GB2230783A - Curable composition comprising an epoxy/silanol resin system - Google Patents

Description

1 CURABLE COMPOSITION The present invention relates to a novel curable

composition.

Known curable compositions include those comprising a hydroxyl-containing resin and a crosslinking agent such as a diisocyanate compound, a melamine resin or the like and curable with the crosslinking agent. These curable compositions, however, have drawbacks. For example, the use of diisocyanate compound gives a coating film unsatisfactory in weatherability and likely to yellow. On the other hand, the use of melamine resin usually necessitates baking at high temperatures of about 1400C or above and provides a coating film having a poor resistance to acids.

Other curable compositions are available. For example, Japanese Unexamined Patent Publication No.67553/1985 discloses a curable composition comprising an aluminum chelate compound and a vinyl polymer of alkoxysilane compound such as methacryloxypropyltrimethoxysilane. Yet the disclosed curable composition is defective. Since the silanol group formed by the hydrolysis of alkoxy silane group is the sole crosslinking functional group, the composition requires a large quantity of water for curing. Consequently large amounts of by-products, such as alcohol, resulting from the hydrolysis give impaired properties to the cured product. Further when the composition is cured in the presence of only the moisture in air, the composition initially becomes cured at the surface, with its interior generally remaining incompletely cured, so that the curing is likely to result in a shrunk product. Further disadvantageously the curable composition forms a coating film of low adhesion to substrates and coating films.

It is an object of the present invention to provide a novel curable composition free of the above drawbacks.

It is another object of the invention to provide a nove.' curable composition which is excellent in curability and which gives a coating film outstanding in resistance to weather and acids, adhesion to substrates and coating films, appearance properties and the like.

These and other objects of the invention will become apparent from the following description.

According to the present invention, there is provided a curable composition comprising: (I) a resin component containing as essential functional groups epoxy group, and silanol group and/or hydrolyzable group directly attached to silicon atom, (II) at least one crosslinking agent selected from the group consisting of carboxylic acid compounds, polyisocyanate compounds and amincaldehyde resins, and (III) at least one curing catalyst selected from the group consisting of organometallic compounds, Lewis acids, protonic acids and compounds having Si-O-Al bond or bonds.

We conducted research and found that a novel curable composition comprising a resin component containing as essential functional groups silanol group and/or hydrolyzable group directly attached to silicon atom (these groups being hereinafter referred to as lisilane group") and epoxy group, the above-specified crosslinking agent 6nd the above-specified curing catalyst can overcome the foregoing drawbacks of conventional curable compositions and are excellent in curability and capable of giving a coating film outstanding in resistance to weather and acids, adhesion to substrates and coating films, appearance properties and the like. The present invention has been accomplished on the basis of this novel finding.

The term "hydrolyzable group directly attached to silicon atom" used herein refers to a group which hydrolyzes in the presence of water or moisture, giving silanol group. Examples of such hydrolyzable groups include those represented by the formulas O-Rl 0 11 (2') 1 R@ l@ \1 (3') W' 11 R' 11 "I" (4') R%' 11 -N "..I R' 1% (51) R" 't 0 11 -N-C-R 1 #1 1 E- W) In the foregoing formulas, R' is an alkyl having 1 to 4 carbon atoms, R", R" and R"" are the same or different and each represent an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group.

Examples of the Cl-8 alkyl group in these formulas are methyl, ethyl, npropyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, noctyl, iso-octyl, etc. Examples of the aryl group are phenyl, toluyl, xylyl, etc. Examples of the aralkyl group are benzyl, phenethyl, etc.

Examples of the hydrolyzable group directly attached to silicon atom include a 1:1--Si-H group.

The curable composition of the present invention comprising (I) the resin component, (II) the crosslinking agent and (III) the curing catalyst as described above. Among these ingredients, (I) resin component containing a essential functional groups silane group and epoxy group will be described below in detail.

Preferred examples of (I) resin component are those containing as essential functional groups silane group. epoxy group and hydroxyl group in view of a high curability.

Suitable examples of the silane group in (I) resin component are the groups of the formula (1') and (2') and silanol group which are useful to improve the curability, storage stability and the like.

Proper examples of the epoxy group in (I) resin component are alicylic epoxy groups which rapidly react with silane group and hydroxyl group and which are useful for improvement of curability.

(I) resin component is a resin or a resin - 6 mixture each containing silane and epoxy groups, or silane, epoxy and hydroxyl groups. Specific examples are given below in (i) to (v): (i) a resin containing silane and epoxy groups (hereinafter referred to as "resin component (i)"); (ii) a resin mixture of a silane-containing resin or compound and an epoxy-containing resin or compound in which at least one of them is a resin (hereinafter referred to as "resin component (ii)"); (iii) a resin containing silane, epoxy and hydroxyl groups (hereinafter referred to as "resin component (iii)"); (iv) a resin mixture which is a resin component (ii) in which hydroxyl group is present in one or both of the silane-containing resin or compound and the epoxycontaining resin or compound (hereinafter referred to as "resin component (iv)"); and (v) a resin mixture which consists of any one of resin components (i) to (iv) and a hydroxyl-containing resin or compound (hereinafter referred to as "resin component M")- The resin components (i) to (v) will be described below in detail. Ai) Resin component The resin component (i) contains at least one epoxy group and at least one sialne goup on the average in z - 7 the molecule and has a number-average molecular weight of about 1,000 to about 200,000, preferably about 3,000 to about 80,000. The resin component (i) having less epoxy and silane groups than the above range gives a composition lower in curability, hence undesirable. The resin component (i) having a number-average molecular weight of less than about 1,000 gives a coating film impaired in the physical properties, resistance to weather and the like, and the resin component (i) having a number-average molecular weight of above about 200,000 increases the viscosity of the composition and deteriorates the amenability of the composition to coating operation, hence undesirable.

Examples-of the resin component (i) include, for example, a reaction product prepared by reacting a resin (A) having functional group, a compound (B) having epoxy group and functional group complementarily reactive with the functional group of the resin (A), and a compound (C) having silane group and functional group complementarily reactive with the functional group of the resin (A).

The resin (A), compound (B) and compound (C) are described below in detail.

The term "functional group complementarily reactive with the functional group" used herein refers to the functional groups reactive with each other. Suitable - 8 functional groups are selectable for example from those listed below.

R 1 v) 11 Resin - Kind Function-al Group Hydroxyl group (1) Carboxyl group (2) Resin (A) Silane group (3) Epoxy group (4) Isocyanato group (5) Mercapto group ( Amino group (NH,NH2) (7) Acid anhydride group (8) Phenolic hydroxyl group (9) Table

Kind Compound (B) Compound (C) Compound - Functional Group Hydroxyl group (1) Silane group (3) Epoxy group (4) Isocyanato group (5) Unsaturated qrc)llr-) (81 Hydroxyl group (1) Carboxyl group (2) Silane group (3) Epoxy group (4) isocyanato group (5) Mercapto group (6) Amino group (NH,NH2) (7) Unsaturated group (8) 1 W 1 - The functional groups complementarily reactive with each other can be suitably selected from the above list to provide a combination. Suitable combinations are given below. Combinations of functional groups of resin (A)/compound (B) (1)/(5), (2)11(4), (3)/(3), (4)/(1), (S)/(1), (6)/(4), (6)/(8), (7)/(4), (7)/(5), (7)/(8), (8)/(1), (9)/(4), etc. Combinations of functional groups of resin (A)/compound (C) (1)/(5), (2)/(3), (2)/(4), (2)/(5), (3)/(3), (4)/(2), (4)/(6), (4)/(7),, (5)/(1), (5)/(2), (5)/(6), (S)/(7), (6)/(4), (6)/(8), (7)/(4), (7)/(5), (7)/(8), (8)/(1), (9)/(4), etc.

The resin (A) can be suitably selected without specific limitation from conventional resins having the foregoing functional groups. Specific examples of the resin (A) are vinyl resins, fluorine-containing resins, polyester resins, alkyd resins, silicone resins, urethane resins, polyether resins, etc.

The resin (A) has at least one functional group reactive with the functional group of the compound (B) and at least one functional group reactive with the functional group of the compound (C) on the average in the t t I- - 11 molecule. The functional groups in the resin (A) may be the same or different.

When the resin (A) has the same functional groups, for example the resin (A) containing at least two hydroxyl groups (1) on the average may be reacted with the compound (B) containing the isocyanato group (5) and the compound (C) containing the isocyanato group (5), or the resin (A) containing at least two isocyanato groups (5) on the average may be reacted with the compound (B) containing the hydroxyl group (1) and the compound (C) containing the hydroxyl group (1).

When the resin (A) has different functional groups, for example the resin (A) containing at least one hydroxyl group (1) and at least one carboxyl group (2) on the average may be reacted with the compound (C) containing the isocyanato group (5) and the compound (B) containing the epoxy group (4).

The functional group of the compound (B) to be reacted with the functional group of the resin (A) may be epoxy. And the functional group of the compound (C) to be reacted with the functional group of the compound (A) may be silane.

Described below are the resins (A) containing hydroxyl, carboxyl, isocyanato, silane, epoxy, mercapto, amino, acid anhydride, phenolic hydroxyl or like functional groups. [Hydroxyl-containing resin] Examples of such resin include those given below in (1) to (6). (1) Hydroxyl-containing vinyl-type resin The resin is a copolymer of a hydroxyl containing polymerizable unsaturated monomer (a) to be described below and when required another polymerizable unsaturated monomer (b). Hydroxyl-containing polymerizable unsaturated monomer (a) Typical of such monomer are the compounds represented by the formulas (1) to (4) CH 2= CH 1 1 OR wherein R' is a hydrogen atom or a hydroxyalkyl group; CH 2=CH 1 1 Uki 2-0-R wherein Rl is as defined above; CH 2= 0 GUL; H OCC H O-H 11 m 2m p 2p q 0 (2) (3) wherein Z is a hydrogen atom or a methyl group, m is an integer of 2 to 8, P is an integer of 2 to 18, and q is an in t, - 13 integer of 0 to 7; CH 2 =CZ 1 L;C)T - OT -OtH 9 1 S 2 U (4) wherein Z is as defined above, Ti and T2 are the same or different and each represent a Cl-20 bivalent hydrocarbon group, and S and U are each an integer of 0 to 10 provided that the sum of S and U is 1 to 10.

The hydroxyalkyl group in the formulas (1) and (2) has 1 to 6 carbon atoms. Specific examples are -C2H40H, -C3H60H, -C4H80H, etc.

Examples of the Cl-20 bivalent hydrocarbon group in the formula (4)-are -CH2-, -CH2-CH2-1 -CH2-CH2-CH21 CH3 1 -CH2CHCH2- 1 Lh3 -CH2CH2-C-Uh2Lh2_ 1 Lh3 -CH2CH2CH2-CH-CH2CH2CH2 1 0 1 _ClOH20- 1 _Cl2H24-, -Cl8H36 CH3 1 -0- 1 -CH2-CH2- etc.

Examples of the monomer component of the formula F are CH2=CHOH, CH2=CH0C4H80H, etc.

Examples of the monomer component of the formula (2) include those represented by the formulas CH 2=CHCH 2 OH.. CH 2=CHCH 2 OCH 2 CH 2 OH, CH 2=CHCH 2 0-CH 2 CH 20-2 H, CH 2=CHCH 2 O+CH 2 CH 2 O-3H Examples of the monomer component of the formula (3) include those represented by the formulas CH 2 =C(CH 3)COOC 2 H 4 OH, CH 2=CHCOOC 3 H 6 OH, 0 CH 2= C(CH 3)COOC 3 H 6-0---CCH 2 CH 2 CH 2 CH 2 CH 2 0-)1_7H.

Examples of the monomer component of the formula (4) include those represented by the formulas CH2=C(CH3)COO---CH2CHCH30-)-5--6H, CH2=C(CH3)COO-CH2CH20-4--5H CH2=CHCOO--+CH2CH20-7--8H, CH2=c-coofcH2CH2CH2CH20-4--5H 6H3 CH2=CH-COO--CH2CH20)5-6(CH2CH(CH3)0-Y-5-6H Also usable as the monomer (a) is an adduct of any of hydroxyl-containing unsaturated monomers of the formulas (1) to (4) with E-caprolactone, y- valerolactone or like lactone. Polymerizable unsaturated monomer (b) Typical of such monomer are those exemplified below in (b-1) to (b-6). (b- 1) Olefin-type compounds such as ethylene, propylene, butylene, isoprene, chloroprene, etc. (b-2) Vinyl ethers and allyl ethers such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert- butyl vinyl ether, pentyl vinyl ether, - is - hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-l- pentyl vinyl ether and like chain-like alkyl vinyl ethers, cyclopentyl vinyl ether, cyclohexyl vinyl ether and like cycloalkyl vinyl ethers, phenyl vinyl ether, o-, m- or p-tolyl vinyl ether and like aryl vinyl ethers, benzyl vinyl ether, phenethyl vinyl ether and like aralkyl vinyl ethers, etc. (b-3) Vinyl esters and propenyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl caprate and like vinyl esters, isopropenyl acetate, isopropenyl propionate and like propenyl esters, etc. (b-4) Esters of acrylic or methacrylic acids such as Cl18 alkyl esters of acrylic or methacrylic acids including methyl acrylate, ethyl acrylate, propyl acrylate, isopropy! acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and lauryl methacrylate; C2-18 alkoxyalkyl esters of acrylic or methacrylic acids including methoxybutyl acrylate, methoxybutyl methaerylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate and ethoxybutyl methacrylate, etc.

16 - (b-5) Vinyl aromatic compounds such as styrene, a-methyl styrene, vinyltoluene, p-chlorostyrene, etc. (b-6) Acrylonitrile, methacrylonitrile, etc. (2) Hydroxyl- and fluorine-containing resin The resin is a copolymer of the hydroxylcontaining polymerizable unsaturated monomer (a), a fluorine-containing polymerizable unsaturated monomer (c) and when required the polymerizable unsaturated monomer (b). Fluorine-containing polymerizable unsaturated monomer (c) Typical of the monomer (c) are the compounds of the forumals (5) and (6) W2=U2 (5) wherein the groups X are the same or different and each represent a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, an alkyl group or a haloalkyl group, provided that the compound contains at least one fluorine atom; CH 2 =CZ 1 0=0 1 2 O-C n H 2n-R (6) wherein Z is as defined above, R2 is a fluoroalkyl group and n is an integer of 1 to 10.

