diethanolamine.

Here, the method of adding dihydroxycarboxylic acid or dialkanolamine to the polyglycidyl ether of the bisphenol compound is not particularly limited, but, for example, by heating to 100 ° C. or more in a solvent without a catalyst. Can be easily added.

In the compounds (b) and (c), the acylacetate group may be introduced into the polyhydroxy compound by, for example, a method of producing a polyhydroxy compound by a transesterification method using a lower ester of acylacetic acid, It can be easily manufactured by a method for causing the above. As the acyl acetic acid lower ester used herein, for example, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, tert-butyl acetoacetate,
Ethyl propionyl acetate, ethyl benzoyl acetate and the like.

An aminoalkylalkoxysilane compound having a reactive group capable of reacting with the compound represented by the general formula (III) to provide the alkoxysilane compound of the general formula (II) is an alkoxysilyl compound. Group is
It is a tri ([C1-4] alkoxy) silyl group in which an amino group is bonded to a silicon atom via a C1-4 alkylene group. Specifically, for example, aminomethyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminoisobutyltrimethoxysilane, N
-(Β-aminoethyl) aminomethyltrimethoxysilane, N- (β-aminoethyl) aminomethyltriethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N- (aminoalkyl) aminoalkoxysilane , Γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane and the like.

Among the above-mentioned alkoxysilane compounds according to the present invention, a compound represented by the above general formula (II) such as one having an acyl acetate ester group is used, and an active hydrogen-containing amino acid is further used as a curing agent. It is preferable to use a curing agent having two or more groups in combination, since a curable composition having excellent storage stability, solvent resistance, and excellent coating film strength can be obtained.
Among the acylacetate groups, those having an acetoacetate group are preferred from the viewpoint of reactivity with the curing agent.

The curing agent used here is a compound containing an active hydrogen-containing amino group which reacts with the keto group of the acyl acetate compound, and is, for example, a polyalkyl such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine. Polyamines; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Oxalic acid dihydrazide, malonic acid dihydrazide,
And dicarboxylic acid dihydrazides such as succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, and sebacic acid dihydrazide. Among these curing agents, those having a molecular weight of 50 to 500, especially 100 to 300 are preferable because they are water-soluble and are compatible with the alkoxysilane compound, so that they can be cured in a one-part aqueous system.

Among these water-soluble curing agents, metaxylene diamine; isophorone diamine; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid It is preferable to use a dicarboxylic acid dihydrazide such as dihydrazide since a cured product excellent in solvent resistance, strength and the like can be obtained.

The amount of the curing agent used is such that its amino group or hydrazide group is 0.5 to 1.5 times, especially 0.1 times the equivalent of the acyl acetate ester of the acyl acetate compound.
The amount is preferably from 8 to 1.1 times, and when the amount is within this range, a cured product having excellent properties such as solvent resistance and strength is preferably provided.

The curable composition of the present invention can be used as a solvent-free, organic solvent-based or water-based curable composition. However, considering the effect on the human body and the environment, the curable composition can be used as a water-based curable composition. Preferably, when the curable composition of the present invention is used as an aqueous curable composition, 10 to 500 parts by weight of water is used based on 100 parts by weight of the acyl acetate ester.

When the curable composition of the present invention is used as an aqueous curable composition, an emulsifier and an organic solvent can be used, if necessary.

Examples of the emulsifier which can be used herein include fatty acid salts, sulfate salts of higher alcohols, sulfate salts of liquid fatty oils, sulfates of aliphatic amines and aliphatic amides, and phosphorus salts of aliphatic alcohols. Anionic surfactants such as acid esters, sulfonic acid salts of dibasic acid fatty acid esters, sulfonic acid salts of fatty acid amides, alkylallyl sulfonic acid, and formalin condensed naphthalate; primary amine salts, secondary amine salts, Triamine salts,
Cationic surfactants such as quaternary amine salts and pyridinium salts; polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, trimethylolpropane fatty acid ester, poly Nonionic surfactants such as oxyethyleneoxypropylene copolymers, condensation products of ethylene oxide with fatty acid amines, amides or acids; amphoteric surfactants such as betaine type, sulfate ester type and sulfonic acid type; polymer interface Activator; reactive surfactant and the like.

