JPH02233703A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition sufficiently curable with a small amount of water and capable of providing a cured material excellent in physical properties by blending a nonaqueous dispersion of polymer particles prepared by a specified method and insoluble in organic solvents with a metallic chelate compound. CONSTITUTION:A compound of formula I (A is formula II or III; R1 is H or methyl; R2 is 1-6C divalent aliphatic unsaturated hydrocarbon; R3 to R5 are OH, phenol, etc., provided that one of R3 to R5 is OH, etc.) and/or a compound of formula II (R6 is 1-8C aliphatic hydrocarbon, R7 to R9 are 1-4C aliphatic hydrocarbon or H) is reacted to synthesize a polymer consisting of a siloxane- based macromonomer having a polymerizable unsaturated (polyverizable) bond, OH and/or an alkoxy in combination. A radically polymerizable monomer is then polymerized in an organic solvent in the presence of a dispersion-stabilizing resin consisting of a mixture composed of the above-mentioned polymer and a polymer containing an epoxy-containing polymerizable monomer as the essential component. In addition, a metallic chelate compound is blended with the resultant nonaqueous dispersion of the above-mentioned polymer particles insoluble in solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel curable composition. Spread out. 1) Conventionally, compositions in which acids, bases, organometallic catalysts, etc. are added to alkoxysilane-containing vinyl polymers are 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 methacrylate-trimethoxysilane.6 However, the above-mentioned conventional composition Since the silanol group produced when alkoxysilane is hydrolyzed is the only crosslinking functional group, a large amount of water is required for curing, and a large amount of by-products such as alcohol are produced during this hydrolysis, resulting in the hardening of the cured product. In addition, 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, resulting in stiffness in the cured product due to the difference in hardening between the surface and the inside. It had drawbacks such as being easy to use. F An object of the present invention is to provide a novel curable composition that can be sufficiently cured with a small amount of water. Another object of the invention is to
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, when cured with only moisture in the air, has a small difference in curing between the surface and the inside and does not cause any stiffness. These and further objects of the invention will become clear from the description below. The present invention uses a general formula hydrogen atom or methyl group, R2 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and Ra. R4 and RIl are the same or different and each represents 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. 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, R6 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and Rt.R. and R are 1 to 4 carbon atoms.
Indicates an aliphatic hydrocarbon group or a 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. A polymer (I) containing a siloxane-based macromonomer having a group as an essential monomer component;
A mixture with polymer (II) containing an epoxy group-containing polymerizable unsaturated monomer as an essential component is used as a dispersion stabilizer resin, and the radically polymerizable unsaturated monomer is polymerized in an organic solvent in the presence of the resin. The present invention relates to a curable composition characterized in that a metal chelate compound is contained in a non-aqueous dispersion of polymer particles insoluble in an organic solvent. The polymer (1) used in the composition of the present invention is a compound (A) represented by the general formula (I) and/or a reaction between the compound (A) and the compound (B) represented by the general formula (l!). These are siloxane-based macropolymers or copolymers with other polymerizable unsaturated monomers. In general formula (I), the number of carbon atoms represented by R1 is 1
Examples of the divalent aliphatic saturated hydrocarbon group of -6 include linear or branched alkylene groups such as methylene, ethylene, brobylene, tetramethylene, ethylethylene, pencumethylene, and hexamethylene groups. R.
,R. The alkyl group having 1 to 6 carbon atoms represented by R5 includes straight or branched alkyl groups such as methyl, ethyl, n-propyl, isobrobyl, n-butyl, isobutyl, sec-butyl, tert- Examples include butyl, n-bentyl, isopentyl, neopentyl, n-hexyl, and isohexyl groups. R.S. Examples of the alkoxy group having 1 to 6 carbon atoms represented by R4 and R include linear or branched alkoxy groups such as methoxy, ethoxy, n-broboxy, isobroboxy, n-ptoxy, isobutoxy, seC-ptoxy, tert- Examples include ptoxy, n-pentoxy, isopentoxy, n-hexyl, isohexyloxy, and the like. ■ Among the compounds of the above general formula (I), examples of those in which A is 10101 include B-C meta)acryloxyethyltriethoxysilane, γ-(meth)acryloxypyltrimethoxysilane, γ-(meth)acryloxib-methyltriethoxysilane, γ-(meth)acryloxib-methyltriethoxysilane, γ-(meth)acryloxib-methyldimethoxysilane, γ-(meth)acryloxib-methyldiethoxysilane, γ- (meth)acryloxypylmethyldibroboxysilane, γ
-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxysilane, γ-(meth)acryloxybutylphenyldibutyboxysilane, γ-(meth)acryloxybutylphenyldimethylmethoxy Examples include silane, γ-(meth)acryloxib-bylphenylmethylethoxysilane, γ-(meth)acryloxib-bylphenylmethylmethoxysilane, and γ-(meth)acryloxib-bylphenylmethylethoxysilane.

