JPH02233750A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a composition, excellent in physical properties of cured products and curable with a small amount of water by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of a specific dispersion stabilizer resin and blending the resultant nonaqueous dispersion with a metal chelating compound. CONSTITUTION:A curable composition obtained polymerizing a radically polymerizable unsaturated monomer in the presence of (A) a dispersion stabilizer resin prepared by copolymerizing (A1) a siloxane-based macromonomer, prepared by reacting a compound expressed by formula I (A is formula II or III; R1 is H or methyl; R2 is 1-6C are OH, phenyl, etc.) and/or a compound expressed by formula IV (R6 is 1-8C aliphatic hydrocarbon group or phenyl; R7 to R9 are 1-4C aliphatic hydrocarbon group or H) with the compound expressed by formula I and having polymerizable unsaturated bonds, OH and/or alkoxy groups with (A2) an epoxy group-containing unsaturated monomer and (A3) an ON group-containing unsaturated monomer in an organic solvent and blending the resultant nonaqueous dispersion of polymer particles insoluble in the above-mentioned solvent with a metal chelating compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel curable composition. Nobinoro Temple Conventionally, compositions made by adding acids, bases, organometallic catalysts, etc. to alkoxysilane-containing vinyl polymers have been known as compositions that can be crosslinked and cured at relatively low temperatures of room temperature to 100°C. For example, JP-A No. 60-67553 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methoxysilane. However, in the conventional compositions described above, the only crosslinking functional group is the silanol group produced by hydrolysis of alkoxysilane, so a large amount of water is required for curing, and therefore a large amount of by-products such as alcohol are produced during this hydrolysis. When curing with only moisture in the air, only the surface that comes in contact with the air is cured and the inside is hardly cured, so the difference in hardening between the surface and the inside causes hardening. There were drawbacks such as the tendency for objects to become stiff. . An object of the present invention is to provide a novel curable composition that is sufficiently cured with a small amount of water.Another object of the present invention is to
The object of the present invention is to provide a new curable composition and a curing method with excellent physical properties of the cured product. Another object of the present invention is to provide a new curable composition that has a small difference in curing between the surface and the inside and does not cause sagging when cured using only moisture in the air. These and further objects of the invention will become clear from the description below. In the present invention, the general formula is a hydrogen atom or a methyl group, R2 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R, R4 and Rs are the same or different, and are a hydroxyl group, a phenyl group, a carbon number Each represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
However, any one of R,, R4 and R@ represents a hydroxyl group or an alkoxy group. ] Compound (A) represented by and/or general formula OR. (In the formula, R. is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and I'ty.Ra and R. are 1 to 8 carbon atoms.
~4 aliphatic hydrocarbon group or hydrogen atom. ) is reacted with the compound (A) represented by the general formula (1), and has an average of one polymerizable unsaturated bond per molecule and a hydroxyl group and/or alkoxy group. As a dispersion stabilizer resin, a copolymer containing a siloxane-based macromonomer (C) having a group and an epoxy group-containing polymerizable unsaturated monomer and a hydroxyl group-containing polymerizable unsaturated monomer as essential monomer components is used as a dispersion stabilizer resin. and containing a metal chelate compound in a non-aqueous dispersion of polymer particles insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the resin. A curable composition. In general formula (1), R. Carbon number 1 indicated by
Examples of the divalent aliphatic saturated hydrocarbon group of ~6 include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene groups, etc. R
The alkyl group having 1 to 6 carbon atoms represented by s% R4 and Re is a straight chain or branched alkyl group such as methyl, ethyl% n-probyl, isobrobyl, n-butyl, isobutyl, sec-butyl, tert. Examples include -butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and isohexyl groups. Ra
, R4 and Rs each having 1 to 6 carbon atoms include straight chain or branched alkoxy groups such as methoxy, ethoxy, . n-proboxy, improboxy,
n-butoxy, isobutoxy, sec-butoxy, te
rt-butoxy, n-pentoxy, isopentoxy, n
Examples include -hexyloxy, isohexyloxy, and the like. ■ Among the compounds of the above general formula (1), those in which A is -C-0- include, for example, β-(mek)acryloxyethyltriethoxysilane, γ-(mek)acryloxib-butyltrimethoxysilane, γ-(meth)acryloxybyltriethoxysilane, γ-(meth)acryloxib-pyltrib-poxysilane, γ-(meth)acryloxib-methyldimethoxysilane, γ-(meth)acryloxybylmethyldiethoxysilane, γ-(meth)acryloxib-methyldimethoxysilane (meth)acryloxib-methyldibroboxysilane, γ
-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxysilane, γ-(meth)acryloxybutylphenyldibutyboxysilane, γ-(meth)acryloxybutylphenyldimethylmethoxysilane , γ-(meth)acryloxib-bilphenylmethylethoxysilane, γ-(meth)acryloxibu-bilphenylmethylmethoxysilane, and γ-(meth)acryloxibu-bilphenylmethylethoxysilane. For example, ocus CH. Examples include OCRs. The main skeleton of the siloxane macromonomer is composed of siloxane bonds, and the Si of this main skeleton has an aliphatic hydrocarbon group,
A compound in which a phenyl group, a hydroxyl group, an alkoxyl group, a polymerizable non-candy bond, etc. are bonded directly or indirectly, and the compound (A) represented by the general formula (1) and the general formula (TI) OR ．． It is obtained by reacting the compound (B) represented by In the above compound (B), R. represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, R,, R. and R. represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom. R. , R. and R, may all be the same or may be partially or completely different. In compound (B), examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, proyl group,
Examples include straight chain or branched butyl groups, and examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include methyl group, ethyl group, proyl group, butyl group, bentyl group,
Examples include straight-chain or branched hexyl groups, hebutyl groups, and cutyl groups. In the above compound (B), R. Especially preferred are methyl group and phenyl group, R, . R. and R are particularly preferably a methyl group, an ethyl group, a proyl group, a butyl group, or a hydrogen atom. Preferred specific examples of compound (B) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, phenyltrisilanol, and methyltrisilanol.
Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol and the like are particularly preferably used. Compound (B) can be used alone or in combination. The siloxane macromonomer can be obtained by mixing the above compound (A) and compound (B) and reacting them. The mixing ratio of both compounds is such that compound (B) is 70 to 99.999 mol%, preferably 90 to 99.9 mol%, more preferably 95 to 99.999 mol%, based on the total amount of both compounds.