The use amount of these emulsifiers is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the alkoxysilane compound according to the present invention. When the amount is less than 0.1 part by weight, the emulsion stability is insufficient, and
If the amount exceeds 20 parts by weight, the properties of a film formed from the obtained aqueous resin may be adversely affected.

Here, examples of the organic solvent include ketones such as acetone, methyl isopropyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone;
Tetrahydrofuran, 1,2-dimethoxyethane, 1,
Ethers such as 2-diethoxyethane; esters such as ethyl acetate and n-butyl acetate; alcohols such as iso- or n-butanol, iso- or n-propanol and amyl alcohol; benzene, toluene, xylene and the like Aromatic hydrocarbons; terpene-based hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, swazol # 310 (Maruzen Petrochemical Co., Ltd.), solvesso # 10
0 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride; halogenated aromatic hydrocarbons such as chlorobenzene; aniline, triethylamine, pyridine, dioxane , Acetic acid, acetonitrile,
Carbon disulfide and the like. These solvents can be used alone or arbitrarily as a mixed solvent of two or more kinds.

These organic solvents are appropriately used in the range of 0 to 100 parts by weight with respect to 100 parts by weight of water.

When the curable composition of the present invention is used as an aqueous curable composition, other alkoxysilane compounds can be used in combination. Examples of these alkoxysilane compounds include tetramethoxysilane and tetramethoxysilane. Ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane Phenyltrimethoxysilane, phenyltriethoxysilane and condensates thereof.

When the curable composition of the present invention is used as a water-based curable composition, another water-based resin can be used in combination. Epoxy emulsions, aqueous urethanes, acrylic emulsions and the like can be mentioned.

When the curable composition of the present invention is used as an aqueous curable composition, if necessary, a curing catalyst; monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc. Reactive or non-reactive diluent (plasticizer); glass fiber, carbon fiber, cellulose, silica sand, cement,
Fillers or pigments such as kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, bituminous substances; thickeners; thixotropic agents; flame retardants; A foaming agent; a rust inhibitor; may contain conventional additives such as colloidal silica and colloidal alumina.
Adhesive resins such as xylene resins and petroleum resins can also be used in combination.

Further, when the curable composition of the present invention is used as an aqueous curable composition, other aqueous resins can be used in combination. Examples of these other aqueous resins include aqueous urethane and acrylic. Emulsions, epoxy emulsions and the like.

Examples of the above aqueous urethane include polyisocyanates, polyols and polyols having a carboxyl group or a sulfonic acid group or a polyol having a basic group in the molecule, which are solvents which are inert to the reaction and have a high affinity for water. In this method, a prepolymer is produced by a urethanization reaction in the solution, and then the prepolymer is neutralized and chain-extended, and water is added to produce an aqueous urethane.

The acrylic emulsion is obtained by emulsifying or dispersing an acrylic unsaturated monomer mixture containing an ester of acrylic acid or methacrylic acid in an aqueous solvent in the presence of an emulsifier and polymerizing the mixture. And, as acrylic acid or methacrylic acid ester,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, cyclohexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl, 2-hydroxyethyl, glycidyl, -Methoxyethyl, 2-ethoxyethyl, 2-methoxypropyl,
Monoesters such as 2-methoxybutyl, 3-methoxybutyl, 4-butoxybutyl, p-methoxycyclohexyl, perfluoroethyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2- (dimethylaminoethoxy) ethyl, or For example, diesters with diethylene glycol, polyethylene glycol, 1,4-butanediol, 1,6-hexanediol and the like can be mentioned.