The alkyl group in the formula (5) has 1 to 6 1 - 17 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples are methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc. The haloalkyl group in the formula (5) has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples are CF31 CHF21 CH2F1 CC131 CHC121 CH2C11 CFC121 (CF2)2CF31 (CF2)3CF31 CF2CH31 CF2CHF21 CF2Br, CH2Br, etc.

Examples of the monamer of the formula (5) include the compounds represented by the formulas cr 2= W 20 CHF=U 2' CH 2= CF29 CH 2 =CHF, CCIF=U 2' CHCl=U 2 CCI 2= CF2P CCIF=CC1P, CHF=CCI.f CH 2 =CCIF, CC1 2 =CC1F, CF 3 CF=W 2' CF 3 CF=CHF, W 3 CH=U 2' W 3 CF=CH 2 CHF 2 CF=CHF, CH 3 CF=W 2/ CH 3 CF=CH 21 W 2 CICF=W 2' W 3 CCI=CF 21 CF 3 CF=UCI, CF 2 CICCI=U 2 CF 2 CICF=UCI, CFC1 2 CF=U 2 W 2 CCI=WIF, W 3 Ccl=cCl 2' CCIF 2 CF== 2 CC1 3 CF=W 21 W 2 C1Ccl=cCl 21 WC1 2 CCI=CCI 2 CP 3 CF=CHCl, CCIF 2 CF=CHCl, W 3 CCI=CHCI, CHF 2 ccl=ccl 2P CF 2 C1CH='CC1 21 W 2 CICCI=CHCl, CCI 3 CF=CHCl, W 2 C1CF=OF 21 W 2 BrCH=W 21 W 3 CBr=CHBr, W 2 CICBr=CH 2' CH 2 BrCF=CCI 21 CF 3 CBr=CH 21 CF 2 CH=CHBr, W 2 BrCH=CHF, CF 2 BrU=U 21 CF 3 cr 2 CF=CF 2' W 3 CF=CFCF3i W 3 CH=CFU 3f W 2= CFU 2 CHF 2f CF 3 CF 2 CF=CH 2' W 3 CH=CHW 3' CF 2= WU 2 CH 31 CF 2=WCH 2 CH 3' CF 3 CH 2 CH=CH.i CF 3 CH=CHCH 3P W 2=CHCH 2 CH 3' CH 3 CF 2 CH=CH 21 M 2 CH=CHM 2 CH 3 CF 2 CH=CH21 CH 2= UCH 2 CH 3P CF 3 (CF 2)2 CF=CF 2/ CF 3 (W 2)3 CF=W 2 The fluoroalkyl group in the formula (6) has 3 18 - to 21 carbon atoms. Specific examples are C4pq, (CF2)6CF(CP3)21 C8F171 C1OF21, etc.

Examples of the monomer of the formula (6) include the compounds represented by the formulas CH 1 3 Ukt =C-CO0C H-C F 2 2 4 4 9 CH 3 W 3 1 Uki =C-CO0C H (CF) W 2 2 4 2 6 \ W 3 CH 3 1 U1h 2=C-CO0C 2 H,1C8F 17 CH 1 3 CH 2=C-COOC 2 HiC I0F21 (3) Hydroxyl-containing polyester resin The resin is prepared by esterification or ester interchange reaction of a polybasic acid with a polyhydric alcohol. Examples of useful polybasic acids include the compounds having 2 to 4 carboxyl groups or methyl carboxylate groups per molecule such as phthalic acid or anhydride, isophthalic acid, terephthalic acid, maleic acid or anhydride, pyromellitic acid or anhydride, trimellitic acid or anhydride, succinic acid or anhydride, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dimethyl isophthalate, dimethyl terephthalate and the like. Examples of useful polyhydric alcohols are alcohols having 2 to 6 hydroxyl groups per molecule such as ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, glycerin, tricyclodecanedimethanol, etc. When required, monobasic acids are usable for preparation of the resin and include fatty acids of castor oil, soybean oil, tall oil, linseed oil or the like, and benzoic acid. (4) Hydroxyl-containing polyurethane resin The resin is an isocyanato-free one prepared by modifying a hydroxyl- containing vinyl-type resin, a hydroxyland fluorine-containing resin, a hydroxylcontaining polyester resin or the like with a polyisocyanate compound such as tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or the like. (5) Hydroxyl-containing silicone resin The resin is an alkoxysilane-free and silanolfree one prepared by modifying a hydroxyl-containing vinyl-type resin, hydroxyl- and fluorine- containing resin, hydroxyl-containing polyester resin or the like with a silicone resin such as Z-6018 or Z-6188 (trademarks for products of Dow Corning Ltd.), or SH 5050, SH 6018 or SH 6188 (trademarks for products of Toray Silicone Co., Ltd.).

- 20 (6) Reaction product prepared by hydrolysis of a portion or the whole of a polyvinyl acetate or a copolymer of vinyl acetate and another polymerizable unsaturated monomer. [Carboxyl-containing resin) Typical examples of such resin are given below in (1) to (3): (1) Carboxylcontaining vinyl resin The resin is a polymer of a carboxyl-containing polymerizable unsaturated monomer (d) and when required the polymerizable unsaturated monomer (b). Carboxyl-containing polymerizable unsaturated monomer (d) Typical of the monomer (d) are the compounds represented by the formulas (7) and (8) R 3 = c R R 5 \ COOH (7) wherein R3 is a hydrogen atom or a lower alkyl group, R4 is a hydrogen atom, a lower alkyl group or a carboxyl group, and R5 is a hydrogen atom, a lower alkyl group or a carboxy-lower alkyl group; R 6 0 1 11 CH 2=C-C-0-CmH2m- COOH wherein R6 is a hydrogen atom or a methyl group, and m is 21 - as defined above.

Preferred lower alkyl groups in the formula (7) are those having 1 to 4 carbon atoms, especially methyl.

Examples of the monomer of the formula (7) are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, etc.

Examples of the monomer of the formula (8) are 2-carboxyethyl acrylate or methacrylate, 2-carboxypropyl acrylate or methacrylate, 5-carboxypentyl acrylate or methacrylate, etc.

Also usable as the monomer (d) is an adduct of 1 mole of the hydroxylcontaining polymerizable unsaturated monamer (a) with 1 mole of a carboxylic anhydride compound such as maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride or the like. (2) Carboxyl- and fluorine-containing resin The resin is a copolymer of the fluorinecontaining pol.ymerizable unsaturated monomer (c), the carboxyl-containing polymerizable unsaturated monomer (d), and when required the polymerizable unsaturated monomer (b). These monomers can be any of the above-mentioned monomers.

Also usable is a resin prepared by reacting the fluorine-containing polyol resin with the carboxylic anhydride compound.

(3) Carboxyl-containing polyester resin Examples of such resin are a resin prepared by esterification of the polybasic acid or the corresponding anhydride with the polyhydric alcohol, a resin prepared by adducting an acid anhydride to the hydroxyl- containing polyester resin, etc. [Isocyanato-containing resin] Examples of such resin include those given below in (1) to (4). (1) Isocyanato-containing vinyl resin The resin is a polymer of an isocyanatocontaining polymerizable unsaturated monomer (e) and when required the polymerizable unsaturated monomer (b). Isocyanato-containing pglymerizable unsaturated monomer (e) Typical examples of the monomer (e) are those represented by the formulas (9) and (10) R 6 1 Uh 2=C-COOiC n H 2n -NCO (9) wherein R6 and n are as defined above, examples of the monomer of the formula (9) being isocyanate ethyl acrylate or methacrylate; and C H -NCO n 2n CH 2= C1697 R R (10) 23 wherein R6 and n are as defined above and R7 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, examples of the monomer of the formula (10) being a,udimethyl-m-isopropenyl benzyl isocyanate.

Also usable as the monomer (e) is a reaction product of 1 mole of the hydroxyl-containing polymerizable unsaturated monomer (a) and 1 mole of a polyisocyanate compound. Examples of useful polyisocyanate compounds are tolylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'diphenylmethane diisocyanate, 4,41-diphenyl ether diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, biphenylene diisocyanate, 3,3'dimethyl4,4'-biphenylene diisocyanate, dicyclohexylmethane, 4, 41diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, bis(4isocyanatephenyl)sulfone, isopropylidenebis(4-phenylisocyanate)j lysine isocyanate and isophorone diisocyanate, polymers thereof, biurets thereof, etc.

Also usable as the isocyanato-containing vinyl resin is a reaction product prepared by reacting a hydroxyl-containing vinyl-type resin with, e.g., the polyisocyanate compound. (2) Isocyanato- and fluorine- containing resin The resin is one prepared by reacting the hydroxyl- and fluorinecontaining resin with the 1, - polyisocyanate compound. (3) Isocyanato-containing polyester resin The resin is one prepared by reacting the hydroxyl-containing polyester resin with the polyisocyanate compound. (4) Isocyanato-containing polyurethane resin The resin is one prepared by reacting a polyether polyol with the polyisocyanate compound. Examples of the polyether polyol are polyether polyols prepared by subjecting glycols (such as ethylene glycol, propylene glycol and the like) and alkylene oxides (such as ethylene oxide, propylene oxide and the like) to polymerization, polytetramethylene ether glycols prepared by subjecting tetrahydrofuran to cationic polymerization, etc. [Silane-containing resin] Examples of the resin are given below in (1) to (4). (1) A resin prepared by reacting the hydroxyl-containing resin with an isocyanato-containing silane compound to be described later. (2) A resin prepared by reacting the isocyanato-containing resin with a hydroxyl-containing silane compound to be described later. (3) A silicone resin used in preparation of the hydroxyl- Z - 25 containing silicone resin.

(4) A polymer of a silane-containing polymerizable unsaturated monomer (9) to be described later with when required the polymerizable unsaturated monomer (b) and the fluorine-containing polymerizable unsaturated monomer (c). [Epoxy-containing resin] Examples of the resin are given below in (1) and (2). (1) A resin prepared by reacting the hydroxyl-containing resin with an isocyanato- containing epoxy compound to be described later (2) A polymer of an epoxy- containing polymerizable unsaturated monomer (f) to be described later and when required the polymerizable unsaturated monomer (b) and the fluorine-containing polymerizable unsaturated monomer (c). [Mercapto- containing resin] The resin is one prepared by reacting the hydroxyl-containing resin or the silane-containing resin with a mercapto-containing compound to be described later. [Amino-containing resin] The resin is one prepared by reacting the hydroxyl-containing resin or the silane-containing resin with an amino-containing compound to be described later. [Acid anhydride group-containing resin) Examples of such resin are given below in (1) - 26 and (2). (1) A polymer of the monomer (d) containing acid anhydride group (such as maleic anhydride, itaconic anhydride, succinic anhydride or the like) and when required the polymerizable unsaturated monomer (b). (2) A resin consisting essentially of an acid anhydride (such as trimellitic acid, pyromellitic anhydride or the like) and a polyhydric alcohol. [Phenolic hydroxyl-containing resin] Examples of the resin are given below in (1) to (4). (1) A phenol- or cresol-type resin (such as phenol-type novolak resin, phenol-type resol resin, cresol-type novolak resin, etc.). (2) A polymer comprising as the esential monomer component a phenolic hydroxyl-containing polymerizable monomer (such as p-vinyl phenol, etc.-) (3) A resin prepared from the epoxy-containing resin and a polyvalent phenolic compound (such as catechol, resorcin, hydroquinone, pyrogallol, hydroxyhydroquinone or the like) in such proportions that the resulting resin contains an excess amount of polyvalent phenolic compound. (4) A resin prepared by reacting an epoxy-containing resin with a phenolic hydroxylcontaining compound (such as hydroxybenzoic acid).

11 - ' 1 The compound (B) useful for the resin component (i) has in the molecule at least one epoxy group and at least one functional group reactive with the functional group of the resin (A). The functional group reactive with the functional group of the resin (A) may be epoxy. When the functional group is epoxy, the compound contains at least two epoxy groups in the molecule.

Described below are typical examples of the compound (B). [Hydroxylcontaining epoxy compound] Examples of such compound include the compounds represented by the formulas (11) to (21) R 6 1 8 CH 2- C-R OH \ 0 / R 6 0 0 CH 1 8 11 9 O-R g- 0±H 2-C-R -0+CNHR -NHC- n \0 / R 6 1 11 all 0 0 CH C-R -0---c-R C-O-R 9-0-H 2 n 0 R 6 0 1 8 11 9 CH C-R -0-+3-R 2 n 0 R 8-OH Oo (11) (12) (13) (14) (15) - 28 0 0 8- H- 9 11 9-0-nH OOR O+C- NH-R -NHC O-R 0 0 ' Ol:DR 8-o+c-R 9-C-O-R 9-0t H 0 8 h g 0 R -O+C-R 0+H :0 n OC R 8-OH 0 R 6 0: C-O-Clo OH O-R 9 OH CH (21) 013- \ O-R In the foregoing formulas, R6 and n are as defined above, R8 is a Cl-8 bivalent hydrocarbon group and the groups R9 are the same or different and each represent a Cl-20 bivalent hydrocarbon group.

In the formulas (11) to (21), the Cl-8 bivalent hydrocarbon group can be suitably selected from the foregoing Cl-20 bivalent hydrocarbon groups, and the Cl-20 bivalent hydrocarbon groups include the above examples of such group.

(16) (17) (18) (19) (20) z Specific examples of the compounds of theformulas (11) to (21) are those represented by th formulas 0 (CH 2)20+C-(CH 2)-0-)-2H ::Cr 11 U 0 - -C)H _]:CH 2 H 1 ch 2- U-Uki 2- OH o / CH 0 1 11 0 Ch U-Uri OU-(CH) -(CH) -OH 2- 2- 2 6-NC-0- 2 2 0 H H CH 1 CH 2- C-(CH 2)3_ oC-(CH 2)5_ CO-(CH 2)2_ O-2H 0 U 0 a CH 2-OH i H 1 UM - C-CH -0C (CH 2 2 11 2 5-0-3H 0 0 CH 3 CH O-CN N-C-O-(CH 2)3-OH 0 2- 1 --, H H 0 0 0 CH 0 CH 2- oc A 0 H 11 1 0 C-O-C 0 :ICT 1 S OH OCH 0 o CH d0H \OCH? [Silane-containing epoxy compound] Examples of such compound include the compounds represented by the formulas (22) to (25) R 6 Y CH 8 8 2-C-R -0-R -Si-Y 0 Y R 6 Y 1 8 1 CH 2- C-R 0 Y Y 8_1 0 R Siy Y 0 Y 11 1 0 C-O-R -SiY o 1 Y (22) (23) (24) (25) In the foregoing formulas, R6 and R8 have the same meaning as above, the groups R8 are the same or 4 j different, and the groups Y are the same or different and each represent a hydrogen atom, a hydroxyl group, a hydrolyzable group, a Cl-8 alkyl group,"an aryl group or an aralkyl group, provided that at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Examples of hydrolyzable groups in the formulas (22) to (25) include those of the formulas (1') to (61). Examples of the Cl-8 alkyl group, aryl group and aralkyl group in the formulas (22) to (25) include the above examples of these groups.

