JPH02228320A - Resin composition, curable composition and coating composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. providing a coating film with excellent smoothness, clarity and build by using a resin component with a hydroxyl group, a silanol group and/or a hydrolyzable group directly bonded to a silicon atom and an epoxy group and a polymer particle component. CONSTITUTION:Using one or more resin compd. selected from a hydroxyl resin compd., an epoxy resin compd. and a resin compd. contg. a silanol group and/or a hydrolyzable group directly bonded to a silicon atom among which at least one compd. is a fluororesin as a dispersion stabilizer, a radical-polymerizable unsatd. monomer (e.g. a mixture of styrene, methyl methacrylate and 2- hydroxyethyl methacrylate) is polymerized in an org. solvent (e.g. a mixture of heptene and n-butyl acetate) in the presence of said dispersion stabilizer to obtain polymer particles insoluble in said. org. solvent. When said three compd. are not simultaneously used as said dispersion stabilizer, the remaining compd. is furthermore compounded in the polymer particles to constitute the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to resin compositions, curable compositions, and coating compositions.

Conventional techniques and their problems As a method for curing resins having hydroxyl groups as functional groups,
Conventionally, a method using diisocyanate, melamine resin, etc. as a curing agent has been adopted.

However, when diisocyanates are used, the resulting film has insufficient weather resistance and is susceptible to yellowing. Additionally, the pot life of the resin composition is short, and there are also problems with the toxicity of the diisocyanate.

On the other hand, when using melamine resin, baking is required at a high temperature of about 140° C. or higher, and the resulting film has insufficient acid resistance, scratch resistance, stain resistance, and weather resistance.

As a one-component, non-toxic, low-temperature curable composition, for example, JP-A-60-67553 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane. is disclosed.

However, in the above-mentioned conventional composition, the only crosslinking functional group is the silanol group produced by hydrolysis of the alkoxysilane, so a large amount of water is required for curing, and a large amount of by-products such as alcohol produced during this hydrolysis. Therefore, the physical properties of the cured product cannot be said to be sufficient, and when curing with only moisture in the air, it hardens from the surface, making it difficult to harden the inside and easily causing stiffness in the cured product, and the feeling of stickiness is insufficient. There are some drawbacks.

Means for Solving the Problems The present inventor has conducted extensive research in order to solve the above-mentioned problems. As a result, hydroxyl groups, silanol groups and/or
Alternatively, by using a resin composition comprising a resin component having a hydrolyzable group directly bonded to a silicon atom and an epoxy group, and a polymer particle component, a coating film with a high finish and excellent durability can be obtained. Moreover, by adding a specific curing catalyst to the resin composition, a composition in which the curing reaction proceeds at a sufficient rate even at a low temperature of 140°C or less can be obtained, and a cured coating film of the composition can be obtained. The present invention was completed based on the discovery that it has excellent weather resistance, acid resistance, scratch resistance, stain resistance, mechanical properties, etc.

That is, the present invention provides the following resin compositions, curable compositions, and coating compositions.

■ Hydroxyl group-containing compound (A), epoxy group-containing compound (
A resin composition containing three components: B) and a compound (C) containing a silanol group and/or a hydrolyzable group directly bonded to a silicon atom (hereinafter referred to as a "silane group"), provided that the compound (A), A resin composition in which at least one compound selected from compound (B) and compound (C) is a resin containing fluorine, wherein the compound (A), compound (
The organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer using at least one compound selected from B) and compound (C) as a dispersion stabilizer. A resin composition containing polymer particles that are insoluble in (referred to as the "first invention").

■ A resin composition containing two components: a hydroxyl group-containing compound (A) and a compound (D) containing a silane group and an epoxy group, provided that at least one compound selected from the above compound (A) and compound (D) The compound is a resin composition containing fluorine, in which at least one compound selected from the compound (A) and the compound (D) is used as a dispersion stabilizer, and an organic solvent is used in the presence of the dispersion stabilizer. A resin composition containing polymer particles insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in the organic solvent,
Furthermore, a resin composition (hereinafter referred to as "second invention") characterized in that, when the above two components are not used simultaneously as the dispersion stabilizer, the remaining component is blended.

■ A resin composition containing two components: a compound (E) containing a hydroxyl group and a silane group, and an epoxy group-containing compound (B), provided that at least one compound selected from the above compound (E) and compound (B) is a resin composition containing fluorine, the compound (E) and the compound (
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 at least one compound selected from B). A resin composition containing particles, and further comprising the remaining component when the above two components are not used simultaneously as the dispersion stabilizer (hereinafter referred to as the "third invention"). ).

■ A resin composition containing two components: a compound (F) containing a hydroxyl group and an epoxy group, and a compound (C) containing a silane group, provided that at least one type selected from the above compound (F) and compound (C) The compound is a resin composition containing fluorine, in which at least one compound selected from the compound (F) and the compound (C) is used as a dispersion stabilizer, and in the presence of the dispersion stabilizer, organic A resin composition containing polymer particles insoluble in an organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in a solvent, and in which the above two components are not used simultaneously as the dispersion stabilizer. and the remaining components (hereinafter referred to as the "fourth invention").

(2) A curable composition (hereinafter referred to as "fifth invention") characterized in that a metal chelate compound is blended as a curing catalyst into the resin composition described in (1) to (2) above.

(2) A curable composition containing the composition described in (1) to (2) above as an essential component.

In this specification, a hydrolyzable group directly bonded to a silicon atom is a group that is hydrolyzed by water or moisture to produce a silanol group. Examples of the groups include those represented by the following general formula.

-0-R' (i)l -0-C-R" (II)-
N-C-R"' Rl l l I (Vl) [In the formula, Ro represents an alkyl group having 1 to 4 carbon atoms.

RI I, Rlo and Rl l l l are the same or different and represent an alkyl group, an aryl group or an aralkyl group having 1 to 8 carbon atoms. ] In the above general formula, examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5ee-butyl, te
Examples include rt-butyl, n-pentyl, isopentyl, n-octyl, and isooctyl groups. Examples of the aryl group include phenyl, tolyl, and xylyl groups. Examples of the aralkyl group include benzyl and phenethyl groups.

Further, in addition to the above-mentioned hydrolyzable group bonded to a silicon atom, a =S f -H group can be mentioned as the hydrolyzable group.

In the resin composition of the present invention, silane groups represented by the above general formulas (I) and (II) and silanol groups are preferred from the viewpoint of storage stability, curability, etc.

The hydroxyl group-containing compound (A) used in the first invention of the present invention has an average of two or more hydroxyl groups in one molecule, and preferably has a number average molecular weight of 1,000 to 200,000, preferably 3
It is from ooo to 5ooo. If the number of hydroxyl groups is less than 2 on average, the curability (gel fraction) will be poor, which is not preferable. The number of hydroxyl groups is preferably 400 or less on average from the viewpoint of weather resistance, water resistance, etc. Number average molecular weight is 1
If it is less than 000, the physical properties (impact resistance), weather resistance, etc. will be poor, while if it exceeds 200,000, the compatibility with other components will decrease, resulting in uneven curing and poor weather resistance of the coating film. I don't like it because it becomes a thing.

As the hydroxyl group-containing compound (A), a fluorine-free hydroxyl group-containing compound (A-1) and a fluorine-containing hydroxyl group-containing compound (A-2) will be described below.

Examples of the hydroxyl group-containing compound (A-1) include the following
~■ can be mentioned.

(2) Hydroxyl group-containing vinyl resin A polymer containing the following hydroxyl group-containing polymerizable unsaturated monomer (a) and, if necessary, other polymerizable unsaturated monomers (b) as monomer components.

Hydroxyl group-containing polymerizable unsaturated monomer (a) Examples include compounds represented by the following general formulas (1) to (4).

[In the formula, R1 represents a hydrogen atom or a hydroxyalkyl group. ” [In the formula, R1 is the same as above. ] In formula 1, Z represents a hydrogen atom or a methyl group, and m is 2 to 8
p is an integer of 2 to 18, and q is an integer of 0 to 7. ] CH2TomiCZ [In the formula, Z is the same as above. T and T2 are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms. S and ■ each represent an integer of 0 to 10. However, S
The sum of V and V is 1 to 10. The hydroxyalkyl group in general formulas (1) and (2) is a hydroxyalkyl group whose alkyl moiety has 1 to 6 carbon atoms. Specifically, -C2H40H, -C3H
60H.

-C4H80H etc. can be mentioned.

Examples of the divalent hydrocarbon group having 4 to 20 carbon atoms in general formula (4) include -CH2--(CH2) 2-
(C)12 ) 3=CH3CH2 CH2 =CH2CH2CCH2CH2(CH2) to-(C
H2) +2-1 (CH2) ta-1(>-1-Q
-1CH2-QCH2-, etc. can be mentioned.

As the monomer component of general formula (1), for example, C11z
-CIIOH CH2-CHO(CH2) 40H and the like can be mentioned.

As the monomer component of general formula (2), for example, CH2-
CHCH20H CH2=CH(CH20CH2CH20HCH2-CH
CH2MCHz CH2oh-HCH2”CHCH20
4CIb CH20)yH and the like.

As the monomer component of general formula (3), for example, CH2-
C(CH3) COOC2HA 0HCH2-CHCO
OCa Hs OHCH2-C(CHa) C00
C3H6-0→C-CH2CH2-CH2CH2CH2
0f-τ""y-1 (etc.).

As the monomer component of general formula (4), for example, C112
-C(C1h)Coo(CH2CHCll3咋rττ
llCH2=CHC00fCH2CH2咋rττHCH
2-C(Cf13)Coo-mark H2CH20;T
HCH2=CHC00fCH2CH2CH2CH20h
−; THCI+2 =C(CHa)Coo→CHz
Examples include CH20h-]-HCH2CHCH30h-2rH.

Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (1) to (4), ε-caprolactone, γ
-Adducts with lactones such as valerolactone can be used.

Other polymerizable unsaturated monomers (b) The following (b-1) to (b-6) can be mentioned.

(b-1) Olefin compounds: for example, ethylene, propylene, butylene, isoprene, chloroprene, etc.

(b-2) Vinyl ether and allyl ether: e.g. ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, te
Chain alkyl vinyl ethers such as rt-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-pentyl vinyl ether,
cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, o-, m+, p-) divinyl ethers, aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether, and the like.

