JPH07304954A - Water-base cross-linkable resin composition - Google Patents

Abstract

PURPOSE:To obtain a cross-linkable resin compsn. for a water-base coating material excellent in weathering resistance and stain resistance by using as the main components a carboxylated resin neutralized with an amine compd. and dissolved or dispersed in an aq. medium in advance and a carboxyl-reactive silicone compd. CONSTITUTION:A water-base cross-linkable resin compsn. is produced by using a carboxylated resin (C) and a silicone compd. (D) as the main components. The resin (C) is prepd. by neutralizing a carboxylated resin (A) having a number average mol.wt. of 1,000-40,000 and an acid value of 10-400-mgKOH/g with an amine compd. (B) and dissolving or dispersing the neutralized resin in an aq. medium; and a silicone compd. (D) has a number average mol.wt. of 200-8, 000 and, on average, at least two carboxyl-reactive groups. Resin A is selected from among an acrylic resin, a polyester resin, a fluororesin, etc. The carboxyl- reactive group is hydrolyzable silyl, hydroxysilyl, or epoxy. Compd. B is ammonia, an alkylamine, or an alkanolamine. The compsn. is further compounded with a light stabilizer having a group of the formula (wherein R<1> to R<4> are each 1-6C alkyl; and R<5> is H or 1-6C alkyl).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous crosslinkable resin composition useful as a raw material for aqueous paints, coating agents and the like having excellent weather resistance, acid resistance, solvent resistance, stain resistance, smoothness, etc.
Regarding

[0002]

2. Description of the Related Art A vinyl polymer having an alkoxysilyl group at a molecular end or a side chain and a coating composition using the same are disclosed, for example, in JP-A-54-36395 and JP-A-54-40893. JP-A-54-123192
It is disclosed in the Japanese Patent Publication and is publicly known. These vinyl polymers are excellent in weather resistance, acid resistance and the like. However, since these vinyl-based polymers have highly hydrolyzable alkoxysilyl groups at the molecular ends or side chains, the vinyl-based polymers are inherently poor in storage stability. In addition, problems such as storage stability may occur due to the effects of water and the like contained in the pigment when the pigment is blended for use as a paint.

Japanese Patent Application Laid-Open No. 4-110350 discloses (a) (A) as a cured product obtained by reacting an epoxy group-containing silicone compound with a carboxyl group-containing resin.
A silane compound having a hydroxyl group and / or a hydrolyzable group directly bonded to a silicon atom, and (B) a reaction product of a silane compound having a hydroxyl group and / or a hydrolyzable group directly bonded to a silicon atom and an epoxy group. And, on average, one or more epoxy groups and two or more hydroxyl groups and / or hydrolyzable groups directly bonded to a silicon atom are contained in each molecule of the reaction product.
A curable resin characterized by containing a polysiloxane resin having one or more and (b) a hydroxyl group- and carboxyl group-containing resin is disclosed. However, among these silicone compounds, those containing a silanol group having a high condensation property in the molecule have drawbacks such as poor stability of the resin and requiring careful handling. Further, in this patent, it is described that water may be used as a coating solvent, but when water is used, the homogeneity of the composition may be impaired and the resulting cured product may become turbid.

Japanese Patent Laid-Open No. 3-250080 discloses a hydrolyzate prepared by blending a vinyl polymer containing a carboxylic acid group and / or an acid anhydride group at an end or a side chain with a silane coupling agent containing an epoxy group. A coating composition for forming a vinyl polymer having a hydrophilic silyl group is described. Japanese Patent Laid-Open No. Hei 4
JP-A-18967 describes a curable composition containing a carboxyl group-containing vinyl polymer and a compound having both an epoxy group and a hydrolyzable silyl group in one molecule as essential components. As a compound having both an epoxy group and a hydrolyzable silyl group in one molecule, it has been proposed to use a silane coupling agent or a vinyl polymer having both an epoxy group and a hydrolyzable silyl group.
Since the silane coupling agent has only one epoxy group in one molecule, the curing is not sufficient to react with the carboxyl group and cure. Further, some silane coupling agents having a low boiling point may not be effectively used when they are cured at a high temperature unless the curing catalyst is sufficient. A vinyl polymer having both an epoxy group and a hydrolyzable silyl group has a highly hydrolyzable alkoxysilyl group at the molecular end or side chain, and therefore has poor intrinsic storage stability and is difficult to handle due to its high molecular weight. Have drawbacks such as.

Further, these patent documents also do not describe the use of a water-soluble resin obtained by neutralizing a carboxylic acid-containing vinyl polymer with an amine. As described above, conventionally, the use of water as a medium in a curable composition having a silanol group that condenses and crosslinks and a hydrolyzable silyl group impairs the stability of the curable resin, which is a practical problem. It has been. Furthermore, it was not considered to use a medium containing water in the presence of an amine that can serve as a condensation catalyst for silanol groups and hydrolyzable silyl groups.

[0006]

A vinyl polymer having a highly hydrolyzable alkoxysilyl group at its molecular end or side chain is said to have excellent weather resistance and acid resistance. Although water-based is desired, it was difficult from the viewpoint of storage stability of the resin. However, in recent years, there has been a demand for conversion to water-based paints due to problems such as ignition and explosion of organic solvents in paints, air pollution, occupational safety and hygiene. The present invention provides a novel aqueous crosslinkable composition which has good stability of the crosslinkable composition, is low in the content of the organic solvent and is aqueous, and is excellent in durability which is a characteristic of the silicone-based cured product. .

[0007]

Means for Solving the Problems The present inventors have described the above by combining a specific resin having no highly hydrolyzable alkoxysilyl group in the molecule with a specific compound containing Si in the molecule. They have found that they can solve the problems and have completed the present invention. It was also found that in a silicone compound containing a silanol group having a high condensation property in the molecule, a gel insoluble in the solvent does not occur during storage when dissolved in a solvent containing an alcohol compound and stored. Contribute to the completion of.

That is, the present invention is an aqueous crosslinkable resin composition comprising the following (A) and (B) as main components. (A) A carboxylic acid-containing resin having a number average molecular weight of 1,000 to 40,000 and an acid value of resin of 10 to 400 mgKOH / g was neutralized with an amine compound and dissolved and / or dispersed in an aqueous medium. Resin containing carboxyl group. (B) A silicone compound having a number average molecular weight of 200 to 8,000 and containing an average of two or more functional groups reactive with a carboxyl group in one molecule.