Specific examples-of the compounds of the formulas (22) to (25) are those represented by the formulas 0 ON(CH 3)2 UN(CH 3)2 0 11 OCCH 3 1 k L;ki Si-OCCH 2 2-1 11 3 CH 3 0 0 0 CH 1 3 YC-O-(CH 2)4-bl-UrU(C2 H 5)2 11 1 0 W1 3 CH 2-CH-CH 2-0-(CH 2)3-si(OCH \ 0 / 3)3 CH 0 -Si-NC-C3H7 2 2)2-0-(CH2)2 6 1 0 / Uki 3 Also usable is a condensation product of each compound of the formulas (22) t.o (25) with a polysilane compound to be described later (such as compounds of the formulas (38) to (40). Specific examples of such compound are those represented by the formula CH 3 CH 3 1 1 CH,-CHCH-,-Si-0::) 1 U L; PI 2 2 10 2 5 \ Y 1 0 CH 3 UU 2 h 5 [Polyepoxy compound] Examples of such compound include the compounds represented by the formulas (26) to (33) R 6 R 6 CH -C-R -0-R -0-R C-CH 2 / 1 2 0 0 (.26) 6 R 1 8 CH -CR -N \2 1 0 C C /1 \ 0 N 18 R 0 R 6 8_1 N-R C-CH % \ 0 / 2 0 6 1 R -C 1 0 H C 33 - 0 R 6 11 8_1 c O-R C-CH \ 0 1 2 2 R 6 R 10 R 10 R 10 R 6 1 8 1 1 1 1 2 CH -C-R -Si-OSi-0 i-C-CH 2/ 1 lo 1 lo lo \ 1 0 R R R 0 R 6 R 11 R 6 1 1 1 CH 2- U-Uki 2-0-& c- O-CH 2- U-Uh 2 1 0 R 0 R 6 1 CH 2/ C -ED-- 0 \.0 R 6 I- B- 11 0 CH 2 -C R O-R \ 0 / R 6 0 1- 8 11 11 - 0 CH -c R _oc R 2 o (28) (29) (30) (31) (32) (33) 34 - In the foregoing formulas, R6 and R8 are as defined above, the groups R6 are the same or different, the Rio groups are the same or different and are each a C1-8 alkyl group, an aryl group or an aralkyl group, the groups Ril are the same or different and are each a hydrogen atom or a Cl- 4 alkyl group, and w is an integer of 0 to 10.

Examples of the compounds of the formulas (26) to (33) are those represented by the formulas 0 CH 2- CH-CH 2-N 0 c 11 \ 0 N /'o 1 2 ktu 0 H 2 c CH 3 CH CH-CH 0- c -WO-CH -CH-CH 2 2- 2.2 0 CH 3 0 CH 3 CH 3 1 1 CH -CH-(CH) -Si-utz:ii-u-,, CH) -CH-CH 2 / 2 3 1 1 10 2 3 \ / 2 0 CH 3 CH 3 0 N-CH 2- CH-CH 2 1 c 0 - CH 2- CH-CH 2-0-CH 2 CH 2-0-CH 2- CH-CH 2 0 0 0 CH 11 1 3 C-O-CH 2 -C-CH 2 \ 0 1 0 CH 3 t I-CH 2- \ 0 1 2 CH 2-CH-0: 0 \ 0 / CH - CH-CH -0-CH 0 2 2 2 0 CH 3 0 1 11 CH 2- C-CH 2-UU-CH 0 \ 0 / ' 2 Further examples of the polyepoxy compound include those represented by the formulas 0 O'dH2-0 0 C-O-CH C CO 0 CH 1 2-0 ot)-C 0 0. 0 t tCH 2-C Also usable as the polyepoxy compound is an adduct of OCH20H with a polyisocyanate compound to. be exemplified below. Examples of useful polyisocyanate compounds are organic diisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate and like aliphatic diisocyanates, hydrogenated xylylene diisocyanate, isophorone diisocyanate and like cyclic aliphatic diisocyanates, tolylene diisocyanate, 4,4' diphenylmethane diisocyanate and like aromatic diisocyanates; an adduct of the organic diisocyanate with a polyhydric alcohol, a low-molecular-weight polyester resin, water or the like; a copolymer of such organic diisocyanates with each other, isocyanate biurets, etc. Representative commercial products of such polyisocyanate compounds are those available under the trademarks: 11BURNOCK D-750, -800, DN-950, DN-970 and -15-4551' (products of Dainippon Ink And Chemicals Incorporated), I'DESMODUL L, NHL, IL and N339011 (products of Bayer AG, West Germany), "TAKENATE D-102, -202, -11ON and -123W (products of Takeda Chemical Industries, Ltd.), ITOLONATEL, -HL, -EH and -2031' (products of Nippon Polyurethane Kogyo K.K.), '1DURANATE 24A-90CX" (product of Asahi Chemical Industry Co., Ltd.), etc. Also usable as the polyepoxy compound are an adduct of a compound of the formula z 1 37 - 0 C-O-CH 2 with a polybasic acid; a product prepared by oxidizing an ester having unsaturated group such as a group Q::: in the molecule with a peracetic acid or the like, examples of the ester being an ester of 900 in number- average molecular weight prepared by esterifying tetrahydrophthalic anhydride, trimethylolpropane, 1,4-butanediol or the like. [Isocyanato- containing epoxy compound] Examples of such compound include those prepared by reacting the hydroxylcontaining epoxy compound with the polyisocyanate compound such that the epoxy and isocyanato groups remain in the reaction product. Examples of such reaction product are a reaction product of the compound of the formula (11) with a hexamethylene diisocyanate 0 11 CH -CH -NH- (CH ±'E-NCO 2_ CH 2-0c 2 6 0 / a reaction product of the compound of the formula (15) with a tolylene diisocyanate 0 CH 3 11 (CH2--20C-NH-( NCO a reaction product of the compound of the formula (18) with an isophorone diisocyanate 0 11 0 11 CH 3 CH -O+C+CH --,0-,C-NH CH 0 2 2 5 2 3 H 3 C-CH 2 NCO a reaction product of the compound of the formula (20) with an isophorone diisocyanate cl C=0 1 0 3 0:CT CH OC N11-,; CH 3 H 3 C CH 2 NCO CH a reaction product of the compound of the formula (21) with a xylylene diisocyanate OCH OCH 2 0 11 C-NH-CH '-Q 2 -\ CH 2 NCO 1 1 - 39 The unsaturated group-containing compound can be any of silane-containing polymerizable unsaturated monomers to be described later.

The compound (C) useful for the resin component (i) has in the molecule at least one silane group and at least one functional group reactive with the functional group of the resin (A). The functional group reactive with the functional group of the resin (A) may be silane. In this case, the compound contains at least two silane groups in the molecule.

Described below are typical examples of the compound (C). [Hydroxylcontaining silane compound] Examples of such compound are those represented by the formulas (34) to (36) Y 8 1 HO-R -si-Y 1 Y 0 0 11 Y 8-0 li-NH-R 9-N 9_) HO-R C H-C-NH-R Si-Y 1 Y 0 _Y 8_11 81 HO-R CO-R Si-Y 1 Y (34) (35) (36) In the formulas, R8, R9 and Y are as defined above; the groups R8 are the same or different, the groups R9 are the same or different, and the groups Y are the same or different, provided that at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Specific examples of the compounds of the formulas (34) to (36) are those represented by the formulas OCH 3 1 HO-(CH 2)3_ Si-OCH 1 OCH 3 3 0 H H 0 H CH 3 CH HO(CH 2)2-OC-N-(CH 2)6 -N-C-N- (CH2) 3-SiONC 3 CH 3 0 CH 3 0 11 1 11 HO-(CH 2)2-0-(CH 2)2-C-O-(CH 2)3-Si-OCCH 3 UUUkt 3 11 0 3 Also usable as such compound is a condensation product of each compound of the formulas (34) to (36) with a polysilane compound to be described later. Examples of such condensation product include the compound represented by the formula t CH 3 1 HO(CH 2)pSi-O-f-,-.OCH, 1 CH [Polysilane compound] The polysilane compound contains, in the molecule, at least two groups selected from hydrolyzabl groups directly attached to silicon atom and silanol group.

Examples of such compound are those represented by the formulas (38) to (40) e Y 1 Y R 10 1 Y' -Si-Y 1 Y 101 R Si-YI 1 Y1 (38) (39) (40) In the foregoing formulas, the groups Y' are the same or different and each represent a hydrogen atom, a hydroxyl group or a hydrolyzable group, R10 is as defined above and the groups Rio are the same or different.

42 - Specific examples of the compounds having the formulas (38) to (40) are dimethyldimethoxysilane, dibutyldimethoxysilane, diisopropyldipropoxysilane, diphenyldibutoxysilane, diphenyldiethoxysilane, diethyldisilanol, dihexyldisilanol,methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyltributyroxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane, di-iso.l-propoxydivaleroxysilane, tetrasilanol, and th compounds represented by the formulas OCH 0 CH 0 1 3 11 1 3 11 p CH 30-SI-OCH 31 CH 3 CO-Si-OCCH 3 c 2 H 5 O-Si-OC 2 H 5 1 1 1 UU11 3 OCCH 3 UC 2 H 5 11 0 c 2 H 5 c 2 H 5 CNO-Si-ONC c 2 H 5 3 CH 3 c 3 H 7-Si--N \ CH 3 0 c 4 H 7 0 -S 2.-.N CC, H 3 1 1 H 7 c 3 CH 3 c 2 H 5 c 2 H 5 ) 3 e 0 1 11 CH O-SI-UGG 3 2 5 c 2 H 5 CH 3 c 2 H 5 NO-Si-ON c 2 H 5 c 2 H 5 - 43 A condensation product of such polysilane compounds with each other is also usable. [Epoxy-containing silane compound) Examples of such compound.include the foregoing silane-containing epoxy compounds. [Isocyanato-containing silane compound] Examples of such compound include the compound represented by the formula (41) Y 8 1 DCN-+R:+si-Y b 1 Y (41) In the foregoing formula, R8 and Y are as defined above and the groups Y are the same or different.

At least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group, and b' is 0 or 1.

Examples of the compound of the formula (41) ar those represented by the formulas OCNC 2 H 4 Si(OCH 3)3 OCNC 3 H 6 Si(OC 2 H 5)3 OCNC 3 H 6 Si(OC 2 H 5)2 CH 3 OUC 2 H 4 Si(OCH 3)2 1 Uki 3 OUCH 2 Si(OC 2 H 5)3 OUCH 2 Si(OCH 3)3 - 44 OUCH Si(OC-H) 21 2 5 2 CH 3 OUCH 2 Si(OCH 3)3 OCNCi 2 Si(OC 2 H 5) 2 0 OCNCH 2 Si(OCH 3)2 6 CH 3 1 OCN-C 3 h 6-SIN-(c 2 H 5)2 1 CH 3 CH 3 c 3 H 7 OCN-C 3 H 6- SiN 6 c 2 H 5 CH 3 OCN-C 3 ki 6- Si-0-N CH 3 c 2 H 5 CH 3 1 OCN-C 3 ki 6-blui(C 3 H 7)2 1 CHI2 0 11 OCN-C 3 H 6-Si(OCCH 3)3 CH 3 1 OCN-C 4 H CSi-OCCH 3 11 0 - OU-Si(OCH) 3 3 0 11 WN-Si(OCCH 3)3 0 11 OCCH 3 0 1 11 UUN-ISI-UUU 4 H 9 1 OCCH 11 3 0 Also usable as the isocyanato-containing silane compound is a compound prepared by reacting the hydroxylcontaining silane compound with the polyisocyanate compound.

Examples of such isocyanato-containing silane compound include a reaction product of the compound of the formula (34) and a hexamethylene diisocyanate or tolylene diisocyanate, such as the compounds represented by the formulas 0 0 11 Y1 11 OCN+CH --6 1CluU-U 3 H 6- Si-NCCH 2 ll 1 1 CH 11,16 3 CH 3 0 CH 3 11 1 OCN--[5 NHCO- C4k' -Si-ON (C2H5)2 1 UN k UP1 3)2 Useful isocyanato-containing silane compounds further include a condensation product of the isocyanato- 46 containing silane compound with, e.g. the polysilane compound, such as the compound represented by the formula CH 3 0 1 11 OUC H6-S'-075'S"-U"-5-b'l (OCCH 3)3 3 1 CH 3 [Mercapto-containing silane compound] Examples of such compound include the compound represented by the formula (42) Y 81 HS-R Si-Y 1 Y (42) wherein R8 and Y are as defined above, and the groups Y are the same or different, provided that at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Specific examples of the compound of the formula (42) are those represented by the formula OC 2 H 5 HS-C 3 H 6-bl-UU 4 11 9 1 UU 2 h 5 0 11 HS-C 3 H 6-si(OCCH 3)2 1 Uh 3 1 CH 3 1 HS-C 4 ki 8_ SI-0-N(C 2 H 5)2 6 Also usable as the mercapto-containing silane compound is a reaction product prepared by reacting the hydroxyl-containing silane compound with the polyisocyanate compound and a thiochol compound (e.g. HS-CmH2m-0H wherein m has the same meaning as above), such as the compound represented by the formula 0 CH 3 0 OCH 3 0 11 11 1 U HS-C 2 H 4_ OC - NH-c NHCO C3h6-bl-kuUUM3)2 Also usable is a condensation product of the mercapto silane compound with, e.g., a polysilane compound. [NH or NH2 group-containing silane compound] Examples of such compound include the compounds represented by the formulas (43) and (44) Y H 2 N-R -Si-Y (43) 1 Y Y 81 HN+R Si-Y) (44) 1 2 Y - 48 In the foregoing formulas, R8 and Y are as defined above, the groups R8 are the same or different, and the groups Y are the same or different, provided that at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Specific examples of the compounds of the formulas (43) and (44) are those represented by the formulas OCH 1 H 2 N-(CH 2)3_ Si-OCH 1 OCH 3 3 CH 1 3 101 H 2 N-(CH2)3-S i-OCCH3 OC 2 H 5 1 HN+(CH Z)3-Si-OC 2 H 5)2 1 UU 2 ki 5 Also usable is a condensation product of the compound of the formula (43) or (44) with the polysilane compound, such as the compound represented by the formula CH 3 c 215 H N-(CH) --Si01 Si-0-N 2 2 2 '8 3 c 2 H 5 - 49 [Unsaturated group-containing silane compound) Usable as such compound is a silane-containing polymerizable unsaturated monomer (9) to be described later.