(b-3) Vinyl esters and propenyl esters: vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl bivaric acid, vinyl caprate, and isopropenyl propion acetate Propenyl esters such as isopropenyl acid, etc.

(b-4) Niacrylic acid or methacrylic acid ester:
For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms such as isopropyl, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methacrylate Alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as methoxyethyl acrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate.

(b-5) Vinyl aromatic compound: for example, styrene,
α-methylstyrene, vinyltoluene, p-chlorostyrene, etc.

(b-6) Others: acrylonitrile, methacrylonitrile, etc.

■ Hydroxyl group-containing polyester resin polybasic acids (e.g. (anhydrous) phthalic acid, isophthalic acid, terephthalic acid 1. (anhydrous) maleic acid, (anhydrous) pyromellitic acid, (anhydrous) trimellitic acid, (anhydrous) succinic acid,
Compounds having 2 to 4 carboxyl groups or carboxylic acid methyl ester groups in one molecule such as cepatic acid, azelaic acid, dodecane dicarboxylic acid, dimethyl isophthalate, dimethyl terephthalate, etc.) and polyhydric alcohols (e.g. ethylene glycol, Alcohols having 2 to 6 hydroxyl groups in one molecule such as polyethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, glycerin, tricyclodecane dimetatool, etc.) It is obtained by carrying out an ester reaction or a transesterification reaction. In addition to the above, monobasic acids (for example, fatty acids such as castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid, etc., benzoic acid, etc.) can be used as necessary.

■ Hydroxyl group-containing polyurethane resin Does not have isocyanate groups obtained by modifying hydroxyl group-containing vinyl resins, hydroxyl group-containing polyester resins, etc. with polyisocyanate compounds (e.g., tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.) resin.

■ Hydroxyl group-containing silicone resin Hydroxyl group-containing vinyl resin, hydroxyl group-containing polyester resin, etc. are combined with silicone resin (e.g. 2-6018, Z-618
8 (more than Dow Corning products), 5H5050,5
A resin that does not have alkoxysilane groups or silanol groups and is obtained by modification with H6018, 5H6188 (all products of Toshi Silicone Co., Ltd.).

As the hydroxyl group-containing compound (A-2) containing fluorine,
For example, the following can be mentioned.

■ Hydroxyl group-containing fluororesin Hydroxyl group-containing polymerizable unsaturated monomer (a), fluorine-containing polymerizable unsaturated monomer (C), and other polymerizable unsaturated monomers (b) as necessary Polymer as an overall component.

Fluorine-containing polymerizable unsaturated monomer (c) Examples include compounds represented by the following general formulas (5) and (6).

CX2 = CX2 (5) [wherein, X is the same or different, HSCI2゜B r s
F N represents an alkyl group or a haloalkyl group. however,
contains at least one F in the formula. ] CH,2-CZ C=O(6) 0-CnH2n-R2 [wherein Z is the same as above. R2 represents a fluoroalkyl group, and n represents an integer of 1 to 10. ] The alkyl group in general formula (5) has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, and pentyl groups. Further, the haloalkyl group is one having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, CF3, CHF2, CH2F5CCΩ3,
CHCQ2, CH2CQ1CFCQ2 (CF2)2
CF3, (CF2)3 CF3, CF2 CH3, C
F2 CHF2, CF2 Br.

CH2Br etc. can be mentioned.

Examples of the monomer represented by general formula (5) include c
i'2=CF2, CHF=CF2, CH2=CF2,
CH2=CHF, CCl2P=CF2, CHC
Q=CF2, CCQ2=CF2, CCQP=CC
QF 5CHF = CCQ2, Cl-12 = CCQ F
5CC122=CCQF 5CP3 CF=CF2,
CF3 CF3CF25CF3 C11=CF2,C
F3 CF=CH2, CHF2 CH=CH2, CH
3CH=CH2, CHa CH=CH2, CF2CQC
F=CF2, CF3 CCQ=CF2, CF3 CP=C
F CQ 5CF2 CQ CH=CH2, CF2
CRCF=CF CQ , CP CQ 2 CF=
CP2, CF2 CCQ = CC (2P, CF3
CCQ-CCQ2, CCQ F 2 CF3CF22
, CCf2 a CF3CF2, CF2 CQCCQ
= CCQ2 , CF2 CQ 2 CCQ = CC
Qz, CF3 CF=CHCQ, C(J! F2
CF3CF2 CQ.

CF3 CCQ =CHCQ 5CHF 2 CCQ
=CC22,CF2 CQ CH=CC(22,CF
2 CQ CCQ = CII CQ.

CCQ 3 CP=CHCQ 5CF2 1 CF=C
F2, CF2 BrCH=CF2, CF3 CBr
=CHBr.

CF2 CQ CBr =CH2, CH2BrCF=
CC22, CF3 CBr=CH2, CF'2 CH
=CHBr.

CF2 BrCH= CHF 5CF2 BrCF=
CF2, CF3 CF2 CF=CF2, CF3C
F-CFCF3, CFa C1 (-CPCF3, CF
2 = CHCH2CHF 2 , CF3CF2 CF=
CH2, CF3 CH=CHCF3, CF2=CHC
H2CH3, CF2 = CFCH2CH3, CFa
CH2CH=CH2, CF3 CH=CH2t(3, C
F2=CHCH2CH3, CH3CF2 CH=CH
2, CFH2CH=CHCFH2, CHa CF2 C
H=CH2, CH2=CFCH2CH3, CF3 (
CF2 ) 2 CF=CP2, CF3 (CF2
) 3 CF=CF2, etc. can be mentioned.

The fluoroalkyl group in general formula (6) has 3 carbon atoms.
~21. Specifically, for example, C4F9,
(CF2)s CF (CF3)2, C8F IF
Examples of monomers represented by general formula 6) include CH3 CH2■C-Coo-C2H4-C4F9Hs CH2=C-COO-C2Ha -Ca PI7H3 C112■C- COO-C2Ha -C+o F2
+The above monomers can be used alone or in combination of two or more.

By using the monomer represented by the general formula (5), it is possible to form a coating film with particularly excellent acid resistance, weather resistance, etc.
When the monomer represented by 6) is used, a coating film particularly excellent in water repellency can be formed.

(2) Hydroxyl group-containing silicone fluororesin A resin having no alkoxy group or silanol group obtained by modifying the hydroxyl group-containing fluororesin with the silicone resin used in (2) above.

■ Hydroxyl group-containing esterified fluororesin The above-mentioned fluorine-containing polymerizable unsaturated monomer (C), carboxyl group-containing polymerizable unsaturated monomer (d), and other polymerizable unsaturated monomers (b) as necessary. ) as a monomer component and the hydroxyl group-containing resin (A) are subjected to an esterification reaction.

Examples of the carboxyl group-containing polymerizable unsaturated monomer (d) include compounds represented by the following general formulas (7) and (8).

[In the formula, R3 represents a hydrogen atom or a lower alkyl group. R
4 represents a hydrogen atom, a lower alkyl group or a carboxyl group. R5 represents a hydrogen atom, a lower alkyl group or a carboxy lower alkyl group. ] [In the formula, R6 represents a hydrogen atom or a methyl group. m is the same as above. ] The lower alkyl group in the general formula (7) is preferably one having 4 or less carbon atoms, particularly a methyl group.

Examples of the compound of general formula (7) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and the like.

Examples of the compound of general formula (8) include 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and 5-carboxypentyl (meth)acrylate.

In addition to the above, hydroxyl group-containing polymerizable unsaturated monomers (
a) 1 mol and polycarboxylic anhydride (e.g. maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride, etc.)
Adducts with 1 mol of the compound can also be used.

■ Hydroxyl group-containing urethane fluororesin Hydroxyl group-containing resin obtained by modifying the hydroxyl group-containing compound (A-1) with the polyisocyanate compound, fluorine-containing polymerizable unsaturated monomer (C), isocyanate group-containing polymerizable An isocyanate group-containing fluorine-based resin containing an unsaturated monomer (e) and, if necessary, other polymerizable unsaturated monomers (b) as monomer components, and the hydroxyl group-containing compound (
A hydroxyl group-containing resin obtained by reacting A-1) with hydroxyl group.

Examples of the isocyanate group-containing polymerizable unsaturated monomer (e) include monomers represented by the following general formulas (9) and (1o).

R5 CH2-C-Coo (CnH2n)NGO (9) [wherein R6 and n are the same as above. ] The monomer of general formula (9) above includes, for example, isocyanate ethyl (meth)acrylate.

[In the formula, R6 and n are the same as above. R7 represents a hydrogen atom or an alkyl group having 5 or less carbon atoms. ]The above general formula (10
), for example, α.

Included is α-dimethyl-m-isopropenylbenzyl isocyanate.

In addition to the above, a reaction product of 1 mol of hydroxyl group-containing polymerizable unsaturated monomer (a) and 1 mol of a polyisocyanate compound can be used. Examples of the polyisocyanate compound include toluene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, dicyclohexylmethane, 4,4'-
Diisocyanate, p-xylene diisocyanate, m
Examples include -xylene diisocyanate, bis(4-isocyanate phenyl) sulfone, isopropylidene bis(4-phenyl isocyanate), lysine isocyanate, isophorone diisocyanate, and polymers and billets thereof.

Furthermore, as the isocyanate group-containing fluorine-based resin, in addition to those mentioned above, those obtained by reacting the hydroxyl group-containing compound (A-2) with, for example, the polyisocyanate compound can also be used.

■Other hydroxyl group-containing fluororesin Carboxyl group-containing polymerizable unsaturated monomer (d), hydroxyl group-containing polymerizable unsaturated monomer (a), and other polymerizable unsaturated monomers (b) as necessary In the presence of a copolymer having as a monomer component, an epoxy group-containing polymerizable unsaturated monomer (for example, glycidyl (meth)acrylate, etc.), a fluorine-containing polymerizable unsaturated monomer (c), and optionally A hydroxyl group-containing resin obtained by polymerizing other polymerizable unsaturated monomers (b) according to the requirements.

The epoxy group-containing compound (B) has an average of two or more epoxy groups in one molecule, and preferably has a number average molecular weight of 12
0 to 1,200,000, preferably 240 to 80,000. If the number of epoxy groups is less than 2 on average, the curability (gel fraction) will be poor, which is not preferable.