In addition, other unsaturated monomers can be copolymerized with the acrylate and / or methacrylate. Examples of these other unsaturated monomers include, for example, aliphatic unsaturated hydrocarbons such as ethylene, propylene, butene, isobutene, butadiene, vinyl chloride, and vinylidene chloride and halogenated aliphatic unsaturated hydrocarbons, styrene, α -Esters of other unsaturated carboxylic acids such as aromatic unsaturated hydrocarbons such as methylstyrene and vinyltoluene, crotonic acid, itaconic acid, fumaric acid, and maleic acid (the above-mentioned acrylic acid and Alcohol components constituting methacrylic acid ester), vinyl esters such as vinyl benzoate and vinyl acetate, (meth) acrylamide, methacrylamide, N-alkyl (meth) acrylamide,
Examples include nitrogen-containing vinyl monomers such as N, N-dialkyl (meth) acrylamide, N-methylol (meth) acrylamide, and acrylonitrile.

Further, it is preferable to include a carbonyl group as a monomer unit, since a more excellent curability can be obtained, and these carbonyl group-containing monomers include an ald group or a keto group-containing ethylenically unsaturated monomer. Examples of the monomer having an ald group include (meth) acrolein, crotonaldehyde, formylstyrene, formyl-α-methylstyrene, diacetoneacrylamide, (meth) acrylamidepivalinaldehyde, and 3- (meth) ) Acrylamide methyl-anisaldehyde, β- (meth) acryloxy-α, α-dialkylpropanals, etc. Examples of the monomer having a keto group include diacetone (meth) acrylamide, vinyl alkyl ketone, vinyl Phenyl ketone, vinyl benzyl keto , Divinyl ketone, diacetone (meth) acrylate, acetonitrile (meth) acrylate, 2-hydroxypropyl (meth) acrylate-acetyl acetate, 3-hydroxypropyl (meth) acrylate-acetyl acetate, 4-hydroxybutyl (meth) acrylate-acetyl acetate,
Butanediol-1,4- (meth) acrylate-acetyl acetate and the like.

The epoxy emulsion may be one obtained by forcibly emulsifying an ordinary epoxy resin using an emulsifier, or a self-emulsifying type having a water-soluble group in the molecule.

The acetoacetate compound of the present invention and these other resins can be used in any ratio, but are preferably 5/95 to 95/5 by weight, more preferably 10/95 by weight. Used at a ratio of 90-90 / 10.

The curable composition of the present invention includes, for example, concrete, cement mortar, various metals, leather, glass,
Paint or adhesive for rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive for floor material; art paper, lightweight coated paper Processed paper such as cast-coated paper, coated paperboard, carbonless copier, impregnated paper; fiber treatment such as sizing agent such as natural fiber, synthetic fiber, glass fiber, carbon fiber and metal fiber, anti-fraying agent and processing agent Agents: Can be used in a wide range of applications such as building materials such as sealing materials, cement admixtures, and waterproofing materials.

[0048]

EXAMPLES Hereinafter, the curable composition of the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited thereto.

Production Example 1 Epicoat # 1002 (manufactured by Yuka Shell Epoxy Co., Ltd.)
Bisphenol A type epoxy resin, epoxy equivalent 65
0) 1300 parts by weight were dissolved at 100 ° C., and 210 parts by weight of diethanolamine were mixed and reacted at 100 ° C. for 2 hours, and it was confirmed that the epoxy equivalent was infinite. After adding 624 parts by weight of ethyl acetoacetate thereto,
After the volatile components were distilled off at normal pressure, the volatile components were further distilled off under reduced pressure. The temperature was raised to 90 ° C., and 442 parts by weight of aminopropyltriethoxysilane were charged.
A dehydration reaction under reduced pressure was performed at 00 ° C. ^{From 1} H-NMR, it was confirmed that the reaction was completed when the 1.5 ppm of NH2 peak of the aminosilane group disappeared and the NH peak of enamine appeared at 9.0 ppm. The residue was diluted with xylene / isopropyl alcohol (weight ratio 25/5) to a solid content of 70% by weight. Thus, a yellow-brown liquid resin having a silicon content of 2.3% by weight, an acetoacetate content of 9% by weight, and a carbonyl group equivalent of 1100 in the solid content was produced.