In addition to the resins prepared by reacting the resin (A) with the compounds (B) and (C), a copolymer is usable as the resin component (i) which copolymer is prepared by copolymerizing the hydroxyl-containing polymerizable unsaturated monomer (a), the epoxycontaining polymerizable unsaturated monomer (f), silane-containing polymerizable unsaturated monomer (9) and when required the polymerizable unsaturated monomer (b) and the fluorine-containing polymerizable unsaturated monomer (c).

The epoxy-containing polymerizable unsaturated monomer (f) is a compound containing epoxy group and radically polymerizable unsaturated group in the molecule. The epoxy group may be alicyclic or aliphatic. Examples of the radically polymerizable unsaturated group include the groups represented by formulas R 6 R 6 R 6 0 R 6 0 1]-& 1 11 1 11 CH CH =c un -1 2= CCOO 2 2= u-CC::, CH 2= C-C-N- CH 2= CHCH 2_ 0-, CH 2=CHO-1 CH 2= CH- - so - In the foregoing formula, R6 is as defined above.

Examples of the epoxy-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH2=C(R6)COO- include the compounds represented by the formulas (45) to (57) R 6 0 R 6 CH 8 2=C-C-O-R -C-CH 2 0 6 R 0 1 11 Uki 2= U - C - 0 0 R 6 0 Ukt 2= C-C-O-R 11 -OcuO R 6 0 W1 2=G-C-O-R lleO R 6 0 8 U.h 2= C C-O-R]O R 0 1 11 8-Q-0- Uh 2=G-C-O-R OH 0 (45) (46) (47) (48) (49) (50) R 6 0 0 1 11 8 11 UM 2=U-C-O-R C-O-CH 2 0 (51) HO:-0 R 6 0 0 1 11 8 11 CH =C-C-O-R CH -OC-- 0 (52) 2 "Ij 2 HO R 6 0 1 11 8 Uki =C-C-O-R -CH 0 2 1 -0:

OH (53) R 6 0 CH 1 11 CH -0.1CH 0 2=C-C-CYCH2_0/ H6 2 R 6 0 CH 2=C-C-0 O-CH 2 / CH-0,- 0 YO-CH HO 2 (54) (55) R 6 0 0 0 R 6 R 6 0 9 1 11 8 -C-O-R 0 (56) CH 2=u-C-O-R -0C-R -0WC-N-R -N R 6 0 0 0 R 6 R 6 0 0 8 9 9 CH2=C-C-O-R -0C-R -0WC-N-R -N-.C-O-R'- (57) In the foregoing formula, R6, R8, R9 and w are as defined above, the groups R6 are the same or different, the groups R8 are the same or different and the groups R9 are the same or different.

Specific examples of the monomers of the formulas (45) to (57) are those represented by the formulas CH 3 0 1 11 CH =C-C-O-CHi-CH-CH2 2 0 - 52 0 11 CH 2 =CH-C-0 C:70 CH 3 0 CH 2=C-C-O-CH 2--GO CH 3 0 CH 2 =C-C-0- (CH 2-5 0 0 11 CH 2=CH-C-0- (CH 2) 2-[> CH 3 0 1 11 CH 2 =C-C-O-(CH 2) 3-Q- 0-1o OH 0 11 CH =CH-C-O-CH2OC-O-CH2-[::o 2 HO CH 3 0 1 11 0 11 CH 2=C-C-O-(CH 2)5 /0 CH 2-0-C-[::::- HO 0 11 CH 2 =CH-C-O--CH 2-CH-(:::): 0 1 OH CH 3 0 1 11 CH 2 =C-C-0 CH 2 0 HdICKCH 2 _0 / -0:

0 1_.

Examples of the epoxy-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH2=C(R6)-C-N"' are those represented by 0 the formulas (58) to (60) R 6 0 R 6 CH 2 =C-C-N? 8CUO R 6 0 R 6 1 11 1 CH 2= C-C-N? 8i: 0 R 6 0 R 6 1 11 1 8_ 0 CH 2=C-C-N-R O-R (58) (59) (60) In the foregoing formulas, R6 and R8 are as defined above, the groups R6 are the same or different, and the groups Re are the same or different.

Specific examples of the compounds of the formulas (58) to (60) include those represented by the formulas 0 CH 3 CH 2=CH-C N-CH 2Q17-0 CH 3 0 C 2 H 5 1 11 1 CH 2= c-C-N-C 2 H 44Do 0 CH 11 1 3 CH 2=CH-C-N-CH 2-0-CH2t"-:0 Examples of the epoxy-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH =C(R6)-C-C: are inclusive of those 2 11, 0 represented by the formulas (61) to (63) R 6 0 1 11 8 Uki 2 =C-C-R R 6 0 1 11 CH 2= C-C-R R 6 0 R 6 1 11 81 Uh 2= C-C R C-CH 2 1 / 0 (61) (62) (63) 1 In the foregoing formulas, R6 and R8 are as defined above, the groups R6 are the same or different, and the groups RB are the same or different.

Specific examples of the compounds of the formulas (61) to (63) are those represented by the formulas 0 11 CH 2= C (CH 3) C-CH 2_ CH 2 0 0 11 CH.,,=CH-C-CH 0 11 - (CH.) 2 2 2 0 CH =C(CH)CCH CH CH-CH 2 3 2_ 2_\ / 2 -0 Examples of the epoxy-containing polymerizable unsaturated monomers having radically polymerizable unsaturated group CH2=C(R6)-C-N"are those represented by 11 ' 0 the formulas (64) to (69) R 6 0 R 6 1 11 1 8 CH,=C-C-N-R R 6 0 R 6 1 11 1 8-.(::"O CH 2=C-C-N-R R 6 0 R 6 R 6 1 11 1 8 1 CH 2=C-C-NR -C-CH 2 0 (64) (65) (66) R 6 0 R 6 0 H H 0 CH 2=C-C-N-C4N-R -N-C-WO-R 0 (67) 56 R 6 0 R 6 0 1 11 1 11 0 Uh 2=U-C-N-CR OCwo 6. 6 R 0 R 0 ) - 11 1 11 CH 2 =C-C-N-C-R 8-C:> (68) (69) In the foregoing formula, R6, R8, R9 and w are as defined above, the groups R6 are the same or different, the groups R8 are the same or different and the groups R9 are the same or different.

Specific examples of the compounds of the formulas (64) to (69) are those represented by the formulas 0 c 2 H 5 11 1 CH 2=C(CH 3)C-N-CH2 0 0 CH 3 11 1 CH 2=CHC-N- (CH 2)2 0 CH 11 1 3 CH =C(CH)C-N-CH -CH-CH 2 3 2 \ / 2 0 0 H 0 H 11 1 11 1 H 0 1 11 CH 2=CHC-NC-N-(CH2)6-N-C-O-CH z f 2 0 - 57 0 0 11 11 0 11 CH =C(CH)C-N-C+(CH) _OC 0 2 3 1 2 5 CH 0 H 0 11 1 11 CH 2=CHC-N-C-CH 2-(:::> Examples of the epoxy-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH2=CHCH20 are those represented by formulas (70) to (73) R 6 CH 2= CHCH 2 O-R -C-CH 2 \ 1 0 C H 2 =CHCH 2 O-R 8 Cr- 0 CH 2=CHCH 2 O-R 8e: 0 H 81 CH CHCH O-R C 0 2= 2 1 OH In the foregoing formulas, R6 and R8 are as defined above, and the groups R8 are the same or different.

Specific examples of the compounds of the formulas (70) to (73) include those represented by the (70) (71) (72) (73) 1 formulas CH 3 1 C=CHCH O-CH C-CH H 2 2 2_ 2 0 CH 2=CHCH 2 O-CH 2 -cz 0 CH 2=CHCH 2 0-(CH 2)21:O H 1 CH CHCH O-CH -C 2= 2 2 1 0 OH Examples of the epoxy-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH2=CHO- are inclusive of those represented by the formulas (74) to (76) R CH 8 2=CHO-R -CCH 2 0 CH 2 =CHO-R 8 E:)o CH 2 =CHO-R 8CUo (74) (75) (76) In the foregoing formulas, R6 and R8 are as 59 - defined above, and the groups R8 are the same or different.

Specific examples of the compounds of the formulas (74) to (76) are those represented by the formulas H 1 CH = CHO(CH C-CH 2 2 3 \ 1 2 0 CH 2=CHO-CH 2 -0-- 0 CH 2= CHO-CH 2 c7"0 Examples of the epoxy-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH2=CH- include the compounds represented by the formulas (77) to (79) R 6 81 CH 2= CH-R 2 0 CH 2 =CH-R 8Cr- 0 CH 2=CH-R 8C::7 0 (77) (78) (79) - 60 In the foregoing formulas, R6 and R8 are as defined above, and the groups R8 are the same or different.

Specific examples of the compounds of the formulas (77) to (79) include those represented by th formulas CH 2= CH-CH 2-CH-CH2 \ 0 1 CH 2=CH-CH 2 -0-- 0 CH 2=CH-CH 21 0 Examples of the epoxy-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH2=C(R6)-0- include the compounds represented by the formulas (80) to (84) R 6 R 6 1 81 un 2=u- O-RC-CH 2 \ 1 0 R 6 1 8C:

Ull 2=U-G- O-R 0 R 6 H 0 1 9 111 0 Uki 2=U-C- R -N C O-R (80) (81) (82) R 6 1 R 0 CH 2= C-C- R 6 CH =C -C- R 90.70 2 (83) (84) In the foregoing formulas, R6, R8 and R9 are as defined above, the groups R6 are the same or different and the groups R9 are the same or different.

Specific examples of the compounds of the formulas (80) to (84) include those represented by the formulas CH 2 =C(CH 3) -C- O-CH 2-CH-CH 2 \ 0 CH 2= CH -C- O-CH 2 -C> CH H 0 1 3 1 11 CH 2= C(CH 3)- & C - N-C-OCH 2 0 1 G Ull 3 CH 2= c (CH 3) -C- (ClY 2 -121 0 CH 2=CH-C- CH 2 C E70 - 62 The silane-containing polymerizable unsaturated monomer (g) is a compound having at least one silane group and radically polymerizable unsaturated group per molecule. Examples of the radically polymerizable unsaturated group are those represented by the formulas R 6 R 6 R 6 1 1 1 CH 2 =CCOO-, CH 2=C-C, CH 2= C-, CH 2= CHO-, CH 2= CHCH 2 0- wherein R6 is as defined above.

Examples of the silane-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group CH2=C(R6)-COO- include the compounds represented by the formula (85) R Y CH 9 2=C-COOR -Si-Y 1 Y (85) wherein R6, R9 and Y are as defined above, the groups Y are the same or different and at least one of groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Examples of the compound of the formula (85) are y-(meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropyltriethoxysilane, Y_ - 63 y-(meth)acryloxypropyltripropoxysilane, y-(meth)acryloxypropylmethyldimethoxysilane, y-(meth)acryloxypropylmethyldiethoxysilane, y-(meth)acryloxypropylmethyldipropoxysilane, y-(meth)acryloxybutylphenyldimethoxysilane, y-(meth)acryloxybutylphenlildiethoxysilane, y-(meth)acryloxybutylphenyldipropoxysilane, y-(meth)acryloxypropyldimethylmethoxysilane, y-(meth)acryloxypropyldimethvlethoxysilane, y-(meth)acryloxypropylphenylmethylmethoxysilane, y-(meth)acryloxypropylphenylmethylethoxysilane, y-(meth)acryloxypropyltrisilanol, y-(meth)acryloxypropylmezhyldihydroxysilane, y-(meth)acryloxybutylphenyldihydroxysilane, -y-(meth)acryloxypropyldimethylhvdroxysilane, y-(meth)acryloxypropylphenylmethylhydroxysilane, and the compounds represented by the formulas CH 3 0 CH2=C(CH 3)COO(CH2)3_ bl-uuurl 3 1 OCCH 3 11 U CH 3 1 CH 2=CHCOO(CH 2)4 CH 3 1 c 2 H 5 c 2 H 5 Examples of the silane-containing polymerizable 64 - unsaturated monomer having radically polymerizable unsaturated group CH =C(R6)-/ include the compounds 2 C represented by the formulas (86) to (88) R 6 Y 1 CH 2 =C- Rg-sli-Y 1 Y R 6 Y 1 -& 1 CH 2 =c bl-Y 1 R 6 Y CH 91 = c D-R Si-Y 2 -C- 1 Y Y (86) (87) (88) 1 9 In the foregoing formulas, RO, R and Y are as defined above, the groups Y are the same or different, and.at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Specific examples of the compounds of the formulas (86) to (88) include the compounds represented by the formulas CH 2 = C H ---W_ c 2 H 4-Si(OCH 1 3 ' 3 CH 2= C(CH 3)-C-C 2 H 4- Si(CH 3)2 OCH 3 CH 2= CH-C- c 2 H 4Si(OH) 3 CH 2=C(CH 3)-C-C 2 H 4-Si(CH 3)20H 0 11 CH 2 =CH-C- c 3 H 6Si(OCCH 3)3 CH 2= C(CH 3)-C-Si(OCH 3)3 CH 2=CHW_ Si(CH 3)2 N(CH 3)2 CH 2 =C(CH 3)-C-O-C 2 H 4 -Si(OC 2 H 5)2 C5 Examples of the silane-containing polymerizable unsaturated monomer containing radically polymerizable unsaturated group of the formula CH2=C(R6)- include the compounds of the formulas (89) and (90) R 6 Y 1 1 CH 2 =C-Si-Y 1 Y R 6 Y 1 9 1 CH 2 =C-R -Si-Y 1 Y (B9) (90) In the formulas (89) and (90), R 6, R9 and Y are as defined above, the groups Y may be the same or - 66 different and at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Specific examples of the compounds of the formulas (89) and (90) are those represented by the formulas CH 2 =CHSi(OCH 3) 3 CH 2 =CHSi(OC 2 H 5)3 CH =CHSi (OCH,,) 9CH,.2 2 '1 --, CH =CHSI(CH) OCH 2. 3 2 3 CH 2=CHCH 2 SI(OCH 3)3 0 11 CH 2 =CHSi(OCCH 3)3 0 CH 2= CHCH 2 SI(OCCH 3)3 CH 2 =CHSi(CH 3)2 N(CH 3)2 CH 3 CH 3 CH 2= CHSi-N-C-CH 3 It) 0 CH 2=CHSi( -c) 2 ON(CH 3)2 Examples of the silane-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group of the formula CH2=CHO- include the compounds represented by the formul-as (91) and (92).