99 mol%, compound (A) 30 to 0.001 mol%,
Preferably 10-0.1 mol%, more preferably 5-1
It is within the range of mol%. When the amount of compound (B) is less than 70 mol%, it tends to gel in the copolymerization reaction;
If it exceeds 99 mol %, the amount of polysiloxane that does not copolymerize increases and the resin liquid becomes cloudy, which is not preferable. The reaction between compound (A) and compound (B) is carried out by dehydration condensation of the hydroxyl groups of both compounds or the hydroxyl groups produced by hydrolysis of alkoxyl groups. At this time, depending on the reaction conditions, not only dehydration condensation but also partial dealcoholization may occur. Although this reaction can be carried out without a solvent, it is preferably carried out using an organic solvent capable of dissolving compound (A) and compound (B), or water as a solvent. Such organic solvents are preferably hydrocarbon solvents such as hebukun, toluene, xylene, saikukun, mineral spirit, etc.
Ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolp acetate, butyl carbitol acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,
Ethanol, imbropanol, n-buknol, se
Alcohol solvents such as c-butanol and isoptanol, ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether can be used. These solvents can be used alone or in appropriate combinations. When used in a solution state, it is appropriate that the concentration of compound (A) and compound (B) be approximately 5% by weight or more in total. In the reaction between compound (A) and compound (B) in the present invention, the reaction temperature is usually about 20 to 180"C, preferably about 50 to 120"C. Further, it is appropriate that the reaction time is usually about 1 to 40 hours. Furthermore, in this reaction, a polymerization inhibitor may be added as necessary. Polymerization inhibitors are effective for preventing unsaturated bonds contained in compound (A) from polymerizing during the reaction with compound (B), and specifically, hydroquinone, hydroquinone monomethyl ether, etc. are used. can. In addition, in the production of this siloxane-based macromonomer, it is possible to further add tetraalkoxysilane, dialkyldialkoxysilane, etc. to the reaction system of the above compound (A) and compound (B), and It can be added in an amount of about 20 mol% or less. In the reaction between compound (A) and compound (B), R,
・R・R. When is a hydroxyl group and R,, R1, and R are hydrogen atoms, it is preferable to carry out dehydration condensation in an organic solvent with heating and stirring. Furthermore, when compound (A) and/or compound (B) have an alkoxy group bonded to Si, it is preferable to hydrolyze the compound prior to condensation.
Usually, hydrolysis and condensation reactions can be carried out continuously by heating and stirring in the presence of water and a catalyst.
The amount of water used in this case is not particularly limited, but it is preferably about 0.1 mole or more per mole of alkoxy group. If the amount is less than about 0.1 mole, the reaction of both compounds may decrease. The most preferred method is to use a large excess of water as a solvent. In addition, in this reaction, if water and a water-soluble organic solvent are used together, the reaction system can be made homogeneous when a water-soluble alcohol is produced by condensation. As the water-soluble organic solvent, the alcohol-based, ester-based, ether-based, ketone-based, and other solvents mentioned above can be preferably used. As a catalyst for this hydrolysis reaction, an acid catalyst or an alkali catalyst can be used. Specifically, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propynic acid, acrylic acid, methacrylic acid, etc. are used as an acid catalyst. Sodium hydroxide, triethylamine, ammonia, etc. can be used as an alkali catalyst. The amount of the catalyst to be added is 0.00% relative to the total amount of the compound (A) and compound (B).
A suitable range is about 0001 to 5% by weight, preferably about 0.01 to 0.1% by weight. In the present invention, the siloxane macromonomer preferably has a number average molecular weight of 400 to
o. ooo degree, more preferably 1.000 to 20.0
Use something around 00. If the number average molecular weight is less than about 400, gelation tends to occur during copolymerization;
．． If it exceeds about 000, compatibility tends to decrease, which is not preferable. In the present invention, the main skeleton of the siloxane-based macromonomer obtained by the reaction of compound (A) and compound (B) is composed of siloxane bonds, and the structure of the main skeleton is mainly linear, ladder-like, etc. ladd
er) or a mixture of these. Among these, it is preferable to use one with a ladder-like structure or a mixed system with many ladder-like parts from the viewpoint of water resistance, heat resistance, light resistance, etc. These structures can be arbitrarily selected depending on the mixing ratio of compound (A) and compound (B), the amount of water and acid catalyst, etc. and,
The siloxane-based macromonomer has Si in the siloxane bond, any one of R, -R, of the general formulas CI) and (TI), CH2=C-A-R. -, RI R6, OR, ~OR. A structure in which any of the following is bonded, and a free functional group such as a hydroxyl group and/or an alkoxyl group having 1 to 4 carbon atoms (i.e., a silanol group and/or an alkoxysilane group) bonded to Si. Each molecule has an average of 2 or more. Further, the polysiloxane-based macromonomer preferably has an average of 0.2 to 1.9 polymerizable unsaturated bonds per molecule, more preferably 0.6 to 1.4, and It is most preferable to have .9 to 1.2.
If there are too few polymerizable unsaturated bonds, the copolymerization reaction product of the macromonomer and vinyl monomer tends to become cloudy, while if there are too many polymerizable unsaturated bonds, there is a risk of gelation during the copolymerization reaction. So I don't like it. Examples of the epoxy group-containing polymerizable unsaturated monomer used in the present invention include those represented by the following general formulas (II+) to (X■). (So-called) [In each general formula, R. has the same meaning as above, and R1.