The resin (A) is at least one selected from acrylic resins, polyester resins and fluorine-containing resins.
It is preferably a seed. The functional group having reactivity with the carboxyl group of the silicone compound (B) is preferably at least one selected from the following (1) to (3). (1) Hydrolyzable silyl group. (2) Hydroxysilyl group. (3) Epoxy group. The amine that neutralizes the carboxylic acid-containing resin (A) is preferably at least one selected from the following (4) to (6). (4) Ammonia. (5) Alkyl amine. (6) Alkanolamine. Further, it is also preferable to contain a light stabilizer containing the structure of the following general formula (I).

[0010]

[Chemical 3] The light stabilizer containing the structure of the following general formula (II) is a resin (A).
May be combined with and incorporated into.

[0011]

[Chemical 4]

In the crosslinkable resin composition of the present invention, the carboxylic acid-containing resin which has not been neutralized with the amine is used as the resin (A) by using the resin which has been hydrated by neutralizing the carboxylic acid-containing resin with the amine. Even if the compatibility of the silicone compound of (B) is somewhat poor, or even if the silicone compound of (B) is difficult to dissolve in water, it is neutralized with amine and mixed with (A). By doing so, even at room temperature (A)
Part of the reaction with the resin proceeds, and a uniform cured product having good compatibility is obtained. Further, it has a sufficient usable time for mixing (A) and (B) and using it as a paint.
Since (A) does not have a highly hydrolyzable alkoxysilyl group, the stability of the resin is good. (B) has a relatively low molecular weight and excellent stability. Further, the stability of a silicone compound containing a silanol group having high hydrolyzable condensability can be improved by dissolving it in a solvent containing an alcohol compound and storing it. Since (A) and (B) are separately stored until just before use, there is no problem in stability.
In addition, for example, one type of (B) compound can be applied to two or more types of different grade (A) resins. Since (B) contains a silicone compound, the cured product obtained by the cross-linking reaction of (A) and (B) can exhibit excellent characteristics of the silicone-based cured product, and is characterized by being aqueous. It is a novel aqueous crosslinkable resin composition which is useful as an aqueous paint or coating agent.

In amine-neutralizing the carboxylic acid-containing resin (A) of the present invention, it is preferable to use an equivalent amount of amine to the carboxylic acid from the viewpoint of dissolution or dispersion, but sufficient dissolution or dispersion for use of the resin solution is required. If it is obtained, the amount may be less than or equivalent to the equivalent of the carboxylic acid of the resin (A). The amine compound used for neutralizing the carboxylic acid-containing resin (A) of the present invention and for dissolving and / or dispersing it in an aqueous medium includes (4) ammonia and (5)
Examples thereof include alkylamine and (6) alkanolamine. As the alkylamine, primary, secondary, and tertiary amines can be used. Further, a tetraalkylammonium hydroxide compound can also be used.

Specific examples include dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, tripropylamine, butylamine, isobutylamine,
Dibutylamine, diisobutylamine, tributylamine, pyridine, pentylamine, tripentylamine,
N, N-dimethylaniline, cyclohexylamine, dicyclohexylamine, piperidine, picoline, morpholine, N-ethylmorpholine, diethylenetriamine,
Examples thereof include N, N-dimethylbenzylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and the like. Preferably triethylamine, tripropylamine, tributylamine, N-
A tertiary amine such as ethylmorpholine is preferred.

Various alkanolamines can be used as the alkanolamine. Specific examples are 2-aminoethanol, 3-aminopropanol,
2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, diethanolamine, N-butyldiethanolamine, tripropanolamine, 1-diethylamino-2-propanol, 3- (dimethylamino) -1-propanol and the like can be mentioned. Preferably 2- (dimethylamino) ethanol, 1-diethylamino-2-propanol, 3- (dimethylamino) -1-
Dialkylalkanolamines such as propanol are preferred.

If desired, a surfactant may be added to improve the dispersion in water. The number average molecular weight of the above (A) is 1,000 to 40,000, and the acid value of the resin is 10 to 10.
A carboxyl group-containing resin obtained by neutralizing a carboxylic acid-containing resin of 400 mgKOH / g with an amine compound and dissolving and / or dispersing it in an aqueous medium reacts with the silicone compound (B) to give a good crosslinkable resin composition. can get. Acrylic resins, polyester resins, and fluorine-containing resins are preferable in terms of use as paints, coating agents, etc., which have good durability as applications, and even if these are used alone, 2
You may use it as a mixture of 2 or more types.

The resin (A) has a resin acidity value of 10 mgKO.
If it is less than H / g, a large amount of organic solvent is required for improving the solubility and / or dispersibility even if neutralized with an amine. or,
The number of functional groups as a cross-linking group is not sufficient, and it reacts with the silicone compound (B), and a good cured product cannot be obtained.
Further, when the resin acid group value is more than 400 mgKOH / g, the crosslinked density of the cured product obtained by reacting with the silicone compound (B) becomes too high, or the amount of carboxylic acid that does not participate in the reaction becomes too much and the cured product becomes too high. The physical properties deteriorate. The preferred resin acid number is 10 to 300 mgKOH / g.

The number average molecular weight of the resin (A) is 1,000.
If it is less than 100, the physical properties of the cured product are poor, and the number average molecular weight is 40,
If it is 000 or more, the viscosity of the polymer becomes high and problems such as difficulty in handling tend to occur. Further, the resin (A) may contain a hydroxyl value at the same time as the carboxyl group. When it has a hydroxyl value, it may contain not more than 300 mgKOH / g as the hydroxyl value of the resin component. Thirty
If it is more than 0 mgKOH / g, the physical properties of the obtained cured product will deteriorate. However, as resin component hydroxyl group, 1 mgKOH / g
If the amount is smaller, the contribution to the solubility or dispersibility of the resin in the aqueous medium as the crosslinking group is small and the inclusion thereof is meaningless.

Further, as will be described later, the hydroxyl group is also reactive with the hydrolyzable silyl group, silanol group and epoxy group of (B), so that it can be used for the crosslinking reaction. The sum of the acid value of the resin component and the hydroxyl value of the resin component is 11 to 500 mg.
KOH / g is preferable. If it exceeds 500 mgKOH / g, the crosslink density becomes too high, and either or both of the hydroxyl groups and carboxylic acids that do not participate in the crosslinking reaction increase, and the physical properties of the cured product deteriorate. The sum of the acid value of the resin component and the hydroxyl value of the resin component is further 20 to 400 mgKOH / g
Is preferred.