Y 1 CH 2= CHO-R 9 -Si-Y 1 Y (91) Y 1 CH 2= CHO-SI-1 1 Y (92) In the foregoing formulas, R9 and Y are as defined above, the groups Y may be the same or different and at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Specific examples of the compounds represented by the formulas (91) and (92) include those represented by the formulas CH 3 0 1 11 CH 2 =CHO(CH 2)3 SI-NCCH 3 1 1 CH 3 H CH 1 3 CH 2= CHO(CH 2)2 Z51-OCH 3 1 uun 3 CH 3 CH = CH 1 CH 2=CHO-Sl0-A CH 3 CH 3 CH 3 c 2 H 5 2 CHobl-ON CH 3 c 2 H 5 - 68 Examples of the silane-containing polymerizable unsaturated monomer having radically polymerizable unsaturated group of the formula CH2=CHCH20include the compounds of the formulas (93) and (94) Y 1 CH 2= CHCH 2 0-si-X 1 Y Y 9 1 CH 2 =CHCH 2 O-R -Si-Y 1 Y (93) (94) In the foregoing formulas (93) and (94), R9 and Y are as defiend above, the groups Y may be the same or different and at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Specific examples of the compounds of the formulas (93) and (94) include those represented by the formulas c 2 H 5 CH 3 CH 2=t-ltlutl 2 O-SI-N CH 0 CH 2 =CHCH 2 O-SI-ECC 2 h 5 1 H 1 - 69 OCH 3 0 1 11 CH 2 =CHCH 2 0-(CH 2)3_ si - OCC 2 H 5 1 OCCH 3 11 0 OC 2 H 5 1 CH 2= CHCH 2 0-(CH 2)2-b'-OC2 H5 CH 3 Also usable as the silane-containing polymerizable unsaturated monomer (9) is a polysiloxane unsaturated monomer containing silane group and polymerizable unsaturated group and prepared by reacting the silanecontaining polymerizable unsaturated monomer with, for example, a polysilane compound such as the compounds of the formulas (38) to (40).

Representative of the polysiloxane unsaturated monomer is a polysiloxane macromonomer prepared by reacting about 30 to about 0.001 mole% of a compound of the formula (85) with about 70 to about 99.999 mole% of a least one of the compounds of the formulas (38) to (40) (for example those disclosed in GB 2202538A). Also usefu as the polysiloxane unsaturated monomer are the compounds represented by the formulas 1 - 70 CH 3 OCH 3 CH 2=C(CH 3)COOC 3 H 6-Si-O-Si-OCH 3 1 1 CH 3 OCH 3 CH 3 OCH 3 1 1 CH =CHCOOC H _Si-u-Si-OCH 3 2 3 6 1 1 Url 3 OCH 3 CH 3 OCH 3 0 1 1 11 CH 2 =C(CH 3) COOCH2-S'-0-l-OSl-uuun3 CH 3 OCCH 3 11 U CH 3 CH 3 CH 3 1 1 CH 2=CHiSi-ut-5-tbi-U-,Si-0-N Uh 3 Ukl 3 CH 3 CH 3 CH 3 CH 3 1 1 CH C(CH Si-O--10-Si-N 2= 3 1 1 CH 3 CH 3 CH 3 CH 3 0 1 11 CH 2=CHCH2--Si-O-7Si-uuum 1 1 CH OCCH 3 11 3 U CH 3 CH 3 /C2 H 5 1 1 CH 2=CHO+Si-O-lOSiON 3 3 c 2 H 5 oc 2 H 5 oc 2 H 5 1 1 CH 2 =CHCH 2 O-C 2 H4--si-o-losi-oc 2 H 5 1 1 CH 3 (;h 3 2 71 - 0 CH 2 =CHCH 2 osi-o', MICC,115 (ii) Resin component The resin component (ii) is a mixture of a silanecontaining resin or compound (hereinafter referred to as "resin (ii-1)11) and an epoxy- containing resin or compound (hereinafter referred to as "resin (ii-2)11), at least one of resins (ii-1) and (ii-2) being a resin.

The resin (ii-1) has at least one silane group on the average in the molecule and the resin (ii-2) has at least one epoxy group on the average in the molecule. The resin or compound having less silane or epoxy group than said range reduces the curability of composition, hence undesirable.

The resins (ii-1) and (ii-2) of the resin component (ii) each have a number-average molecular weight of about 1,000 to about 200,000, preferably about 3,000 to about 80,000.

It is suitable to use as the resin (ii-1), for example, a silanecontaining resin prepared from the starting materials useful for the resin component (i) such 72 - that the resulting resin is free of epoxy.

Suitably usable as the resin (ii-2) is, for example, an epoxy-containing resin prepared from the starting materials for the resin component (i) such that the resulting resin is free of silane.

The proportions of the resins (ii-1) and (ii-2) are such that the resin component (ii) has an epoxy/silane ratio of between about 1/99 and about99/1, preferably between about 1/5 and about 99/1. The resins (ii-1) and (ii-2) used in the ratio outside said range give a composition having a los.., curability and provide a coating film poor in resistance to xylol, hardness and mechanical properties, hence undesirable.

Iiii) Resin component The resin component (iii) contains at least one of each of hydroxyl, epoxy and silane groups on the average in the molecule and has a number- average molecular weight of about 1,000 to about 200,000, preferably about 3,000 to about 80,000. The number of hydroxyl group is preferably about 2 to about 400 on the average in the molecule in view of a high resistance to weather and water and the like. The epoxy and silane groups less than said range deteriorate the curability of composition, hence undesirable. The number-average molecular weight lower than about 1,000 impairs the physical properties, weather resistance and the like, and the number-average molecular weight of more than about 200,000 increases the viscosity of composition, decreasing the amenability to coating operation, hence undesirable.

The resin component (i) containing hydroxyl group is usable as the resin component (iii). The hydroxyl groups in the resin component (i) can be any of those introduced into the resin component (i), those formed by reacting the resin (A) with the compound (B) or (C) (e.g., reacting epoxy and carboxyl groups), and those introduced by reacting the reaction product of the resin (A) and the compounds (B) and (C) (e.g. a product prepared by reacting an isocyanato-containing resin (A) with the hydroxyl- containing compounds (B) and (C) such that the resin contains an excess amount of isocyanato group) with a polyhydric alcohol. (iv) Resin component The resin component (iv) is a resin mixture of resins (ii-1) and (ii-2) useful for the resin component (ii) wherein one or both of them contain hydroxyl. Examples of combinations of resins or compounds constituting the resin component (iv) are a mixture of hydroxyl- and silane-containing resin/hydroxyl- and epoxycontaining resin, a mixture of hydroxyl- and silanecontaining resin/epoxy-containing resin or compound, a 74 - mixture of silane-contaiing resin or compound/hydroxyland epoxy- containing resin, etc.

The hydroxyl- and silane-containing resin contains at least one of each of hydroxyl and silane groups on the average in the molecule and has a numberaverage molecular weight of about 1,000 to about 200,000, preferably about 3,000 to about 80,000.

Less than one hydroxyl group on the average in the molecule decreases the curability of composition, hence undesirable. The number cf hydroxyl group is preferably about 2 to about 400 on the average in the molecule in view of a high resistance to weather and water and the like. Less than one silane group impairs the curability of composition, hence undesirable. The molecular weight of less than 1,000 deteriorates the physical properties, weather resistance and the like, and the molecular weight of above 200,000 increases the viscosity of composition and impairs the amenability thereof to coating operation, hence undesirable.

The resin may be a silane- and hydroxylcontaining resin prepared from the starting materials useful for the resin component (iii) such that the resulting resin is free of epoxy.

The hydroxyl- and epox-v-containing resin contains at least one of each of hydroxyl and epoxy groups t - 75 on the average in the molecule and has a number-average molecular weight of about 1,000 to about 200,000, preferably about 3,000 to about 80,000.

Less than one hydroxyl group on the average in the molecule decreases the curability of composition, hence undesirable. The number of hydroxyl group is preferably about 2 to about 400 on the average in the molecule in view of a high resistance to weather and water and the like. Less than one epoxy group impairs the curability of composition, hence undesirable. The molecular weight of less than 1,000 deteriorates the physical properties, weather resistance and the like, and the molecular weight of above 200,000 increases the viscosity of composition and impairs the amenability thereof to coating operation, hence undesirable.

The resin may be an epoxy- and hydroxylcontaining resin prepared from the starting materials useful for the resin component (iii) such that the resulting resin is free of silane.

The proportions of the two resins or compounds in the resin component (iv) are such that the resin component (iv) has an epoxy/silane ratio of between about 1/99 and about 99/1, preferably between about 1/5 and about 99/1. The epoxy/silane ratio outside said range gives a composition with a low curability and forms a 76 - coating film poor in resistance to xylol, hardness and mechanical properties, hence undesirable. (v) Resin component The resin component (v) can be any of the resin components (i) to (iv) which contains a hydroxylcontaining resin or compound.

The hydroxyl-containIng resin or compound contains at least one hydroxyl group on the average in the molecule and has a number-average molecular weight of about 1,000 to about 200,000, preferably about 3,000 to about 80,000. Less than one hydroxyl group on the average in the molecule decreases the curability of composition, hence undesirable. The number of hydroxyl group is preferably about 2 to about 400 on the average in the molecule in view of a high resistance to weather and water and the like. The molecular weight of less than 1,000 deteriorates the physical properties and weather resistance, and the molecular weight of over 200, 000 increases the viscosity of composition and impairs the amenability thereof to coating operation, hence undesirable.

Usable as the hydroxyl-containing resin is, for example, one useful as the resin component (i).

The hydroxyl-containing resin is used in such amount that at least one hydroxyl group is present per - 77 silane or epoxy group.

The resin components described hereinbefore can be prepared by conventional methods. More specifically the reaction between hydroxyl and isocyanato groups. condensation reaction of silane group, copolymerization reaction and the like can be conducted in a conventional manner. For example, the reaction between isocyanato and hydroxyl groups is effected at a temperature between room temperature and 1300C for about 30 to about 360 minutes. The condensation reaction of silane group is conducted in the presence of an acid catalyst (for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid or the like) with heating at a temperature of about 40 to about 1500C for about 1 to about 24 hours. The copolymerization reaction is carried out in the same manner under the same condictions as the reaction for synthesis of conventional acrylic or vinyl resins or the like. Such synthetic reaction can be performed, for example, by dissloving or dispersing the monomer component in an organic solvent and heating the solution or dispersion in the presence of a radical polymerization initiator at a temperature of about 60 to about 1800C with stirring. The reaction time usually ranges from about 1 to about 10 hours. Useful organic solvents include those inactive to the monomer or the compound to be used for polymerization, such as ether solvents, ester solvents or hydrocarbon solvents. The hydrocarbon solvent is preferably used in combination with another solvent in view of a high solubility. The radical polymerization initiator can be any of polymerization initiators commonly employed and including peroxides such as benzoyl peroxide, t-butyl peroxy-2- ethylhexanoate and the like, and azo compounds such as 2,2'- azobisisobutyronitrile, 2,2' azobis(2,4-dimethylvaleronitrile) and the like.

(I) resin component containing carboxyl group as well as the epoxy, sialne and hydroxyl groups are preferred because it results in increase of curability.

Also useful are modified resins prepared by chemically combining the resin component useful as (I) resin component with another resin (such as vinyl resin, polyester resin, urethane resin, silicone resin, epoxy resin or the like).

According to the invention, (I) resin component may be used as dissolved or dispersed in a solvent or in the form of a nonaqueous dispersion of polymer particles prepared in the presence of said resin component as a dispersion stabilizer. Examples of useful solvents are toluene, xylene and like hydrocarbon solvents; methyl ethyl ketone, methyl isobutyl ketone and like ketone solvents; ethyl acetate, butyl acetate and like ester - 79 solvents; dioxane, ethylene glycol diethyl ether and like ether solvents; and butanol, propanol and like alcohol solvents.

The nonaqueous dispersion is described below in detail.

The nonaqueous dispersion can be prepared by polymerizing at least one radically polymerizable unsaturated monomer in the presence of a polymerization initiator and the dispersion stabilizer in an organic solvent in which the monomer and the dispersion stabilizer are soluble but the polymer particles formed by the polymerization are insoluble. The monomers as described hereinbefore are all usable for preparing the polymer present as the polymer particles in the non-aqueous dispersion. Since the polymer used as the particle component in the non-aqueous dispersion is not to be dissolved in the organic solvent used, it is desirable to use a copolymer prepared by polymerizing a predominant amount of monomer having a high polarity. Preferred monomers for use herein include methyl acrylate or methacrylate, ethyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, 2-hydroxy acrylate, 2hydroxy methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyl - 80 toluene, a-methyl styrene, N-methylol acrylamide or methacrylamide and the like. The polymer particles contained in the non-aqueous dispersion can be crosslinked ones when desired. The polymer particles can be internally crosslinked by various methods, as by copolymerizing polyfunctional monomers such as divinylbenzene, ethylene glycol dimethacrylate or the like. organic solvents useful in preparation of the non-aqueous dispersion include those substantially incapable of dissolving the dispersed polymer particles prepared by the polymerization but capable of dissolving well the dispersion stabilizer and the radically polymerizable unsaturated monomers. Examples of useful organic solvents are pentane, hexane, heptane, octane, mineral spirit, naphtha and like aliphatic hydrocarbons; benzene, toluene, xylene and like aromatic hydrocarbons; alcohol solvents, ether solvents, ester solvents 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 organic solvents can be used singly 1 or at least two of them are usable in mixture. Preferred solvents are combinations of a major amount of aliphatic hydrocarbon and a minor amount of aromatic hydrocarbon or the above-mentioned alcohol, ether, ester or ketone solvents. Trichlorotrifluoroethane, metaxylenehexafluoride, tetrachlorohexaflucrobutane and the like are also usable when so required.

The polymerization of the above monomers is conducted using a radical polymerization initiator. Useful radical polymerization initiators are, for example, 2,21-azobisisobutyronitrile, 2,2'-azobis(2, 4dimethylvaleronitrile) and like azo-type initiators; and benzoyl peroxide, lauryl peroxide, tert-butyl peroctoate and like peroxide-type initiators. These polymerization initiators are used in an amount of about 0.2 to about 10 parts by weight per 100 parts by weight of the monomers to be polymerized. The amount of the dispersion stabilizer used for the polymerization is determinable over a wide range depending on the kind of the dispersion stabilizer. Generally it is suitable to use the radically polymerizable unsaturated monomer or monomers in an amount of about 3 to about 240 parts by weight, preferably about 5 to about 82 parts by weight, per 100 parts by weight of the dispersion stabilizer.