For example, OCHs CI. ocus etc. 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 phenyl group, a hydroxyl group, an alkoxy group, a polymerizable unsaturated bond, etc. are bonded directly or indirectly, and the compound (A) represented by the general formula (I) and the general formula (If) OR? /R. -Si-OR. (
H)\OR. (In the formula, R., R, .Ra and R. are obtained by reacting with the compound (B) represented by the same formula as above. In the above compound (B), R6 has 1 to 8 carbon atoms. Represents an aliphatic hydrocarbon group or a phenyl group. Rt, R, and R represent an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom. R7, R, and R. may all be the same or partially Or they may all be different. In compound (B), examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a probyl group,
Examples include linear or branched butyl groups, and examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include methyl groups, ethyl groups, proyl groups, butyl groups, pentyl groups,
Examples include straight-chain or branched hexyl groups, heptyl groups, octyl groups, and the like. In the above compound CB), R6 is particularly preferably a methyl group or a phenyl group. R,,R. and R. Especially preferred are methyl group, ethyl group, probyl group, butyl group, and hydrogen atom. Preferred specific examples of compound (B) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltriptoxysilane, 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%, and 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 << is 10 to O. 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, which is not preferable because the resin liquid becomes cloudy. 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 hebutane, toluene, xylene, saikukun, mineral spirits, etc.
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, inbrobanol, n-butanol, se
Alcohol solvents such as c-butanol and imptanol, 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. The polymerization inhibitor is effective for preventing unsaturated bonds contained in the compound (B.) from polymerizing during the reaction with the compound (A), and specifically, for example, hydroquinone, hydroquinone 1000-methyl ether, etc. 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 (B), and It can be added in an amount of about 20 mol% or less. In the reaction between compound (A) and compound (B), R3,
R4, R. is a hydroxyl group 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. Furthermore, when compound (A) and/or compound (B) have an alkoxy group bonded to Si, it is preferable to hydrolyze them prior to condensation (usually by heating and stirring in the presence of water and a catalyst). This allows the hydrolysis reaction and condensation reaction to be carried out sequentially.
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. Furthermore, in this reaction, if water and a water-soluble organic 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 aforementioned alcoholic myester, ether, and ketone solvents 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, bromine 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 0.001 to 5% by weight, preferably about 0.001 to 0.1% by weight. In the present invention, the siloxane macromonomer preferably has a number average molecular weight of 400 to 10.
About 0.000, 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, the compatibility tends to decrease, so it is not preferable. In the present invention, the main skeleton of the siloxane-based macromonomer obtained by the reaction between compound (A) and compound (B) is constituted by siloxane bonds, and the structure of the main skeleton is mainly linear or ladder-like. (la
dder) 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. Then, the siloxane-based macromonomer has R, ~R of the general formulas (r) and (II) at 51 of this siloxane bond.
, any one of CHz・C-A-R2-, Rc 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. The polysiloxane macromonomer preferably has an average of 0.2 to 1.9 polymerizable unsaturated bonds per molecule. It is more preferable to have 0.6 to 1.4 pieces, and most preferably 0.9 to 1.2 pieces.
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. The polymerizable unsaturated monomer that can be used as a monomer component in the polymer (I) can be selected from a wide range depending on the desired performance. Representative examples of such unsaturated monomers are as follows. (a) Two examples of esters of acrylic acid or meccrylic acid: methyl acrylate, ethyl acrylate, probyl acrylate, isobrobyl acrylate, butyl acrylate,
Hexyl acrylate, lactyl alkrylate, lauri acrylate, methyl meccrylate, ethyl methacrylate, probyl methacrylate,
Acrylic acid or methacrylic acid with 1 carbon number, such as isoprobyl methacrylate, butyl methacrylate, hexyl methacrylate, methacrylate, lauryl methacrylate, etc.