As the monomer for introducing a carboxyl group into the acrylic resin which is one type of (A), acrylic acid,
Methacrylic acid, maleic acid, etc. may be mentioned. As a monomer for introducing a hydroxyl group, (meth) acrylic acid-2-
Examples thereof include hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate. Acrylic monomers and other vinyl monomers that are simultaneously copolymerized include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Examples include hexyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, maleic anhydride, styrene, and acrylonitrile.

Upon copolymerization, solution polymerization using an organic solvent in the presence of a polymerization initiator such as a peroxide or an azo compound is preferably used in a conventional manner. As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene; ethyl acetate, propyl acetate, butyl acetate, amyl acetate, acetic acid-2
-Ethyl butyl, methoxy butyl acetate, methyl isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, methyl propionate,
Esters such as ethyl propionate, propyl propionate, butyl propionate and isoamyl propionate;
Alcohols such as ethanol, propanol, butanol, pentanol; acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, methyl isobutyl ketone, and other ketones; dipropyl ether, dibutyl ether,
Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl acetate, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Butyl ether, dipropylene glycol monomethyl ether, ethers such as dipropylene glycol monomethyl ether or the like is used. It is also possible to use compounds such as butyl mercaptan and dodecyl mercaptan, and chain transfer agents such as halogenated hydrocarbons.

The polymerization temperature varies depending on the type and amount of the polymerization initiator, but is selected from the range of room temperature to 150 ° C. The molecular weight of the obtained copolymer can be controlled by the type and amount of the polymerization initiator and the polymerization temperature. (A)
Examples of the polyester resin which is one of the components include acids such as phthalic anhydride, phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic acid and trimellitic anhydride, and ethylene glycol, propylene glycol, butanediol, Known polyester resins obtained from alcohols such as trimethylolpropane and glycerin can be used.

Examples of the monomer for introducing a carboxyl group into the fluororesin, which is one type of component (A), include acrylic acid, methacrylic acid and maleic acid. Examples of the monomer for introducing a hydroxyl group include vinyl alcohol, allyl alcohol, allyloxyethanol, tetrafluoroethylene, trifluoroethylene,
A known fluororesin obtained by polymerizing a fluoromonomer such as difluoroethylene, trifluorochloroethylene, or trifluorodichloropropylene can be used.

When a hydroxyl group is used as a functional group in the component (A) for the crosslinking reaction, the functional group of the silicone compound (B) is (1) a hydrolyzable silyl group, (2)
The hydroxysilyl group of and the epoxy group of (3) can be used. These functional groups in (B) may be used alone or in combination of two or more kinds, and may be contained in the same molecule or may be a mixture. In the case of an epoxy group, it is preferable that a hydrolyzable silyl group or a hydroxysilyl group coexists at the same time.

When only a carboxyl group is used as the functional group in (A) for the crosslinking reaction, a hydrolyzable silyl group, a hydroxysilyl group or an epoxy group is used as the functional group of the silicone compound (B). However, from the viewpoint of curability, the epoxy group is superior to the hydrolyzable silyl group and the hydroxysilyl group.

Number average molecular weight (B) of 200 to 8,000
As the silicone compound having an average of two or more functional groups reactive with a hydroxyl group and / or a carboxyl group in the molecule, the functional group reactive with the hydroxyl group or the carboxyl group in (A) is included in the molecule. There is no particular limitation as long as it is a compound containing an average of two or more, but examples of functional groups for causing a practical crosslinking and curing reaction include hydrolyzable silyl groups, hydroxysilyl groups, and epoxy groups. As the hydrolyzable silyl group, an alkoxysilyl group, an acyloxysilyl group, an aminoxysilyl group, an acetoxysilyl group, a phenoxysilyl group, a thioalkoxysilyl group,
Examples thereof include a ketoxime silyl group.

The number average molecular weight of the silicone compound (B) is not particularly limited as long as it has an average of two or more functional groups reactive with a hydroxyl group and / or a carboxyl group in the molecule, and may be a low molecular weight monomer or oligomer. . However, when the number average molecular weight is 8,000 or more, the storage stability of the silicone compound becomes poor, and the silicone compound has reactivity with the hydroxyl group and / or the carboxyl group (hereinafter abbreviated as [A-functional group]) in (A). The reactivity of the functional group (hereinafter abbreviated as [B-functional group]) becomes poor, and problems such as not effectively using the [B-functional group] easily occur, which is not preferable.
The number average molecular weight is preferably 200 to 5,000.

The compounding ratio of the resin of (A) and the silicone compound of (B) is not particularly limited, and [A in the resin of (A) is used.
-Functional group] sufficient to cure and cure [B-functional group]
The silicone compound (B) may be blended so as to contain Usually, (B) is added to 100 parts by weight of the resin (A).
When the amount of the silicone compound is less than 1 part by weight, the resulting cured product is not sufficiently cured, and the physical properties of the cured product tend to be poor. When the amount of the silicone compound (B) is 100 parts by weight or more with respect to 100 parts by weight of the resin (A), the [B-functional group] does not participate in the reaction with the [A-functional group] in the resin (A). ], And the physical properties of the obtained cured product tend to deteriorate. The amount of the silicone compound as the component (B) is preferably 1 to less than 100 parts by weight, more preferably 10 to 90 parts by weight, based on 100 parts by weight of the component (A) resin. As the silicone compound as the component (B), one type or a mixture of two or more types may be used, or a hydrolysis-condensation product of one or more types of silicone compounds may be used.

Specific examples thereof include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, 1,3-bis (3-glycidoxypropyl) -1,
1,3,3-tetramethyldisiloxane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 3-glycidoxymethyldimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-β- (aminoethyl) γ -Aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-
Aminopropyltriethoxysilane, methyltris (N, N-diethylaminoxy) silane, dimethoxysilane, diethoxysilane, trimethoxysilane, triethoxysilane, 1,4-bis (hydroxydimethylsilyl) benzene, 1,3-bis ( Acetoxymethyl) tetramethoxysilane, bis (trimethoxysilylethyl)
Hydrolyzed condensate of benzene or the like and / or one or more compounds thereof, reaction silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-163A, X-22-16
9AS, KF-105 and the like.