According to the present invention, the dispersion stabilizer and the polymer particles are combind together, whereby the storage stability of the non-aqueous dispersion is improved and a coating film is formed which is outstanding in transparency, surface smoothness and mechanical properties. The dispersion stabilizer and the polymer particles can be combined together as by polymerizing the radically polymerizable unsaturated monomer(s) in the presence of the dispersion stabilizer having polymerizable double bond to cause concurrently the formation of polymer particles and the bonding of the resin to the polymer particles.

The polymerzable double bond can be most conveniently introduced into the dispersion stabilizer by adducting an acrylic acid, methacrylic acid, itaconic acid or like a,s-ethylenically unsaturated monocarboxylic acid to some of epoxy groups present in the dispersion stabilizer. Also the introduction can be effected by adducting isocyanoethyl methacrylate or like isocyanatocontaining monomer to the hydroxyl group contained in the dispersion stabilizer.

The dispersion stabilizer can be combined with the polymer particles also using a reactive monomer as a monomer component for formation of polymer particles, such as y-methacryloxypropyl trimethoxysilane, ymethacryloxypropyl triethoxysilane, y-acryloxypropyl trimethoxy- silane, y-methacryloxybutyl triethoxysilane, acryloxypropl trisilanol or the like.

When the dispersion stabilizer is a 2- or 3component resin or compound, the nonaqueous dispersion is prepared by polymerizing the radically polymerizable unsaturated monomer or monomers in the presence of such mixture as a dispersion stabilizer. Optionally the nonaqueous dispersion can be prepared by polymerizing the radically polymerizable unsaturated monomer or monomers in the presence of a portion of 2- or 3-component (1or 2component) resin or compound as a dispersion stabilizer, and admixing the rest of the resin or compound with the polymer thus formed.

Described below is (II) crosslinking agent which is at least one substance selected from carboxylic compounds, polyisocyanate compounds and aminoaldehyde resins and which combines with (I) resin component and (III) curing catalyst to provide the curable composition of the invention.

The crosslinking agent is mixed with (I) resin component dissolved or dispersed in the solvent or present as the dispersion stabilizer in the nonaqueous dispersion of polymer particles. (II) crosslinking agent can be incorporated into the nonaqueous dispersion also by mixing with (I) resin component as the dispersion stabilizer 84 before preparation of nonaqueous dispersion.

Carboxylic acid compounds for use as the crosslinking agent in the invention include, for example, a resin or compound having at least 2 carboxyl groups on the average in the molecule, or a resin or compound having at least one carboxylic anhydride group on the average in the molecule. The carboxylic acid compound has a numberaverage molecular weight of about 100 to about 200,000, preferably about 100 to about 100, 000.

Carboxylic acid compounds useful in the invention include those given below in (1) to (8). (1) Carboxylic acid Examples of useful carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroterephthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, trimellitic acid, hexahydrotrimellitic acid, pyromellitic acid, cyclohexanetetracarboxylic acid, methyl tetrahydrophthalic acid, methyl cyclohydrophthalic acid, endomethylenehexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, suberic acid, pimelic acid, dimer acid (dimer of tall oil fatty acid), tetrachlorophthalic acid, - naphthalenedicarboxylic aicd, 4,4'-diphenylmethanedicarboxylic acid, 4,4'- dicarboxybiphenyl and the like, and the corresponding anhydrides. (2) Polyester resin Useful polyester resins include, for example, resins prepared from a mixture of a carboxylic acid selected from the examples given above in (1) and a polyhydric alcohol to be exemplified below.

Examples of useful polyhydric alcohols are ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol,,4-butanediol, 1,3butanediol, 2,3butanediol, 1,2-butanediol, 1,5-pentanediol, 1, 4pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3pentanediol, 1,6-hexanediol, 1,5hexanediol, 1,4-hexanediol, 2,5hexanediol, 1,4cyclohexanedimethanol, neopentyl glycol, hydroxypivalate neopentyl glycol, polyalkylene oxide, bishydroxyethyl terephthalate, adduct of (hydrogenated) bisphenol A with alkylene oxide, glycerin, trimethylolpropane, trimethylolethane, diglycerin, pentaerythritol, dipentaerythritol, sorbitol, etc.

It is possible to use, conjointly with the above carboxylic acid compounds and polyhydric alcohols, Cardula E 10 (trademark for product of Shell Chemical Co., Ltd.), - 86 a-olefinepoxide, butyleneoxide, Epon #828 (trademark for product of Shell Chemical Co., Ltd.), Epon #1001 (trademark for product of Shell Chemical Co., Ltd.) and like epoxy-containing compounds, dimethylol propionic acid, pivalic acid, 12-hydroxystearic acid, ricinolic acid and like compounds having hydroxyl and carboxyl groups in the molecule; c-caprolactone, c- methyl-6-valerolactone, y -valerolactone, 6-valerolactone, 6-caprolactone, ybutyrolactone and like lactones; benzoic acid, p-tbutylbenzoic acid, abietic acid, acetic acid, propionic acid, butyric acid, caproic acid and like monocarboxylic acids; 2-ethylhexanol, lauryl alcohol, stearyl alcohol and like monohydric higher alcohols; coconut oil, cottonseed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, fatty acids thereof, dimers thereof, trimers thereof (these being optionally hydrogenated ones), etc. (3) Carboxyl-containing vinyl resin The carboxyl-containing vinyl resins described hereinbefore as useful for the resin component (i) can be used as such resin. (4) Carboxyl- and fluorine-containing resin The carboxyl- and fluorine-containing resins described hereinbefore as useful for the resin component (i) can be used as such resins. (5) Carboxyl-containing urethane resin Useful resins include a reaction product of a resin or compound containing hydroxyl and carboxyl groups in the molecule (such as the hydroxyl- and carboxylcontaining compounds mentioned above in (2) polyester resin and the polyester resin, carboxyl-containing vinyl resin and the carboxyl- and fluorine-containing resin, all described above in (2), (3) and (4), respectively and each prepared such that the resulting resin contains hydroxyl group) with, e.g. the polyisocyanate compound (such as polyisocyanate compounds exemplified hereinbefore as useful for the isocyanato-containing resin to be used for the resin component (i)). (6) Carboxyl-containing silicone resin Useful resins include resins prepared by modifying one of the polyester resin, carboxyl-containing resin and carboxyl- and fluorine-containing resin all mentioned above in (2), (3) and (4) respectively and each prepared such that the resulting resin contains hydroxyl group, with a silicone resin or a hydrolyzable silylcontaining compound such as methyltrimethoxysilane, methyltriacetoxysilane, dimethyldimethoxysilane or the like, examples of the silicone resin being those available under Z6018 and Z-6118 (trademarks for products of Dow 88 - Corning Ltd.), and SH-5050, SH-6018 and SH-6188 (trademarks for products of Toray Silicone Co., Ltd.). (7) Carboxyl-containing polyether resin Useful resins include an adduct of the acid anhydride exemplified above with a polyoxyalkylene polyol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like. (8) Carboxyl-containing epoxy resin Useful resins include an adduct of the polycarboxylic acids exemplified above as the polycarboxylic acid compound mentioned above in (1) with an epoxy compound such as Epon #828 (trademark for epoxy resin of Shell Chemical Co., Ltd.), Epon #1001 (trademark for epoxy resin of hell Chemical Co., Ltd.), digIvcidyl ether or the like.

The amount of the carboxylic acid compound used in the invention is about 1 to about 40 parts by weight, preferably about 3 to about 30 parts by weight, more preferably about 5 to about 25 parts by weight, per 100 parts by weight of (I) resin component. Use of more than 40 parts by weight of the acid decreases the storage stability of the curable composition, and use of less 1 part by weight of the acid impairs the adhesion to metals and coating films, hence undesirable.

Polyisocyanate compounds useful as the t than crosslinking agent in the invention include those which have in the molecule at least 2, preferably 2 or 3 isocyanato groups and which can be any of aliphatic, alicyclic, aromatic and aromatic-aliphatic compounds. Examples of useful polyisocyanate compounds are hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and like aliphatic diisocyanates; (hydrogenated) xylylene diisocyanate, isophorone diisocyanate and like alicyclic diisocyanates; and tolylene diisocyanate, 4,41-diphenylmethane diisocyanate and like aromatic diisocyanates. Also usable are an adduct of the diisocyanate compound with a polyhydric alcohol, lowmolecular weight polyester resin or water; a polymer of diisocyanate compounds with each other; isocyanate biurets of such dlisocyanate compounds, etc. Representative commercial products of these compounds are those available under the trademarks: "BURNOCK D-750, -800, DN-950 and DN97P (products of Dainippon Ink And Chemicals Incorporated), 'SUMIDUL L, N, HL, IL and N-33901' (products of Sumitomo Bayer AG), 'ITAKENATE D-102, -202, -11ON and -123W' (products of Takeda Chemical Industries, Ltd.), 11COLONATE-L, -HL, -EL and -20Y' (products of Nippon Polyurethane Kogyo K.K.), "DECORANATE 24A-90=' (product of Asahi Chemical Industry Co., Ltd.), etc.

Examples of the polyisocyanate compound include blocked polyisocyanate compounds prepared by blocking the polyisocyanate compound with a blocking agent such as aliphatic or aromatic monohydric alcohol oxime, lactam, phenol or the like. Specific examples of such compounds are TAKENATE B-815N (trademark for product of Takeda Chemical Industries, Ltd.), BURNOCK D-550 (trademark for product of Dainippon Ink And Chemicals Incorporated), ADITOL VXL-80 (trademark for product of Hoechst AG, West Germany), COLONATE-2507 (trademark for product of Nippon Polyurethane Kogyo K.K.), etc.

A suitable amount of the polyisocyanate compoudd used is about 1 to about 30 parts by weight, preferably about 2 to about 20 parts by weight, per 100 parts by weight of (I) resin component (calculated as solids). The amount smaller than said range fails to improve the mechanical properties of the coating film and the adhesion to plastic substrates (such as urethane ones), hence undesirable.

When required, a curing catalyst for the polyisocyanate compound can be used. Examples of useful curing catalysts are dibutyltin diacetat-e, dibutyltin dioctate, dibutyltin dilaurate and like organotin compounds, and triethylamine, diethanolamine and like amine compounds, etc. The amount of the curing catalyst used is preferably about 0.01 to about 10 parts by weight z per 100 parts by weight of (I) resin component (calculated as solids).

Examples of aminoaldehyde resins useful as the crosslinking agent in the invention are a condensation product prepared by condensing an amino compound with an aldehyde compound by conventional methods; and an aminoaldehyde resin prepared by modifying the condensate with an alcohol. Examples of the amino compound are melamine, urea, benzoguanamine, spiroguanamine, acetoquanamine, steroquanamine, etc. Examples of the aldehyde compound are formaldehyde, paraformaldehyde, acetoaldehyde, etc. While Cl-4 monohydric alcohol is desirable as the alcohol for the modification in view of low-temperature curability, usable in combination therewith are 2-ethylhexanol, cyclohexanol, lauryl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether and like alcohols containing at least 5 carbon atoms.

Melamine resins are most suitable among the above aminoaldehyde resins when a coating film of high weatherability is required. Examples of useful melamine resins are hexamethyl etherified methylol melamine, hexabutyl etherified methylol melamine, hexamethylbutyl etherified methylol melamine, methyl etherified methylol melamine, n-butyl etherified methylol melamine, i- butylated methylol melamine, etc. Commercially available products of such melamines are Cymel-303, Cymel-235, Cymel-238, Cymel-1130, Cymel-254 and Cymel-327 (trademarks for melamine resins manufactured by Mitsui Cyanamide Co., Ltd.), Sumimal M-55, Sumimal M-100 and Sumimal M-40S (trademarks for melamine resins of Sumitomo Chemicals Co., Ltd.), U-Van 20SE-60, U-Van 225 and U-Van 28SE-60 (trademarks for melamine resins manufactured by Mitsui Toastu Chemicals Inc.), Superbeckamin G-840, Superbeckamin G-821-60 and Superbeckamin L-127-75 (trademarks for melamine resins manufactured by Dainippon Ink And Chemicals Inc.).

A suitable amount of the aminoaldehyde resin used is about 1 to about 50 parts by weight, preferably about 3 to about 40 parts by weight, more preferably about 5 to about 30 parts by weight, per 100 parts by weight of (I) resin component (calculated as solids). The amount above said range reduces the curability of composition, whereas the amount below the range tends to deteriorate the coating suitability in conjoint application with an aminoalkyd (polyester) coating composition or an aminoacryl coating composition, hence undesirable.

The term "coating suitability" used herein is intended to denote the adhesion between the topcoat of the curable composition of the invention and the undercoat of z the aminoalkyd or aminoacryl coating composition, and the appearance properties of a coating film formed on applying these compositions by a wet-on-wet coating method.

It remains to be clarified why the curable composition of the invention exhibits an excellent coating suitability with conventionally employed aminoalkyd (polyester) coating compositions, aminoacryl coating compositions and like compositions. Presumably this feature may be attributable to the amenability of the composition of the invention to similar substances (aminoaldehyde resin).

Further the use of aminoaldehyde resin results in coating of high curability due to the reaction between the aminoaldehyde resin and the hydroxyl group present in the curable composition and also to the selfcondensation reaction of aminoaldehyde resin. These reactions can be accelerated by use of a catalyst which can be any of conventional ones such as carboxylic acid compounds, phosphoric acid compounds, sulfonic acid compounds, salts of these compounds with basic compounds, etc.

Described below is (III) curing catalyst which is used conjointly with (I) resin component and (II) crosslinking agent to provide the curable composition of the invention. (III) curing catalyst is at least one compound selected from the group consisting of - 94 organometallic compounds, Lewis acids, protonic acids and compounds with Si-O-Al bonds.

The curing catalyst is admixed with the other essential ingredients for the curable composition of the invention in a suitable manner without specific limitation. (1) Organometallic compound Useful organometallic compounds include metal alkoxide compounds, metal chelate compounds, metal alkyl compounds, etc. [Metal alkoxide compound] Useful metal alkoxide compounds include the compounds having alkoxy group attached to a metalsuch as aluminum, titanium, zirconium, calcium, barium or the like. These compounds may contain an association of molecules. Preferred metal alkoxide compounds include, for example, aluminum alkoxide, titanium alkoxide and zirconium alkoxide. Specific examples of such compounds are exemplified below.