is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms;
indicates a divalent hydrocarbon group having 1 to 10 carbon atoms. m represents an integer of 0 and 1-10. ] Among these epoxy group-containing polymerizable unsaturated monomers, those of general formulas (II1) to (X■
) is preferably used from the viewpoint of curability. In the above, examples of the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene,
Examples include hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 1O carbon atoms include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, and polymethylene. Furthermore, examples of the hydroxyl group-containing polymerizable unsaturated monomer used in the present invention include compounds represented by the following general formulas (XIX) to (XXI[). General Formula (XIX) In the formula, R1 represents a hydrogen atom or a hydroxyalkyl group. General formula (XX) In the formula, RI2 has the same meaning as above. General formula (X
XI) In the formula, R1 has the same meaning as above, n is an integer of 2 to 8, P is an integer of 2 to 18, and q is. and an integer from 1 to 7. General formula (XXII) CII11ICRl C-04C. H. O}-rfC. H, Oh+l
(XX[[)■ In the formula, R. has the same meaning as above, S and T are respectively 0 and an integer of 1 to 8, provided that the sum of S and T is 1 to 8. The "hydroxyalkyl group" in general formulas (XtX) and (XX) is 01-. It is an individual thing. Specifically, for example, C. H. OH. C. H60H. C4H. Examples include OH. As the monomer component of general formula (X■), for example, CI. =CHOH CH2=CHOC4H. Examples include OH. As the monomer component of general formula (XX), for example, CI. =CICI. OH CH. =CHCH. OCH! CH. OHCHs=CHC
H! O {CHaCH20h-HCHs:CHCH*0
Examples include {CH*CHtO}yH. As the monomer component of general formula (X XI), for example (:H!=CG}I.COOC.H.OHCI.-CH
COOCsH@OH UCH. -CCH. COO-C3H Fist-0 {C-CI. −
CH. -CH. -CHa-CHs-Oh-T}I and the like. As the monomer component of general formula (xxn), for example, CH*:CCHsCOO{CH*CHCHsOh-8{
{CI. =CHCOO{CI. CI20hF1CH. =
CCH. COO{CI. CH. Examples include 0 torrTH. Furthermore, in addition to the above, formulas (XtX) to (XX[I
) and adducts of hydroxyl group-containing unsaturated monomers with lactones such as ε-cabrolactone and γ-valerolactone can be used. In addition to the monomers mentioned above, other polymerizable unsaturated monomers can also be used as monomer components in the copolymer used in the composition of the present invention. Such other polymerizable unsaturated monomers can be selected from a wide range depending on the desired performance. Representative examples of such unsaturated monomers are as follows. (a) Esters of acrylic acid or methacrylic acid, such as methyl acrylate, ethyl acrylate, probyl acrylate, isobrobyl acrylate, butyl acrylate,
Hexyl acrylate, octyl acrylate, lauryl acrylate, methyl meccrylate, ethyl methacrylate,
C1-18 alkyl esters of acrylic acid or meccrylic acid such as probyl methacrylate, isobrobyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl meccrylate, lauryl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate, Acrylic acid or meccrylic acid having 2 or more carbon atoms, such as methoxyethyl acrylate, methoxyethyl meccrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate
Alkoxyalkyl ester of 18: Alkenyl ester of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as allyl acrylate or allyl methacrylate; Alkenyl xyalkyl ester. (b) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene. (C) Polyolefin compound: For example, butadiene,
Isobrene, chlorobrene. (d) Others: acrylonitrile, methacrylic nitrile, methyl isobropenyl ketone, vinyl acetate monomer (Shell Chemical Products), vinyl brobynate, vinyl biparate, etc. In the copolymer used in the composition of the present invention,
The amount of each monomer used is approximately 0.00% of the compound (A) and/or the siloxane macromonomer (C). Ol~80 wt%, preferably about 0.1~6 omm%, epoxy group-containing polymerizable unsaturated monomer about 1~90 wt%, preferably about 3~60 mm%
% by weight, about 1 to 60% by weight of hydroxyl group-containing polymerizable unsaturated monomers, preferably about 12 to 50% by weight, and about 0 to 97% by weight of other polymerizable unsaturated monomers, preferably about 0 to 90% by weight. %. If the amount of compound (A) and/or siloxane macromonomer (C), epoxy group-containing polymerizable unsaturated monomer, or hydroxyl group-containing polymerizable unsaturated monomer is less than the above range, curability will decrease, Moreover, if the amount exceeds the above range, the physical properties of the cured product tend to deteriorate and sagging tends to occur, which is not preferable. The above-mentioned copolymer can be obtained by the same method and conditions as those for the synthesis of ordinary acrylic resins, vinyl resins, etc. As an example of such a synthesis reaction, the method of dissolving or dispersing each monomer component in an organic solvent and heating it with stirring at a temperature of about 60 to 180°C in the presence of a radical polymerization initiator is shown. Can be done. The reaction time is usually 1 to 10 hours. In addition, examples of organic solvents include alcoholic solvents, etheric solvents similar to those mentioned above,
Ester solvents, hydrocarbon solvents, etc. can be used. When using a hydrocarbon solvent, it is preferable to use other solvents together from the viewpoint of solubility. Further, as the radical initiator, any commonly used radical initiator can be used; examples thereof include peroxides such as benzoyl peroxide, t-butyl baroxy-2-ethylhexanoate,
Examples include azo compounds such as azoisobutylnitrile and azopisdimethylvaleronitrile. The above copolymer has a number average molecular fi of 2.000 to 50.0
A value of about 00 is preferable. The composition of the present invention uses the copolymer as a dispersion stabilizer, and in the presence of the dispersion stabilizer, one or more radically polymerizable monomers and a polymerization initiator are combined with the monomer and the dispersion stabilizer. is dissolved in an organic solvent, but the polymer particles obtained from the monomer are not dissolved therein, and a polymer that becomes a particle component of an avA fat composition is formed by adding it to an organic solvent and carrying out a polymerization reaction. All of the monomers mentioned above can be used. Since the polymer forming the particle component must not be dissolved in the organic solvent used, it is preferably a copolymer containing a large amount of highly polar monomer. Namely, methyl(meth)acrylate, ethyl(meth)acrylate, (meth)acrylonitrile, 2-hydroxy(meth)acrylate, hydroxybutyl(meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, ichconic acid, styrene. , vinyltoluene, a-methylstyrene, and N-methylol(mek)acrylamide. Further, the particles of the resin composition can be crosslinked if necessary. There are two methods for cross-linking the inside of the particles: one is to copolymerize two or more monomers with complementary reactive functional groups into the particles, and the other is to copolymerize into the particles a polyfunctional monomer such as divinylpenzene or ethylene glycol dimecacrylate. There is a method of copolymerization. Complementary functional groups can be a combination of epoxy group and carboxylic group. Monomers that can be used include glycidyl meccrylate, (meth)acrylic acid, isocyanoethyl meccrylate, m-isobuconvex penyl a. a'-dimethylbenzylisocyanate, 2-hydroxyethyl (meth)acrylate, 1,4-butanediolquino(meth)acrylate, etc. can be used. The organic solvent to be used includes those that do not substantially dissolve the dispersed polymer particles produced by the polymerization, but are good solvents for the dispersion stabilizer and radically polymerizable monomer. Examples of organic liquids that can be used include aliphatic hydrocarbons such as pentane, hexane, hebukun, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols, ethers, and esters. and ketone solvents, such as isobutyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methyl hexyl ketone, ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate,
