JPH02233751A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a composition, curable with a small amount of water and suitable as coatings, etc., excellent in low-temperature curability, etc., by polymerizing an unsaturated monomer using resultant nonaqueous dispersion of polymer particles with a metal chelating agent. CONSTITUTION:A curable composition obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent using (A) a polymer having >=2 hydroxyl groups in one molecule, (B) a polymer having >=2 epoxy groups in one molecule and (C) a polymer containing (C1) a compound expressed by formula I (A is formula II, etc.; R1 is H or methyl; R2 is 1-6C bifunctional aliphatic saturated hydrocarbon; R3 to R5 are hydroxyl group, etc.) and/or (C2) or siloxane-based macromonomer obtained by reacting the component (C1) with a compound expressed by formula III (R6 is phenyl, etc.; R7 to R9 are 1-4C aliphatic hydrocarbon, etc.) as essential components as a dispersing agent and blending the resultant nonaqueous dispersion of polymer particles insoluble in the above-mentioned organic solvent with a metal chelating compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel curable composition. Ma's ・Bisono. Conventionally, compositions in which an acid, a base, an organometallic catalyst, etc. are added to an alkoxysilane-containing vinyl polymer are known as compositions that can be crosslinked and cured at a relatively low temperature of room temperature to 1-00''C. Japanese Patent Publication No. 67553/1983 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as Mekkuri-kip-bin-trimethoxysilane. However, the above-mentioned conventional compositions , Since the silanol group produced when alkoxysilane is hydrolyzed is the only crosslinking functional group, a large amount of water is required for curing. - Therefore, a large amount of by-products such as alcohol are produced during this hydrolysis, resulting in poor physical properties of the cured product. Also, when curing with only moisture in the air, only the surface that comes into contact with the air is cured, and the inside is hardly cured, so the cured product is likely to sag due to the difference in hardening between the surface and the inside. It is an object of the present invention to provide a new curable composition which is sufficiently cured with a small amount of water. ，
The object of this invention is to provide a new curable composition 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. That is, the present invention provides: (1) a polymer having an average of two or more hydroxyl groups in one molecule (
A). Polymer (B) having an average of two or more oxirane groups in one molecule, flQ formula CII2=C-A-R2-Si-11,R, hydrogen atom or methyl group, R2 is a carbon number of 1 to 6 In the divalent aliphatic saturated hydrocarbon group, R3, R4 and Rl1 are the same or different and represent a hydroxyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, respectively. However, 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, R6 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R, .R. and R9 are 1 to 4 carbon atoms.
Indicates an aliphatic hydrocarbon group or a hydrogen atom. ) is reacted with the compound (i) represented by the general formula (I), and has an average of one polymerizable unsaturated bond and a hydroxyl group and/or alkoxy group per molecule. Using a polymer (C) having a siloxane macromonomer (C) as an essential monomer component as a dispersion stabilizer, radically polymerizable unsaturated monomers are mixed in an organic solvent in the presence of the dispersion stabilizer. A curable composition comprising a metal chelate compound (D) in a non-aqueous dispersion of polymer particles insoluble in the organic solvent obtained by polymerization; Polymers with hydroxyl groups (
A), using a polymer (E) containing an epoxy group-containing polymerizable unsaturated monomer, the compound (a) and/or the siloxane macromonomer (c) as essential monomer components as a dispersion stabilizer; The metal chelate compound (D) is contained in a non-water-reduced liquid 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 dispersion stabilizer. A curable composition characterized by: (i) a hydroxyl group-containing polymerizable unsaturated monomer; and the compound (
b) and/or the siloxane macromonomer (c)
Polymer (F) containing the monomer as an essential component. 2 in 1 molecule
A polymer insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an IJI solvent in the presence of the dispersion stabilizer using a polymer (B) having at least 3 epoxy groups as a dispersion stabilizer. A curable composition comprising a metal chelate compound (D) in a non-aqueous dispersion of polymer particles, (1) a hydroxyl group-containing polymerizable unsaturated monomer and an epoxy group-containing polymerizable unsaturated monomer; Polymers whose essential monomer components are
G), a polymer containing the compound (a) and/or the siloxane macromonomer (c) monomer as an essential component (
C) as a dispersion stabilizer, to a non-water-reduced liquid 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 dispersion stabilizer,
A curable composition containing a metal chelate compound (D), (1) the polymer (A) (B) (C) (E) (F) (G);
A polymer insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer using one or more polymers selected from among the above as a dispersion stabilizer. Polymers (A) (B) (C) are added to the nonaqueous dispersion of the combined particles.
) (E) (F) (G) A metal chelate compound (D ) A curable composition characterized by adding: (1) the polymers (A) (B) (C) (E) (F) (G);
A polymer insoluble in an organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer using one or more polymers selected from the following as a dispersion stabilizer. The present invention relates to a curable composition containing the polymer (H) and the chelate compound (D) in a non-aqueous dispersion of particles. In general formula (I). Carbon number 1 indicated by Ri
-6 divalent aliphatic saturated hydrocarbon groups include linear or branched alkylene groups such as methylene, ethylene, brobylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. R.