300 parts by weight of the yellowish-brown liquid resin obtained here, ADEKANOL NK-961S (Asahi Denka Kogyo Co., Ltd.)
28 parts by weight manufactured by Asahi Denka Kogyo Co., Ltd .; tin-based catalyst)
1.4 parts by weight at 40 ° C. or lower using a triaxial mixer
After stirring for a minute, water was gradually added to obtain a milky white emulsion having a solid content of 40%.

Production Example 2 1300 parts by weight of Epicoat # 1002 and 268 parts by weight of dimethylolpropionic acid were mixed, heated to 130 ° C., and reacted until the acid value became 1 or less. There,
After adding 624 parts by weight of ethyl acetoacetate, the volatile components were distilled off at normal pressure, and then the volatile components were distilled off under reduced pressure. The temperature was raised to 90 ° C, 442 parts by weight of aminotriethoxysilane was charged, and a dehydration reaction under reduced pressure was performed at 90 to 100 ° C. ^{From 1} H-NMR, NH 2 of aminosilane group was
Disappeared, and the peak of enamine NH appeared at 9.0 ppm, indicating that the reaction was completed. The residue was diluted with xylene / isopropyl alcohol (weight ratio 25/5) to a solid content of 70% by weight. Thereby, the silicon content in the solid content is 2.3.
A yellow-brown liquid resin having an acetoacetate content of 10% by weight and a carbonyl group equivalent of 1000 was prepared.

300 parts by weight of the obtained yellow-brown liquid resin, 28 parts by weight of ADEKANOL NK-961S and 1.4 parts by weight of ADEKA FOMLETS UL-28 were stirred at 40 ° C. or lower for 30 minutes using a triaxial mixer. And water was gradually added to obtain a milky emulsion having a solid content of 40%.

Production Example 3 Adeka Resin EP-4100 (manufactured by Asahi Denka Kogyo KK; bisphenol A type epoxy resin, epoxy equivalent: 190)
380 parts by weight and 268 parts by weight of dimethylolpropionic acid were mixed, heated to 130 ° C., and reacted until the acid value became 1 or less. After adding 624 parts by weight of ethyl acetoacetate thereto, the volatile components were distilled off at normal pressure, and then the volatile components were further distilled off under reduced pressure. If this is 90 ° C,
442 parts by weight of aminotriethoxysilane were charged and 9
A vacuum dehydration reaction was performed at 0 to 100 ° C. ^{From 1} H-NMR, it was confirmed that the reaction was completed when 1.5 ppm of the NH ₂ peak of the aminosilane group disappeared and the NH peak of the enamine appeared at 9.0 ppm. The residue was diluted with xylene / isopropyl alcohol (weight ratio 25/5) to a solid content of 70% by weight. This allows
A yellow-brown liquid resin having a silicon content of 3.7% by weight, an acetoacetate content of 18% by weight, and a carbonyl group equivalent of 500 in the solid content was produced.

300 parts by weight of the obtained yellow-brown liquid resin, 28 parts by weight of ADEKANOL NK-961S and 1.4 parts by weight of ADEKA FOMRETZ UL-28 were stirred at 40 ° C. or lower for 30 minutes using a triaxial mixer. And water was gradually added to obtain a milky emulsion having a solid content of 40%.