2-ethylhexyl acetate, etc., and these may be used alone or in a mixture of two or more, but in general, aliphatic hydrocarbons are the main component, and aromatic hydrocarbons are added as appropriate to this. or a combination of alcohol, ether, ester, or ketone solvents such as those mentioned above are preferably used. Furthermore, trichlorotrifluoride ethane, metaxylene hexafluoride,
Tetrac, hexafluor, butane, etc. can also be used if necessary. Polymerization of the above monomers is carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2,2-azoisobutyronitrile, 2,2'-azobis(2,4-dimethylbaretonitrile); benzoyl peroxide, lauryl peroxide, etc. ,
Examples include peroxide-based initiators such as tert-butyl peroctoate, and these polymerization initiators are generally used in a range of 0.2 to 10 parts by weight per 100 parts by weight of monomers to be subjected to polymerization. Can be done. The formulation of the dispersion stabilizer to be present during the above polymerization can be selected from a wide range depending on the type of the I-removal agent, but in general, radically polymerizable unsaturated monomers are added to 100 parts by weight of the dispersion stabilizer. It is appropriate that the amount is about 3 to 240 parts by weight, preferably 5 to 82 parts by weight. In the present invention, the storage stability of the non-aqueous dispersion of the resin composition is improved by combining the degradation stabilizer resin and the polymer particles, and the transparency, smoothness, and
A cured film with excellent mechanical properties can be formed. The dispersion stabilizer and polymer particles can be bonded by polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable double bond. A method for introducing a polymerizable double bond is to add α. The most convenient method is to add a β-ethylenically unsaturated monocarboxylic acid, but it is also possible to add an incyanate group-containing monomer such as isocyanoethyl methacrylate to the hydroxyl group that has been incorporated into the copolymer in advance. There are ways to do this. Furthermore, as a method for bonding the dispersion stabilizer and the polymer particles, in addition to the above-described method, monomer components forming the polymer particles may be used, such as γ-methacryloxib-trimethoxysilane, γ-methacryloxib-methoxysilane, etc. Triethoxysilane, γ-acryloxib-based trimethoxysilane,
Bonding can also be achieved by using reactive monomers such as γ-methacryloxybutyltriethoxysilane and γ-acryloxybutyltrisilanol. The composition of the present invention is a mixture of the above copolymer and a metal chelate compound. The metal chelate compound is preferably an aluminum chelate compound, a titanium chelate compound, or a zirconium chelate compound. Among these chelate compounds, chelate compounds containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring are preferred. Examples of compounds γ that can constitute a keto-enol tautomer include β-ditons (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic esters (ethyl malonate, etc.), and Ketones with a hydroxyl group in the β-position (such as diaseptone alcohol), aldehydes with a hydroxyl group in the β-position (such as salicylaldehyde)
, esters having a hydroxyl group at the β position (methyl salicylate), etc. can be used. In particular, suitable results can be obtained by using acetoacetic acid esters and β-diketones. The aluminum chelate compound has, for example, the general formula RIIO-Af-OR+! [In the formula, Rrs are the same or different and have 1 to 2 carbon atoms
0 alkyl or alkenyl group. ] Preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of usually about 3 moles or less with respect to 1 mole of the aluminum alkoxide represented by the formula, and heating as necessary. As the alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms may be
In addition to the 10 alkyl groups, examples include undecyl, dodecyl, tridecyl, tetradecyl, octadecyl, etc., and examples of alkenyl groups include vinyl, allyl, etc. The aluminum alcoholates represented by the -lift formula (XXIII) include aluminum trimethoxide, aluminum triethoxy-aluminum tri-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, and aluminum triisobutoxide. , aluminum tri-sec-butoxide, aluminum tri-tert-butoxide, etc., and it is particularly preferable to use aluminum triisopropoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, etc. The titanium chelate compound has, for example, the general formula [where m
and R+s have the same meaning as above. ] For 1 mole of Ti in titanates,
It can be suitably prepared by mixing the compounds that can constitute the above-mentioned keto-enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary. Titanates represented by the general formula (XXIV), where m is 1, include tetramethyl titanate, tetraethyl titanate, tetra n-probyl titanate,
Tetraisobutyl titanate, Tetra-n-butyl titanate, Tetra-isobutyl titanate, Tetra-te
These include rt-butyl titanate, tetra n-pentyl titanate, tetra n-hexyl titanate, tetraisooctyl titanate, tetra n-lauryl titanate, and especially tetraisobutyl titanate, tetra n-butyl titanate, and tetra isobutyl titanate. ,
Suitable results are obtained by using tetra-tert-butyl titanate and the like. Also, for those where m is 1 or more,
Tetraisobutyl titanate, Tetra n-butyl titanate, Tetra isobutyl titanate, Tetra
A dimer to a 11-mer (m=1 to 10 in the general formula (XXff)) of rt-butyl titanate gives preferable results. The zirconium chelate compound has, for example, the general formula [wherein m and Rls have the same meanings as above. ] A compound capable of forming the above-mentioned keto enol tautomer is mixed with 1 mole of Zr in the zirconates represented by the formula at a molar ratio of usually about 4 moles or less, and is preferably heated if necessary. It can be prepared. Examples of the zirconates represented by the general formula (XXV) include tetraethyl zirconate, tetra n-probyl zirconate, tetraisobutyl zirconate, tetra n-butyl zirconate, tetra sec-butyl zirconate, and tetratert-butyl zirconate. Tetra n-pentyl zirconate, Tetra tert-
These include pentyl zirconate, tetratart-hexyl zirconate, tetra n-heptyl zirconate, tetra n-octyl zirconate, tetra n-stearyl zirconate, and in particular, tetraisobutyrzirconate, tetra n-propyl zirconate, Suitable results are obtained when using tetraisobutylzirconate, tetran-butylzirconate, tetrasec-butylzirconate, tetratert-butylzirconate, and the like. In addition, for those where m is 1 or more, tetraisobuvir zirconate, tetra n-propyl zirconate, tetra n-butyl zirconate, tetra isobutyl zirconate, tetrasee-butyl zirconate, tetra tert-butyl zirconate. dimer to 11-mer (m=1 to 1 in general formula (XXV)
0) gives suitable results. It may also contain a constituent unit in which these zirconates are associated. Particularly preferred chelate compounds in the present invention include tris(ethyl acetoacetate)aluminum, tris(n-pro and ruacetoacetate)aluminum, tris(isobro and ruacetoacetate)aluminum, and tris(n-butylacetoacetate)aluminum. acetate)aluminum, imbroboxylbis(ethyl acetoacetate)aluminum, diisobutyloxyethylacetoacetate anoleminium-tris(acetinoleacetonato)aluminum, tris(propynylacetonato)aluminum, diisopropoxypropyleneacetoacetate Aluminum chelate compounds such as natoaluminum, acetylacetonato bis(probionyl acetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisobroboxy bis(ethylacetoacetate) titanate , diisobroboxy bis(
acetylacetonato) titanate, diisopropoxy
Titanium chelate compounds such as bis(acetylacetonato) titanate: tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonato)
Zirconium, tetrakis (ethyl acetoacetate)
Examples include zirconium chelate compounds such as zirconium. Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or 2f11 or more may be used in combination as appropriate.