．． R. and R. Examples of the alkyl group having 1 to 6 carbon atoms include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isobrobyl, n-butyl, isobutyl. see-butyl, tert-butyl, n-
Examples include pentyl, inpentyl, neopentyl, n-hexyl, isohexyl, and the like. R*. R
．． The alkoxy group having 1 to 6 carbon atoms represented by
butoxy, isobutoxy, SeC-butoxy, tert
Examples include -butoxy, n-pentoxy, isopentoxy, n-hexyloxy, and isohexyloxy groups. Among the compounds of the above general formula (I), those in which A is 1C-0- include, for example, β-(meth)acryloxyethyltriethoxysilane, γ-(meth)acryloxybutyltrimethoxysilane, γ-(meth)acryloxypyltriethoxysilane, γ-(meth)acryloxypyltributoxysilane, γ-(meth)acryloxib-pylmethyldimethoxysilane, γ-(meth)acryloxib-pylmethyldiethoxysilane, γ- (meth)acryloxypylmethyldibroboxysilane, γ
- (meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxysilane, γ-(meth)acryloxybutylphenyldipoxysilane, γ-(meth)acryloxybutylphenyldimethylmethoxysilane , γ-(meth)acryloxybupyruphenylmethylethoxysilane, γ-(meth)acryloxibupylphenylmethylmethoxysilane, and γ-(meth)acryloxibupylphenylmethylethoxysilane. Among the compounds of general formula (1), examples of those in which A is include ocns. The siloxane-based macromonomer (c) has a main skeleton composed of siloxane bonds - aliphatic hydrocarbon groups, phenyl groups, hydroxyl groups, alkoxyl groups, polymerizable unsaturated bonds, etc. are attached directly or indirectly to the SL of this main skeleton. A compound (a) which is bonded to and is represented by the general formula (I) above
and a compound represented by the general formula (If) \ORs (wherein R●.Rv, R. and R. are the same as above). In the above compound (oral), R. represents an aliphatic hydrocarbon group or phenyl group having 1 to 8 carbon atoms. R,. R. and R● represent an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, Ry, R. and R- may all be the same or partially or completely different. In compound (a), the aliphatic hydrocarbon group having 1 to 4 carbon atoms includes, for example, a methyl group, an ethyl group, probyl group,
Examples include straight chain or branched ones such as butyl group, and examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include methyl group, ethyl group, proyl group, butyl group, pentyl group,
Examples include straight-chain or branched hexyl groups, hebutyl groups, octyl groups, and the like. In the above compound (mouth). As Rs, a methyl group and a phenyl group are particularly preferred. R,,R. and R are particularly preferably a methyl group, an ethyl group, a probyl group, a butyl group, or a hydrogen atom. Preferred specific examples of compound (a) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, and methyltriethoxysilane. Examples include methyltriptoxysilane, phenyltrisilanol, and methyltrisilanol. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol and the like are particularly preferably used. The compounds can be used alone or in combination. The siloxane macromonomer can be obtained by mixing the above compound (a) and the compound (a) and reacting them. The mixing ratio of both compounds is based on the total amount of both compounds, and the compound (mouth) is 70 to 99.999 mol%, preferably 90 to 99.9 mol%, more preferably 95 to 99.999 mol%.
99 mol%, compound (a) 30 to 0.001 mol%,
Preferably 10-O. 1 mol%, more preferably 5-1
It is within the range of mol%. When the amount of the compound is less than 70 mol%, it tends to gel due to the copolymerization reaction;
If the amount is more than 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 (2) 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 or wood as a solvent that can dissolve compound (a) and compound (l). Such organic solvents are preferably hydrocarbon solvents such as heptane, toluene, xylene, octane, and mineral spirits;
Ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolve acetate, butyl carbitol acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,
Ethanol, imbropanol, n-butanol, se
Alcohol solvents such as c-butanol and imptanol, ether solvents such as n-butyl ether, dioxane, ethylene glycol 1,000 methyl 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 (a) be approximately 5% or more in total. In the reaction between compound (a) and compound (i) 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. Additionally, in this reaction, a polymerization inhibitor may be added as necessary. The polymerization inhibitor is effective for preventing the unsaturated bonds contained in the compound (a) from polymerizing during the reaction with the compound (a), and specifically includes hydroquinone, hydroquinone 1000-methyl ether, etc. can be used. 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 (1). It can be added in an amount of about 20 mol% or less. In the reaction between compound (a) and compound (a), R,,
R4 and R6 are hydroxyl groups and R,,R. , R. When is a hydrogen atom, it is preferable to carry out dehydration condensation in an organic solvent with heating and stirring. In addition, when compound (a) and (or) compound (2) have an alkoxyl group bonded to St, it is preferable to hydrolyze it 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 alkoxyl 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 aiso solvent are used together, the reaction system can be made homogeneous when an alcohol that is sparingly soluble in water 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, acid catalysts include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid,
Propionic acid, acrylic acid, methacrylic acid, etc. can be used, and sodium hydroxide, triethylamine, ammonia, etc. can be used as an alkali catalyst. The amount of catalyst added is
With respect to the total amount of the above compound (a) and compound (ku), 0
．． 0001 to 5% by weight, preferably 0.01 to 0.1
A range of about % by weight is suitable. In the present invention, the siloxane macromonomer preferably has a number average molecular weight of 400 to io
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 the compound (a) and the chemical compound (i) is composed of siloxane bonds, and the structure of the main skeleton is mainly linear, ladder
der) 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 (a), the amount of water and acid catalyst, etc. Then, the siloxane-based macromonomer has the above-mentioned general formula (I) and (H) (F) on the Si of this siloxane bond.