The silicone compound as the component (B) has a general formula of R _a HSiX _3-a (wherein R is an alkyl group having 1 to 10 carbon atoms or a phenyl group, X is a halogen atom or an alkoxyl group having 1 to 4 carbon atoms). And a is 0, 1 or 2)
A silicone compound obtained by reacting a silicone compound obtained by hydrolyzing and condensing a silane compound containing a silane compound having H as an essential component with an epoxy group and a carbon-carbon double bond-containing compound can be used.

Examples of the silane compound represented by the above general formula include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane,
Dimethoxysilane, diethoxysilane, dipropoxysilane, dibutoxysilane, methyldimethoxysilane, methyldiethoxysilane, methyldipropoxysilane, methyldibutoxysilane, dimethylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, dimethylpropoxysilane, dimethyl Examples include butoxysilane, methyldichlorosilane, methylphenylchlorosilane, and the like.

One or more kinds of silane compounds having Si--H as essential components and / or other silicon compounds, for example,
Dimethyldichlorosilane, diethyldichlorosilane, trimethylchlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexamethyldisiloxane,
S obtained by hydrolysis and condensation with octamethyltetracyclosiloxane, diphenyldichlorosilane, diphenyldimethoxysilane, dimethyldiacetoxysilane, etc.
Obtained by hydrosilylating a silicone compound having i-H to a compound containing an epoxy group such as allyl glycidyl ether, 3,4-epoxycyclohexylethylene, and limonene oxide, and a carbon-carbon double bond using a platinum catalyst or the like. You can 1, 3,
5,7-tetramethylcyclotetrasiloxane, 1,
Obtained by hydrosilylating a silicone compound having Si—H such as 1,1,3,5,7,7,7-octamethyltetrasiloxane and polymethylhydrosiloxanes PS118 and PS119 manufactured by Chisso Corporation. be able to.

An alkyldihalosilane represented by RHSiX ₂ (where R and X are the same as above), for example, a bifunctional silane such as methyldichlorosilane is hydrolyzed alone to obtain a silane compound having a cyclic structure. It is possible,
It is also possible to use a silicone compound having an epoxy group obtained by hydrosilylating this silane compound into an epoxy group- and carbon-carbon double bond-containing compound using a platinum catalyst or the like. As a specific example of the synthesis, a method of hydrolyzing methyldichlorosilane to synthesize the silicone compound (B) will be described. 1 mol of methyldichlorosilane is added to about 120 g of an ether solvent such as isopropyl ether and about 230 g of methyldichlorosilane. When dropped into a suspension of water, a ring-shaped body containing a ring-shaped body having 4 to 6 Si as a main component is obtained with a yield of about 70%. By removing the hydrogen chloride produced by washing the reaction solution with water and then distilling, the cyclic compound having 3 to 12 Si atoms can be separated and purified. When it is used as the silicone compound of (B), the cyclic silicone compound having an epoxy group is obtained by reacting with the allyl glycidyl ether as it is as a mixture of distilled cyclic compounds having 3 to 12 Si.

Monofunctional represented by RHSiX ₂ and R ^x R ^y R ^z SiX (wherein R ^x , R ^y and R ^z represent the same or different hydrogen atoms, alkyl groups and the like, and X is the same as above). The silane compound of Si—H having a chain structure can be obtained by synthesizing the silane of Example 1 by a method known in the art such as hydrolysis of the mixture. It is also possible to use a silicone compound having an epoxy group obtained by reacting this silane compound with an epoxy group and a compound containing a carbon-carbon double bond.

Further, it is obtained by hydrolyzing and condensing trichlorosilane in a dioxane solvent, as disclosed in JP-A-3-21741.
No. 8, JP-A-3-217419, and JP-A-3-217419.
The silicone compound having a Si—H group described in JP-A-217420 and the like is hydrolyzed by a method described in JP-A-5-222198 and the like by using a platinum catalyst or the like for one or more compounds having a carbon-carbon double bond. A silicone compound obtained by silylation can be used.

Specific examples of the compound having a carbon-carbon double bond include 1-hexene, 1-heptene, 1-octene, isobutene and 5-methyl, in addition to the epoxy group and the compound containing a carbon-carbon double bond. Olefins such as -1-butene, cyclohexene, allylbenzene; allyl esters such as allyl acetate, allyl propionate, allyl 2-ethylhexanoate, allyl benzoate; allyl methyl ether, allyl ethyl ether, allyl propyl ether, Allyl ethers such as allyl hexyl ether, allyl cyclohexyl ether, allyl-2-ethylhexyl ether, allyl phenyl ether; (meth)
(Meth) acrylic acid esters such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, -2 ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth) acrylate; Vinyl acetate, vinyl propionate, vinyl butyrate,
Carboxylic acid vinyl esters such as vinyl stearate and vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether; styrene, (meth) acrylonitrile, crotonic acid ester, 2- (allyloxy) Examples thereof include ethanol, allylamine, allylcyclohexylamine and allyl alcohol.

As these vinyl compounds, 1-hexene, allylbenzene, allyl glycidyl ether, allyl phenyl ether, allyl acetate, allyl propyl ether, styrene and the like are preferable, and allyl glycidyl ether is more preferable. Of course 1,1,
1,3,5,7,7,7-octamethyltetradisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, Si- It can also be obtained by hydrosilylating a silicone compound having H to an epoxy group- and carbon-carbon double bond-containing compound using a platinum catalyst or the like.

As the silicone compound (B), 1,3
-Bis (3-glycidoxypropyl) -1,1,3,3
It goes without saying that tetramethyldisiloxane can be used. When curing the crosslinkable resin composition, a catalyst may be used, and the type of catalyst is appropriately selected according to the type of crosslinking reaction.

When the functional group of (B) is a water-decomposable silyl group or a hydroxysilyl group, examples of the catalyst include tris (acetylacetonate) aluminum, organic aluminum such as aluminum isopropoxide, dibutyltin dilaurate and dibutyl. tin dimaleate, tin 2-ethylhexanoate, dimethyltin bis (isooctyl mercaptoacetate), tin such as _{(n-C 8 H 17)} 2 Sn = S, diisopropoxy bis (ethyl acetate) titanate,
Organometallic compounds such as titanium such as diisopropoxy bis (acetylacetonate) titanate, cobalt naphthenate, iron naphthenate, lead naphthenate, zinc 2-ethylhexanoate, BF ₃ ether complex compounds,
Examples thereof include BF ₃ amine complex.