The amount of the crosslinking reaction curing agent is based on the solid content of the non-aqueous dispersion:
It is appropriate to set the amount to about 30 parts by weight to 00 parts by weight. If the amount is less than this range, crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable.
The preferred amount is 0.1 to 10 parts by weight. The composition of the present invention may optionally contain a vinyl copolymer or other resin having one or more functional groups selected from hydroxyl group, epoxy group, alfoxysilane group, and silanol group, such as Ebicoat 1001 (manufactured by Shell Chemical Co., Ltd.). ), etc.: For example, hydroxyl group-containing resins such as styrene allyl alcohol copolymers Mono- or polyfunctional epoxy compounds: Low molecular weight silane compounds such as triphenylmethoxysilane and diphenyldimethoxysilane, etc. It is also possible to add other resins such as general silicone resins having alkoxysilane groups. Among these, it is advantageous to add a compound containing two or more alicyclic xylan groups in one molecule, since it is possible to achieve a high solid content of the curable composition without reducing the curability. Such compounds include, for example, adducts with compounds represented by the following chemical formula (polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate: Cycloaliphatic diisocyanates such as diisocyanate or inphorone diisocyanate; organic diisocyanates such as aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or in combination with each of these organic diisocyanates; Examples of typical commercially available products include addition products with alcohols, low molecular weight polyester resins, water, etc., polymers of each organic diisocyanate as listed above, and isocyanate biuret bodies. "Parnock D-750, -800, DN
-950, -970 or 15-455J [The above are products of Dainippon Ink and Chemicals], "Desmodule L
．． NHL. IL or N3390J [West German Bayer product], "Takenate D-102.-202
, -110N or -123NJ [Takeda Pharmaceutical (!Kiku Products), "Coronate L.HL.EH or 2
03' [Nippon Polyurethane Kogyo ■ product] or [Denylanate 24A-90CXJ [Asahi Kasei Kogyo ■ product], etc.): n Esterified products (e.g., tetrahydrophthalic anhydride,
Examples include those obtained by oxidizing polyester obtained by esterifying trimethylolpropane, 1,4-butanediyl, etc. with peracetic acid, etc. The curable composition of the present invention may optionally contain an inorganic pigment,
Organic pigments etc. can be added. Inorganic pigments include oxide-based (titanium dioxide, red iron oxide, chromium oxide, etc.), sulfate-based (precipitated barium sulfate, etc.), carbonate-based (precipitated calcium carbonate-based, etc.), and sulfate-based (clay, etc.) , carbon-based (carbon black, etc.), metal powder (aluminum powder, bronze powder, zinc powder, etc.). Further, examples of tin-containing materials include azo-based products (Lake Red, Fast Ero 1, etc.) and lidocyanine-based products (Phthalocyanine Pur 1, etc.). The curable composition of the present invention may contain an organic solvent if necessary. From the viewpoint of the curing speed of the composition, the organic solvent preferably has a boiling point of about 150° C. or lower, but is not limited thereto. Preferred organic solvents include hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as dioxane and ethylene glycol diethyl ether. , alcoholic solvents such as butanol and propanol. These solvents can be used alone or in an appropriate mixture, but when using an alcoholic solvent, it is preferable to use it in combination with another solvent from the viewpoint of solubility of the resin. The concentration of the resin solvent varies depending on the purpose of use, but it may generally be about 10 to 70% by weight. In addition to the above, the above-mentioned chelating agents can be added. The curable composition of the present invention can be suitably used in paints, adhesives, inks, etc. As for paint, it ranges from room temperature drying to 60~
It can be applied to a wide range of applications, from low-temperature baking types of 100°C to high-temperature baking types of 100 to 160°C. It can be applied to all kinds of objects that are conventionally coated with paint, such as iron plates, plastic materials, and wood. Painting of automobile bodies is also an example where the curable composition of the present invention is suitably used. Solid color, metallic color,
It can be painted in the form of clear paint, etc., using a wet multi-coat method (so-called 2CIB painting), a monocoat method, and other methods. It can be used as an intermediate coating for automobile bodies, and as a top coat or undercoat for various plastic materials and metal parts used as automobile parts. When the curable composition of the present invention is used as a coating material, there are no particular limitations on the coating method, and conventional methods can be used as is. For example, methods such as air spray electrostatic air spray, airless spray, Bell electrostatic coating, Mini Bell electrostatic coating, roll coating, and Yatsuka coating can be applied. The curable composition of the present invention can be easily crosslinked and cured at a low temperature of 140°C or lower. For example, when cured at room temperature without any heating, it is usually sufficiently cured in about 8 hours to 7 days. Moreover, when heated to about 40 to 100°C, it can be sufficiently cured in about 5 minutes to 3 hours. The reason why the curable composition of the present invention has excellent low-temperature curability is thought to be as follows. That is, as the first reaction,
The metal chelate compound reacts with the silane group to form the following bond. / \ Next, this bond coordinates to the silanol group (for alkoxysilane groups, it becomes a silanol group due to moisture in the air), becoming \ and polarizing the silanol group. This polarized silanol group reacts with the epoxy group, resulting in the following. This then reacts with a hydroxyl group to form -c-o-c-c-0H. This reaction between epoxy groups and hydroxyl groups proceeds at relatively low temperatures. The curable composition of the present invention contains a hydroxyl group-containing compound as an essential component, and furthermore, since the epoxy group, silane group, and metal chelate compound are present in the composition, the above reaction proceeds rapidly, resulting in low-temperature curability. It is estimated that it will be excellent. Furthermore, the curable composition of the present invention is a non-aqueous dispersion in which a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase in which a dispersion stabilizer resin is dissolved in an organic solvent. This is a liquid containing a chelate compound. This makes it possible to significantly increase the solids content of the composition during coating, and also to increase the viscosity after coating, making it possible to form a film with an excellent finished appearance without sagging or running. Furthermore, the formed film is a photo- and chemically stable film in which the continuous phase of the film has a siloxane bond, and the polymer particle component in the film is stabilized by the continuous phase, and the film is stabilized by the particles. Because it is reinforced with ingredients, it has excellent optical and chemical properties, as well as mechanical properties such as impact resistance. 1 The present invention will be explained in more detail with reference to Examples below. Unless otherwise specified, "part" and "%" refer to weight. a-1 in a mixed solvent of xylene/butyl acetate = 125 parts/35 parts. α′-Azobisisobutyronitrile (AIBNJ
The following monomers were polymerized using as an initiator. Glycidyl methacrylate 30 parts l OCHs 2-ethylhexyl mechacrylate 35 parts styrene
10 parts 2-hydroxyethyl 15 parts meccrylate The number average molecular weight of the obtained copolymer was 13.000. The solution had a solid content of 50% and a Gardner viscosity (at 25°C) of P. Next, methacrylic acid was added to the copolymer, and 0.3 polymerizable double bonds were introduced per molecule of the copolymer, calculated based on the number average molecular weight.