-18 alkyl ester: alkoxy of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl meccrylate, etc. Alkyl esters: Alkenyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as allyl acrylate and allyl methacrylate: Acrylic acid or methacrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyl methacrylate, hydroxyl methacrylate, etc. C2-8 hydroxyalkyl ester of acid: allyloxyethyl acrylate,
Alkenyl oxyalkyl esters having 3 to 18 carbon atoms of acrylic acid or methacrylic acid such as allyloxy methacrylate. (b) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, p-monochlorostyrene. (C) Polyolefin compound: For example, buxien,
Isobrene, chloroprene. (d) Others: Acrylic nitrile, methacrylic nitrile, methyl isobrobenyl ketone, vinyl acetate, vinyl monomer (Shell Chemical Products), vinylbrobinate, vinyl biparate, etc. The amount of compound (A) and siloxane macromonomer used in the above polymer (I) is usually about 0.02 to 100% by weight based on the monomers used, preferably <<
ranges from 0.2 to 80% by weight. Usage amount is 0.02
If it is less than % by weight, the curing properties of the cured product will decrease. The polymer (II) used in the composition of the present invention is the same polymer of an epoxy group-containing polymerizable unsaturated monomer or the same polymerizable polymerizable monomer as described above. It is a copolymer with an unsaturated monomer. Examples of the epoxy group-containing polymerizable unsaturated monomer include alicyclic epoxy group-containing polymerizable unsaturated monomers represented by the following general formulas (II1) to (xxn). (XVI) <<X■>> [In each general formula, R has the same meaning as above6. R,
．． represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms *R++ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
m represents 0 and an integer from 1 to 10 ++Rl, Rla and R. may be the same or different. ] In the Joki, the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms represented by R+o includes linear or branched alkylene groups such as methylene, ethylene, brobylene, tetramethylene, ethylethylene, pentaethylene, etc. methylene,
Examples include hexamethylene groups. Also, R1
Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by , include methylene, ethylene, brobylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, and phenyle. Further, typical examples of epoxy group-containing polymerizable unsaturated monomers other than alicyclic ones include those represented by the following general formula (X■). [In the formula, R, and R 1 (1 has the same meaning as above.] Among the above-mentioned epoxy group-containing unsaturated monomers, unsaturated monomers containing an alicyclic epoxy group are particularly preferred. In other words, when using an alicyclic epoxy group-containing polymerizable unsaturated monomer, the ring-opening polymerization reaction of the epoxy group has high reactivity, so curing is quick and easy. The effect of further improving the physical properties of the cured coating film is obtained.The amount of the epoxy group-containing polymerizable unsaturated monomer used in the above polymer (II) is usually about 3 to 100% of the monomers used.
% by weight, preferably in the range of about 20-100% by weight. If the amount used is less than about 3% by weight, the curability of the composition will decrease. The above-mentioned polymer (1) and polymer (I1) can be produced using conventional methods and conditions, and their number average molecular weights are preferably in the range of about 3.000 to 100.000. In addition, the blending ratio of polymer (I) and polymer (II) is
Based on the total amount of both, 5 to 95% by weight of polymer (1), preferably 10 to 80% by weight, and polymer (II)
in the range of 95 to 5% by weight, preferably 90 to 20% by weight. When the polymer (I) is less than 5% by weight or the polymer (II) is more than 95% by weight, the curability decreases,
On the other hand, if the content of the polymer (1) is more than 95% by weight or if the content of the polymer (If) is less than 5% by weight, the physical properties of the cured product will deteriorate and sagging will easily occur, which is not preferable. The non-aqueous dispersion used in the present invention uses a mixture of the polymers (I) and (II) as a dispersion stabilizer, and in the presence of the dispersion stabilizer, one or more radically polymerizable monomers. The polymerization initiator is dissolved in the monomer and the dispersion stabilizer, but the polymer particles obtained from the monomer are not dissolved. A non-water liquid can be produced by adding it to a Ti-containing solvent and causing a polymerization reaction. All of the above-mentioned monomers can be used to form the polymer forming the particle component of the resin composition. 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)acrylic nitrile, 2-hydroxy (meth)acrylate,