When the functional group of (B) is an epoxy group, the catalyst used in (A) is a catalyst for the crosslinking reaction because the carboxyl group in (A) is neutralized with ammonia, amine or the like. Will also be. If not particularly required, crosslinking and curing can be performed without addition of other catalysts. Of course, in addition to the above-mentioned ammonia, alkylamine, alkanolamine, the above-mentioned organometallic compound, BF ₃ ether complex compound, BF ₃ amine complex catalyst and the like, known epoxy compound curing catalysts can be used.

Specific examples include 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3.
Amines such as aminopropyltrimethoxysilane, triethylenediamine, 1,5-diazabicyclo [4,3,0] -non-5-ene, tetra-n-butylphosphonium chloride, tetra-n-butyphosphonum bromide, Phosphonium compounds such as benzyltriphenylphosphonium chloride, quaternary ammonium salts such as tetrabutylammonium acetate, triethylbenzylammonium chloride, 2-methyl-4-ethylimidazole, triphenylphosphine, tributylphosphine, trioctyl Hosfun etc. can be mentioned.

These catalysts may be used alone or in combination of two or more. The amount of catalyst added is selected from the range of 0.05 to 5% by weight based on the resin. Further, the composition of the present invention may contain a light stabilizer containing a structure of the following general formula (I).

[0043]

[Chemical 5]

The trade names of the light stabilizers having the above structures are Sanol LS-770 and Sanol L manufactured by Sankyo Co., Ltd.
S-765, SANOL LS-2626, SANOL LS-
1114, Sanol LS-744, Chimassorb 944LD manufactured by Ciba-Geigy, Adeka Stab LA-57 and Adeka Stab LA-62 manufactured by Asahi Denka Co., Ltd.
ADEKA STAB LA-67 etc. are mentioned. These are 1
You may use 1 or more types. Addition amount is 0.005 relative to resin
Is selected from the range of up to 5% by weight. The light stabilizer containing the structure of the following general formula (II) may be incorporated in the resin of (A) and incorporated therein.

[0045]

[Chemical 6]

In order to bond and incorporate in the resin of (A), for example, when the resin of (A) is an acrylic resin,
It can be obtained by coexisting and polymerizing the following monomers as the resin-polymerizing monomer (A). Specific monomers include 1,2,2,6,6-pentamethyl-
4-piperidyl (meth) acrylate, 2,2,6,6
-Tetramethyl-4-piperidyl (meth) acrylate, 4- (meth) acryloylamino-2,2,6,6
-Tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine and the like can be mentioned. The amount of the light stabilizer monomer is selected from the range of 0.005 to 5% by weight based on the total amount of the monomers.

When the carboxylic acid-containing resin (A) of the present invention is neutralized with an amine compound to prepare a carboxy group-containing resin dissolved and / or dispersed in an aqueous medium, it is prepared by a method known in the art. can do. For example, the solution obtained by polymerization is concentrated to remove the solvent, and then heated and dissolved in highly water-soluble isopropanol, isobutanol, butyl cellosolve, diethylene glycol dimethyl ether, etc., and then neutralized with an aqueous solution of an amine compound to make it aqueous. be able to. If the polymerization solvent is a highly water-soluble solvent, it can be used as it is, but it is possible to use a method of partially removing the solvent and then neutralizing it with an aqueous solution of an amine compound to make it aqueous.

When used, additives such as antioxidants and viscosity control agents, pigments, metal powders such as aluminum paste and the like may be added, if necessary. The curing temperature may be selected from the range of natural drying under atmospheric temperature to baking curing at about 200 ° C.

[0049]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples. The NMR analysis in the examples used "PMX60Si" manufactured by JEOL Ltd., and the infrared absorption spectrum (IR) used "FT / IR5300" manufactured by JASCO Corporation. The molecular weight was measured by gel permeation chromatography (GPC).

The coating film performance was evaluated according to the following method. 1) Appearance of coating film: Visual observation ○: Good Δ: Some turbidity ×: White turbidity 2) Mitsuzawa: JIS K5400-7.6 (60)
)): Specular gloss = 85% or more Δ: 61-84
X: 60 or less 3) Gel fraction: The cured coating film was immersed in acetone at 20 ° C.
Residual rate of coating film weight after standing for 24 hours (%) 4) Pencil hardness: JIS K5400-8.4.1 (Scratch evaluation) 5) Adhesion: JIS K5400-8.5.2
◯: 10 to 8 points, Δ: 6 to 4 points, ×: 2 to 0 points 6) Weather resistance: ASTM G-53 Gloss retention rate after 2500 hours exposure ◯: Gloss retention rate = 90% or more, X: Gloss retention rate = 90
% Less 7) Acid resistance: JIS K5400-8.22 8) Pot life: Time that can be used after preparing the coating solution

Example of Synthesis of Component (A) (Synthesis Example 1) 50 g of toluene and 50 g of butyl acetate were charged into a 0.5 liter 4-necked flask equipped with a thermometer, stirring blades, a cooling tube, and a nitrogen supply introduction tube. , 68 g of methyl methacrylate, n-butyl acrylate 1 in a dropping funnel
9.5 g, methacrylic acid 5 g, 2-hydroxyethyl methacrylate 7.5 g, azobisisobutyronitrile (A
IBN (abbreviated as IBN) was charged with 1.5 g of a mixed solution, and the mixture was attached to the 4-neck flask. Nitrogen was supplied into the 4-neck flask, and the inside of the reactor was sufficiently replaced with nitrogen. Start stirring and heating, 4
The mixed solution was added dropwise while maintaining the inside of the neck flask at 90 ° C.
After the completion of dropping, the mixture was stirred at 90 ° C for 5 hours.

After completion of the reaction, gas chromatographic analysis of the reaction mixture revealed that the reaction rates of methyl methacrylate, n-butyl acrylate, methacrylic acid and 2-hydroxyethyl methacrylate were all 100%. This liquid was dissolved in tetrahydrofuran, and the molecular weight of this solution was measured by gel permeation chromatography (hereinafter abbreviated as GPC method). The number average molecular weight (hereinafter abbreviated as Mn) 9800 and the weight average molecular weight (hereinafter Mw) were obtained. Abbreviated) 1
It was 9000, and the acid value in the resin was 32 mgKOH / g and the hydroxyl value was 32 mgKOH / g.

This reaction liquid was put into 5 times the amount of n-hexane to obtain a highly viscous polymer. This polymer was vacuum dried at 70 ° C. for 2 hours to completely remove the residual solvent to obtain a solid polymer. 50 g of the obtained polymer was dissolved by heating in 25 g of butyl cellosolve, and then 3.2 g of triethylamine
150 g of an aqueous solution containing was added to obtain an aqueous resin solution.