It is difficult to obtain a compound with a number average molecular weight of less than 120, and - if the blade number average molecular weight exceeds 200,000, the compatibility with other components will be poor, resulting in a decrease in the weather resistance of the resulting coating film, so it is preferable. do not have.

Specific examples of the epoxy group-containing compound (B) that does not contain fluorine include compounds represented by the following general formula.

H, C H, C [wherein R6 is the same as above. R8 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. R6 and R8 may be the same or different. Further, R9 is the same or different and represents an alkyl group, an aryl group, or an aralkyl group having 1 to 8 carbon atoms.

RIO is the same or different and has a hydrogen atom or a carbon number of 1 to
4 shows the alkyl group. W represents 0 and an integer from 1 to 10. ] Here, the divalent hydrocarbon group having 1 to 8 carbon atoms can be selected from the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms.

Specific examples of the compounds represented by formulas (11) to (.18) include the following.

In addition to the above, for example, the following can be used.

(Polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate; Organic diisocyanates themselves such as aromatic diisocyanates such as diisocyanate or 4,4'-diphenylmethane diisocyanate, or adducts of each of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc., or as mentioned above. Polymers of various organic diisocyanates, and isocyanate biuret bodies, etc. can be mentioned, and typical commercially available examples of these include "Parnock D-750, -8
00, DN-950, -970 or 15-455J
[The above products are Dainippon Ink & Chemicals ■ products], ``Desmodule LSNHLSIL or N3390J [product of Bayer AG, West Germany], ``Takenate D102, -202
, -LION or -123N” [Takeda Pharmaceutical Company ■
Product], [Coronate L, HL, EH or 203J
[Nippon Polyurethane Kogyo Co., Ltd. product] or [Duranate 24A-90CXJ (Asahi Kasei Kogyo product), etc.); Esterified products with unsaturated groups such as CH2=C-COO- (e.g., tetrahydrophthalic anhydride, trimethylolpropane) and 1,4
Examples include those obtained by oxidizing an esterified product with a number average molecular weight of 900 obtained by esterifying -butanediol etc. with peracetic acid etc.

In addition, as the epoxy group-containing compound (B), a polymer containing an epoxy group-containing polymerizable unsaturated monomer (f) and, if necessary, other polymerizable unsaturated monomers (b) as monomer components. can also be used.

As the epoxy group-containing polymerizable unsaturated monomer (f), 1
It is a compound that has an epoxy group and a radically polymerizable unsaturated group in its molecule. Examples of the radically polymerizable unsaturated group include C12=C-C-C- CH2 CH2 CH2 CH2 =C-C-N- =CHCH2-0- =CHO- =CH- [wherein R6 is the same as above. ] etc.

The saturated monomer (f) in which the radically polymerizable unsaturated group is CH2=C-COO- is, for example, the following general formula (one)
Compounds represented by (31) can be mentioned.

[In each formula, R6, R8 and W are the same as above.

R11 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and R6
, R8 and R11 may be the same or different. ] Specific examples represented by general formulas (19) to (31) include the following.

As the monomer (f) having a saturated radically polymerizable unsaturated group, for example, the following general formula (32) is used.
Compounds represented by (34) can be mentioned.

[In each formula, R6 and R8 are the same as above. R6 and R8 may be the same or different. ] General formula (32) ~ (
Specific examples of the compound represented by 34) include the following.

As the monomer (f) having a saturated radically polymerizable unsaturated group, for example, the following general formula (35) is used.
Compounds represented by (37) can be mentioned.

[In each formula, R6 and R8 are the same as above. R6 and R8 may be the same or different. ] General formula (35) ~ (
Specific examples of the compound represented by 37) include the following.

As the epoxy group-containing unsaturated monomer (f) having 11 radically polymerizable unsaturated groups, for example, the following general formula (38)
Compounds represented by (43) can be mentioned.

[In each formula, R6, R8, R11 and W are the same as above.

R6, R8 and R11 may be the same or different. ] As specific examples of the compounds represented by the general formulas (38) to (43), for example, as the unsaturated monomer (f), for example, the following general formula (44)
) to (47) can be mentioned.

t) omitted etc. can be mentioned.

Epoxy group-containing polymerizable radically polymerizable unsaturated group of CR2=CHCR20- [R6 and R8 in each formula are the same as above. R8 may be the same or different. Specific examples of the compounds represented by general formulas (44) to (47) include:

Examples of the epoxy group-containing polymerizable unsaturated monomer (f) in which the radically polymerizable unsaturated group is CH2=CHO- include compounds represented by the following general formulas (48) to (50).

[In each formula, R6 and R8 are the same as above. R8 may be the same or different. ] Specific examples 11 of the compounds represented by formulas (48) to (5o) include, for example.

Examples of the epoxy group-containing polymerizable unsaturated monomer (f) in which the radically polymerizable unsaturated group is Cl2=CH- include compounds represented by the following general formulas (51) to (53).

p@ [In each formula, R6 and R8 are the same as above. R8 may be the same or different. Specific examples of the compounds represented by general formulas (51) to (53) include the following.

Examples of the monomer (f) having a saturated radically polymerizable unsaturated group include compounds represented by the following general formulas (54) to (58).

[In each formula, R6, R8 and RII are the same as above.

R6 and R11 may be the same or different. ] Specific examples of the compounds represented by general formulas (54) to (58) include the following.

Furthermore, as the epoxy group-containing compound (B), a compound having one isocyanate group and one epoxy group in one molecule (for example, and in the hydroxyl group-containing compound (A-1)) is added to the hydroxyl group-containing compound (A-1). 1 mole or more of the compound is reacted per hydroxyl group of hydroxyl group-containing compound (A-
A product in which all the hydroxyl groups in 1) are reacted can also be used.

As the epoxy group-containing compound (B) containing fluorine,
For example, the fluorine-containing polymerizable unsaturated monomer (C), the epoxy group-containing polymerizable unsaturated monomer (f), and if necessary, other polymerizable unsaturated monomers (b) are copolymerized. and the hydroxyl group-containing compound (A-
Examples of 2) include resins obtained by reacting compounds having the above-mentioned isocyanate groups and epoxy groups.

The silane compound (C) has on average one or more silane groups in one molecule, and if the number of silane groups is less than one on average, the curability (gel fraction) will be poor. In addition, as the number of silane groups increases, the reaction between silane groups and epoxy groups takes place preferentially, and fewer epoxy groups are required for reaction with hydroxyl groups, resulting in poor curing properties (gel fraction). , it is preferable that the average number is 2,500 or less in one molecule.

The silane compound (C) has a number average molecular weight of 104 to 2000
00 is used. Those with a number average molecular weight of less than 104 are difficult to obtain, and those with a number average molecular weight of more than 200,000 have poor compatibility with other components, making it impossible to obtain a coating film with excellent weather resistance.

Specific examples of silane group-containing compounds that do not contain fluorine include the following (1) and (2).

(2) Polysilane Compound Compounds represented by the following general formulas (59) to (61) can be mentioned.

Y' -8i -Y'Y'R'' -8i -Y' (61)Y
' [In each formula, Y' is the same or different and represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. R9 is the same as above,
R9 may be the same or different. ] Specific examples of the compounds represented by general formulas (59) to (61) include dimethyldimethoxysilane, dibutyldimethoxysilane, di-1so-propyldipropoxysilane, diphenyldibutoxysilane, diphenyljethoxysilane, and diethyldisilanol. , dihexyldisilanol methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyltributyloxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol,
Tetramethoxysilane, tetraethoxysilane, tetrapropioxysilane, tetraacetoxysilane, G1
Examples include so-propioxydivaleroxysilane, tetrasilanol, and the like.

In addition to those mentioned above, condensates of the above-mentioned polysilane compounds can also be used.

For these silane compounds, the number average molecular weight is 104
-40,000 is preferable, and 104 - 30,000 is more preferable. Those with a number average molecular weight of less than 104 are difficult to obtain, while those with a number average molecular weight of more than 40,000 are not preferred because the compatibility with other components decreases and the resulting coating film has poor weather resistance.

(2) A homopolymer of a silane group-containing polymerizable unsaturated monomer (g) or a copolymer with another polymerizable unsaturated monomer (b).

A compound having at least one silane group and a radically polymerizable unsaturated group in one molecule of the silane group-containing polymerizable unsaturated monomer (g). Examples of the radically polymerizable unsaturated group include CH2-=C- CH2-CHo- CH2=CHCH20- [wherein R6 is the same as above. ] etc.

Examples of the unsaturated monomer (g) having a radically polymerizable unsaturated group include the following - general formula (6
Compounds represented by 2) can be mentioned.

[In the formula, R6, RI I and Y are the same as above, and Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] As a specific example of the compound represented by general formula (62),
For example, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ -(meth)acryloxypropylmethyljethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxy Silane, γ-
(meth)acryloxybutylphenyldipropoxysilane, γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane, γ-(meth)acryloxypropylphenylmethylmethoxysilane, γ -(meth)acryloxypropylphenylmethylethoxysilane, γ-(meth)acryloxypropyltrisilanol, γ-(meth)
Acryloxypropylmethyldihydroxysilane, γ-
Examples include (meth)acryloxybutylphenyldihydroxysilane, γ-(meth)acryloxypropyldimethylhydroxysilane, γ-(meth)acryloxypropylphenylmethylhydroxysilane, and CCHs Hs Js.

Examples of the unsaturated monomer (g) having a radically polymerizable unsaturated group include the following - general formula (6
Compounds represented by 3) to (65) can be mentioned.

[In the formula, R6, R11 and Y are the same as above, and Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (63) to (65) include CH2=C (CHpe>5L(OCHx)x R' Y ).

Examples of the monomer (g) in which the radically polymerizable unsaturated group is CH2=C- include the following general formulas (66) to
A compound represented by (67) can be mentioned.

CHz=C51T [In the formula, R6, R11 and Y are the same as above, and Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (66) to (67) include CH2=CH-81(OCH3) 3 CH2=CH5i(QC2Hs) 3CH2=CHS
i(OCH3) 2 CH3CH2-CHSi (CH
3) 20CH3CH2=CH-CH25t(OCH
a) 3CH2= e)l Si (OCOCIh
) aC112=Cl1−C11231(OCOCI
I3 ) 3CH2=CH-8i (CH3) 2 N
(CHa) 2CToWCHSi(Beko)xON(C
Ha)* etc. can be mentioned.