Useful aluminum alkoxide compounds include those represented by the formula OR 12 12 1 12 R 0-Al-OR (95) wherein the groups R12 are the same or different and each - 95 represent an alkyl group having 1 to 20 carbon atoms or an alkenyl group.

Examples of the alkyl group having 1 to 20 carbon atoms include nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl and the like as well as the examples of alkyl groups of 1 to 8 carbon atoms given hereinbefore. Examples of the alkenyl group are vinyl, allyl and the like.

Examples of the aluminum alkoxide having the formula (95) are aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec-butoxide, aluminum tri- tert-butoxide and the like. Among them, preferable are aluminum triisopropoxide, aluminum tri-sec-butoxide, aluminum tri-n-butoxide, etc.

Useful titanium alkoxide compounds include the titanates represented by the formula OR 12 OR 12 12 1 1 12 R 0 Ti-0 Ti-OR 1 12 1 12 OR w OR (96) wherein w and R12 are as defined above.

Examples of the titanate of the formula (96) wherein w is 0 are tetramethyl titanate, tetraethyl - 96 titanate, tetra-n-propyl titanate, tetraisopropyl titanater tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert- butyl titanate, tetra-n-pentyl titanate, tetran-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, etc. Suitable results can be achieved by use of tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate or the like. of the titanates wherein w is 1 or more, those which can achieve good results are dimers to hendecamers (w = 1 to 10 in the formula (96)) of tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate or the like.

Useful zirconium alkoxide compounds include those represented by the formula OR 12 OR 12 12 1 1 12 R 0 Zr-0 Zr-OR 1 12 1 12 OR w OR (97) wherein w and R12 are as defiend above.

Examples of the zirconate of the formula (97) wherein w is 0 are tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl zirconate, tetratert-hexyl zirconate, tetra-n-heptyl Q zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate and the like. Suitable results can be obtained by use of tetraisopropyl zirconate, tetra-n-propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate or the like. Of the zirconates wherein w is 1 or more, those which can produce suitable results are dimers to hendecamers (w = 1 to 10 in the formula (97)) of tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra n- butyl zirconate, tetraisobutyl zirconate, tetra-secbutyl zirconate, tetra- tert-butyl zirconate or the like. The zirconium alkoxide compound may contain an association of such zirconates as a constituent unit. [Metal chelate compound] Preferred metal chelate compounds include, for example, aluminum chelate compounds, titanium chelate compounds and zirconium chelate compounds. Among these chelate compounds, preferred are those containing as a ligand for forming a stable chelate ring a compound capable of forming a keto- enol tautomer.

Examples of the compound capable of forming a keto-enol tautomer are sdiketones (such as acetyl acetone), esters of acetoacetic acids (such as methyl acetoacetate), esters of malonic acids (such as ethyl malonate), ketones having hydroxyl group in the 0-position - 98 (such as diacetone alcohol), aldehydes having hydroxyl group in the 0- position (such as salicylaldehyde), esters having hydroxyl group in the $- position (such as methyl salicylate), etc. The use of esters of acetoacetic acids or 0-diketones can achieve suitable results.

The aluminum chelate compound can be suitably prepared for example by admixing about 3 moles or less of the compound capable of forming a ketoenol tautomer with about 1 mole of the aluminum alkoxide, followed when required by heating. Examples of preferred aluminum chelate compounds for use in the invention are tris(ethylacetoacetate)aluminum, tris(npropylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(nbutylacetoacetate)aluminum, isopropoxy-bis(ethylacetoacetate)aluminum, diisopropoxyethylacetoacetate aluminum, tris(acetylacetonato)aluminum, tris(propionylacetonato)aluminum, diisopropoxypropionylacetonato aluminum, acetylacetonato-bis(propionylacetonato)aluminum, monoethylacetoacetatebis(acetylacetonato) aluminum, tris(acetylacetonato)aluminum and the like.

The titanium chelate compound can be suitably prepared for example by admixing about 4 moles or less of the compound capable of forming a ketoenol tautomer with about 1 mole of the titanium alkoxide, followed when required by heating. Examples of preferred titanium chelate compounds are diisopropoxy-bis(ethylacetoacetate)titanate, diisoprpoxybis(acetylacetonato)titanate, diisopropoxy-bis(acetylacetonato)titanate, etc.

The zirconium chelate compound can be suitably prepared for example by admixing about 4 moles or less of the compound capable of forming a ketoenol tautomer with about 1 mole of the zirconium alkoxide, followed when required by heating. Examples of preferred zirconium chelate compounds for use in the invention are tetrakis(acetylacetonato)zirconium, tetrakis (npropylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate)zirconium and the like.

The aluminum chelate compounds, zirconium chelate compounds and titanium chelate compounds can be used singly or at least two of them are usable in mixture. [Metal alkyl compound] The compound has alkyl group, preferably Cl-20 alkyl group, bonded to a metal such as aluminum, zinc or the like. Examples of such compound are triethyl aluminum, diethyl zinc, etc. (2) Lewis acid Useful Lewis acids include metal halides, compounds having metal, halogen and other substituents, - 100 and complexes of these compounds.

such compounds are:

Specific examples of A1C1 3 ' A1F3J. AlEtCl 2 AlEt 2 Cl, TiCI 4 TiBr., TiF 4' zrcl 4/ ZrBr 41 ZrF 4' SnCl 4, FeC 13' SbC13, PC131 PC1 5 GaCl., GaF 31 InF.. BC1 31 BBr., BF,, BF 3:(OC 2 H 5)2' BF:(OC H)3f BC1:(OC H) BF NH C H54p 4 2 5 3 2 5 2' 3' 2 2 BF 3:NH?.c 2 H 4 0Hf BF 3:NHCH 2 CH 2 CH 2 CH 31 pp 6 S+:C)3 (3) Protonic acid Useful protonic acids include organic protonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, ptoluenesulfonic acid and the like, and inorganic protonic acids such as phosphoric acid, phosphorus acid, phosphinic acid, phosphonic acid, sulfuric acid, perchloric acid and the like. (4) Compound having Si-O-Al bond or bonds Specific examples of such compounds include aluminum silicate.

Among the curing catalysts described above, a metal chelate compound is preferred because it can form a coating composition having a high curability.

A suitable amount of each curing catalyst used among those described above in (1) to (3) is about 0.01 to about 30 parts by weight per 100 parts by weight of - 101 - combined amount of (I) resin component and (II) crosslinking agent, calculated as solids. Less than about 0.01 part by weight of the catalyst is likely to decrease the curability and over about 30 parts thereof tends to remain in the cured product and to reduce the water resistance, hence undesirable. A preferred amount of the catalyst is about 0.1 to about 10 parts by weight and a more preferred one is about 1 to about 5 parts by weight.

A suitable amount of the curing catalyst stated above in (4) is about 1 to about 100 parts by weight per 100 parts by weight of combined amount of (I) resin component and (II) crosslinking agent, calculated as solids. The amount less than the range tends to reduce the curability and the amount above the range tends to impair the properties of the coating film, hence undesirable.

When required, the curable composition of the invention may contain a chelating agent, polyepoxy compound, polysilane compound, organic solvent, pigment, additive resin and the like. The chelating agent is used to improve the storage stability and can be any of the above-exemplified chelate compounds. The polyepoxy compound and polysilane compound are used to enhance the curability of coating composition and can be any of those described hereinbefore.

- 102 - Preferred organic solvents include those having a boiling point of 1500C or less in view of a high curing rate of the curable composition, but are not specifically limited to the above. Preferable organic solvents are toluene, xylene and like hydrocarbon solvents; methyl ethyl ketone, methyl isobutyl ketone and like ketone solvents; ethyl acetate, butyl acetate and like ester solvents; dioxane, ethylene glycol diethyl ether and like ether solvents; and butanol, propanol and like alcohol solvents. While these solvents may be used alone or in a suitable combination, alcohol solvents are preferably used in mixture with another solvent in view of a high solubility of the resin. The resin concentration in the solvent is variable depending on the purpose of use but is generally in the range of about 10 to about 70 % by weight.

Useful pigments can be inorganic or organic. Inorganic pigments useful in the invention include oxidetype pigments such as titanium dioxide, red iron oxide, chromium oxide and the like; hydroxide-type pigments such as alumina white and the like; sulfate-type pigments such as precipitated barium sulfate and the like; carbonatetype pigments such as precipitated calcium carbonate and the like; silicate-type pigments such as clay and the like; carbon-type pigments such as carbon black and the - 103 - like; and metallic powders such as aluminium powders, bronze powders, zinc powders and the like. Organic pigments useful in the invention include azo-type pigments such as lake red, first yellow and the like; and phthalocyanine-type pigments such as phthalocyanine blue and the like.

Useful additive resins can be any of cellulose acetate butyrate, bisphenol-type epoxy resins, petroleum resins, phenolic resins, etc. from which a suitable one is selected according to a particular application.

The curable composition of the invention, when required, may contain other additives commonly employed such as surface improvers, cissing inhibitors, viscosity modifiers, bubble inhibitors, weatherability improvers (ultraviolet absorbers, light stabilizers, oxidation inhibitors, quenchers and the like), etc. For use, these additives may be simply admixed or chemically bonded to resins, or optionally added such that it is present within the resin particles in the nonaqueous dispersion.

The curable composition of the invention can be easily cured by crosslinking at a low temperature of not higher than 1400C and can accomplish curing, for example, in about 8 hours to about 7 days at room temperature without heating or in about 5 minutes to about 3 hours by heating at about 40 to about 1000C.

- 104 - The curable composition of the invention is suitable for use as coating compositions, adhesives, inks or the like, and can be provided as coating compositions curable at room temperature and as those of various baking types curable in a wide temperature range from low temperatures of 60 to 1000C to high temperatures of 100 to 1600C. Substrates to be coated with the curable composition of the invention include all kinds of substrates heretofore employed for coating, such as those of iron, plastics, wood or like materials. The curable composition of the invention is particularly suitable for application to automotive body panels or the like.

For use as a topcoating composition, the curable composition of the invention can be formulated into a solid color, metallic color, or clear coating composition and is applied by a wet-on-wet coating method (socalled two-coat one-bake coating), or by a single-layer coating method or the like. The curable composition of the invention can be used to form an intercoating on automotive bodies or a topcoating or undercoating on automotive parts of plastics, metals or the like.

The curable composition of the invention for use as a coating composition can be applied by conventional coating methods without specific limitation, as by air spraying, electrostatic air spraying, airless spraying, - 105 - bell electrostatic coating, mini-bell electrostatic coating, roll coating, brushing or the like.

The curable composition of the invention can achieve the following remarkable results. 1. It exhibits an excellent curability at low temperatures. 2. It provides a coating film excellent in resistance to weather and acids and the like. 3. It gives a coating films having an excellent adhesion to various substrates or coating films. 4. It forms a coating film having outstanding appearance properties.

The present invention will be described below in more detail with reference to the following Preparation Examples, Examples and Comparison Examples.

Preparation Example 1 Preparation of Copolymer-I' CH2=CHCOW2H40H 30 parts by weight CH2=CH. 0 20 parts by weight CH2=C(CH3)c00C4H9 50 parts by weight The above mixture was subjected to radical polymerization in 100 parts by weight of xylene in the presence of 2,2'-azobisisobutyronitrile (AIBN) at a temperature of 900C for 3 hours, giving a solution of a copolymer (copolymer-l') having a nonvolatile content of - 106 - 50% by weight. The copolymer-11 had a number-average molecular weight of 5,000 (as determined by gel permeation chromatography, the measurements shown hereinafter having been obtained by this method). Preparation of Copolymer-2' CH2=C(CH3)c00C3H6S'(OCH3)3 CH2=C(CH3)c00C2H4NCO CH =CH-J-\\ 2 CH2=C(CH3)c00C4H9 The above mixture was reacted conditions as those for preparation of the copolymer-l', giving a solution of a copolymer (copolymer-21) having a nonvolatile content of 50 wt.%. The copolymer-V had a number-average molecular weight of 6,200.

Preparation of Copolymer-3' CH2=CHCOOH 5 parts by weight CH =CH-//"-\ 30 parts by weight 2 CH2=C(CH3)c00C4H9 65 parts by weight The above mixture was reacted under the same conditions as those for preparation of the copolymer-l', giving a solution of a copolymer (copolymer-3') having a nonvolatile content of 50 wt.%. The copolymer-3' had a number-average molecular weight of 5,800. Preparation of Copolymer- la parts by weight 37 parts by weight 10 parts by weight 33 parts by weight under the same CH2=C(CH3)c00C2H40H C c parts by weight 107 CH2=CHCOOCH2 0 30 parts by weight CH2=CHCO0C2H40CONH-.NHCOCH2-(3[-_-,0 parts by weight CH2=C(CH3)c00C3H6Si(OCH3)3 10 parts by weight Macromonomer (described below) 10 parts by weight CH2=C(CH3)c00C4H9 30 parts by weight The above mixture was reacted under the same conditions as those for preparation of the copolymer-l', giving a solution of a copolymer (copolymer-1a) having a nonvolatile content of 50 wt.%. The copolymer-la had a number-average molecular weight of 6,000. Preparation of Macromonomer \\-Si(OH)3 7,800 -9 CH2=CHCO0C3H6Si(OCH3)3 200 g Toluene 4,500 9 The above mixture was reacted at 1170C for 3 hours, followed by dehydration. The obtained polysiloxane macromonomer had a number-average molecular weight of 7,000 and contained one vinyl group and 5 to 10 silanol groups on the average per molecule. Preparation of Copolymer-1b CH2=CHCOW2H40H CH2=CHCOOCH2 -0o CH2=CHCO0C2H40CONH-C-NHCOCH2 parts by weight 30 parts by weight parts by weight - 108 - CH2=C(CH3)c00C3H6Si(OCH3)3 10 parts by weight CH2=C(CH3)c00C4H9 30 parts by weight The above mixture was reacted under the same conditions as those for preparation of the copolymer-l', giving a solution of a copolymer (copolymer-1b) having a nonvolatile content of 50 wt.%. The copolymer-1b had a number-average molecular weight of 6,000.