R 3 ~R s (D which is 'CHt=C-A
-Rg-, ■ RI R-. ORy〜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 St. It has an average of 2M or more per molecule. Further, the polysiloxane 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 (II1) to (X■). (W) [In each general formula, R1 has the same meaning as above, R l
o is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R
+ + indicates a divalent hydrocarbon group of carbon fil-10. m represents 0 and an integer from 1 to 10. ] Among these epoxy group-containing polymerizable unsaturated monomers, those having the general formula (Il
From the viewpoint of curability, it is preferable to use alicyclic epoxy group-polymerizable unsaturated monomers represented by (XVII) to In the above, examples of the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms include methylene, ethylene, brobylene, tetramethylene, ethylethylene, pencumethylene,
Examples include hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 10 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 (xxn). General formula (XIX)? Rl! In the formula, R+■ represents a hydrogen atom or a hydroxyalkyl group. General formula (XX) (:Hz-0-R+z, . In the formula, RI2 has the same meaning as above. General formula (X
XI) In the formula, R+ has the same meaning as above, n represents an integer of 2 to 8, P' represents an integer of 2 to 18, and q represents an integer of 0 to 7. General formula (XX[I) CI. =CR, C − Q { C . H. O }y{ C −
H a O 'f-+ pull (X penalty) In the formula, R1 has the same meaning as above, S and T are each integers from 0 to 8, provided that the sum of S and T is 1 to 8. The "hydroxyalkyl group" in general formulas (XIX) and (XX) has ~6 C atoms. Specifically, for example, CIH40H. CSHSOH%C. H. Examples include OH. As the monomer component of the general formula (XtX), for example, CHl=CHOH CI. =CHOC. H. Examples include OH. As the monomer component of general formula (XX), for example, CHg"CICHgOH CHa"CICHxOCHiCH-OHCH*=CIC
HtO{CH*CH20}yHCHi=CHCHtO
{CHzCHi Kano RyoH etc. can be mentioned. Examples of monomer components of the general formula (X
CI1. -CH. -(:H.-CI.-Oh), etc. As the monomer component of the general formula (XXI[), for example, CHa=CCH.COO{CH-CHCHsOh-TH
CH*:CHCOO {CHzCHJh-THCH. =
CCH. COO{CH. C.I. 0}--TH, etc. Furthermore, in addition to the above, the general formulas (X IX) to (X
Adducts of hydroxyl group-containing unsaturated monomers represented by (2) and lactones such as εcabrolactone and γ-valerolactone can be used. Polymers (A) (B) (C) (E) used in the composition of the present invention
(F) In addition to the above-mentioned monomers, other polymerizable unsaturated monomers can also be used as monomer components for (F) and (G). 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 meccrylic acid, such as methyl acrylate, ethyl acrylate, probyl acrylate, isobrobyl acrylate, butyl acrylate,
Hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
Alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms such as probyl meccrylate, isobrobyl meccrylate, butyl meccrylate, hexyl methacrylate, octyl methacrylate, and lauryl meccrylate: methoxybutyl acrylate, methoxybutyl methacrylate, Acrylic acid or methacrylic acid with 2 or more carbon atoms, such as methoxyethyl acrylate, methoxyethyl meccrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate
18 alkoxyalkyl ester; C2-8 alkenyl ester of acrylic acid or methacrylic acid such as allyl acrylate and allyl meccrylate; carbon number of acrylic acid or methacrylic acid such as allyl xyethyl acrylate and allyl xymethacrylate 3-18 alkenyloxyalkyl ester. (b) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene. (C) Polyolefin compounds: for example, butadiene,
Isobrene, chlorobrene. (d) Others: acrylonitrile, methacrylic nitrile, methyl isobropenyl ketone, vinyl acetate monomer (Shell Chemicals), vinyl brobionate, vinyl biparate, etc. The monomer components of the polymer used in the present invention can be used within the following ranges. Polymer (A): About 0 hydroxyl group-containing polymerizable unsaturated monomer
1 to 60% by weight, preferably 1 to 50% by weight, Polymer (B): about 1 epoxy-containing polymerizable unsaturated monomer
~90% by weight, preferably 5~60% by weight, Polymer (C): Mt Compound (a) represented by formula (I) and/or siloxane macromonomer (c) from about 0.1 to
90% by weight, preferably 1 to 80% by weight, Polymer (E): about 1 to 90% by weight of the epoxy group-containing polymerizable unsaturated monomer, preferably 5 to 60% by weight, and the compound (
b) and/or siloxane macromonomer (c) to about 0
．． 1 to 90% by weight, preferably 1 to 80% by weight, Polymer (F): About 0.0% of the hydroxyl group-containing polymerizable unsaturated monomer.
1 to 60% by weight, preferably 1 to 50% by weight, and about 0.1 to 90% by weight, preferably 1 to 80% by weight of compound (a) and/or siloxane macromonomer (c), copolymer ( G): Approximately 0 hydroxyl group-containing polymerizable unsaturated monomer
．． 1 to 60% by weight, preferably 1 to 50% by weight, and about 1 to 90% by weight, preferably 5 to 60% by weight of an epoxy group-containing polymerizable unsaturated monomer, or a monomer component having a silanol group. If the amount is below the above range, the curability will be poor, whereas if it exceeds the above range, the physical properties of the cured product will deteriorate, and the surface of the cured coating film will be prone to wrinkles, which is not preferable. Polymers (A), (B), (C), (E) used in the present invention
). (F), CG) are respectively number average molecules jl (Mn)
A value of about 2.000 to 50.000 is 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, each monomer component is dissolved in an organic solvent, and in the presence of a radical polymerization initiator, 60 to 18
A method of heating while stirring at a temperature of about 0"C can be shown.The reaction time is usually about 1 to 10 hours.Also, as the organic solvent, alcoholic solvents similar to those mentioned above can be used. , ether solvents, ester solvents, hydrocarbon solvents, etc. can be used. When using hydrocarbon solvents, it is preferable to use other solvents together from the viewpoint of solubility. Also, as a radical initiator, , any of the commonly used ones can be used, examples of which include benzoyl peroxide, t-butylperoxy-2
- Peroxides such as ethylhexanoate, azo compounds such as azoisobutylnitrile and azobisdimethylvaleronitrile, etc. The non-aqueous dispersion of the present invention contains the polymers (A), (B) and (
C) mixture (1), mixture (2) of the polymers (A) and (E), mixture (2) of the polymers (B) and (F), mixture (2) of the polymers (C) and (F), Union (A) ~ (
C) and at least 1 fl of a polymer (or mixture) selected from one or more polymers selected from (E) to (G) as a dispersion stabilizer in the presence of the degradation stabilizer,
adding one or more radically polymerizable monomers and a polymerization initiator to an organic solvent in which the monomers and the dispersion stabilizer are dissolved but the polymer particles obtained from the monomers are not dissolved; It can be manufactured by carrying out a polymerization reaction. The types of monomers that can be used to form the polymer which becomes the particle component of the resin composition include the above-mentioned copolymers (A) to (C).