Production Example 4 Bisphenol A ethylene oxide 4 mol adduct 40
After adding 312 parts by weight of ethyl acetoacetate to 4 parts by weight, 1
After the temperature was raised to 20 ° C. and the volatile components were distilled off at normal pressure, the volatile components were further distilled off under reduced pressure. The temperature was raised to 90 ° C., 221 parts by weight of aminotriethoxysilane was charged, and a dehydration under reduced pressure was performed at 90 to 100 ° C. ¹ H-N
From MR, peak 1.5 pp of NH ₂ of aminosilane group
When m disappeared and the NH peak of enamine appeared at 9.0 ppm, it was confirmed that the reaction was completed. The residue is xylene / isopropyl alcohol (weight ratio 25 /
In 5), the mixture was diluted to a solid content of 70% by weight. This produced a yellow-brown liquid resin having a silicon content of 3.0% by weight, an acetoacetate content of 12% by weight, and a carbonyl equivalent of 850 in the solid content.

300 parts by weight of the obtained yellow-brown liquid resin, 28 parts by weight of ADEKANOL NK-961S and 1.4 parts by weight of ADEKA FOMRETZ UL-28 were stirred at 40 ° C. or lower using a triaxial mixer for 30 minutes. And water was gradually added to obtain a milky emulsion having a solid content of 40%.

Production Example 5 1300 parts by weight of Epicoat # 1002 was dissolved at 100 ° C., and 210 parts by weight of diethanolamine was mixed therewith and reacted at 100 ° C. for 2 hours to confirm that the epoxy equivalent was infinite. . Ethyl acetoacetate 62
After adding 4 parts by weight, the volatile components were distilled off at normal pressure, and then the volatile components were distilled off under reduced pressure. The temperature was raised to 90 ° C, 221 parts by weight of aminopropyltriethoxysilane was charged, and a dehydration reaction under reduced pressure was performed at 90 to 100 ° C. ¹
From H-NMR, the peak of NH2 of the aminosilane group was 1.
5 ppm disappeared, and the enamine NH peak was 9.0 pp.
The completion of the reaction was confirmed by appearing at m. The residue was diluted with xylene / isopropyl alcohol (weight ratio 25/5) to a solid content of 70% by weight. Thereby, in the solid content, the silicon content of 1.1% by weight,
A tan liquid resin having an acetoacetate content of 14% by weight and a carbonyl equivalent of 730 was produced.

300 parts by weight of the obtained yellow-brown liquid resin, 28 parts by weight of ADEKANOL NK-961S and 1.4 parts by weight of ADEKA FOMULETS UL-28 were stirred at 40 ° C. or lower for 30 minutes using a triaxial mixer. Water was gradually added to obtain a milky emulsion having a solid content of 40%.

Production Example 6 1300 parts by weight of Epicoat # 1002 was dissolved at 100 ° C., and 210 parts by weight of diethanolamine was mixed therewith and reacted at 100 ° C. for 2 hours to confirm that the epoxy equivalent was infinite. . There, ethyl acetoacetate 6
After adding 24 parts by weight, the volatile components are distilled off at normal pressure,
Further, volatile components were distilled off under reduced pressure. The temperature was set to 90 ° C., 663 parts by weight of aminopropyltriethoxysilane was charged, and a dehydration reaction under reduced pressure was performed at 90 to 100 ° C.
^{From the 1} H-NMR, 1.5 ppm of the NH2 peak of the aminosilane group disappeared, and the NH peak of the enamine was 9.0.
It was confirmed that the reaction was completed by coming out to ppm. The residue was diluted with xylene / isopropyl alcohol (weight ratio 25/5) to a solid content of 70% by weight. Thereby, the silicon content in the solid content is 2.5% by weight,
Acetoacetate content 5% by weight, carbonyl equivalent 2
100 yellow-brown liquid resins were produced.

[0060] 300 parts by weight of the tan liquid resin thus obtained, 28 parts by weight of ADEKANOL NK-961S and 1.4 parts by weight of ADEKA FOMULETS UL-28 were stirred at 40 ° C or lower using a triaxial mixer for 30 minutes. Water was gradually added to obtain a milky emulsion having a solid content of 40%.

Production Example X 300 parts by weight of Epicoat # 1002, Adekanol N
28 parts by weight of K-961S and Adeka Foamlets UL
-28 1.4 parts by weight and stirred at 40 ° C. or lower for 30 minutes using a triaxial mixer.
A milky white emulsion was obtained.