Hydroxybuvir (meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, iconic acid, styrene, vinyltoluene, α-methylstyrene, N
- It is preferable that it contains a large amount of monomer such as methylol (meth)acrylamide. Furthermore, the particles of the non-aqueous dispersion can be crosslinked if necessary. The method of crosslinking the inside of particles is to
There are two methods: one is to copolymerize more than one monomer into particles, and the other is to copolymerize polyfunctional monomers such as divinylbenzene and ethylene glycol dimethacrylate. Complementary functional groups can be a combination of epoxy group and carboxylic group. Monomers that can be used include glycidyl methacrylate, (mec)acrylic acid, isocyanoethyl mecrylate, m-isobropenyl a. α゛-Dimethylbenzyl isocyanate, 2-hydroxyethyl (meth)
Acrylate, 1,4-butanediylmono(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, hebutane, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols, esters, and esters; and ketone solvents, such as isopropyl 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 Examples include ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. Each of these may be used alone or in a mixture of two or more, but in general, aliphatic hydrocarbons It is preferable to use a combination of aromatic hydrocarbons and alcohol-based, ether-based, ester-based, or ketone-based solvents as described above. Furthermore, trichlorotrifluoride ethane, meta-xylene hexafluoride, tetrachlorotrifluoride butane, etc. can also be used if necessary. Polymerization of the above monomers is carried out using a radical polymerization initiator. Examples of usable radical polymerization initiators include 2,2-azoisobutyronitrile. 2.2'-azobis (2.4-dimethylbaret nitrile and other azo initiators: benzoyl peroxide, lauryl peroxide.
Examples include peroxide-based initiators such as tert-butyl peroctoate, and these polymerization initiators are generally used within 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 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 dispersion stabilizer resin and the polymer particles, the storage stability of the non-aqueous dispersion of the resin composition is improved, and transparency and smoothness are improved.
A cured film with excellent mechanical properties can be formed.
As a method for binding the dispersion stabilizer and polymer particles,
This can be achieved 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. Adding β-ethylenically unsaturated monocarboxylic acid is convenient, but other methods include adding isocyanate group-containing monomers such as isocyanoethyl methacrylate to hydroxyl groups that have been incorporated into the polymer in advance. There is. Furthermore, as a method for bonding the dispersion stabilizer and the polymer particles, in addition to the above-mentioned method, as a monomer component forming the polymer particles, for example, γ-methacrylate xib-trimethoxysilane, γ-methacrylate xib, etc. Trimethoxysilane, γ-acrylic trimethoxysilane,
Bonding can also be achieved by using reactive monomers such as γ-meccryloxybutyltriethoxysilane and γ-acryloxybutyltriethoxysilane. The composition of the present invention is a composition in which a metal chelate compound is blended into the above-mentioned non-aqueous dispersion. 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-ditons (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid 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. Are aluminum chelate compounds common? l20-
AI-ORl* [wherein R1 is the same or different and has 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 1- to 20-carbon atoms
In addition to the 10 alkyl groups, examples include undecyl, dodecyl, tridecyl, tetradecyl, octadecyl, etc., and examples of alkenyl groups include vinyl, allyl, etc. Examples of the aluminum alcoholates represented by the general formula (XIX) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-proboxide, aluminum tri-isobroboxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-s -butoxide,
There are aluminum tri-tert-butoxide, etc.