All monomers used in the production of (E) to (G) 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(
methacrylate, hydroxybutyl(meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene,
It is preferable that it contains a large amount of monomers such as α-methylstyrene and N-methylol (meth)acrylamide. Further, the particles of the resin composition can be crosslinked if necessary. Methods for crosslinking the inside of the particles include copolymerizing monomers of 2 PJ or more having complementary reactive functional groups into the particles, and copolymerizing polyfunctional monomers such as divinylbenzene and ethylene glycol dimecrylate. There is a way to do that. Examples of complementary functional groups include the combinations described in epoxy groups. Monomers that can be used include glycidyl methacrylate, (meth)
Acrylic acid, isocyanoethyl methacrylate, m-imbropenyl α. α-Dimethylpenzyl isocyanate, 2-hydroxyethyl (meth)acrylate, l
．． 4-Pukunji Saiichi Rumono (meku) acrylate, etc. can be used. The organic solvent used for the non-aqueous dispersion is one that does not substantially dissolve the dispersed polymer particles produced by the polymerization, but is a good solvent for the above-mentioned degradation stabilizer and radically polymerizable monomer. Included. Organic liquids that can be used include:
For example, aliphatic hydrocarbons such as pentane, hexane, heptane, mineral spirits, naphtha; aromatic hydrocarbons such as benzene, toluene, xylene; alcohol-based, ether-based, ester-based and ketone-based solvents such as isobrobil Alcohol, n-butyl alcohol, isobutyl alcohol, lactyl 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, Examples include acyl acetate, 2-ethylhexyl acetate, etc., and these may be used alone or in a mixture of two or more. Combinations of aromatic hydrocarbons and the above-mentioned alcohol, alcohol, ester, or ketone solvents are preferably used. Furthermore, trichlorotrifluoride ethane, mexylene hexafluoride, tetrachlorotrifluoride 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-butylbar octoate, and these polymerization initiators are generally used in an amount 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 resin, but in general, 3 parts by weight of the radically polymerizable unsaturated monomer are added to 100 parts by weight of the dispersion stabilizer. It is appropriate that the amount is about 240 parts by weight, preferably 5 to 82 parts by weight. In the present invention, by combining the degradation stabilizer resin and the polymer particles, the storage stability of the non-aqueous dispersion is improved, and a cured film with excellent transparency, smoothness, and mechanical properties is formed. can do. 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 β-ethylenically unsaturated monocarboxylic acid, but it is also possible to add monomers containing incyanate groups such as isocyanoethyl meccrylate to the hydroxyl groups that have been incorporated into the copolymer in advance. There are ways to add . Furthermore, as a method for bonding the dispersion stabilizer and the polymer particles, in addition to the method described above, monomer components forming the polymer particles may be used, such as γ-methacryloxysilane, γ-methacryloxysilane, and γ-methacryloxysilane. Brobyltriethoxysilane, γ-acryloxypyltrimethoxysilane,
Bonding can also be achieved by using reactive monomers such as γ-meccryloxybutyltriethoxysilane 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. Compounds that can constitute keto-enol tautomers include β-di●tones (acetylacetone, etc.), acetoacetate esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones with a hydroxyl group in the β position (diacetone alcohol, etc.), aldehydes with a hydroxyl group in the B position (salicylaldehyde, etc.)