This was used as a dispersion stabilizer solution. The solid content concentration of the solution was 50%. Next, 100 parts of the fractional stabilizer solution and 200 parts of ethylcyclohexane were charged into a flask, and at reflux temperature, the following monomers and polymerization initiator were added dropwise over a period of 4 hours. 1 part and then aged for 3 hours to form a non-aqueous dispersion (a-
1) was manufactured. styrene
10 parts methyl methacrylate 40 parts glycidyl methacrylate} 20 parts 2-hydroxyethyl 20 parts acrylate acrylonitrile 1 part AIBN
The solid content concentration of 1 part (a-1) was 55%, and the Gardner viscosity (25°C) was L. A dispersion stabilizer with the following monomer composition was synthesized using the same method as in step (a-1). No polymerizable double bond was added to the dispersion stabilizer. H lauryl methacrylate 20 parts 2-ethylhexyl methacrylate 20 parts 2-hydroxyethyl methacrylate 20 parts The solid content concentration of the obtained dispersion stabilizer is 50%, the Gardner viscosity (25°C) is K, and the number average molecular weight of the resin component is It was 10.100. Next, a non-aqueous dispersion (a-2) containing the following monomer mixture as a particle component was synthesized using the dispersion stabilizer in the same manner as in (a-1) above. styrene
12 parts methyl methacrylate 3
1 part acrylonitrile 15 parts 2-hydroxyethyl acrylate 15 parts (a-2) had a solid content concentration of 55% and a Gardner viscosity (at 25°C) of 1. a-3 A Non-aqueous dispersion (a-2) except that the monomers are added dropwise in the presence of a dispersion stabilizer to form particles.
A non-aqueous dispersion (a-3) was synthesized in the same manner as in the case of . Methyl methacrylate 70 parts Acrylonitrile 10 parts Ethylene glycol dimethacrylate 5 parts Glycidyl methacrylate
Solid content concentration of 15 parts non-aqueous dispersion (a-3) is 55%
, Gardner viscosity (25°C) was M. a-4
A The following mixture was reacted at 80°C for 5 hours to synthesize a polysiloxane macromonomer M1. deionized water
1134 parts 36% hydrochloric acid
2 parts hydroquinone 1
This macromonomer had a number average molecular weight of 2.000, and had an average of one polymerizable double bond and four hydroxyl groups per molecule. A mixture of 20 parts of macromonomer M1, 10 parts of styrene, 35 parts of 2-ethylhexyl methacrylate, and 15 parts of 2-hydroxyethyl acrylate was added dropwise into 100 parts of xylene at 120°C, and polymerized to obtain a transparent copolymer solution. Ta. The number average molecular weight of the obtained copolymer was 19,500,
In addition, the solution has a solid content concentration of 50% and a Gardner viscosity (2
0°C) was UV. Isocyanoethyl methacrylate is added to the copolymer, and the number average molecular weight is 1
0.3 polymerizable double bonds were introduced per molecule. Using this vinyl copolymer as a dispersion stabilizer, a non-aqueous dispersion (a-4) was synthesized as follows. 100 parts of the above vinyl copolymer solution (dispersant solution), 180 parts of ethylcyclohexane, and 20 parts of n-butanol were placed in a flask, and at reflux temperature, the following monomers and polymerization initiator were added dropwise over 4 hours. Then, 0.2 part of t-butyl percutoate was added, and the mixture was aged for 3 hours.
Thereafter, the solvent was removed under reduced pressure to produce a non-aqueous dispersion (a-4). Styrene methyl methacrylate 2-hydroxyethyl acrylate Acrylic nitrile l O parts 45 parts 10 parts 15 parts Macromonomer Ml 10 parts 2.2'
-Azopisiso 1 part The solid content concentration of the non-aqueous dispersion of butyronitrile (a-4) was 55%, and the Gardner viscosity (25°C) was T.゛ A-5 A
{48 moles of daphenyltrimethoxysilane and 2 moles of γ-meccryloxyethyltriethoxysilane were reacted in the same manner as in Example 1 to form a polysiloxane macromonomer M2.
I got it. Obtained polysiloxane macromonomer M2
The number average molecular weight of the compound was about 5.000, and each molecule contained on average one vinyl group and 5 to 10 methoxy groups. A mixture of 30 parts of macromonomer M2 and 20 parts of glycidyl methacrylate, 32 parts of lauryl methacrylate, 18 parts of 2-hydroxyethyl methacrylate, and 3 parts of t-butyl peroctoate was added dropwise into 100 parts of xylene at 120°C, and polymerized to form a copolymer. A solution was obtained. The number average molecular weight of the obtained copolymer was 15.000, the solid content concentration of the solution was 50%, and the Gardner viscosity (25°C) was S. 120 parts of upper vinyl copolymer solution (dispersant solution), 180 parts of ethylcyclohexane. 20 parts of n-buknol was placed in a flask, and at reflux temperature, the following monomers and initiator were added dropwise over 4 hours. Furthermore, 0.2 parts of t-butyl percutoate was added, and then for 3 hours. Maturing.