In particular, it is preferable to use aluminum triisobroboxide, aluminum tri-sec-butoxide, aluminum tri-n-butoxide, and the like. For example, the titanium chelate compound has the general formula [where m
and R1. has the same meaning as above. ] For 1 mole of Ti in titanates represented by
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. -e Titanates represented by formula (XX) include m
In those with 1, tetramethyl titanate, tetraethyl titanate, tetra n-probyl titanate, tetraisobutyl titanate, tetra n-butyl titanate, tetra isoptyl 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 butyltichnate, tetraisobutyltitanate, tetratert-butyltitanate, and the like. In addition, for those where m is 1 or more, the dimer to 1l-mer of tetraisobutyl titanate, tetra-n-butyltichnate, tetra-tert-butyl titanate, and tetra-tert-butyl titanate (m= 1 to 10) give suitable results. The zirconium chelate compound has, for example, the general formula [wherein m and Rl1 have the same meanings as above]. ] A compound capable of forming the above-mentioned keto-enol tautomer is mixed with 1 mol of Zr in the zirconates represented by the formula at a molar ratio of usually about 4 mol or less, and is preferably heated if necessary. It can be prepared. Examples of the zirconates represented by the -M formula (X butyl zirconate, tetra n-bentyl zirconate, tetra te
Examples include rt-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-cutyl zirconate, tetra-n-stearyl zirconate, and especially tetra-isoprobilurconate, tetra-n-pro Bilzirconate,
Preferred results are obtained when using tetraisobutylzirconate, tetran-butylzirconate, tetrasee-butylzirconate, tetratert-butylzirconate, 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 monomer (general formula (XXf) where m=1 to 10) gives suitable results. Also,
It may also contain a constituent unit in which these zirconates are associated. Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-pro-and-ruacetoacetate)aluminum, tris(isobrobylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, and tris(n-butylacetoacetate)aluminum. ) Aluminum, imbroboxybis(ethyl acetoacetate)aluminum, diisobutoxyethylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(propoxynylacetonato)aluminum, diisobutoxypoxybenylacetonatoaluminum, acetylacetonate Aluminum chelate compounds such as nato-bis(probionylacetonato)aluminum, monoethylacetoacetatebis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisobroboxy-bis(ethylacetoacetatetone titanate, diisobroboxy-bis( acetylacetonato) titanate, diisopropoxy bis(
Titanium chelate compounds such as acetylacetonato) titanate: Zirconium chelates such as tetrakis(acetylacetonato)zirconium, tetrakis(n-pro and ruacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate)zirconium, etc. I can list some special features. 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 100% of the solid content of the non-aqueous dispersion.
It is appropriate that the amount is about 0.01 to 30 parts by weight. If it is less than this range, the 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, and the more preferred amount is 1 to 5 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 a hydroxyl group, an epoxy group, an alkoxysilane group, and a silanol group. ) and other epoxy group-containing resins: e.g. Hydroxyl group-containing resins such as styrene allyl alcohol copolymers; monofunctional or polyfunctional epoxy compounds: low molecular weight silane compounds such as triphenylmethoxysilane and diphenyldimethoxysilane, and general silicones with alkoxysilane groups. It is also possible to add other resins such as resin. Among these, it is advantageous to add a compound containing two or more alicyclic group 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 formulas (polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; xylylene diisocyanate) or cycloaliphatic diisocyanates such as isophorone diisocyanate; organic diisocyanates themselves such as tolylene diisocyanate or aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, or each of these organic diisocyanates, polyhydric alcohols, and low molecular weight polyester resins. or adducts with water, etc., polymers of each organic diisocyanate as described above or above, and isocyanate biuret bodies, etc. Typical commercial products of these include "Parnock D-750". , -800.DN-950, -97
0 or l5-455J [The above are products of Dainippon Ink & Chemicals], "Desmodule L.NHL.IL or N3390J [Products of Bayer, West Germany]
, "Takenate D-102.-202, -110N or -123NJ [Takeda Pharmaceutical Co., Ltd. (...product)], "Coronate L.HL.EH or 203" [Nippon Polyurethane Industries ■ product] or "Duranate 24A-90
CXJ [Asahi Kasei Kogyo Product Co., Ltd.]: N esterified products (for example, polyester obtained by esterifying tetrahydrophthalic anhydride, trimethylolpropane, 1,4-phthalic anhydride, etc.) with peracetic acid. 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.), sulfate-based (clay, etc.), Examples include carbon-based powders (carbon black, etc.) and metal powders (aluminum powder, bronze powder, zinc powder, etc.). Examples of organic pigments include azo-based pigments (lake red, fast yellow, etc.) and phthalocyanine-based pigments (phthalocyanine puri-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, for example, 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 ethers such as dioxane and ethylene glycol diethyl ether. Examples include alcohol-based 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 tl fat solvent varies depending on the purpose of use, but generally it may 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. A wide range of paints can be used, ranging from those that dry at room temperature, to those that are baked at low temperatures of 60 to 100°C, and those that are baked to high temperatures of 100 to 160 degrees Celsius. 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 wet-on-wet layered coatings (so-called 2CIB coatings), monocoat coatings, and other coating 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, minibell 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 it is 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 is easily crosslinked and cured at low temperatures in the presence of a small amount of water is considered to be as follows, taking the case of using a zirconium chelate compound as an example. That is, as the first reaction, the alkoxy groups in the polymer (1) are hydrolyzed in the presence of moisture using a zirconium chelate compound as a catalyst to generate silanol groups. Next, as a second reaction, the silanol groups are crosslinked by dehydration condensation and reacted with a zirconium chelate compound to coordinate to another silanol group to polarize the silanol group, and this polarized silanol group forms a polymer (II ) Crosslinking occurs by ring-opening polymerization of the epoxy groups in ). In comparison with the conventional case, in the conventional curable composition of this kind, crosslinking and curing was performed only in the second reaction, whereas in the curable composition of the present invention, especially the polymer (11)
By using , the second-stage reaction and third-stage reaction occur in parallel in a chain, resulting in crosslinking and curing.