, 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 R,, 0 to AI-OR r x [wherein R+s 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. be able to. As the alkyl group having 1 to 20 carbon atoms, the above-mentioned alkyl group having 1 to 20 carbon atoms
In addition to the 10 alkyl groups, examples include undecyl, dodecyl, tridecyl, tetradecyl, and tadecyl groups, and examples of alkenyl groups include vinyl and allyl groups. The aluminum alcoholates represented by the flu formula (xxm) include aluminum trimethoxide,
Aluminum triethoxide, aluminum tri-n-
aluminum tri-isoproboxoxide, aluminum tri-isoproboxoxide, aluminum tri-n-butoxide, aluminum tri-isobutoxide, aluminum tri-sec-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisobroboxoxide, aluminum tri-sec-butoxide, aluminum tree n-
It is preferable to use 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 represented by
It can be suitably prepared by mixing compounds capable of forming the above keto-enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary. Titanates expressed by the general formula (X calendar) include m
In those with 1, tetramethyl titanate, tetraethyl titanate, tetra n-probyl titanate, tetra isobyl titanate, tetra n-butyl titanate, tetra isobutyl titanate, tetra tert
-butyl titanate, tetra n-pentyl titanate, tetra n-hexyl titanate, tetraisooctyl titanate, tetra n-lauryl titanate, etc., especially tetraisobutyl titanate, tetra n-
Suitable results are obtained using butyl titanate, tetraisobutyl titanate, tetratert-butyl titanate, and the like. In addition, for those where m is 1 or more, tetraisobutyl titanate, tetra n-butyl titanate, tetra isobutyl titanate, tetra tert
-2ffi form to lit form of butyltichnate (general formula (XVI) c.=ok6m=1-10) 0
)Mo(D) gives the results.The zirconium chelate compound is, for example, the above-mentioned relative to 4 moles of Zr in the zirconates represented by the general formula [wherein m and R13 have the same meanings as above]. It can be suitably prepared by mixing compounds that can constitute a keto-enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary. Zirconate represented by the 11i1t formula (XXV) Examples include tetraethyl zirconate, tetra n-probyl zirconate, tetraisovir zirconate, tetra n-butyl zirconate, tetrasee-butyl zirconate, tetra tert-butyl zirconate, tetra n-bentyl zirconate. , Tetler te
rt-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-cutyl zirconate, tetra-n-stearyl zirconate, etc., especially tetra-isovir zirconate, tetra-n - provir zirconate,
Preferable results are obtained when using tetraisobutyl zirconate, tetra n-butyl zirconate, tetra SeC-butyl zirconate, tetra tert-butyl zirconate, and the like. Also, for those where m is 1 or more,
Tetraisobutyl zirconate, tetra n-probyl zirconate, tetra n-butyl zirconate, tetra isobutyl zirconate, tetra sec-butyl zirconate, tetra tert-butyl zirconate dimer to 11-mer (general Formula (XV[I) where m=1 to 10) 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-propylacetoacetate)aluminum, tris(isobro and ruacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, and tris(n-butylacetoacetate)aluminum. ) aluminum, imbropoxypis(ethylacetoacetate)aluminum, diisopropoxyethylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(probionylacetonato)aluminum, diisopropoxypis(ethylacetoacetate)aluminum, acetyl Aluminum chelate compounds such as acetonato bis(probionylacetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisopropoxy bis(ethylacetoacetate) titanate, diisobropoxy bis (acetylacetonato)tichunate, diisopropoxy bis(
Titanium chelate compounds such as acetylacetonato) titanate: Zirconium chelate compounds such as tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate)zirconium, etc. can be mentioned. Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or two or more types 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 that the amount is about 0.01 to 30 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 0.1-10 parts by weight. The composition of the present invention may optionally contain, for example, Epicoat l.
Epoxy group-containing resins such as O01 (manufactured by Shell Chemical); examples include hydroxyl group-containing resins such as styrene allyl alcohol copolymer. Monofunctional or polyfunctional epoxy compounds such as low molecular weight silane compounds such as cotriphenylmethoxysilane and diphenyldimethoxysilane, and other resins such as general silicone resins having alkoxysilane groups can also be added. . Among these, it is advantageous to add a compound containing two or more aliphatic oxirane groups in one molecule, since it is possible to achieve a high degree of solidification of the curable composition without deteriorating the curability. Such compounds include, for example, adducts with compounds represented by the following chemical formula (polyisocyanate compounds that can be used include aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; Cycloaliphatic diisocyanates such as phorone diisocyanate; organic diisocyanates such as tolylene diisocyanate or aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, or each of these organic diisocyanates together with polyhydric alcohols and low molecular weight polyesters. Examples of typical commercially available products include adducts with resins or water, polymers of organic diisocyanates as listed above, and isocyanate biurets. , -800, D
N-950, -970 or 15-455J [The above, Dainippon Ink and Chemicals (...products], "Desmodule L'.N" IL, IL or N3390J [West German Bayer product 1, [Kukenate D-102,
-202, -110N or -123N" [Takeda Pharmaceutical Co., Ltd. (+υ product)", "Coronate L.HL.EH or 203" [Nippon Polyurethane Kogyo (+1 product)] or "Duranate 24A-90CXJ [Asahi Kasei Co., Ltd. (empty product)], etc. ) n esterified products (e.g., tetrahydrophthalic anhydride,
Examples include those obtained by oxidizing polyester obtained by esterifying trimethylolbroban, 1,4-butanediol, etc. with peracetic acid, etc. The curable composition of the present invention may optionally include a mineral-free 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.), sulfate-based (clay, etc.), Examples include carbon-based materials (carbon black, etc.) and metal powders (aluminum powder, bronze powder, zinc powder, etc.). Further, examples of Ariiso-based materials include azo-based materials (Lake Red, Fast Yellow, etc.) and futakuchi cyanine-based materials (Phthalocyanine Pur-1, etc.). The curable composition of the present invention may contain an organic solvent if necessary. From the viewpoint of curing speed of the resin composition, as an organic solvent,