Production Example Y 1300 parts by weight of Epicoat # 1002 was dissolved at 100 ° C., and aminopropyltriethoxysilane was added to 22 parts by weight.
One part by weight was charged and reacted at 110 ° C. for 4 hours. Thus, a yellow-brown liquid resin having a silicon content of 1.8% by weight and an epoxy equivalent of 1200 in the solid content was produced.

300 parts by weight of the obtained yellow-brown liquid resin, 28 parts by weight of ADEKANOL NK-961S and 1.4 parts by weight of ADEKA FOMRETZ UL-28 were stirred at 40 ° C. or lower using a triaxial mixer for 30 minutes. And water was gradually added to obtain a milky emulsion having a solid content of 40%.

Production Example Z 1300 parts by weight of Epicoat # 1002 was dissolved at 100 ° C., and 210 parts by weight of diethanolamine was mixed therewith and reacted at 100 ° C. for 2 hours to confirm that the epoxy equivalent was infinite. . Ethyl acetoacetate 62
After adding 4 parts by weight, the volatile components were distilled off at normal pressure, and then the volatile components were distilled off under reduced pressure. The residue was diluted with xylene / isopropyl alcohol (weight ratio 25/5) to a solid content of 70% by weight. As a result, a yellow-brown liquid resin having an acetoacetate content of 18% by weight and a carbonyl group equivalent of 500 in the solid content was produced.

300 parts by weight of the obtained yellow-brown liquid resin, 28 parts by weight of ADEKANOL NK-961S and 1.4 parts by weight of ADEKA FOMRETZ UL-28 were stirred at 40 ° C. or lower using a triaxial mixer for 30 minutes. And water was gradually added to obtain a milky emulsion having a solid content of 40%.

Example 1 A water-based curable composition was prepared by blending the composition obtained in the above-mentioned production example with a curing agent in the composition (parts by weight) shown in Tables 1 and 2, and the following test was carried out. Was done.

(Storage stability) The above water-based curable composition was mixed with 4
It was stored in a gear oven at 0 ° C., and the state after one week was observed. 3: No change 2: Slight precipitation, separation, or slight increase in viscosity 1: Precipitation, separation or increase in viscosity is clearly seen.

(Water resistance) The above water-based curable composition was applied to a tin plate at 20 μm, and allowed to stand for 24 hours. One drop of water was dropped on the cured coating film obtained with a spoid, and the state of the coating film was observed. . 3: No change in dropped spot portion 2: Dropped spot portion was slightly peeled. 1: The dropped spot portion was completely peeled off.

(Toluene resistance) The above water-based curable composition was applied to a tin plate at 20 μm, and the cured coating film obtained by standing for 24 hours was repeatedly subjected to toluene rubbing, and the number of times of peeling of the coating film was examined. Was.

(Tensile Strength) The above water-based curable composition was applied on a release paper, and left for 24 hours to prepare a No. 2 dumbbell test piece from the cured coating film obtained, according to JIS K 7113.
The tensile strength (kgfcm2) was measured according to the following.

(Mortar Adhesion) The above-mentioned water-based curable composition was applied on a mortar plate at a thickness of 100 μm, left to stand for one day to form a cured coating film, and cross-cut to determine the degree of peeling with a tape according to the following criteria. Was evaluated (mortar adhesion). 5: No abnormality in the coating film. 4: Floating is observed in an area of 5% or less of the coating film. 3: Floating is observed in an area of more than 5% to 20% or less of the coating film. 2: Floating is observed in an area of more than 20% to 50% of the coating film. 1: Floating is seen in more than 50% of the area of the coating film.

(Adhesion to Light Kal Plate) The above water-based curable composition was applied to a light kal plate at a thickness of 100 μm, left to stand for one day to form a cured coating film, cross-cut and peeled off with a tape. Was evaluated according to the following criteria. 5: No abnormality in the coating film. 4: The coating film is slightly lifted (area of 5% or less). 3: The coating film is slightly lifted (more than 5% to 20% or less in area). 2: The coating film slightly floats (more than 20% area). 1: The coating film is completely peeled off.