(Synthesis Example 2) 50 g of toluene and 50 g of butyl acetate were charged in the same reactor as in Synthesis Example 1, and a mixed solution having the following composition was added dropwise while stirring at 90 ° C. Then, the mixture was further stirred at 90 ° C. for 5 hours. Methyl methacrylate 70.0 g n-Butyl acrylate 20.0 g Methacrylic acid 10.0 g AIBN 1.5 g

As a result, the molecular weight of the obtained polymer was M.
n = 10600, acid value in resin 64 mgKOH /
It was g. Then, the same procedure as in Synthesis Example 1 was performed to obtain a solid polymer, 50 g of the obtained polymer was dissolved in 25 g of butyl cellosolve by heating, and then 125 g of an aqueous solution containing 5.4 g of N, N-dimethylethanolamine was added. An aqueous resin solution was obtained.

(Synthesis Example 3) 67 g of diethylene glycol dimethyl ether was charged in the same reactor as in Synthesis Example 1,
While stirring at 90 ° C., a mixed solution having the following composition was added dropwise. Then, a mixed solution of AIBN: 0.17 g and diethylene glycol dimethyl ether 3 g was added dropwise, and the mixture was further stirred at 90 ° C. for 5 hours.

Methyl methacrylate 65.0 g n-butyl acrylate 15.0 g 2-hydroxyethyl methacrylate 15.0 g Acrylic acid 5.0 AIBN 1.5 g Dodecanethiol 3.0 g

As a result, the molecular weight of the obtained polymer was M
n = 3500, acid value in resin 31 mgKOH /
and the hydroxyl value was 62 mgKOH / g. The reaction solution was concentrated under reduced pressure at 70 ° C. with an evaporator until the solid content became 70%. Thereafter, as in Synthesis Example 1, an aqueous resin solution was obtained by adding 257 g of an aqueous solution containing 7 g of triethylamine.

(Synthesis Example 4) 67 g of diethylene glycol dimethyl ether was charged in the same reactor as in Synthesis Example 1,
While stirring at 90 ° C., a mixed solution having the following composition was added dropwise. Then, a mixed solution of AIBN: 0.17 g and diethylene glycol dimethyl ether 3 g was added dropwise, and the mixture was further stirred at 90 ° C. for 5 hours.

Methyl methacrylate 40.0 g n-butyl acrylate 10.0 g 2-hydroxyethyl methacrylate 35.0 g Lauryl methacrylate 10.0 g Methacrylic acid 5.0 g AIBN 3.0 g Dodecanethiol 3.0 g

As a result, the molecular weight of the obtained polymer was M
n = 3100, acid value in resin 31 mgKOH /
and the hydroxyl value was 143 mgKOH / g. The reaction solution was concentrated under reduced pressure at 70 ° C. with an evaporator until the solid content became 70%. Thereafter, as in Synthesis Example 1, 257 g of an aqueous solution containing 1.1 g of ammonia was added to obtain an aqueous resin solution.

(Synthesis Example 5) Thermometer, stirring blade, water separator,
118 g of 1,6-hexanediol, 104 g of neopentyl glycol, 134 g of trimethylolpropane, 220 g of phthalic anhydride, and 175 g of hexahydrophthalic anhydride were placed in a 2-liter four-necked flask equipped with a cooling pipe and a nitrogen supply inlet pipe. It was heated at 160 ° C. for 2 hours. Then, while continuously supplying nitrogen, it was heated to 220 ° C. for about 8 hours to esterify until the acid value became about 10 mgKOH / g. After cooling to 120 ° C., a mixture of tetrahydrophthalic anhydride (46 g) and 4-methylhexahydrophthalic anhydride (50 g) was added, and the mixture was heated at 130 to 135 ° C.
The mixture was heated and stirred at, and reacted until the acid value reached about 55 mgKOH / g. Thereafter, 200 g of diethylene glycol dimethyl ether and 50 g of N-methylpyrrolidone were added.
Triethylamine aqueous solution was added to this solution to adjust the pH to 8-9.
Then, the solid content concentration was adjusted to about 30% to obtain an aqueous dispersion resin solution.

(Comparative Synthesis Example 1) 92.3 g of diethylene glycol dimethyl ether was charged into the same reactor as in Synthesis Example 1, and a mixed solution having the following composition was added dropwise while stirring at 90 ° C. Then, a mixed solution of AIBN: 0.17 g and diethylene glycol dimethyl ether 3 g was added dropwise, and the mixture was further stirred at 90 ° C. for 5 hours.

Methyl methacrylate 70.0 g n-butyl acrylate 20.0 g Acrylic acid 10.0 AIBN 1.5 g Dodecanethiol 3.0 g As a result, the molecular weight of the obtained polymer was Mn = 3500.
And the acid value in the resin was 65 mgKOH / g.

Comparative Synthesis Example 2 50 g of the reaction solution obtained in Comparative Synthesis Example 1 was added with 63 g of an aqueous solution containing 2.93 g triethylamine in the same manner as in Synthesis Example 1 to obtain an aqueous resin solution.

Example of Production of Component (B) [Synthesis of Intermediate Material a] 840 g of dioxane and 0.75 mol of trichlorosilane were charged and stirred in a 2-liter four-necked flask equipped with a thermometer, a stirring rotor and a cooling tube. The dropping funnel containing 33.8 g of a dioxane solution containing 20% water was added to the above 4
It was attached to a neck flask and added dropwise while maintaining at 25 to 30 ° C. After the dropping, the stirring was continued for another 2 hours, and then a dropping funnel containing 2.26 mol of methanol was attached and 20 to 3
The solution was added dropwise while keeping it at 0 ° C. After that, the mixture was further stirred for 2 hours. The reaction solution was taken out, and the solvent was completely distilled off under reduced pressure of about 50 ° C. or lower to obtain 35.8 g of a low-viscosity silicone compound. This liquid was dissolved in tetrahydrofuran and the molecular weight was measured. As a result, Mn = 350, Mw
= 410. OCH ₃ / Si by ¹ H-NMR
-H was about 1.6. In addition, by adding this silicone compound to 2N-NaOH, the generated hydrogen gas causes
When the content of Si-H was measured, it was 10.9 mmol /
g hydrogen gas was generated.