Those with a boiling point of about 150°C or lower are preferred, but are not limited to this. 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; Examples include monoter solvents, alcohol 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 is generally 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 widely applied to low bulk baking types at 100℃ and high temperature baking types from 100 to 160℃. 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 to which the curable composition of the present invention is suitably applied. Solid color, metallic color,
It can be applied in the form of clear paint, etc., using coating methods such as wet layered coating (so-called 2CIB coating) and monocoat coating. 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 painting, Mini Bell electrostatic painting, roll painting, and brush painting 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. Furthermore, 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 with the silanol group (for alkoxysilane groups, etc., it becomes a silanol group due to moisture in the air), forming \ / \ and polarizing the silanol group. This polarized silanol group reacts with the epoxy group, resulting in the following. This then reacts with the hydroxyl group to form. 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 a disappointing one. Furthermore, the curable composition of the present invention is a non-aqueous composition in which a solid phase, which is polymer particles obtained 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 dispersion 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. The present invention will be explained in more detail with reference to the following examples. Unless otherwise specified, "part" and "%" refer to weight. Synthesis of vinyl copolymer solution (A-1) A vinyl copolymer solution with the following monomer composition in a mixed solvent of xylene/butyl acetate = 80/20 using azobisisobutyronitrile (AIBN) as an initiator. (A-1) was synthesized. (Part) Styrene 1On-Butyl methacrylate 102-Ethylhexyl methacrylate 502-Hydroxyethyl methacrylate 30 The solid content concentration of the copolymer solution (A-1) is 5
00%, and the number average molecular weight of the resin was 11.000. Vinyl copolymer solution (A-2), (B-1), (B-2
), (C-1), (C-2), (E1●Synthesized in the same manner.The solvent composition of all these copolymer solutions was xylene/butyl acetate; 80/20, and the solid content concentration was The monomer composition and number average molecular weight (Mn) of each copolymer resin are shown below. Vinyl copolymer (A-2) (parts) Styrene 10n-butyl methacrylate 102-ethylhexyl Methacrylate 50 Plaxel FM-3”
152-hydroxyethyl acrylate 15M
n=9,000 0 Braxel FM-3: Adduct of 1 mole of 2-hydroxyethyl meccrylate and 3 moles of ε-cabrolactone (Gycel Chemical Industry (national product)) Vinyl copolymer (B-1) (part) Styrene 2-Ethylhexyl methacrylate n-butyl methacrylate lWn=14.000 Vinyl copolymer (B-2) l 0 Glycidyl meccrylate styrene 2-ethylhexyl methacrylate n-butyl methacrylate Mn=13.000 Vinyl copolymer (C-1) (parts) (parts) C OCH. ) Siloxane macromonomer M1''' 402-ethylhexyl methacrylate 40n-butyl meccrylate 20 Mn=21.OOO 0 Siloxane macromonomer M1 was produced as follows. The following mixture was reacted at 80°C for 5 hours. A polysiloxane-based macromonomer Ml was synthesized. (Part) Methyltrimethoxysilane 272o (20 mol) γ-methacrylate 256trimethoxysilane (1 mol) Deionized water 36% Hydroquinone hydrochloride 1 l 34 l This The 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. Vinyl copolymer (E-1) (part) M OCHs 2 -Ethylhexyl methacrylate n-butyl methacrylate Mn=12.OOO Vinyl copolymer (E-2) (part) I Siloxane macromonomer M1 2-Ethylhexyl methacrylate n-butyl methacrylate l 0 Mn=16. 000 Vinyl copolymer (F-1) Hydroxybutyl acrylate 2-hydroxyethyl acrylate (part) CHi”C-GO-0-Cl{xcH*-CJIf-S
L-OCHsOCU* 2-ethylhexyl methacrylate Mn=10. ooo Vinyl copolymer (F-2) Part C) Siloxane macromonomer M2” 302-hydroxyethyl acrylate 202-ethylhexyl meccrylate 40 styrene
10Mn=22.0000 Siloxane macromonomer M2 was produced as follows. 48 moles of phenyltrimethoxysilane and 2 moles of γ-methacryloxyethyltriethoxysilane were reacted in the same manner as in Example 1 to obtain a polysiloxane-based macromonomer M.
I got 2. Obtained polysiloxane macromonomer M
The number average molecular weight of No. 2 was about 5.000, and it had on average one vinyl group and 5 to 10 methoxy groups per molecule. Vinyl copolymer (G-1) (part) 2-hydroxyethyl methacrylate 22H 2-ethylhexyl mechacrylate In=14. ooo Vinyl copolymer (H) (part) 2-hydroxyethyl methacrylate siloxane macromonomer Ml 2On-butyl meccrylate 30Mn= 1 2.0
0.0 Vinyl copolymer (I) (part) n-butyl methacrylate 40 styrene
10Mn=lO. OOO Vinyl copolymer (A-1') Isocyanoethyl methacrylate is added to the vinyl copolymer (A-1) to form 0.3 polymerizable double bonds per molecule based on the number average molecular weight (Mn). This was made into a vinyl copolymer (A-1'). Vinyl copolymer (B-1') Adding methacrylic acid to vinyl copolymer (B-1), M
Cl per molecule based on n. 41 polymerizable double bonds were introduced. Vinyl copolymer (E-1') Adding methacrylic acid to vinyl copolymer (E-1), M
0.3 polymerizable double bonds were introduced per molecule based on n. Vinyl copolymer (F-1') Isocyanoethyl methacrylate is added to the vinyl copolymer (F-1), and 08 5 per molecule is added based on Mn.
Polymerizable double bonds were introduced. Vinyl copolymer (G-1') Meccrylic acid is added to the vinyl copolymer (G-1), and M
Based on n, 0.3 polymerizable double bonds were introduced per molecule. 40 parts of A-based vinyl copolymer solution (A-1') of No.N-1), (B-1'
), 50 parts of (C-1), and 20Q parts of ethylcyclohexane were charged into a flask, and the following particle-forming monomer components and polymerization initiator were added dropwise at reflux temperature over a period of 4 hours. - adding 0.2 part of butyl bar octoate;
After that, it was aged for 3 hours, and then concentrated under reduced pressure to form a non-aqueous dispersion (
N-1) was synthesized. (Part) Methyl methacrylate 66 styrene
10 acrylonitrile
10 glycidyl methacrylate
10 methacrylic acid
The solid content concentration of 4AIBN 1 non-water liquid (N-1) was 55%, and the Gardner viscosity (25°C) was R. N-2 to N-13
The non-aqueous dispersion (N-1) was prepared in the same manner as in the case of the A non-aqueous dispersion (N-1).