[0073]

[Table 1]

[0074]

[Table 2]

Example 2 The same test as in Example 1 was conducted with the compositions (parts by weight) shown in Tables 3 and 4. However, the carbonyl group-containing acrylic emulsion used here was blended with the composition obtained in the production example before blending the curing agent to obtain an aqueous curable composition.

[0076]

[Table 3]

[0077]

[Table 4]

As is evident from the above results, the curable composition containing a normal epoxy resin and a water-soluble curing agent (Comparative Examples 1-1 and 2-1) was inferior in storage stability and the cured product thereof Are not satisfactory in water resistance and solvent resistance. In addition, the curable composition containing an alkoxysilane compound other than that according to the present invention (Comparative Examples 1-2 and 2-2) has improved water resistance, solvent resistance or strength, although the adhesion to inorganic materials is improved. Inferior in terms of etc. On the other hand, the acetoacetate group-modified curable compositions (Comparative Examples 1-3 and 2-3) have improved water resistance and solvent resistance, but are inferior in strength or adhesion to inorganic materials. Things.

On the other hand, the curable composition containing the specific alkoxysilane compound according to the present invention has excellent stability, excellent water resistance and solvent resistance of the cured product, high strength, and Excellent adhesion to inorganic materials. Furthermore, the water-based curable composition of the present invention has excellent storage stability when formed into a mixed emulsion with another resin, and a mixed emulsion with a carbonyl group-containing acrylic resin emulsion has remarkably excellent water resistance and solvent resistance. Things.

[0080]

The curable composition of the present invention has excellent physical properties such as water resistance, solvent resistance and adhesion to inorganic materials, and has excellent storage stability in an aqueous dispersion system. In particular, when used as a water-based curable composition, the composition has a high curing rate and can be used for paints, adhesives, and the like having excellent cured physical properties.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kiyoshi Masamune, Inventor: 20 Showa-numa, Shobu-cho, Minami-Saitama-gun, Saitama Asahi Denka Kako Kogyo Co., Ltd. F-term (reference) in Chemical Industry Co., Ltd. 4J002 BG021 CD001 CK001 CP092 CP122 EN037 EN077 EQ027 EX076 FD147 GH00 HA04 HA07

Claims (11)

[Claims] 1. A curable composition comprising an alkoxysilane compound having a group represented by the following general formula (I): Embedded image 2. The curable composition according to claim 1, wherein the alkoxysilane compound is a compound represented by the following general formula (II). Embedded image 3. The curable composition according to claim 2, wherein in the general formula (II), at least one of X ₁ , Y, Y ₁ and Y ₂ is —COCH ₂ COR ₃ . 4. In the general formula (II), B ₁ is a group represented by the formula (a-
The curable composition according to claim 2, wherein the group is represented by 1), and m, n, p, and q are 0. 5. In the general formula (II), B ₁ is a group represented by the formula (a-
The curable composition according to claim 2, wherein the group is represented by 2), and m, n, p, and q are 0. 6. The curable composition according to claim 2, wherein in the general formula (II), B ₁ is a direct bond, m and q are 0, and r is 0. . 7. The composition according to claim 2, further comprising a curing agent having two or more active hydrogen-containing amino groups.
The curable composition according to any one of the above. 8. The curable composition according to claim 7, wherein the curing agent is a curing agent having a molecular weight of 50 to 500. 9. The curable composition according to claim 8, wherein the curing agent is dicarboxylic dihydrazide, and the curable composition is an aqueous curable composition. 10. The curable composition according to claim 8, wherein the curing agent is meta-xylene diamine, and the curable composition is an aqueous curable composition. 11. The curable composition according to claim 8, wherein the curing agent is isophorone diamine, and the curable composition is an aqueous curable composition.