Thereafter, the solvent was removed under reduced pressure to produce a non-aqueous dispersion (a-5). Styrene 15 parts Methyl methacrylate 40 parts 2-hydroxyethyl acrylate 10 parts Acrylonitrile
15 parts Glycidyl mekuacrylate 10 parts Macromonomer M2 10 parts 2.2'-
The solid content concentration of the azobisiso 1 part petit nitrile non-aqueous dispersion (a-2) was 55%, and the Gardner viscosity (25°C) was P. a-6 A Same as in the synthesis example of the non-aqueous dispersion (a-4) except that the monomer composition of the dispersion stabilizer and the monomer composition forming the particles are as follows. A non-aqueous dispersion (a-6) was synthesized. Monomer composition of dispersion stabilizer Macromonomer M1 20 parts Styrene
10 parts H 2-ethylhexyl methacrylate 30 parts 2-hydroxyethyl 20 parts Composition of monomers forming acrylate particles Styrene 10 parts Methyl meccrylate 65 parts Acrylonitrile
10 parts glycidyl methacrylate
The solid content concentration of the non-aqueous dispersion (a-6) obtained in 10 parts was 55%, and the Gardner viscosity (25°C) was W. In a mixed solvent of xylene/n-buknol = 4/1 of vinyl A b-1, A
A vinyl copolymer solution (b-1) having the following monomer composition was synthesized using IBN as an initiator. Glycidyl meccrylate 30 parts O
OH Styrene 20 parts n-butyl methacrylate 20 parts (b-1'
) had a solid content concentration of 50%, a Gardner viscosity (25°C) of XY, and a number average molecular weight of the resin component of 22,000. A vinyl copolymer solution (b-2) with the following monomer composition was synthesized in the same manner as in the case of A (b・-1) of type vinyl f''b-2. Vill methacrylate 20 parts styrene
10 parts n-butyl meccrylate 10 parts 2-ethylhexyl meccrylate 20 parts (b-2) has a solid concentration of 50% and a Gardner viscosity of UV. The number average molecular weight of the resin component is 16.500
Met. A vinyl copolymer solution (b-3) having the following monomer composition was synthesized in the same manner as in the synthesis of A (b-1) of vinyl A b-3. H o CHs ocns Styrene 10 parts n-butyl meccrylate 15 parts 1.4 butanediol mono 15 parts The solid concentration of acrylate (b-3) is 50%, Gardner viscosity (2
5°C) was YZ, and the number average molecular weight of the resin component was 34,500. A vinyl copolymer solution (b-4) having the following monomer composition was synthesized in the same manner as in the synthesis of A(b-1) of one-liquid vinyl copolymer A b-4. The solid concentration of 10 parts of styrene and 20 parts of 2-ethylhexyl methacrylate (b-4) was 50%, the Gardner viscosity (25°C) was V, and the number average molecular weight of the resin component was 16.800. Molten vinyl f. A vinyl copolymer solution (b-5) having the following monomer composition was synthesized in the same manner as in the synthesis of A (b-1) of A b-5. Glycidyl meccrylate 25 parts Polysiloxane macromonomer 10 parts M2 Styrene 10 parts n-butyl methacrylate 15 parts 2-ethylhexyl methacrylate 20 parts 2-hydroxyethyl acrylate 20 parts The solid concentration of (b-5) is 50% , Gardner viscosity (25”C) is U, average number of resin fractions, average molecular weight is 1
It was 5.500. punishment vinyl f. A vinyl copolymer solution (b-, 6) having the following monomer composition was synthesized in the same manner as in the synthesis of A b-6 1 (b-4). M1 Styrene 20 parts Methyl meccrylate 20 parts (b-6) has a solid concentration of 50% and a Gardner viscosity (25°C) of X. The number average molecular weight of the lH fat component was 29.000. A vinyl copolymer solution (b-7) having the following monomer composition was synthesized in the same manner as in the synthesis of A-formation (b-1) of solution-type vinyl copolymer A b-7. 1l O QC}l. Styrene 20 parts n-butyl methacrylate 20 parts 2-hydroxyethyl
The solid content concentration of 20 parts acrylate (b-7) is 50%, and the Gardner viscosity (25
°C) is T, and the average molecular weight of the resin component is 15.000
Met. Example 1 A composition was prepared using the following formulation. Acetylacetone 5 parts The above composition was mixed with isobutyl acetate/cellosolve acetate = 1/l weight ratio thinner in a #4 dry cup for 35 seconds (20'C).
) and used for painting. Apply cationic electrodeposition epoxy paint to a zinc phosphate treated steel plate using the electrodeposition method to a dry film thickness of 20μ and bake at 170°C for 20 minutes. Next, sand the painted surface with #400 sandpaper and wipe the painted surface with gauze soaked in petroleum benzene to degrease it. Then, apply amine polyester automotive coating O4 to a dry film thickness of 30 μm and bake at 140°C for 30 minutes. The painted surface was then water sanded with #400 sandpaper, drained and dried, and the painted surface was wiped with petroleum benzene. The viscosity-adjusted composition was air-sprayed onto the material to a dry smoke film thickness of about 50 μm, left in a room for 10 minutes, and then baked at 100° C. for 20 minutes. Table 1 shows the evaluation results of the coating film.

In the following Examples and Comparative Examples, the materials and adjustments to coating viscosity are the same as in Example 1 unless otherwise specified. Example 2 A composition was prepared with the following formulation. Dispersion of titanium white was performed using vinyl copolymer (b-1). Dry film thickness 50
I painted it so that it was U and baked it at 80°C for 20 minutes. Example 3 A base coat for wet-on-wet painting was prepared using the following formulation. (Acetylacetone) Aluminum paste #4919 5 parts (Toyo Aluminum ((1) product) Aluminum paste #55-519 10 parts (Toyo Aluminum (Kawa product)) Adjust the viscosity of this with xylene at 14FC for 15 seconds (20℃) Separately, a two-component clear composition consisting of acrylic polyol/polyisocyanate was prepared for Totsubu Coat.The above base coat was air-sprayed onto the material to a dry thickness of about 18μ, and then left at room temperature. After leaving it for 5 minutes, air spray the above top coat to a dry film thickness of about 30μ.
After leaving it at room temperature for an additional 10 minutes, it was baked at 80°C for 20 minutes. Example 4 A clear composition for a wet-on-wet top coat was prepared with the following formulation. Separately, a metallic base coat consisting of acrylic polyol/cellulose acetate butyrate/polyisocyanate/aluminum paste was prepared. Air spray L to apply a base coat to the above painting material to a dry film thickness of approximately 18μ.