It is thought that it can be cured suitably at low temperatures with a small amount of moisture. 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.
Furthermore, since the first to third stage chain reactions in a non-aqueous dispersion system are carried out in a continuous phase, curing can be achieved with even smaller amounts of water. The present invention will be explained in more detail with reference to Examples below. "
Unless otherwise specified, "parts" and "%" are based on weight. Synthesis example of non-aqueous dispersion (a-1) α,α'-azobisisobutyronitrile (AIBN) in a mixed solvent of xylene/butyl acetate = 125 parts/35 parts
A copolymer (
A) was synthesized. (Part) CH-=C-C-0-CHaCH--C}I--Si-
OCH-20OCR. Styrene 102-ethylhexyl methacrylate 40n-butyl methacrylate 30 The number average molecular weight (Mn) of the obtained copolymer (A) is 11
, 000, and the solution had a solids content of 50% and a Gardner viscosity (at 25° C.) of H.

Copolymer (B) was synthesized using the following monomers in the same manner as for copolymer (A). (Part) Glycidyl methacrylate 602-Ethylhexyl meccrylate 30 Styrene
10 The Mn of the obtained copolymer (B) was 10.500, the solid content concentration of the solution was 50%, and the Gardner viscosity (25°C) was E. Next, methacrylic acid was added to the copolymer to introduce 0.3 polymerizable double bonds per molecule of the copolymer, calculated based on Mn, and the copolymer (
B'). Next, 50 parts each of copolymer solutions (A) to (B') and 200 parts of ethylcyclohexane were charged into a flask, and the following monomers and polymerization initiator were added dropwise at reflux temperature over a period of 4 hours.
Further, 0.2 part of t-butylbar octoate was added, and the mixture was aged for 3 hours and then concentrated under reduced pressure to obtain a non-aqueous dispersion (a-
1) was manufactured. Styrene methyl methacrylate glycidyl methacrylate 2-hydroxyethyl aquacrylonitrile (parts) Nolate 20 Methacrylic acid 2AIBN
The solid content concentration of 1(a-1) was 55%, and the Gardner viscosity (25°C) was I. Synthesis Example of Non-Aqueous Dispersion (a-2) A copolymer (C) was synthesized using the following monomers in the same manner as the copolymer (A). (Department) CH. CH. ”C-C-C}I*CH*CH.-Si-OCH
3 1 5 books OCHz 2-ethylhexyl meccrylate 60 styrene
lOobtained copolymer (C
) had a Mn of 16.000, a solids concentration of 50%, and a Gardner viscosity of P. Copolymer (D) was synthesized using the following monomers in the same manner as copolymer (A). (Part) 2-ethylhexyl methacrylate 40 styrene
Mn of the 10 copolymer (D) is 1
2.500, the solid content concentration of the solution was 50%, and the Gardner viscosity was Q. Adding methacrylic acid to copolymer (D). ? Calculated based on Wn, 0.6 polymerizable double bonds were introduced per molecule of the copolymer to obtain a copolymer (D'). Using 40 parts of the copolymer solution (C) and 40 parts of the copolymer solution (D'), the monomers are added dropwise in the presence of a dispersion stabilizer to form particles.The composition of the monomers is as follows. The non-aqueous dispersion (a-2) was prepared in the same manner as the non-aqueous dispersion (a-1) except that