Examples of the silane group-containing polymerizable unsaturated monomer (g) in which the radically polymerizable unsaturated group is CH2-CHo include compounds represented by the following general formulas (68) to (69).

At least one is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

] Specific examples of compounds represented by general formulas (68) to (69) include C1,H CHl CHa''CHO-(CHJ 1si-OCRs00H).

C1, CI.

[In the formula, R11 and Y are the same as above, and Y may be the same or different. CHs with less Y C-H
5 etc. can be mentioned.

As the silane group-containing polymerizable unsaturated monomer (g) whose radically polymerizable unsaturated group is CH2-CHC)I20-, for example, the following general formulas (70) to (
71) can be mentioned.

[In the formula, R11 and Y have the same meanings as above, and Y may be the same or different. Any one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (70) to (71) include CHa''CMCI(*0-(C1,)s-5i-→CC
CCIb CJi CHt”CHCH*O-(CH,) x-5t-OCJ
sOH.

etc. can be mentioned.

In addition to the silane group-containing polymerizable unsaturated monomer, the silane group-containing polymerizable unsaturated monomer (g) and, for example, a polysilane compound (for example, a compound represented by general formulas (59) to (61)) A polysiloxane unsaturated monomer having a silane group and a polymerizable unsaturated group obtained by reacting the same can also be used.

Specific examples of the polysiloxane unsaturated monomer include the compound of the general formula (62) and the general formulas (59) to (
61) and the former 30 to 0.
Examples include polysiloxane macromonomers (for example, those disclosed in JP-A No. 62-275132) obtained by reaction, and the following compounds.

Hs CH3 0CCH.

CM, OCH* (1) A reaction product with a compound having an isocyanate group and a silane group in one molecule for each hydroxyl group in the hydroxyl group-containing compound (A-1).

Examples of the isocyanate group-containing silane compound include compounds represented by the following general formulas (72) and (73).

[In the formula, R6 and Y are the same as above, and Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (72) to (73) include 0CNC-HaSi (OCzHs).

0CNCtH4Si rOcH,)! .

0CNCJaSitOcJslx.

CH3 OCNC*HJi l0CHzl *, CH.

0CNCH*5rFOCJsl　s.

0CNCHxSi (OCR-]s.

0CNCHxSt (OCJi) i.

CH3 OCNCHiSI l0cHs)s.

0CNCHtSi　1OcHsl　x.

CHs0CN-Si (OCCHz)Yuzono0CN-Si (OCCHi)3Ding0CN-CyuHs-St (OCCH3)s, etc. can be mentioned.

In addition to the above, compounds obtained by reacting the hydroxyl group-containing silane compounds described below with the polyisocyanate compounds can be used.

Specifically, the following can be mentioned.

A reaction product of a hydroxyl group-containing silane compound and hexamethylene diisocyanate or tolylene diisocyanate, for example, can be mentioned.

Furthermore, condensates of the above-mentioned isocyanate group-containing silane compounds and, for example, the above-mentioned polysilane compounds can also be used. As examples of the compound, for example, those listed below can be used.

(2) A reaction product between the hydroxyl group-containing compound (A-2) and the polysilane compound.

(2) A reaction product between the hydroxyl group-containing compound (A-2) and the isocyanate group-containing silane compound.

■ A fluorine-containing polymerizable unsaturated monomer (C), an isocyanate group-containing polymerizable unsaturated monomer (e), and if necessary, other polymerizable unsaturated monomers (b) as monomer components. A reaction product of a copolymer and a hydroxyl group-containing silane compound.

As the hydroxyl group-containing silane compound, the following general formula (74) is used.
Compounds represented by (76) can be mentioned.

can be exemplified.

As the silane compound (C) containing fluorine, [in the formula R
8, RI + and Y are the same as above, R8, R1+
and Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (74) to (76) include QC)I.

HO-(CHal x-5L-OCHxOCH.

can be mentioned.

■ The fluorine-containing polymerizable unsaturated monomer (n) (the unsaturated silane group-containing polymerizable unsaturated monomer (g) and, if necessary, other polymerizable unsaturation rate bases (b)) as monomer components. A copolymer with

The compound (D) containing an epoxy group and a silane group used in the second invention of the present invention has an average of two or more epoxy groups in one molecule and an average of one or more silane groups in one molecule. However, if the number of epoxy groups and silane groups is less than the above range, the curability (gel fraction) will be poor, which is not preferable. On the other hand, as mentioned above, when the number of silane groups increases, the epoxy groups are consumed and fewer epoxy groups are needed for the curing reaction of hydroxyl groups (this results in poor curability of the resin composition, so the silane groups is an average of 2500 in one molecule.
It is preferable that the number is less than or equal to 1. Further, the number average molecular weight of compound (D) is 1000 to 200000, preferably 30
00~5ooo.

If it is less than 1,000, the curability, weather resistance, etc. will be poor, while if it is more than 200,000, the compatibility with other components will decrease, which is not preferable.

Examples of the compound (D) that does not contain fluorine include the following compounds (1) to (2).

■ Monomerize the silane group-containing polymerizable unsaturated monomer (g), the epoxy group-containing polymerizable unsaturated monomer (f), and if necessary, other polymerizable unsaturated monomers (b). A copolymer used as a body component.

(2) A reaction product with the hydroxyl group-containing compound (A-1), the isocyanate group-containing epoxy compound, and the isocyanate group-containing silane compound.

■ General formula [In the formula, R6, R9, R11 and Y' are the same as above. R9
may be the same or different. ].

Specific examples of the above general formula include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriacetoxysilane, glycidoxyethyltrimethoxysilane,
β-glycidoxyethyltriethoxysilane, β-(3
゜4-Epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3゜4-epoxycyclohexyl)ethyltriacetoxysilane, γ-(3,4-
Examples include epoxycyclohexyl)propyltriethoxysilane.

Examples of the fluorine-containing compound (D) include the following (1) and (2).

■ The silane group-containing polymerizable unsaturated monomer (g), the epoxy group-containing polymerizable unsaturated monomer (f), the fluorine-based polymerizable unsaturated monomer (C), and others as necessary. A copolymer containing a polymerizable unsaturated monomer (b) as a monomer component.

(2) A reaction product of the hydroxyl group-containing compound (A-2), the isocyanate group-containing epoxy compound, and the isocyanate group-containing silane compound.

As the hydroxyl group-containing compound (A), the same fluorine-free hydroxyl group-containing compound (A-1) as mentioned above and the fluorine-containing hydroxyl group-containing compound (A-2) can be used.

The hydroxyl group- and silane group-containing compound (E) used in the third invention of the present invention has an average of two or more hydroxyl groups in one molecule and an average of one or more silane groups in one molecule,
If the hydroxyl group and silane group are below the above range, the curability (gel fraction) will be poor, which is not preferable. The hydroxyl group is
From the viewpoint of weather resistance, water resistance, etc., the number of silane groups is preferably 400 or less in one molecule, and from the viewpoint of curability (gel fraction), it is preferable that the number of silane groups is 2,500 or less in one molecule. . The number average molecular weight of compound (E) is 1000
-200,000, preferably 3,000-80,000; if it is less than 1,000, the weather resistance will be poor, while if it exceeds 200,000, the compatibility with other components will decrease, which is not preferred.

Examples of the fluorine-free compound (E) include the following.

■ Monomerize the hydroxyl group-containing polymerizable unsaturated monomer (a), the silane group-containing polymerizable unsaturated monomer (g), and if necessary, other polymerizable unsaturated monomers (b). Copolymer as a component.

(2) A product obtained by reacting the hydroxyl group-containing compound (A-1) with the isocyanate group-containing silane compound so that each molecule has one or more hydroxyl groups and one or more silane groups on average.

Examples of the fluorine-containing compound (E) include the following.

■ The hydroxyl group-containing polymerizable unsaturated monomer (a), the silane group-containing polymerizable unsaturated monomer (g), the fluorine-containing polymerizable unsaturated monomer (C), and other components as necessary. A copolymer containing a polymerizable unsaturated monomer (b) as a monomer component.

(2) A product obtained by reacting the hydroxyl group-containing compound (A-2) with the isocyanate group-containing silane compound so that each molecule has one or more hydroxyl groups and one or more silane groups on average.

As the compound (B), the same compounds as mentioned above can be used.

The hydroxyl group- and epoxy group-containing compound (F) used in the fourth invention of the present invention has an average of two or more hydroxyl groups in one molecule, and one
It has an average of two or more silane groups in the molecule, and if the hydroxyl group and epoxy group are below the above range, curability (
This is not preferable because it results in an inferior gel fraction). The number of hydroxyl groups is preferably 2,500 or less in one molecule from the viewpoint of weather resistance, water resistance, etc. The number average molecular weight of compound (F) is 1,000 to 200,000, preferably 3,000 to 200,000.
If it is less than 1,000, the weather resistance will be poor, while if it is more than 200,000, the compatibility with other components will be reduced, which is not preferable.

Examples of the fluorine-free compound (F) include the following.

■ Monomerizing the hydroxyl group-containing polymerizable unsaturated monomer (a), the epoxy group-containing polymerizable unsaturated monomer (f), and if necessary, other polymerizable unsaturated monomers (b) Copolymer as a component.

(2) A product obtained by reacting the hydroxyl group-containing compound (A-1) with the isocyanate group-containing epoxy compound so that each molecule has one or more hydroxyl groups and one or more epoxy groups on average.

Examples of the fluorine-containing compound (F) include the following.

■ The hydroxyl group-containing polymerizable unsaturated monomer (a), the epoxy group-containing polymerizable unsaturated monomer (f), the fluorine-containing polymerizable unsaturated monomer (C), and other components as necessary. A copolymer containing a polymerizable unsaturated monomer (b) as a monomer component.

(2) A product obtained by reacting the hydroxyl group-containing compound (A-2) with the isocyanate group-containing epoxy compound so that each molecule has one or more hydroxyl groups and one or more epoxy groups on average.

As the compound (C), the same compounds as mentioned above can be used.