．． ! II for 5 minutes, the above top coat was air-sprayed to a dry film thickness of 40 μm, left at room temperature for 10 minutes, and then baked at 80° C. for 20 minutes. Alicyclic oxirane group-containing compound (*l) n Acetylacetone 5 parts The above clear paint was mixed with a thinner of Swasol-1000 (aromatic solvent manufactured by Cosmo Oil ■) and n-Buknol in a weight ratio of 80/20 in #4FC for 35 minutes. The viscosity was adjusted within seconds and used for painting. A compound having a terminal alicyclic oxirane group (number average molecular weight 650) obtained by reaction with Example 5 A composition was prepared using the following formulation. Tetrakis (acetylacetone) 0.5 parts Zirconium A composition was prepared using the following formulation. Acetylacetone 3 parts Dry film thickness 50μ
Paint it so that it looks like this. Baked at 90"Ct' for 20 minutes. Alicyclic oxirane group-containing compound (*2) cyanate 1
A composition was prepared by blending a compound having a terminal hexacycloaliphatic oxirane group (number average molecular weight 392), Example 6 Shimoki. Acetylacetone 3 parts Thoroughly dried 5 parts
It was painted to give a weight of 0g and baked at 120°C for 20 minutes to harden it. Example 8 A curable composition was prepared from the following formulation, coated with 3 parts of acetylacetone to a thickness of approximately 50 μm, and baked and cured for 20 minutes. At 80°C Example 7 5 parts of acetylacetone
The viscosity was adjusted to 35 seconds (20°C) using a Ford cup and used for painting. Air spray to a dry film thickness of approximately 50μ,
It was left at room temperature for 10 minutes and then baked at 80°C for 20 minutes. In the following examples, adjustments to coating viscosity are the same as in Example 8 unless otherwise specified. Example 9 A composition was prepared with the following formulation. Dispersion of titanium white was performed using vinyl copolymer (b-5). Example 10 A base coat for wet painting was prepared using the following formulation. 3 parts of acetylacetone The viscosity of this product was adjusted to 15 seconds (20°C) with xylene using a #4 dipstick and used for painting. A clear composition for Totsubu coat for wet-on-wet painting was prepared using the following formulation. It was coated with 5 parts of acetylacetone to a dry film thickness of about 50μ, and baked at 80°C for 20 minutes to harden it. Acetylacetone 3 parts The above clear paint was adjusted to a viscosity of 35 seconds using a #4 Ford cup with a thinner of Swasol-1000 (Cosmo Oil (aromatic solvent manufactured by Kiki) and n-butanol in an 80/20 FFI ratio) and used for painting. The base coat was air-sprayed onto the coating bag material to a dry film thickness of approximately 18μ, and after being left at room temperature for 5 minutes, the above-mentioned top coat was air-sprayed to a dry film thickness of approximately 40μ, and after being left at room temperature for 10 minutes, the temperature was 80°. Example 11 A composition was prepared using the following formulation. 5 parts of zirconium acetylacetone was coated to a dry film thickness of approximately 50 μm and baked at 90°C for 20 minutes. Example 12 The following formulation An adduct of 5 parts acetylacetone and 1 mol of ethylene diisocyanate was coated to a dry film thickness of about 50 Li and heated at 100°C for 200 ml.
Bake for a minute. Example 13 A composition was prepared using the following formulation. Non-aqueous dispersion (a-5) 91 parts (*l)
: 1 mole of adivic acid and vinyl copolymer solution (b-5) 100 parts acetylacetone 2 parts It was coated to a dry film thickness of about 50 μm and baked and cured at 120°C for 20 minutes. Comparative Example 1 A composition was prepared using the following formulation. A copolymer solution (b-8) was synthesized in exactly the same manner as in (b-2) except for the following. The solid content concentration of this product is 50%, and the Gardner viscosity is R. The number average molecular weight of the resin component was 16,000. Using this, the following composition was created. Dry film thickness approx. 50
It was painted so that it had a thickness of μ and baked at 80°C for 30 minutes to harden it. Comparative Example 2 As a solution-type vinyl copolymer solution, OCH. All iIn-butyl methacrylate was replaced with paint so that the dry film thickness was approximately 50μ, and baked at 100°C for 30 minutes. Comparative Example 3 A solution-type vinyl copolymer was produced in exactly the same manner as in (b-4) except that the entire amount of the polysiloxane macromonomer Ml in (b-4) was replaced with n-butyl methacrylate. A solution (b-9) was obtained. The solid content concentration of this product is 50%, and the Gardner viscosity (25°C) is M
The number average molecular weight of the resin component was 12,000. Using this, the following composition was created. Dry film thickness approx. 50
It was coated so that it was μ and baked at 100℃ for 20 minutes. Example 1-13. Table 1 shows the evaluation results of the cured films of Comparative Examples 1 to 3. Notes in Table 1 (Note 1) Finished appearance was evaluated visually. (Note 2) Gasoline wiping resistance Nisseki Shinolever gasoline was moistened with gauze, and a 10 cm length of the painted surface was vigorously rubbed 8 times, and then the painted surface was observed. Items with almost no scratches or dullness on the painted surface were considered good. (Note 3) Impact resistance: Using a DuPont impact tester, firing pin tip radius 1/2 inch, dropping weight 1! Test with k500g. Indicates the maximum height without cracks on the painted surface (in 5 cm increments). (Note 4) Water resistance: Immerse the test piece in a constant temperature water bath at 40°C for 240 hours. Items with no abnormalities such as glossiness or blisters on the paint film after removal were considered good. (Note 5) Acid resistance 0.5 cc of 1O% sulfuric acid was spotted on the painted surface and left at 20°C and 75% RH for 48 hours, then washed with water and the painted surface was observed. (Note 6) Indicates the gloss retention rate when irradiated for 800 hours with a weather-resistant Sunshine Weather-Ometer.

Claims (1)

[Claims] [1] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. Showing ▼. R_1 is a hydrogen atom or a methyl group, R_2 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R_3, R_4, and R_5 are the same or different and are a hydroxyl group, a phenyl group, or an alkyl group having 1 to 6 carbon atoms. group or an alkoxy group having 1 to 6 carbon atoms. However, any one of R_3, R_4 and R_5 represents a hydroxyl group or an alkoxy group. ] Compound (A) and/or general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R_6 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, R_7, R_8 and R_9 represent an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom.) The compound (B) represented by the above formula (I) is reacted with the compound (A) represented by the general formula (I), In addition, each molecule contains an average of one polymerizable unsaturated bond, a hydroxyl group, and (
or) a copolymer containing as essential monomer components a siloxane macromonomer (C) having an alkoxy group, an epoxy group-containing polymerizable unsaturated monomer, and a hydroxyl group-containing polymerizable unsaturated monomer as a dispersion stabilizer. A metal chelate compound is contained in a non-aqueous dispersion of polymer particles used as a resin and insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in the presence of the resin. Characteristic curable composition.