(Production Example 1) 0.28 g of isopropyl alcohol containing 8% chloroplatinic acid in a 0.5-liter four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introduction tube. , Allyl glycidyl ether 250
g, 20 g of the silicone compound obtained by the synthesis of [intermediate raw material a] was charged. Pour a small amount (about 5 ml / min) of nitrogen, stir, and monitor the temperature inside the flask at 60-7.
The temperature was raised to 0 ° C. After the temperature was maintained at 60 to 70 ° C for 15 minutes, the temperature was further raised to 80 ° C and the temperature was maintained for 1 hour. Then, the temperature was raised to 138 ° C., and the mixture was stirred for 15 hours. After the reaction was completed, the reaction solution was filtered through a 0.5 micron filter, and the solvent was distilled off under reduced pressure at 70 ° C. or lower to obtain 46 g of a product. When the molecular weight of this liquid was measured by the GPC method, it was Mn = 820 and Mw = 1250. This liquid was added to 2N-NaOH, but no hydrogen gas was generated and the reaction rate of Si-H was 100%. Further, by IR (infrared absorption spectrum), there was absorption of an epoxy group at 910 cm ^-1 . Further, this product was dissolved in propanol, added with a bromphenol blue indicator and an aqueous potassium iodide solution, and titrated with 0.5N hydrochloric acid under heating to determine the amount of epoxy. It was a value.

Synthesis of [intermediate raw material b] 1460 g of dioxane and 1.321 mol of trichlorosilane were charged into a 2-liter four-necked flask equipped with a thermometer, a stirring rotor and a cooling tube and stirred. A dropping funnel containing 118.8 g of a dioxane solution containing 20% of water was attached to the above 4-neck flask, and the mixture was added dropwise while maintaining the temperature at 25 to 30 ° C. After the dropping, the stirring was continued for another hour, and then a dropping funnel containing 3.96 mol of methanol was attached and
The solution was added dropwise while maintaining at -30 ° C. After that, the mixture was further stirred for 2 hours. When the reaction solution was taken out and the solvent was completely distilled off under reduced pressure of about 60 ° C. or less, 146.4 g of a low-viscosity silicone compound was obtained. Si-H of this silicone compound
The content of was measured to be 13.6 mmol / g.

(Production Example 2) 0.97 g of an isopropanol solution containing 8% chloroplatinic acid was added to a 2-liter four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introducing tube, and allyl. Glycidyl ether 596.5 g,
Silicone compound 5 obtained by synthesis of [intermediate raw material b]
Charge 7.29 g and react in the same manner as in Production Example 15
9.8 g of liquid product was obtained. When the molecular weight of this liquid was measured by the GPC method, it was Mn = 2200.
When this liquid was added to 2N-NaOH and the residual Si-H was measured, the reaction rate of Si-H was 94.1%.

(Production Example 3) 3-glycidoxypropyltrimethoxysilane 100 was placed in a 200 ml three-necked flask equipped with a thermometer, a stirring rotor and a condenser.
g, water 17.85 g, 1N-hydrochloric acid 1.27 g, and methanol 200 g were charged and stirred. Raise the temperature to 60 ℃, 60 ℃
And reacted for 2 hours. When the reaction solution was analyzed after the reaction was completed, the reaction rate of 3-glycidoxypropyltrimethoxysilane was 95%. Then, when the solvent was completely distilled off under reduced pressure of about 60 ° C. or lower, 88 g of a silicone compound was obtained. Molecular weight of this liquid Mn = 360, Mw = 400
And the viscosity at 30 ° C. was 75 mPas. The epoxy equivalent of this silicone compound was 226, and it was soluble in water. Further, this silicone compound was dissolved in methanol to prepare a 50% solution. It was stored at room temperature for 6 months, but no gel formation was observed.

(Production Example 4) In a 50 ml eggplant flask equipped with a thermometer, a stirring rotor and a cooling tube, 25 g of the silicone compound obtained in Production Example 3 was charged.
Heated at ° C for 2 hours. Then, when water and methanol produced under reduced pressure of about 60 ° C. or less were distilled off, 23.75 g of a silicone compound was obtained. Molecular weight of this liquid Mn =
520, Mw = 730, viscosity 191 m at 30 ° C.
It was Pas. The epoxy equivalent of this silicone compound was 229, and it was soluble in water. Further, this silicone compound was dissolved in methanol to prepare a 50% solution. It was stored at room temperature for 6 months, but no gel formation was observed.

(Production Example 5) As in Production Example 3, 100 g of 3-glycidoxypropyltrimethoxysilane and 36.
91 g, 1N-hydrochloric acid 1.27 g and methanol 200 g were charged and stirred. The reaction was carried out at 60 ° C. for 2 hours, and the reaction solution was analyzed. The reaction rate of 3-glycidoxypropyltrimethoxysilane was 100%. Then, the solvent was completely distilled off under reduced pressure below about 60 ° C., and Mn = 480 and Mw = 5.
A silicone compound having 80 and an epoxy equivalent of 210 was obtained.
It was also soluble in water. It was stored at room temperature for 6 months, but no gel formation was observed.

(Production Example 6) 0.10 g of an isopropanol solution containing 8% chloroplatinic acid was added to a 300 ml four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introducing tube, and allyl. Glycidyl ether 77.
1 g and 15.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane were charged and reacted at 100 ° C. for 3 hours. When the reaction solution was taken out and the solvent was completely distilled off under reduced pressure of about 80 ° C. or lower, 11.9 g of a low-viscosity silicone compound was obtained. When the molecular weight of this liquid was measured by the GPC method, it was Mn = 700. This liquid is 2N-
Although added to NaOH, no hydrogen gas was generated and Si-H
The reaction rate was 100%.

Synthesis of [intermediate raw material c] 240 g of isopropyl ether and pure water were placed in a 2-liter four-necked flask equipped with a thermometer, a stirring rotor, a cooling pipe capable of cooling with dry ice / ethanol, and a nitrogen supply introducing pipe. 480 g was charged and stirred. Nitrogen is supplied and the inside of the 4-neck flask is replaced with nitrogen. Methyldichlorosilane 24
A dropping funnel containing 5.6 g was attached to the four-necked flask and added dropwise over 90 minutes while maintaining the temperature at 15 to 20 ° C.
After the dropping, the reaction solution was transferred to a separating funnel and separated into an organic layer and an aqueous layer. The aqueous layer was re-extracted by adding 90 g of isopropyl ether, and the organic layer was combined with the previous organic layer and then about 300
It was washed 3 times with ml water. The organic layer obtained after separation and washing with water was 395 g. 197 g of this organic layer was charged in a simple distillation apparatus capable of reducing the pressure, and 113 g of isopropyl ether was initially distilled at normal pressure, and then distilled until a final pressure of 2 mmHg and a bottom temperature of 160 ° C. Distillate containing siloxane compound (abbreviated as intermediate raw material c) 64.7
It was 2 g and the residual amount of the kettle was 18.1 g. The distillate containing the siloxane compound was analyzed by gas chromatography.
3,5,7-tetramethylcyclotetrasiloxane is 3
7%, 1,3,5,7,9-pentamethylcyclopentasiloxane was obtained in a yield of 19%, and other cyclic siloxanes having 6 to 12 Si were obtained in a total yield of 15%.