Each of the above-mentioned ingredients can be obtained by conventionally known methods. That is, reactions between hydroxyl groups and isocyanate groups, condensation reactions between silane groups, copolymerization reactions, etc. can be carried out based on conventionally known methods. For example, the reaction between a hydroxyl group and an isocyanate group is sufficient for about 30 to 360 minutes at room temperature to about 130°C. The condensation reaction of silane groups is carried out in the presence of an acid catalyst (e.g. hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.) with a
Heating at about 0°C for about 1 to 24 hours is sufficient. In addition, the copolymerization reaction can be carried out using the same method and conditions as those used for general synthesis reactions of acrylic resins, vinyl resins, and the like. An example of such a synthesis reaction is a method in which each monomer component is dissolved or dispersed in an organic solvent and heated with stirring at a temperature of about 40 to 180°C in the presence of a radical polymerization initiator. can. The reaction time may normally be about 1 to 24 hours. Further, as the organic solvent, one that is inert to the monomer or compound used, such as an ether solvent, an ester solvent, a hydrocarbon solvent, etc., can be used.

When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility. In addition, as the radical polymerization initiator, any commonly used initiator can be used, and examples thereof include peroxides such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, azo Examples include azo compounds such as isobutyronitrile and azobisdimethylvaleronitrile.

In the above compounds (B), (D), and (F), when a resin composition into which an alicyclic epoxy group is introduced as the epoxy group is used, the addition reaction of the epoxy group to the hydroxyl group is rapid, and the curability of the catalyst is improved. The effect of doing so can be obtained.

In the above compounds (A) to (F), when the monomer represented by the general formula (5) is used as the fluorine-containing polymerizable unsaturated monomer (C), the polymer formed from this monomer is mainly Since it has a structure in which fluorine atoms are bonded to the chain, it exhibits excellent weather resistance and acid resistance, and when the monomer represented by the general formula (6) is used, the fluorine atoms bonded to the side chains are repellent. Demonstrates excellent effects on water-based products, etc.

In the resin composition of the present invention, the fluorine content is about 1 to 70% by weight, preferably about 5 to 60% by weight in the mixture, using the fluorine-containing polymerizable unsaturated monomer (C) as a monomer component. can have a range of

If the content is less than the above range, the resulting coating film will have poor scratch resistance, stain resistance, weather resistance, acid resistance, etc. If it exceeds the above range, the unit price of the resin composition will become high, which is not practical.

The first to fourth aspects of the present invention are the compound (A), the compound (
At least one compound selected from B) and compound (C), or at least one compound selected from compound (A) and compound (D), or compound (E) and compound (B). at least one compound,
Or obtained by using at least one compound selected from the above compound (F) and compound (C) as a dispersion stabilizer, and polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer. It is a resin composition containing polymer particles insoluble in the organic solvent, and if the above-mentioned component is not used as the dispersion stabilizer, it is a non-aqueous dispersion obtained by blending the remaining components.

The above polymer particles can have an average particle diameter of usually about 50 to 1000 μm, preferably about 100 to 500 μm. If the average particle diameter is below the above range, there is a possibility that the characteristics of the dispersion system will not be exhibited. On the other hand, if it exceeds the above range, the storage stability of the composition may deteriorate or the transparency of the coating film may be impaired.

As monomers that can be used to form the polymer that becomes the particle component of the above-mentioned non-aqueous dispersion, all the monomers already described can be used. Preferably, the polymer serving as the particle component is a copolymer containing a large amount of highly polar monomer, since it must not be dissolved in the organic solvent used. That is, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, It is preferable to contain a large amount of monomers such as vinyltoluene, α-methylstyrene, and N-methylol(meth)acrylamide. Also,
The particles of the non-aqueous dispersion can be crosslinked if necessary. Examples of methods for crosslinking the inside of the particles include a method of copolymerizing polyfunctional monomers such as divinylbenzene and ethylene glycol dimethacrylate, and a method of simultaneously using an epoxy group-containing monomer and a carboxy group-containing monomer. Can be done.

The organic solvent used for the non-aqueous dispersion does not substantially dissolve the dispersed polymer particles produced by the polymerization, but is a good solvent for the dispersion stabilizer and radically polymerizable unsaturated monomer. Included. Specific examples of organic solvents that can be used include (aliphatic hydrocarbons such as pentane, hexane, heptane, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene;
Alcohol, ether, ester and ketone solvents, such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methyl hexyl ketone , ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. These may be used alone or in a mixture of two or more, but in general, fatty acids Preferably, the solvent is mainly composed of group hydrocarbons, in combination with aromatic hydrocarbons or the above-mentioned alcohol, ether, ester, or ketone solvents. Furthermore, halogenated hydrocarbons such as trichlorotrifluoroethane, metaxylene hexafluoride, and tetrachlorohexafluorobutane can also be used if necessary.

Polymerization of the above polymer is carried out using a radical polymerization initiator. Examples of usable radical polymerization initiators include azo initiators such as 2,2-azoisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, and lauryl peroxide. Examples include peroxide-based initiators such as oxide and tert-butyl peroctoate, and these polymerization initiators are generally used in an amount of 0.05% per 100 parts by weight of monomers to be polymerized. It can be used within a range of about 2 to 10 parts. The amount of the dispersion stabilizer resin present during the above polymerization is 3 to 400 parts of the radically polymerizable unsaturated monomer per 100 parts of the resin.
It may be used in an amount of about 5 to 240 parts by weight, preferably about 5 to 240 parts by weight.

In the present invention, by combining a dispersion stabilizer resin and polymer particles, the storage stability of a non-aqueous dispersion is improved, and a cured film with excellent transparency, smoothness, mechanical properties, etc. is formed. can do. Examples of the method for bonding the dispersion stabilizer resin and polymer particles include a method of polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable double bond. .

The most effective method for introducing polymerizable double bonds is to add α,β-ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid to a portion of the oxysilane groups in the resin. Although convenient, there are other methods, such as adding an isocyanate group-containing monomer such as isocyanoethyl methacrylate to hydroxyl groups that have been incorporated in the resin in advance, and adding glycidyl methacrylate to some of the carboxyl groups in the resin. There are methods such as adding a monomer.

Furthermore, as a method for bonding the dispersion stabilizer and the polymer particles, in addition to the method described above, as a monomer component forming the polymer particles, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc. Ethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-
There is a method using a reactive monomer such as acryloxypropyltrisilanol.

The non-aqueous dispersion can be used alone or by adding a binder component to the non-aqueous dispersion.

As the binder component, binder components conventionally used for non-aqueous dispersions and dispersion stabilizers used in the non-aqueous dispersion of the present invention can be used.

The mixing ratio of the non-aqueous dispersion and the binder component may be such that the non-aqueous dispersion is about 1 to 100% by weight, preferably about 10 to 80% by weight, based on the total resin solid content of both.

The curable composition of the present invention comprises the resin composition containing a metal chelate compound as a curing catalyst.

The metal chelate compound is preferably an aluminum chelate compound, a titanium chelate compound, or a zirconium chelate compound. Moreover, among these chelate compounds, a chelate compound containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring is preferable.

Compounds that can constitute keto-enol tautomers include β-diketones (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as diaheptone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β
- Favorable results are obtained using diketones.

Aluminum chelate compounds can be prepared, for example, by the general formula [wherein R12 is the same or different and has 1 to 1 carbon atoms]
20 alkyl or alkenyl groups are shown. It is suitably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of usually 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, octadecyl, etc., and examples of alkenyl groups include vinyl, allyl, etc.

Examples of the aluminum alcoholades represented by the general formula (79) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-5ee-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-5ee
-butoxide, aluminum tri-n-butoxide, etc. are preferably used.

The titanium chelate compound has, for example, the general formula [wherein W and R12 are the same as above]. ] A compound capable of forming the above-mentioned keto-enol tautomer is mixed with 1 mol of Ti in the titanates 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.

Titanates represented by the general formula (80) include W
is 1, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl 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 tetraisopropyl titanate, tetra-n-
-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, etc. are used to give suitable results. In addition, for those where W is 1 or more, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tar
2- to 11-mer of t-butyl titanate (general formula (
W-1 to W-10) in 80) give suitable results.

The zirconium chelate compound has, for example, the general formula [wherein W and R12 are the same as above]. ] The above-mentioned compound capable of forming the 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.

The zirconates represented by the general formula (81) are:
Tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-
n-butylzirconate, tetra-5ee-butylzirconate, tetra-tert-butylzirconate, tetra-n-pentylzirconate, tetra-tert-
Pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-hebutyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, etc., especially tetraisopropyl zirconate, tetra-n- -Propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-8ec-butyl zirconate, tetra-
Suitable results are obtained using tert-butyl zirconate and the like. In addition, for those where W is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetra-isobutyl zirconate, tetra-5ee-butyl zirconate, tetra-tert-butyl Zirconate dimer to 11-mer (W in general formula (81) = 1 to 10
) gives suitable results. Further, it may contain a structural unit in which these zirconates are associated with each other.

Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, Isopropoxy bis(ethylacetoacetate)aluminum, diisopropoxyethylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(propionyl acetonato)aluminum, diisopropoxypropionyl acetonatoaluminum, acetylacetonatoto bis(propionyl acetonate) Aluminum chelate compounds such as monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisopropoquine bis(ethylacetoacetate) titanate, diisopropoxy bis(acetylacetonato) titanate , diisopropoxy bis(acetylacetonato) titanate, and other titanium chelate compounds; tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)
Examples include zirconium chelate compounds such as zirconium, tetrakis(acetylacetonato)zirconium, and tetrakis(ethylacetoacetate)zirconium.

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.

In the resin composition of the first aspect of the present invention, the blending amounts of each component are as follows: hydroxyl group-containing compound (A) and epoxy group-containing compound (B).
) Based on the total amount of hydroxyl group-containing compound (A) 5 to 9
5% by weight, preferably 20-80% by weight, 95-5% by weight of epoxy group-containing compound (B), preferably 80-20% by weight
Weight%.

If the ratio of both is outside this range, low temperature curability will deteriorate, which is not preferable. The amount of the silane compound (C) is 0.61 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the hydroxyl group-containing compound (A) and the epoxy group-containing compound (B). The silane compound (C) is 0. If it is less than 1 part by n, the curability will be significantly reduced;
If it exceeds 0 parts by weight, the remaining silane compound (C) will reduce the solvent resistance of the coating film, which is not preferable. The metal chelate compound is 0.01 parts by weight per 100 parts by weight of the hydroxyl group-containing compound (A) and the epoxy group-containing compound (B).
~10 parts by weight, preferably 0.1 to 5 parts by weight. If the amount of the metal chelate compound is less than 0.01 parts by weight, the curability will decrease, while if it exceeds 10 parts by weight, the water resistance of the coating will decrease, which is not preferable.