) was synthesized. (Parts) Methyl methacrylate 70 Acrylonitrile 1O Ethylene glycol dimethacrylate 5 Glycidyl methacrylate} 15 The solid content concentration of the non-aqueous dispersion (a-2) was 55%, and the Gardner viscosity (25°C) was T. Example of synthesis of non-aqueous dispersion (a-3) The mixture of the following was reacted at 80°C for 5 hours to synthesize a polysiloxane macromonomer Ml. (Part) Methyltrimethoxysilane 2720 (20 mol) Deionized water 113436% Hydrochloric acid 2 Hydroquinone
1 This macromonomer had a number average molecular weight of 2.000 and an average of one polymerizable double bond and four hydroxyl groups per molecule. (Part) Macromonomer Ml 40 Styrene 102-ethylhexyl methacrylate 40n-butyl methacrylate
10 using AIBN as a polymerization initiator,
Xylene/n-butanol = 11 in 7 0/3 0
Polymerization was performed at 0°C to obtain copolymer (E). Copolymer (E) had an Mn of 18.000, a solids concentration of 50%, and a Gardner viscosity of S. Copolymer (F) was synthesized using the following monomers in the same manner as in the synthesis of copolymer (E). (Part) The Mn of the lauryl methacrylate styrene copolymer (F) was 17.000, the solid content concentration of the solution was 50%, and the Gardner viscosity was U. Next, acrylic acid is added to the copolymer (F) to introduce 0.8 polymerizable double bonds per molecule of the copolymer, calculated based on Mn, to form the copolymer (F'). It was. A flask was charged with 40 parts of copolymer solution (E), 40 parts of copolymer solution (F'), 180 parts of ethylcyclohexane, and 20 parts of n-pukunol, and the following monomers and polymerization initiator were added at reflux temperature. was added dropwise over a period of 4 hours, and 0.2 part of t-butyl bartate was further added, followed by aging for 3 hours. Thereafter, the solvent was removed under reduced pressure to produce a non-aqueous dispersion (a-1). Styrene methyl methacrylate 2-hydroxyethyl acrylate acrylic nitrile (parts) l 0 l 5 Macromonomer Ml 2.2'-azobisisobutyronitrile l The solid content concentration of the non-aqueous dispersion (a-1) is 55%, Gardner viscosity (25°C) was U. Non-aqueous dispersion (a-4)
Synthesis Example: 48 moles of phenyltrimethoxysilane and 2 moles of γ-methacryloxyethyltriethoxysilane were reacted in the same manner as in Example 1 to obtain a polysiloxane macromonomer M.
I got 2. Obtained polysiloxane macromonomer M
The Mn of No. 2 was about 5.000, and it had on average one vinyl group and 5 to 10 methoxy groups per molecule. Macro 1,000 Nomer M2 2-ethylhexyl methacrylate styrene n-butyl methacrylate (parts) Using the above monomers, a copolymer (G) was synthesized in the same manner as the copolymer (E). The Mn of the copolymer (G) was 10.000, the solid content concentration of the solution was 50%, and the Gardner viscosity was M. Copolymer (H) was synthesized using the following monomers in the same manner as copolymer (G). (Part) 0H 2-Ethylhexyl methacrylate 30 Styrene
Mn of 10 copolymer (H)
was 11.000, the solid content concentration of the solution was 50%, and the Gardner viscosity (25°C) was S. Methacrylic acid was added to the copolymer (H), and 0.8 polymerizable double bonds were introduced per molecule of the copolymer, calculated based on Mn, to form a copolymer (H'). 40 parts of copolymer solution G, 40 parts of copolymer solution (H')
A non-aqueous dispersion (a-3
) A non-aqueous dispersion (a-4) was synthesized in the same manner as (a-4). (Part) Methyl methacrylate 53 Acrylonitrile 10 Methyl acrylate 102-Hydroxyethyl acrylate 15 Glycidyl methacrylate
The solid content concentration of the 10 acrylic acid 2 non-aqueous dispersion (a-4) was 55%, and the Gardner viscosity was R.