N-2) to (N-13) were synthesized. (N-2) ~ (N
-1 3) The formulation and Gardner viscosity are shown below. The solid content concentration of all non-water-resolved liquids is 55%. Non-aqueous dispersion (N-2) (parts) Dispersion stabilizer vinyl copolymer solution (A-1') 40//
(B-2) 5 0//
(C-2) Same monomer components, polymerization initiators and their usage amounts as in the case of non-aqueous dispersion (N-1) Gardner viscosity/T Non-aqueous dispersion (N-3) ) (Part) Dispersion stabilizer: Vinyl copolymer solution (A-21 66'/
(B-1') 66// (C -
2) 6 6 (parts) Particle-forming monomer. Methylmethacrylate siloxane macromonomer M1 Acrylonitrile AIBN Gardner viscosity: W Non-aqueous liquid (N-4) (parts) Dispersion stabilizer: Vinyl copolymer solution (A-1') // (E-1') Part C ) Particle-forming monomer: Methyl meccrylate 6o 2-hydroxyethyl acrylate 2oυH Acrylic acid ethylene glycol diacrylate AIBN Gardner viscosity: V Non-aqueous dispersion (N-5) (parts) Dispersion stabilizer: Vinyl copolymer solution (A-1') 40"
(E-2) 68 Particle-forming monomer: Same monomer components, polymerization initiator, and amounts used as in the case of non-aqueous dispersion (N-1) Gardner viscosity: OP Non-aqueous dispersion (N-6) ) (Part) Dispersion stabilizer: Vinyl copolymer solution (B-1') 67/l
(F-1) 67 (parts) Particle-forming monomer: Methyl meccrylate 30 l OCHs Acrylonitrile 20 2-hydroxyethyl acrylate 20 Glycidyl meccrylate 20 Gardner viscosity: Q Non-aqueous dispersion (N-7) (parts) Dispersion Stabilizer: Vinyl copolymer solution (B-1'"I 67/J
(F-2) 67 particle-forming monomer: Same monomer, polymerization initiator, and amount used as in the case of non-aqueous dispersion (N-1) Gardner viscosity: M Non-aqueous dispersion (N-8) (Part) Dispersion stabilizer: Vinyl copolymer solution (C-2) 67II
(G-1') 67 Particle-forming monomer: Same monomer, polymerization initiator, and amount used as in the case of non-aqueous dispersion (N-1) Gardner viscosity: R Non-aqueous dispersion (N-9) ) (Part) Dispersion stabilizer: Vinyl copolymer solution (A-1') 108 particle-forming monomer: Same monomer, polymerization initiator, and use thereof as in the case of non-aqueous dispersion (N-1) Amount Gardner viscosity: H Non-aqueous dispersion (N-10) (parts) Separation stabilizer: Vinyl copolymer solution (B-1') 134 Particle-forming monomer: Non-aqueous dispersion (N-1) Same monomers, polymerization initiators, and amounts used as in case Gardner viscosity 2M Non-aqueous dispersion (N-11) (parts) Dispersion stabilizer: Vinyl copolymer solution (E-2) 134 particle-forming monomers Body: Same monomers, polymerization initiators, and amounts used as in the case of non-aqueous dispersion (N-1) Gardner viscosity: H Non-aqueous dispersion (N-12) (part) Separation stabilizer: Vinyl Copolymer solution (A-1') 54/J
(B-1') 54 Particle-forming monomer: Same monomer, polymerization initiator, and amount used as in the case of non-aqueous dispersion (N-1) Gardner viscosity: S Non-aqueous dispersion (N-13) ) (Part) Dispersion stabilizer vinyl copolymer solution (C-2) 67//
(G-1') 67 particle-forming monomer. Same monomers, polymerization initiators, and amounts used as in the case of non-aqueous dispersion (N-1) Gardner viscosity/T Examples, Comparative Examples Example 1 A composition was obtained with the following formulation. (Part) Non-aqueous dispersion (N-1) 9 l Vinyl copolymer solution 100 Tris (ethyl acetoacetate) 2 Aluminum The above composition was mixed in xylene/n-butanol = 80/20 (
The viscosity was adjusted to 25 seconds using a #4 dry cup with a mixed solvent of 20% by weight (weight ratio) and used for painting. Apply cationic electrodeposition epoxy paint to a zinc phosphate-treated glue steel plate using the electrical coating 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 aminopolyester automotive paint 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 film thickness of about 50 μm, left at room temperature for 10 minutes, and then baked at 90° C. for 20 minutes. Table 1 shows the evaluation results of the coating film. In the following Examples and Comparative Examples, adjustments to materials and coating viscosity are the same as in Example 1 unless otherwise specified. Example 2 (Part) Non-aqueous dispersion (N-2) Vinyl copolymer solution (H) 9 l Toluol butylaluminum acetate Example 3 (Part) Non-aqueous dispersion (N-3) Tetrakis (acetylacetone) Zirconium Example 4 A base coat for wet-on-wet painting was created using the following formulation. Non-aqueous dispersion (N-4) Vinyl copolymer solution (I) Vinyl copolymer solution (E-2) (parts) Tol/xylol/n-butanol = 4 0/4
The viscosity was adjusted to 15 seconds (25°C) using a #4 Ford cup using a 0/20 mixed solvent. Totsubu Coat for wet painting was created using the following formulation. (Part) Non-aqueous dispersion (N-5) 91 Vinyl copolymer solution (G) 60n The solvent for adjusting the aluminum viscosity was a #4 Ford cup using a mixed solvent of Swasol 1000°/n-butanol = 80/20. for 25 seconds (25°C). (0 Swazol 1