In the resin composition of the second invention of the present invention, the hydroxyl group-containing compound (A) is preferably 5 to 95% by weight, based on the total amount of the hydroxyl group-containing compound (A) and the epoxy group- and silane group-containing compound (D). 20 to 80% by weight, 95 to 5% by weight of epoxy group- and silane group-containing compound (D), preferably 80% by weight
~20% by weight. If the ratio of both is outside this range, the curability, especially the low temperature curability, will deteriorate, which is not preferable. In addition, the metal chelate compound is a hydroxyl group-containing compound (A
) and the epoxy group- and silane group-containing compound (D) in a total amount of 100 parts by weight, from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight. 0 metal chelate compounds
If the amount is less than 11 parts by weight, the curability decreases, while if it exceeds 10 parts by weight, the water resistance of the coating film decreases, which is not preferable.

In the resin composition of the third invention of the present invention, based on the total amount of the hydroxyl group- and silane group-containing compound (E) and the epoxy group-containing compound (B), the hydroxyl group- and silane group-containing compound (E)
5 to 95% by weight, preferably 20 to 80% by weight, 95 to 5% by weight of epoxy group-containing compound (B), preferably 80% by weight
~20 weight n%. If the ratio of both is outside this range, the curability, especially the low temperature curability, will deteriorate, which is not preferable. Further, the metal chelate compound is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts of the total amount of the hydroxyl group- and silane group-containing compound (E) and the epoxy group-containing compound (B). Sebe. 0 metal chelate compounds
．． If the amount is less than 10 parts by weight, the curability will decrease, while if it exceeds 10 parts by weight, the water resistance of the coating will decrease, which is not preferable.

In the resin composition of the fourth aspect of the present invention, based on the total amount of the hydroxyl group- and epoxy group-containing compound (F) and the silane compound (C), the hydroxyl group- and epoxy group-containing compound (F) 5 to
95% by weight, preferably 20 to 80% by weight, and 95 to 5% by weight, preferably 80 to 20% by weight of the silane compound (C).

If the ratio of both is outside this range, the curability, especially the low temperature curability, will deteriorate, which is not preferable. The metal chelate compound is used in an amount of 0.01 to 100 parts by weight based on 100 parts by weight of the hydroxyl group- and epoxy group-containing compound (F) and the silane compound (C).
10 parts by weight, preferably 0. The amount is 1 to 5 parts by weight. If the amount of the metal chelate compound is less than 0.01 parts by weight, the curability will decrease, while if it exceeds 10 parts by weight, the water resistance of the coating will decrease, which is not preferable.

The above-mentioned metal chelate compounds, preferably compounds such as acetoacetic acid esters and β-diketones, can be added to the curable composition of the present invention in order to improve storage stability.

The coating composition of the present invention can be used as a top coat and/or intermediate coat for automobiles by blending various known additives as required.

When the coating composition of the present invention is used as a top coat, examples of the composition include a top coat solid color paint, a two-coat paint, and a two-coat paint.
When used as a top clear paint for one-bake coating or a top clear paint for three-coat/two-bake coatings, 100 parts by weight of base resin, 0.1 to 30 parts by weight of metal chelate compound, and 01 to 0 parts by weight of swelling pigment. The degree is appropriate. As the swelling pigment, both inorganic and organic highly weather-resistant swelling pigments used in conventional automotive top coatings can be used, such as inorganic pigments such as rutile-type titanium oxide or carbon black, and quinacridone. Organic pigments such as quinacridone pigments such as red, azo pigments such as pigment red, and phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green can be used. When used as a clear paint for 2 coats/1 bake coat or a clear paint for 3 coats/2 bake coats, it is usually used without adding any swelling pigment.

Among the top coat paints, when used as a base coat paint for 2 coats/1 bake coat or a metallic paint for 1 coat/1 bake coat, the composition is base resin 100%
Suitable parts by weight include 0.1 to 30 parts by weight of the metal chelate compound, 2 to 36 parts by weight of the metallic pigment, and 0 to 40 parts by weight of the swelling pigment. As the metallic pigment, known ones can be used, for example, scaly metallic powders of aluminum, copper, mica-like iron oxide, bronze, stainless steel, etc. can be used, and as the swelling pigment, the above-mentioned ones can be used. Either can be used.

In addition, as a modified resin for rheology control to adjust the arrangement of metallic pigments and improve the metallic feel, acrylic dispersions with core crosslinking obtained by heterogeneous polymerization obtained by known methods, cellulose acetate butyrate, etc. It is also possible to mix up to about 20 parts.

In addition, when the coating composition of the present invention is used as an intermediate coating for automobiles, the composition includes 100 parts by weight of the base resin, 0.1 to 30 parts by weight of the metal chelate compound, 5 to 150 parts by weight of the pigment, and 2 parts by weight per molecule. The amount is about 0 to 100 parts by weight of a low molecular weight compound having 1 or more oxirane groups. As the pigment, inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and clay, and organic pigments for swelling can be used.

The coating composition of the present invention can be used, for example, as an electrostatic coating (bell type, REA
Painting can be done by air spray painting, etc., and conventional painting machines and painting equipment can be used as they are.

The coating viscosity at the time of painting is as follows:
About 15-35 seconds (Ford Cup No. 4.20°
C) When used as a top coat, it is appropriate to apply for about 12 to 30 seconds (Ford Cup No. 4.20°C), and the coating time can be selected appropriately depending on the coating machine, type of solvent, coating conditions, etc. good.

As the solvent for diluting the paint, all solvents used in conventional acrylic resin/melamine resin paints can be used, such as hydrocarbon solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. , ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether, and alcohol solvents such as butanol and propatool. These solvents can be used alone or in an appropriate mixture, but when an alcoholic solvent is used, it is preferable to use it in combination with another solvent from the viewpoint of solubility of the resin. Further, from the viewpoint of hardness rate, those having a boiling point of about 150'C or less are preferable, but are not limited thereto.

The coating composition of the present invention can be prepared, for example, by electrodepositing a primer on a chemically treated copper plate, and applying an intermediate coating (which may be omitted in some cases).
Intermediate paint and / Or it can be used as a top coat.

When used as an intermediate coating, the appropriate film thickness is about 25 to 60 μm based on the film thickness after drying. On the other hand, the film thickness when used as an f9 paint is based on the film thickness after drying.
When used as a metallic color paint for one coat/one bake coat, a top clear paint for two coats/one bake coat, a top clear paint for three coats/two bake coats, etc., the thickness is about 20 to 60 μm, preferably 30 to 40 μm.
When used as a two-coat/one-bake metallic base coat paint, the appropriate thickness is about 10 to 25 μm, preferably about 10 to 20 μm.

The coating 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 can be sufficiently cured usually in about 8 hours to 7 days. The curable composition of the present invention has excellent low-temperature curability because the curable composition of the present invention has excellent low-temperature curability. It can be thought of as follows. That is, in the -th stage reaction, the metal chelate compound reacts with the silane group to form the following bond.

■ ”::, A Q -0-8i- Next, this bond coordinates to a silanol group (alkoxysilane groups, acyloxysilane groups, etc. become silanol groups due to moisture in the air), and becomes This polarized silanol group reacts with an epoxy group to form.Next, this reacts with a hydroxyl group to form -c-o-c-c-H.This epoxy group and hydroxyl group The reaction proceeds at relatively low temperatures.

The curable composition of the present invention contains a hydroxyl group-containing compound as an essential component, and further contains an epoxy group, a silane group, and a metal chelate compound, so that the above reaction proceeds quickly and has excellent low-temperature curability. It is estimated that the

The fluorine component in the composition of the present invention has poor compatibility with components containing alkoxy groups and epoxy groups, and there is no fear of inhibiting the reaction between alkoxy groups and epoxy groups, so that excellent curability can be achieved.

In addition, fluorine atoms chemically bonded to the cured product can be exposed to light, heat,
It is possible to obtain a cured product that is chemically stable against external contributions such as water and has low surface energy.

Furthermore, the composition of the present invention is a non-aqueous dispersion in which a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase in which a dispersion stabilizer resin is dissolved in an organic solvent. It contains a metal chelate compound. As a result, the workability during coating of the composition is improved, and a film with good durability and excellent finished appearance can be formed. Furthermore, the formed film has a continuous phase of siloxane bonds and C.
- It is a photo- and chemically stable film having a -F bond, and the polymer particle component in the film is stabilized by the continuous phase, and the film is reinforced by the particle component, so it is photo- and chemically stable. It has excellent 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.

Effects of the Invention According to the composition of the present invention, the following excellent effects can be achieved.

(1) A coating film having a high degree of smoothness, sharpness, and texture can be obtained. That is, since the main curing reaction is an ionic polymerization reaction and an addition reaction, the generation of reaction by-products is extremely small, and since it is a dispersed resin composition, the volumetric shrinkage during the coating film curing process is small. It is possible to obtain a highly smooth coating film with excellent durability and no slight unevenness (chirpy skin). Therefore, the image clarity is also excellent.

■ One-component paint with good low-temperature curing properties. If the baking time is 30 to 40 minutes, a sufficient crosslinking reaction will occur even at a temperature of about 80°C.

■ One-component paint with good paint stability and low toxicity.

■ Extremely good acid resistance. That is, the basic resin skeleton has a C-F bond with excellent chemical stability, and the crosslinking points have a structure that is resistant to acids, so the acid resistance is extremely good. Therefore, problems such as stains, glossy pique, and etching caused by acid rain etc. do not occur at all.

(!5) Strong stain resistance. That is, it has high resistance to various pollutants due to its dense crosslinking density, polysiloxane bonds present in the base resin, low surface energy effect based on the fluorine component, and high water repellency.

0 Good water repellency. That is, due to the polysiloxane bond and fluorine component present in the base resin, the resin has high hydrophobicity and good water repellency. In particular, the fluorine component in the side chain of the base resin lowers the surface energy of the coating film, and exhibits high water repellency, especially as a coating film for automobiles.

(7) Good scratch resistance. Good scratch resistance is achieved due to the synergistic effect of the frictional resistance reducing effect based on the dense crosslinking density and the polysiloxane bonds and C-F bonds present in the base resin.