(Production Example 7) 13 mg of an isopropanol solution containing 8% chloroplatinic acid and 62.3 g of allyl glycidyl ether were placed in a 200 ml four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube and a dropping funnel. After charging, the temperature was raised to 65 ° C. with stirring. A mixed solution of 32.33 g of the intermediate raw material c and 18.7 g of isopropyl ether was added dropwise with a dropping funnel. Then, the mixture was reacted at 80 ° C. for 1 hour. The reaction solution was taken out and the solvent was completely distilled off under reduced pressure at 80 ° C. or lower to obtain 64.5 g of a low-viscosity silicone compound. When the molecular weight of this liquid was measured by the GPC method, it was Mn = 720. This liquid is 2N-NaOH
Although it was added to the inside, the reaction rate of Si-H was 1 without generating hydrogen gas
It was 00%.

(Comparative Production Example 1) 50 g of toluene and 50 g of n-butanol were charged in a reactor similar to that used in Synthesis Example 1, and 9
While stirring at 0 ° C, a mixed solution having the following composition was added dropwise. Then, the mixture was further stirred at 90 ° C. for 5 hours. Methyl methacrylate 50.0 g n-butyl acrylate 20.0 g Glycidyl methacrylate 10.0 g 3-methacryloxypropyl-trimethoxysilane 20.0 g AIBN 1.5 g As a result, the molecular weight of the obtained polymer was Mn = 1100.
It was 0.

(Examples 1 to 10) The resin solutions obtained in Synthesis Examples 1 to 5 as the component (A) and the silicone compounds obtained in Production Examples 1 to 7 as the component (B) were used in a resin weight ratio. Component (A) / component (B) = 80/20 were mixed to obtain a composition. The results are shown in Table 1. This composition was painted using an applicator. After left at room temperature for about 1 hour, 120
The coating film performance was evaluated for the coating film obtained by heat curing at 30 ° C. for 30 minutes. The results are shown in Table 2.

(Comparative Examples 1 to 3) The compositions of Comparative Examples 1 to 3 were obtained with the formulations shown in Table 1. The coating film performance was evaluated in the same manner as in the examples. The results are shown in Table 2. In addition, in Table 1, GP
TMS is 3-glycidoxypropyltrimethoxysilane. Dilauric acid-n-dibutyltin was used as the tin catalyst, and tris (acetylacetonato) aluminum was used as the aluminum catalyst. Pure water was added to the resin solid content.

[0079]

[Table 1]

[0080]

[Table 2]

(Example 11) In order to examine the effect of the light stabilizer, the light stabilizer with and without the light stabilizer was used for a longer time than that of the first embodiment.
The weather resistance at 500 hours was checked. The coating film was prepared by the following method. The resin solution obtained in Synthesis Example 1 as the component (A) was used as a resin component in an amount of 80 parts by weight, and the silicone compound obtained in Production Example 1 as the component (B) was used as a resin component in an amount of 20 parts by weight. = A composition containing 2% by weight of N, N-dimethylbenzylamine with respect to the resin content and 0.1% by weight of light stabilizer Sanol 765 with respect to the resin content (with light stabilizer) and a composition without light stabilizer (light stability No agent) was created. After that, a solution of toluene / butyl acetate / diethylene glycol dimethyl ether = 5/5/1 weight ratio was used as a thinner and the viscosity was adjusted to 15 seconds with a Ford cup # 4, and the coating was performed at 120 ° C.
The coating performance of the coating obtained by heating and curing for 20 minutes was evaluated. As a result, the gloss retention rate at 3500 hours was the following value. With light stabilizer 98% or more Without light stabilizer 70%

[0082]

EFFECTS OF THE INVENTION A cured product using the aqueous crosslinkable resin composition of the present invention has high safety and excellent gloss and weather resistance. Also, in order to exhibit acid resistance, solvent resistance, water repellency, and stain resistance, for example, new car middle coating and top coating, automobile repair,
It is used as a high-performance water-based paint applicable to the fields of building exteriors, building materials, plastics, various metal products, etc. In addition, the storage stability is excellent by storing the component (A) and the component (B) separately.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C09D 183/04 PMU // C08G 77/14 NUB

Claims (6)

[Claims] 1. An aqueous crosslinkable resin composition comprising the following (A) and (B) as main components. (A) A carboxylic acid-containing resin having a number average molecular weight of 1,000 to 40,000 and an acid value of resin of 10 to 400 mgKOH / g was neutralized with an amine compound and dissolved and / or dispersed in an aqueous medium. Resin containing carboxyl group. (B) A silicone compound having a number average molecular weight of 200 to 8,000 and containing an average of two or more functional groups reactive with a carboxyl group in one molecule. 2. The aqueous crosslinkable resin composition according to claim 1, wherein the resin (A) is at least one selected from acrylic resins, polyester resins, and fluorine-containing resins. 3. The aqueous crosslinkable composition according to claim 1, wherein the functional group having reactivity with the carboxyl group of the silicone compound (B) is at least one selected from the following (1) to (3). Resin composition. (1) Water-decomposable silyl group. (2) Hydroxysilyl group.
(3) Epoxy group. 4. The aqueous crosslinkable resin according to claim 1, wherein the amine for neutralizing the carboxylic acid-containing resin of (A) is at least one selected from the following (4) to (6). Composition. (4) Ammonia. (5) Alkyl amine. (6) Alkanolamine. 5. The aqueous crosslinkable resin composition according to claim 1, further comprising a light stabilizer containing a structure of the following general formula (I). [Chemical 1] 6. The aqueous crosslinkable resin composition according to claim 1, wherein a light stabilizer having a structure represented by the following general formula (II) is incorporated in the resin (A) by being bonded thereto. [Chemical 2]