000: Cosmo Oil (manufactured by..., aromatic solvent) The above base coat was air-sprayed onto the material to a dry film thickness of approximately 18U, and after being left at room temperature for 5 minutes, the above Totsubu coat was applied to a dry film thickness of approximately 40μ. After being left at room temperature for another 10 minutes, it was baked at 90°C for 30 minutes. Example 5 (Part) Non-aqueous dispersion (N-6) 91 Vinyl copolymer solution (G-1) 80 Titanium CR95 (manufactured by Ishihara Sangyo Co., Ltd.) Tris (ethyl acetoacetate) Aluminum (titanium white CR-95) The dispersion is made using vinyl copolymer (G-1
) was used. ) Example 6 Non-aqueous dispersion (N-7) Vinyl copolymer solution (B-1) Tris(ethyl acetoacetate) Aluminum Example 7 Non-aqueous dispersion (N-8) Vinyl copolymer solution (G- 1) Tris (ethyl acetoacetate) Aluminum titanium white CR-95 Example 8 Non-aqueous dispersion (N-9) Vinyl copolymer solution (E-2) Tris (acetylacetone) Aluminum (part) (part) (part) Example 9 Non-aqueous dispersion (N-10) Vinyl copolymer solution (F-2) Vinyl copolymer solution (H) Example 10 Non-aqueous dispersion (N-11) Vinyl copolymer solution (A- 2) Vinyl copolymer solution (H) Tetrakis (acetylacetone) Zirconium Example 11 Non-aqueous dispersion (N-12) Vinyl copolymer solution (C-2) Vinyl copolymer solution (H) Tetrakis (n-pro (Bilacetoacet) Zirconium Example 12 (Parts) Non-aqueous dispersion (N-13) Vinyl copolymer solution (H) (Parts) Comparative Example 1 (Parts) (Parts) 9l Vinyl copolymer solution (C- 1) Tris (acetylacetone) Aluminum Comparative Example 2 (Part) Vinyl copolymer solution (B-1) (Part) The evaluation results of the cured films of Examples 1 to 12 and Comparative Examples 1 to 2 are shown in Table 1. Notes in 1 (Note 1) Finished appearance was visually evaluated. (Note 2) Gasoline wiping-resistant Nisseki Shinolever gasoline was placed on gauze, and the l of the painted surface was
After rubbing the length of oCm strongly 8 times, the painted surface was observed. Items with almost no scratches or dullness on the painted surface were considered good. (Note 3) Impact resistance Test using a DuPont impact tester with a firing pin tip radius of 1/2 inch and a dropped bell weight of 500 g. 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. 0.5 cc of acid-resistant 10% 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) Weather resistance C Note 5) The gloss retention rate when irradiated for 800 hours with a Sunshine Weather-Ometer is shown.

Claims (1)

[Claims] [1] A polymer (A) having an average of two or more hydroxyl groups in one molecule, a polymer (B) having an average of two or more epoxy groups in one molecule, General formula ▲ Numerical formula , 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 or phenyl group having 1 to 8 carbon atoms, 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 general 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 polymer (C) containing a siloxane macromonomer (c) having an alkoxy group as an essential monomer component is used as a dispersion stabilizer, and a radically polymerizable unsaturated monomer is used in an organic solvent in the presence of the dispersion stabilizer. 1. A curable composition comprising a metal chelate compound (D) in a non-aqueous dispersion of polymer particles insoluble in the organic solvent obtained by polymerizing a polymer. [2] A polymer (A) having an average of two or more hydroxyl groups in one molecule, an epoxy group-containing polymerizable unsaturated monomer, the compound (A) and/or the siloxane macromonomer (
The organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer using the polymer (E) containing c) as an essential monomer component; A curable composition comprising a metal chelate compound (D) in a non-aqueous dispersion of insoluble polymer particles. [3] A polymer (F) containing a hydroxyl group-containing polymerizable unsaturated monomer and a monomer of the compound (a) and/or the siloxane macromonomer (c) as essential components, containing 2 in one molecule. A polymer insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer using a polymer (B) having 1 or more epoxy groups as a dispersion stabilizer. A curable composition comprising a metal chelate compound (D) in a non-aqueous dispersion of combined particles. [4] A polymer (G) containing a hydroxyl group-containing polymerizable unsaturated monomer and an epoxy group-containing polymerizable unsaturated monomer as essential monomer components, the compound (A) and/or the siloxane macro A polymer obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer using a polymer (C) containing the monomer (c) as an essential component. A curable composition comprising a metal chelate compound (D) in a non-aqueous dispersion of polymer particles insoluble in an organic solvent. [5] The polymer (A) (B) (C) (E) (F) (G
) is used as a dispersion stabilizer, and a radically polymerizable unsaturated monomer is polymerized in an organic solvent in the presence of the dispersion stabilizer. Polymers (A) (B) (
A metal chelate compound ( A curable composition characterized by adding D). [6] The polymer (A) (B) (C) (E) (F) (G
) is used as a dispersion stabilizer, and a radically polymerizable unsaturated monomer is polymerized in an organic solvent in the presence of the dispersion stabilizer. A curable composition comprising the polymer (H) and the chelate compound (D) in a non-aqueous dispersion of combined particles.