■ A coating film with high weather resistance (no gloss, cracking, chalking, blistering, etc.) can be obtained. That is, in addition to the presence of C-F bonds with extremely high chemical stability, crosslinking reactions include ionic polymerization of epoxy groups, addition reactions of epoxy groups with silanol groups and hydroxyl groups, and condensation reactions of silanol groups. Since there are few by-products during curing and curing, there is little difference in curability between the surface and inside of the coating, and almost no uncured material remains, resulting in a high degree of weather resistance.

Due to the above characteristics, the composition of the present invention can be suitably used as, for example, a top coating for automobiles.

Example Examples are given below to further clarify the present invention.

First, an example of producing a copolymer will be shown.

Production Example 1 [Production of Copolymer (1)] In a stainless steel autoclave with a stirrer and a capacity of 400 mQ, CH2=CHO(CH2)40H15 parts by weight CH2=C
H0-() 30 parts by weight CH2=CH0C
65 parts by weight of each monomer and 200 parts by weight of methyl isobutyl ketone, 2 parts by weight of azobisisobutyronitrile, and 0.5 parts by weight of sodium borate were charged, and after purging with nitrogen, solidifying by cooling, and degassing, CF2=CFCQ
50 parts by weight was introduced into the autoclave, and the temperature was gradually raised until the internal temperature of the autoclave reached 60°C.

Thereafter, the reaction was continued with stirring for 16 hours or more, and when the internal pressure of the autoclave decreased to 1 kg/cJ or less, the autoclave was ice-cooled to stop the reaction. The obtained resin solution was poured into excess hebutane to precipitate the resin, which was then washed and dried to obtain 93 g of resin. Yield 9
3%. The number average molecular weight by GPC was 5,000.

The obtained resin was dissolved in xylene of the same seedling to obtain a resin solution containing 50% non-volatile components.

Production Examples 2 to 5 Various copolymers (copolymer (2) to
(5)) was obtained. Table 1 shows the amount (parts by weight) of monomer and the number average molecule ffi (Mn) of the copolymer.

Production Examples 6 to 8 Acrylic copolymer fabrics (copolymers (
6) to (8)) were obtained. Both are xylene solutions with a non-volatile content of 50% by weight. Table 2 also lists the number average molecular weights determined by GPC.

The FM-3 monomer in Table 2 is a caprolactone-modified methacrylic ester containing a hydroxyl group, and has an average molecular weight of 472 and a theoretical hydroxyl value of 119K OHB/g [manufactured by Daicel Chemical Co., Ltd.].

Moreover, a manufacturing example of macromonomer B is listed below.

Production Example of Macromonomer B Phenyltrisilanol 7800g - The blending amount in Table 2 is the total amount of the active ingredient as a macromonomer.

Production Example 9 [Production of copolymer (9)] 200 parts by weight (CH30) of copolymer (1) solution (non-volatile content 50%) was placed in a ff1400111Q glass flask with a stirrer. a S i C3H6N C013,3
Weight part γ-acryloxypropyltrisilanol 200gC11z
-CIICOOC3II 65i (0 (Jb) a
(1 mol) Toluene 4500
g the mixture of the above components was reacted at 117°C for 3 hours,
Dehydrated. The number average molecular weight of the obtained polysiloxane macromonomer was 7,000, with an average molecular weight of 1 per molecule.
It had 5 to 10 vinyl groups and 5 to 10 hydroxyl groups.

23.5 parts by weight of xylene and 36.8 parts by weight were charged, and the addition reaction of 10H groups and -NGO groups was continued at 90°C for 5 hours with stirring.

In the infrared absorption spectrum, -
〇Since the absorption of H groups has disappeared, copolymer (1) of Production Example 1 contains 3 -S i (OCH3) groups and 400 customers.
In a glass flask with a stirrer, add 200 parts by weight of copolymer (2) solution (non-volatile content 50%)! 3 CO) 3 Si Ca Hs SH45
45 parts by weight of xylene at the mold opening and -S
An addition reaction of H groups was carried out.

completely disappeared, confirming that three -8i (OCH3) groups were introduced into the copolymer of Production Example 2.

A polyester polyol was produced by the method shown below.

Production Example 11 In a glass flask with a capacity of 400 and equipped with a stirrer, 192 parts by weight of phthalic anhydride, 256 parts by weight of hexahydrophthalic anhydride, and 107 parts by weight of adipic acid.
Parts by weight Neopentyl glycol 357 parts by weight Trimethylolpropane 88 parts by weight were charged and heated at 160°.
℃ to 230℃ over 3 hours, then 23℃
After keeping at 0°C for 1 hour, 50g of kijirole was added and reacted until the acid value reached 7.5. After cooling this, xylene/
Solid content weight% is 50% with n-butanol = 4/1 solvent
It was diluted so that The number average molecular weight of the obtained resin by GPC was about 5,000.

Preparation of Dispersion Stabilizer (1) Introduction of Double Bonds into Copolymer (1) Into a glass flask equipped with a stirrer with a capacity of ff 1400 rrlQ, a solution of copolymer (1) (non-volatile content 5091200 parts by weight CH, =C ( CH3) COOC2H4NCO3.1 parts by weight Hydroquinone 0.02 parts by weight Xylene
Add 3.1 parts by weight and add 110 parts by weight while stirring.
The addition reaction was carried out at ℃ for 5 hours, and the isocyanate value was 0.
I confirmed that it was below 001. This means that an average of 1.0 copolymerizable double bonds were introduced per molecule of the copolymer.

Production of dispersion stabilizers (3), (5) and (7) Dispersion stabilizers (
Similarly to the production of 1), copolymers (3), (5) and (7)
) introduced a double bond.

Table 3 lists the copolymer, the added isocyanate monomer, and the average number of copolymerizable double bonds per molecule of the copolymer. The number of copolymerizable double bonds was adjusted by adjusting the amount of isocyanate monomer charged.

[Production of dispersion stabilizer (2)] Introducing double bonds into copolymer (2) Into a glass flask equipped with a stirrer and having a capacity of ff 1400w2, 200 parts by weight of copolymer (2) solution (non-volatile content 50%) was added H2C. =C(CHa)COOH1,2 parts by weight 4-t
ert-butylpyrocatechol 0.04 parts by weight dimethylaminoethanol 0.1 parts by weight xylene
1. Prepare 2 polymerization parts and add 1 while stirring.
Addition reaction was carried out at 20°C for 5 hours, and the resin acid value was 0.00.
It was confirmed that the concentration was 1 mgKOH/g or less. This means that an average of 0.6 copolymerizable double bonds were introduced per molecule of the copolymer @ Manufacturing of dispersion stabilizers (4), (6), (8) and (9) Dispersion stabilizers Double bonds were introduced into each copolymer in the same manner as in the production of (2). Table 4 shows the copolymer, added α,
The average number of copolymerizable double bonds per molecule of β-ethylenically unsaturated monocarboxylic acid and copolymer is listed. The number of copolymerizable double bonds was adjusted by adjusting the amount of α,β-ethylenically unsaturated monocarboxylic acid.

[Production of dispersion stabilizer (8)] Introducing double bonds into copolymer (8) Into a glass flask equipped with a stirrer and having a capacity f1400 mQ, 200 parts by weight of copolymer (8) solution (non-volatile content 50%) 1 .8 parts by weight Hydroquinone 0.01 parts by weight Dimethylaminoethanol 0.1 parts by weight Xylene
1.8 parts by weight was added and an addition reaction was carried out at 120°C for 5 hours with stirring, resulting in a resin acid value of O, OO1mgKOH/g.
I confirmed that the following has happened. This means that an average of 0.8 copolymerizable double bonds were introduced per molecule of the copolymer.

Example 1 [Production of dispersed polymer liquid (1)] Heptane
80 ffl parts n-butyl acetate
10 parts by weight dispersion stabilizer (1) solution (non-volatile content 50
%) was placed in a flask, heated to reflux, and the following monomer and polymerization initiator were added dropwise into the flask over 3 hours. After further aging for 2 hours, 10 parts by weight of n-butyl acetate was added. .

CH2=CH() 10 parts by weight CH2=C
(CH3) COOCH355 weight H2=C(CH3)COOC2HA 0H35 parts by weight 2.2'-Azobisisobutyronitrile 2 parts by weight (total of particle-forming n-body components 100 parts by weight, particle components/dispersion stabilizer ( Solid content ratio) = 50150) The nonvolatile content of the obtained dispersant was adjusted to 50% with n-butyl acetate. The polymer particles were a milky white stable dispersion having a particle size (average particle size measured by Coulter N4 (Coulter)) of 0.times.10 .mu.m. No precipitation or coarse particles were observed in this product even after 3 months at room temperature.

Examples 2 to 10 [Production of dispersed polymer liquids (2) to (10)] Dispersed polymer liquids were produced in the same manner as in Example 1. Table 5 shows the content of the dispersion stabilizer in the total resin (solid content polymerization %), the monomer composition ratio of the particle forming components (weight %), and the average particle size of the produced polymer particles.

1) Copolymer (10).

2)...Manufactured by Daicel Chemical ■, hydroxyl group-containing caprolactone-modified methacrylic ester 3)...Average particle size by Coulter N4 (Coulter Co., Ltd.) Example 11 Copolymer obtained in the above production example and Example 1 An automobile top coat was prepared using the obtained dispersed polymer liquid. As the top coat, a solid color (white) and a two-coat, one-bake clear coat were prepared. In addition, base coat A was produced as a two-coat, one-bake base coat.

Preparation example of solid color (white) (Paint No., S-1 to 5
-5) are shown in Table 6. Titanium oxide was dispersed using a copolymer solution in a paint shaker for 1 hour, and then the dispersed polymer was added. The pigment blender has a resin solid content of 10
The amount was 80 parts by weight based on 0 parts by weight. The amounts of copolymers and dispersion polymers shown in Table 6 are all weight % of the active ingredient (resin content). Further, the amount of the metal chelate compound is expressed in weight percent (PHR) based on 100 resin content. still,
Table 6 shows the amount of particle components in the dispersed polymer (degree of disversion) in weight % in the total resin content.

Preparation example of clear coat for 2 coats and 1 bake (Paint N (
LM-1 to M-10) are shown in Table 7. The meanings of the numbers in the table are the same as for solid colors.

At this time, the following metal chelate compounds were used.