・Synthesis of solution type vinyl copolymer (b-1) xylene/n
- AIB in a mixed solvent of butanol = 70/30
A solution type vinyl copolymer (b-1) having the following monomer composition was synthesized at 120°C using N as an initiator. Part C) CH-=C-C-0-CH*C}12CH--Si-O
Synthesis of CH-ocox styrene n-butyl methacrylate/solution-type vinyl copolymer (b-2) Produced in the same manner as vinyl copolymer (b-1) using the following monomers. Polymer (b-2) was synthesized. (Part) Styrene n-butylmethacuvinyl copolymer (solid content concentration of b solution was 5 L. Pn of 5 relate 35 2) was 9.500, 0.0%, Gardner viscosity/solution Synthesis of vinyl copolymer (b-3) was produced in the same manner as vinyl copolymer (b-1) using the following monomers to synthesize vinyl copolymer (b-3). ．． (Part) CHz=C-C-0-CH-CH-(:H--St-O
CH-20OCR, styrene 10n-butyl methacrylate 40 Mn of vinyl copolymer (b-3) is 9.200. The solid content concentration of the solution was 50%, and the Gardner scale was J. Example 1 A composition was prepared using the following formulation. (Part) Acetylacetone 5 The viscosity of the above composition was adjusted to 35 seconds (20°C) using a #4 Ford cup using a thinner with a weight ratio of isobutyl/cellosolve acetate = 1/1, and the composition was applied for painting. Apply epoxy-based 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, the painted surface was polished with #400 sandpaper, and then wiped with gauze containing 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 approximately 50 μm, left at room temperature for 10 minutes, and then baked at 100° C. for 30 minutes. Table 1 shows the evaluation results of the coating film. In the following Examples and Comparative Examples, adjustments to the binder and coating viscosity are the same as in Example 1 unless otherwise specified. Example 2 A composition was prepared using the following formulation. Dispersion of titanium white was performed using vinyl copolymer (b-2). It was coated to a dry film thickness of 50 μm and baked at 90°C for 30 minutes. (Part) (Ila ff? Rana 50%) I created a skort. (Part) Example 3 A composition was prepared with the following formulation. The solvent for adjusting the viscosity was a mixed solvent of Swasol 1000"/n-butanol = 80/20, and was heated in a #4 Ford cup for 25 seconds (25°C).
It was. (0 Swasol 1000: manufactured by Cosmo Oil ■, aromatic solvent) (Part) Butyl acetate Example 4 Betol/xylol/n-buknol for wet painting with the following formulation = 4 0/4 0/2
15 seconds in a #4 Ford cup using a mixed solvent of 0.
The viscosity was adjusted to 25"C). The clear paint composition of Example 3 was used as it was as a top coat to be applied wet on top of the base coat. The above base coat was applied on the material to a dry film thickness. Air spray the top coat to a dry film thickness of about 18μ, leave it for 5 minutes at room temperature, and then air spray the top coat to a dry film thickness of about 30μ.
After leaving it at room temperature for another 10 minutes, it was baked at 100°C for 30 minutes. Comparative Example 1 A composition was prepared using the following formulation. Air spray paint to a dry film thickness of approximately 50L1.
Baked at 00℃ for 30 minutes. Comparative Example 2 A composition was prepared with the following formulation. Air spray paint to a dry film thickness of approximately 50μ,
Bake at 0℃ for 30 minutes. Examples 1-4, Comparative Examples 1-
The evaluation results of the cured film of No. 2 are shown in Table 1. Notes in Table 1 (Note 1) Finished appearance was evaluated visually. (Note 2) Gasoline wiping resistance Nisseki Shinolever gasoline was moistened with gauze and the painted surface was rubbed vigorously 8 times back and forth over a 10 cm length, 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 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. (Note 5) 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) Indicates the gloss retention rate when irradiated for 800 hours with a weather-resistant Sunshine Weather Meter.

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) Polymer (I) containing a siloxane macromonomer having an alkoxy group as an essential monomer component
and a polymer (II) containing an epoxy group-containing polymerizable unsaturated monomer as an essential component as a dispersion stabilizer resin, and in the presence of the resin, a radically polymerizable unsaturated monomer is A curable composition comprising a metal chelate compound in a non-aqueous dispersion of polymer particles insoluble in an organic solvent obtained by polymerizing the organic solvent.