・Chelate compound I...tris(acetylacetonato)aluminum chelate compound■...tris(ethylacetoacetate)aluminum chelate compound■...tetrakis(acetylacetonato)zirconium chelate compound■...di Isopropoxy bis(acetylacetonato) titanate 2 coats 1 bake base coat (Baseco)
A production example of A) is shown.

Preparation of Base Coat A A base coat combining two coats and one bake clear coat was prepared as follows.

Preparation of siloxane macromonomer Methyltrimethoxysilane 2720 g (20 mol) γ-methacryloxypropyl 256 g Rutrimethoxysilane (1 mol) Deionized water
1134g 60% hydrochloric acid 2
gHydroquinone 1g A mixture of the above components was reacted at 80°C for 5 hours. The number average molecular weight of the obtained polysiloxane macromonomer was 200.
0, and on average had one vinyl group (polymerizable unsaturated group) and four hydroxyl groups per molecule.

A copolymer was produced using the obtained macromonomer.

Polysiloxane macromonomer 150g 2-hydroxyethyl acrylate 100g 50g n-butyl acrylate 500g styrene 100g azobisisobutyronitrile A mixture of 10g was dropped into 1000g of an equal weight mixture of butanol and xylene at 120°C, polymerized, and a transparent A copolymer was obtained. The number average molecular weight was approximately 30,000.

Using the obtained copolymer, a two-coat, one-bake metallic base having the following composition was prepared.

All formulations are expressed in solids weight.

Above copolymer 95 parts Cellulose acetate butyrate 5 parts Aluminum paste #55-519
13 parts [manufactured by Toyo Aluminum ■] 1 part aluminum trisacetylacetone This was then mixed with a mixed thinner of toluene/Sufsol #1500 (trade name, manufactured by Maruzen Sekiyu ■) = 80/20 for 13 seconds (Ford Cup No. 4.
The viscosity was adjusted to 20° C.) and used for coating.

[Preparation of coating material] A coating material was prepared as follows.

Preparation of Material (A) A chemical conversion treated dull steel plate was coated with approximately 25 μm of epoxy resin-based cationic electrodeposition paint, heated and cured at 170°C for 30 minutes, and then coated with Lugabake AM [trade name, manufactured by Kansai Paint ■] as an intermediate coating. , polyester resin/melamine resin automotive paint] was applied to a dry film thickness of about 30 μm, and baked at 140° C. for 30 minutes. Next, the coated surface was sanded with #400 sandpaper, drained and dried, and the coated surface was wiped with petroleum benzene to prepare a material.

Preparation of material (B) Apply 15 to 20 μm of Solex No. 2500 as a primer to polypropylene resin, and heat at 80°C for 20 minutes.
The material that was baked for a minute was used as a paint material.

Preparation of test coated plate (I) Apply the top coat solid color prepared above to the above material A with Swazol #1000 [trade name, Maruzen Sekiyu ■
made in a petroleum-based mixed solvent for 22 seconds (Ford Cup No.
The viscosity is adjusted to 4.20℃) and the dry film thickness is 40 to 50μm.
After painting it so that it looks like this and leaving it for 10 minutes at room temperature,
A test plate was baked at 0°C for 30 minutes.

In addition, the angle of the coated plate for evaluating the feeling of texture during the above-mentioned leaving and baking was set at an angle of about 75° with respect to the horizontal plane.

As a comparison sample, Lugabake AM white (paint Nα5-6
), a comparative test board was created in the same manner.

Further, the above material B was coated in the same manner and baked at 80° C. for 30 minutes. As a comparative product, Retan PG80 White [trade name, manufactured by Kansai Paint Co., Ltd., paint No. S-7] was used.

The test results are shown in Table 8. In Table 8, paint No.
S-6 and S-7 are comparative examples.

Preparation of test coated plate (II) Base coat A was applied to the above material A, left for about 5 minutes, and then immediately coated with clear (paints NCLM-1 to M-10) diluted with Swasol #1000 for 22 seconds. . Paint film thickness is base coat 15-20μm in dry film thickness.
1 clear coat was 35 to 45 μm. Painting approx. 10
After standing at room temperature for a minute, baking was performed at 100°C and 140°C for 30 minutes.

Here, the angle of the coated plate for evaluating the feeling of texture during the above-mentioned leaving and baking was set at an angle of about 75° with respect to the horizontal plane.

Further, Magikron #1000 Silver was applied as a base coat, and Magikron #1000 Clear (manufactured by Kansai Paint ■, acrylic/melamine resin paint, No. M-11, Comparative Example) was applied as a clear coat, and baked in the same manner. It did not cure at 100°C. The results are shown in Table 9.

3) Pencil hardness: Scratch the paint surface with the lead of a Mitsubishi Uni pencil,
The maximum hardness of the core that will not scratch the painted surface is indicated by a symbol.

4) IMAGE CLARITY METE
R: Measured with Suga Test Instruments ■. The numbers in the table are ICM
The value ranges from 0 to 100%, and the larger the value, the better the image clarity, and an ICM value of 80 or more indicates extremely excellent image clarity.

5) Feeling of texture As mentioned above, the texture of the coated plate which was left and baked at an angle of 75° with respect to the horizontal plane was visually observed and evaluated.

◎...Excellent meatiness.

○...There is a feeling of sufficient fleshiness.

Δ...The finish is poor in texture and is rejected.

×...There is no feeling of meatiness. The finished appearance is particularly poor.

6) Resistance to Kijiroll Hold the gauze soaked in Kijiroll with your fingers and rub the coated surface back and forth 1
Rub hard 0 times. The condition of the coating surface is ◎, 0, ■, Δ, ×, with the degree of scratches and swelling being good (◎) and markedly poor (X).
It was judged on a five-point scale.

7) Impact resistance A DuPont impact tester was used (striking core diameter 1/2 inch, weight 0.5 kg). The maximum weight drop height that does not cause cracks in the paint film is indicated.

8) Weather resistance After immersing in 40% sulfuric acid at 40°C for 5 hours, take it out and wash it with water.
The condition of the painted surface was evaluated. ◎, O1 ■, △, X
It was judged on a five-point scale.

9) Scratch resistance A dyed product rubbing fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho) was used. Knead polishing powder (Daruma Cleanser) with water, place it on the painted surface, press the top with the testing machine terminal, and weigh 0.5 kg.
Apply a load and rub it back and forth 25 times. After washing with water, the degree of scratches was evaluated in five stages: ◎, ○, ■, Δ, and ×.

10) Water resistance The test piece is immersed in a constant temperature water bath at 40°C for 240 hours. After taking it out, the paint film was rated ◎ if there were no abnormalities such as gloss, piquancy, or blistering.

11) Spread the JIS 1st bay uniformly on a 5x5cm coated plate,
It was left standing at 20°C for 24 hours. Next, this was washed under running water using a clean brush, and the degree of contamination was examined.

◎...No stains observed at all.

0: Slight stains are observed.

△: Considerable dirt is observed.

×... Significant stains are observed.

12) Water repellency It is expressed as a value obtained by measuring the contact angle of water with the painted surface.

The contact angle was measured 3 minutes after dropping 0.03 mQ of distilled water (at 20° C.) using a contact angle meter manufactured by Kyowa Kagaku ■ as a measuring device. The larger the number, the greater the water repellency.

13) Weather resistance: Based on QUV accelerated bakuro test using an accelerated weather resistance tester manufactured by Q Panel Co., Ltd.

Test conditions: UV irradiation 16H/60℃ water condensation 8H1
The coating film was evaluated after testing at 50° C. for 3000 hours (125 cycles).

◎...It maintains almost the same luster as the initial one.

○: There is a slight decrease in gloss, but there are no defects such as cracking or whitening.

×: Significant reduction in gloss, cracking, and whitening (chalking) phenomena were observed, resulting in a failure.

14) Storage stability The paint diluted to a constant viscosity (22 seconds/Ford Cup No. 4) was stored at 40°C for one week with a lid on to prevent contact with the outside air.

◎...Viscosity increase for less than 5 seconds.

■...Viscosity increase within 5 to 10 seconds.

X...Gelification.

(Hereafter Up)

Claims (1)

[Scope of Claims] [1] Three components: a hydroxyl group-containing compound (A), an epoxy group-containing compound (B), and a compound (C) containing a silanol group and/or a hydrolyzable group directly bonded to a silicon atom. A resin composition containing the compound (A), the compound (
A resin composition in which at least one compound selected from B) and compound (C) is a fluorine-containing resin,
At least one compound selected from the compound (A), compound (B) and compound (C) is used as a dispersion stabilizer, and the radically polymerizable unsaturated monomer is mixed in an organic solvent in the presence of the dispersion stabilizer. It is a resin composition containing polymer particles that are insoluble in the organic solvent obtained by polymerization, and if the above three components are not used simultaneously as the dispersion stabilizer, the remaining components are added. Characteristic resin composition. [2] A resin composition containing two components: a hydroxyl group-containing compound (A), and a compound (D) containing a silanol group and/or a hydrolyzable group directly bonded to a silicon atom and an epoxy group, provided that the above compound At least one compound selected from (A) and the compound (D) is a resin containing fluorine, the at least one compound selected from the compound (A) and the compound (D) A resin composition that is used as a dispersion stabilizer and contains 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,
Furthermore, when the above two components are not used simultaneously as the dispersion stabilizer, the resin composition is characterized in that the remaining component is blended. [3] A resin composition containing two components: a compound (E) containing a hydroxyl group and a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, and an epoxy group-containing compound (B), provided that the compound ( A resin composition in which at least one compound selected from E) and the compound (B) is a fluorine-containing resin, wherein the compound (E) and the compound (B) contain fluorine.
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 at least one compound selected from B). 1. A resin composition containing particles, further comprising the remaining component as a dispersion stabilizer when the above two components are not used at the same time. [4] A resin composition containing two components: a compound (F) containing a hydroxyl group and an epoxy group, and a compound (C) containing a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, provided that the above-mentioned A resin composition in which at least one compound selected from compound (F) and compound (C) is a fluorine-containing resin, wherein at least one compound selected from compound (F) and compound (C) is a fluorine-containing resin. A resin composition containing 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, using as a dispersion stabilizer, Furthermore, when the above two components are not used simultaneously as the dispersion stabilizer, the resin composition is characterized in that the remaining component is blended. [5] A curable composition characterized in that a metal chelate compound is blended as a curing catalyst into the resin composition according to claims [1] to [4]. [6] A curable composition containing the composition according to any one of claims [1] to [5] as an essential component.