Preparation of Copolymer-lc CH2=CHCO0C2H40H 20 parts by weight CH =CHCOOCH -0 30 parts by weight 2 2 --CP CH =CHCOOC H OCONH-F\-NHCOCHn-rl",-0 z 4 1 parts by weight CH2=C(CH3)c00C3H6S'(OCH3)3 10 parts by weight CH2=C(CH3)c00C4H9 10 parts by weight CH2=CHCOW2H4C8F17 20 parts by weight The above mixture was reacted under the same conditions as those for preparation of the copolymer-l', giving a solution of a copolymer (copolymer-lc) having a nonvolatile content of 50 wt.%. The copolymer-lc had a number-average molecular weight of 7,000. Preparation of Copolymer2a FM-3 monomer Macromonomer CH2=C(CH3)c00C4H9 CH2=CHCO0C2H4C8F17 c parts by weight 30 parts by weight 30 parts by weight 10 parts by weight - 109 Note: FM-3 monomer is a trade name for a hydroxylcontaining caprolactonemodified ester of methacrylic acid having an average-molecular weight of 472 and a theoretical hydroxyl value of 119 KOH mg/g, product of Daicel Chemical Co., Ltd.

The above mixture was reacted under the same conditions as those for preparation of the copolymer-l', giving a solution of a copolymer (copolymer-2a) having a nonvolatile content of 50 wt.%. The copolymer-2a had a number-average molecular weight of 5,000.

Preparation of Copolvmer-2b FM-3 monomer 30 parts by weig ht Macromonomer 30 parts by weight CH2=CHCOW2H4C8F17 40 parts by weight The above mixture was reacted under the same conditions as those for preparation of the coplymer-l', giving a solution of a copolymer (copolymer-2b) having a nonvolatile content of 50 wt.%. The copolymer-2b had a number-average molecular weight of 4,900. Preparation of Copolymer- 3 CH2=C(CH3)COOC2H40H CH2=C(CH3)COOCH2CH-CH2 \01 CH =CH-// 20 parts by weight 2 CH2=C(CH3)c00e4H9 25 parts by weight The above mixture was reacted under the same parts by weight parts by weight - 110 - conditions as those for preparation of the copolymer-l' giving a solution of a copolymer (copolymer-3) having a nonvolatile content of 50 wt.%. The copolymer-3 had a number-average molecular weight of 10,500. Preparation of Copolymer-4 A 400 ml-vol. glass flask equipped with a stirrer was charged with the following ingredients:

Solution of Copolymer-l' (nonvolatile content 50%) 200 parts by weight (CH3C00)3sic3H6NCO 10 parts by weight CH3 C H OCONH CH j 30 parts by weight CH NCO YC112 CH3 Xylene 40 parts by weight The mixture was reacted at 1000C for 5 hours with stirring to adduct the hydroxyl group to the isocyanato group. Then it was confirmed that the NCO value reduced to 0.001 or less. The reaction gave a copolymer (copolymer-4) containing groups -OH, -Si(OCOCH3)3 and -0-1p.

Preparation of Copolymer-5 A 400 ml-vol. glass flask equipped with a stirrer was charged with the following ingredients:

Solution of Copolymer-2' (nonvolatile content 50%) 200 parts by weight O: CH20H 30 parts by weight z Xylene 30 parts by weight The mixture was reacted at 1000C for 5 hours with stirring to adduct the hydroxyl group to the isocyanato group. Then it was confirmed that the NCO value reduced to 0.001 or less. The reaction gave a copolymer (copolymer-5) containing groups -Si(OCH3)3 and -(::--p - Preparation of Copolymer-6 A 400 ml-vol. glass flask equipped with a s-'L--irrer was charged with the following ingredients:

Solution of Copolymer-3' (nonvolatile content 50%) (CH H -CH-CH2 30)3S'C3 6 \cr Tetraethylammonium bromide Xylene parts by weight 14.3 parts by weight 0.1 part by weight 14.3 parts by weight The mixture was reacted at 1100C for 6 hours with stirring to adduct the group -COOH to the group -CH-CH2. Then it was confirmed that the acid value \ 0/ reduced to 0.01 or lower. The reaction gave a copolymer (copolymer-6) having a group -Si(OCH3)3' Preparation of Copolymer-7 A glass flask equipped with a stirrer and a water separator was charged with the following ingredients:

- 112 Phthalic anhydride 192 parts by weight Hexahydrophthalic anhydride 256 parts by weight Adipic acid 107 parts by weight Neopentyl glycol 357 parts by weight Trimethylolpropane 88 parts by weight The temperature was elavated from 1600C to 2300C over a period of 3 hours. After the temperature was maintained at 2300C for 1 hour, 50 9 of xylene was added and the mixture was reacted until the acid value reached 8. The reaction mixture was cooled and diluted with a xylene/n-butanol solvent mixture (4/1, part by weight) to a resin solids concentration of 50% by weight.

The thus obtained copolymer (copolymer-7) was about 3,500 in numberaverage molecular weight. Preparation of Copolymer-8 A 400 ml-vol. autoclave of stainless steel equipped with a stirrer was charged with the following ingredients:

and CH2=CH-O-C4H80H CH2=CHO-C2H5 CH =CH-O--(1)7 2 p Methyl isobutyl ketone 2,21-Azobisisobutyronitrile Sodium borate z parts by weight 5 parts by weight.40 parts by weight parts by weight 2 parts by weight 0.5 part by weight - 113 - After nitrogen replacement, solidification by cooling and deaeration, 45 parts by weight of a compound CF2==1 was placed into the autoclave wherein the temperature was gradually elevated to 600C. The mixture was reacted with stirring for 16 hours or longer. When the internal pressure in the autoclave was reduced to 1 kg/cm2 or lower, the autoclave was cooled with water to terminate the reaction. The obtained resin solution was added to an excess amount of heptane to precipitate the resin. The precipitate was washed and dried, giving 91 9 of resin (copolymer-8) in a yield of 91%. The copolymer-8 was 6,300 in number-average molecular weight. The copolymer-8 was dissolved in an equal amount of xylene to obtain a resin solution having a nonvolatile content of 50 wt.%. Preparation of Copolymer-9 The same procedure as in preparation of the copolymer-8 was repeated with the exception of using the following monomers in place of the monomers for the copolymer-8, giving a solution of a copolymer (copolymer9) having a nonvolatile content of 50 wt.%. The copolymer-9 had a number-average molecular weight of 7,200.

CH2=CHCH2OCH2 -uo:::33 CH2=CHOCOCH3 parts by weight parts by weight - 114 CH2=CHOCOC3H7 CF2=CM Preparation of Copolymer-10 The same procedure as for preparation of the copolymer-8 was repeated with the exception of using the following monomers in place of the monomers for the copolymer-8, giving a solution of a copolymer (copolymer10) having a nonvolatile content of 50 wt.%. The copolymer-10 had a number-average molecular weight of 6,800. CH2=CHSi(OH)(OCH3)2 CH2 =CH-0-0 CH2=CH0C2H5 CF2==1 CP2=CF2 Preparation of Copolymer-11 The same procedure as for preparation of the copolymer-8 was repeated with the exception of using the following monomers in place of the monomers for the copolymer-8, giving a solution of a copolymer (copolymer11) having a nonvolatile content of 50 wt.%. The copolymer-11 had a number-average molecular weight of 5,000. CH2=CH0C4H80H CH2=CH-0-0 parts by weight 40 parts by weight parts by weight 10 parts by weight 15 parts by weight 45 parts by weight 10 parts by weight z parts by weight parts by weight - 115 CH2=CHOC2H 5 CF2==1 parts by weight 55 parts by weight Preparation of Copolymer-12 A 400 ml-vol. glass flask equipped with a stirrer was charged with the following ingredients:

Solution of Copolymer-8 (nonvolatile content 50%) (CH3C00)2S'_C3H6SH CH3 Xylene 30 parts by weight The mixture was reacted with stirring at 960C for 9 hours. From the disappearance of absorption of -SH group in infrared absorption spectrum, it was confirmed that the reaction gave a copolymer (copolymer-12) having introduced therein a group -OH, epoxy group and a group -Si(CH3HOCOCH3)2. The copolymer-12 had a number-average molecular weight of 8100. Preparation of Nonagueous dispersion (1) A 400 ml-vol. glass flask equipped with a stirrer was charged with the following ingredients:

Soluti-on of Copolymer-4 (nonvolatile content 50%) 200 parts by weight CH2=C(CH3)COOC2H4NCO 3.1 parts by weight Hydroquinone 0.02 part by weight Xylene 3.1 parts by weight The mixture was subjected to an addition parts by weight parts by weight - 116 - reaction with stirring at 1000C for 5 hours. Then it was confirmed that the isocyanate value reduced to 0.001 or less. The thus obtained solution contained a copolymer (dispersion stabilizer (1)) having one polymerizable double bond on the average introduced per molecule.

A glass flask was charged with the following ingredients:

Heptane 95 parts by weight n-Butyl acetate 5 parts by weight Solution of dispersion stabiliz er (1) (nonvolatile content 50%) 244 parts by weight The resulting mixture was refluxed with heating. Then the following particle-forming monomers and a polymerization initiator were placed dropwise into the flask over a period of 3 hours, and the mixture was aged for 2 hours.

CH =CH-n/\ 10 parts by weight 2 CH2=CHCN 15 parts by weight CH2=C(CH3)COOCH3 20 parts by weight CH2=CHCOOC2H40CONH-W-NHCO-CH2-{ 30 parts by weight 25 parts by weight CH2 CH-CM -C3H6Si(CH3)2ON(CH3)2 \=::511 2,2'-Azobisisobutyronitrile 1.5 parts by weight (Particle-forming monomers used totalled 100 parts by weight. Particles/dispersion stabilizer ratio 45/55, calculated as solids) Z - 117 - The nonaqueous dispersion (1) thus obtained was milky white and stable, had a nonvolatile content of 50 wtA and contained polymer particles having a mean particle size of 0.15 pm (as determined by Colter-N4, trade name for a product of Colter Co., Ltd.). Neither precipitation nor formation of coarse particles occurred in the dispersion even after the dispersion was left to stand at room temperature for 3 months. Preparation of Nonagueous dispersion (2) A 400 ml-vol. glass flask equipped with a stirrer was charged with the following ingredients:

Solution of copolymer-8 (nonvolatile content 50%) CH2=C(CH3)COOH 4-tertButylpyrocatechol parts by weight 1.6 parts by weight 0.02 part by weight Diethylaminoethanol 0.1 part by weight Xylene 1.6 parts by weight The mixture was subjected to an addition reaction with stirring at 1200C for 5 hours and it was confirmed that the acid value of the resin reduced to 0.001 mgKOH/9 or lower. The reaction gave a solution of a copolymer (dispersion stabilizer (2)) having 0.6 polymerizable double bond on the average introduced per molecule.

A flask was charged with the following ingredients:

i_ - 118 - Heptane 80 parts by weight n-Butyl acetate 10 parts by weight Solution of dispersion stabiliz er (2) (nonvolatile content 50%) 200 parts by weight The mixture was refluxed with heating. The following particle-forming monomers and polymerization initiator were placed dropwise into the flask over a period of 3 hours. Then the mixture was aged for 2 hours and 10 parts by'weight of n-butyl acetate was added thereto.

CH =CH-/\ 2 CH2=CH-CN CH2=C(CH3)COOCH3 CH2=C(CH3)c00C2H40H CH2=C(CH3)COOCH2 -(ip CH2=CH-O-CH=CH2 t-Butylperoxy-2-ethylhexanoate parts by weight 10 parts by weight 30 parts by weight 15 parts by weight 30 parts by weight 5 parts by weight 1.5 parts by weight (Particle-forming monomers used totalled 100 parts by weight. Particles/dispersion stabilizer ratio 50/50, calcualted as solids) -The nonaqueous dispersion (2) thus obtained was adjusted with n-butyl acetate to a nonvolatile content of 50% by weight. The nonaqueous dispersion (2) was milky white and stable, and contained polymer particles having a mean particle size of 0.25 pm (as determined by Colter-N4, trade name for a product of Colter Co., Ltd.). Neither W - 119 - precipitation nor formation of coarse particles occurred even when the dispersion was left to stand at room temperature for 3 months. Preparation of epoxy- and alkoxysilane-containing compound A 1 i-vol. glass flask equipped with a stirrer was charged with the following ingredients:

QC-CH2-OH 128 parts by weight WN-C3H6-si(OC2H5)3 247 parts by weight Butyl acetate 94 parts by weight The mixture was reacted at 900C for 3 hours with stirring, giving a solution of a compound having a nonvolatile content of 80 wt.% and represented by the formula: oz: CH2-OCONH-C3H6-si(OC2H5)3 Preparation Example 2 Preparation of

carboxylic acid compound (C) Methacrylic acid 10 parts by weight Styrene 20 parts by weight n-Butyl methacrylate 60 parts by weight 2-Hydroxyethyl methacrylate 10 parts by weight The above mixture was subjected to radical polymerization in a solvent mixture of xylene/n-butanol (80/20, part by weight) in the presence of AIBN, giving a solution of a resin (compound (C)) which was 50% by weight in solids content. The compound (C) was 8,000 in number- - 120 average molecular weight and 62 in acid value. Preparation of carboxylic acid compound (D) Itaconic acid 15 parts by weight Styrene 20 parts by weight n-Butyl acrylate 30 parts by weight 1,4-Butanediol monoacrylate 10 parts by weight n-Butyl methacrylate 30 parts by weight The above mixture was subjected to radical polymerization in a solvent mixture of xylene/n-butanol (50/50, part by weight) in the presence of AIBN, giving a solution of a resin (compound (D)) which was 50% by weight in solids content. The compound (D) was 15,500 in numberaverage molecular weight and 62 in acid value. Preparation of carboxylic acid compound (E) Phthalic anhydride Adipic acid 19.5 parts by weight 19.3 parts by weight Hexahydrophthalic anhydride 20.3 parts by weight Trimethylol propane 18.0 parts by weight Neopentyl glycol 32.3 parts by weight -The above mixture was placed into a flask. The temperature was gradually heated to 2300C at which condensation reaction was effected while distilling off the bound water. When the acid value reached 30, the reaction mixture was cooled to 1600C. To the mixture was added 5.4 parts of trimellitic anhydride and the mixture c 121 - was maintained at the same temperature for 1 hour and cooled. The mixture was diluted with a solvent mixture of xylene/n-butanol (60/40, part by weight), giving a solution of a resin (compound (E)) having a solids content of 50% by weight. The compound (E) had an acid value of 55 and a number-average molecular weight of 2,800. Preparation of carboxylic acid compound (F) A flask was charged with the following ingredients:

Phthalic anhydride 18.0 parts by weight Hexahydrophthalic anhydride 18.7 parts by weight Adipic acid 11.8 parts by weight Trimethylol propane 12.3 parts by weight Neopentyl glycol 29.8 parts by weight The temperature was gradually heated to 2300C at which the mixture was subjected to condensation reaction. When the acid value reached 25, the mixture was cooled. xylene was added to the mixture in such amount as to achieve a concentration of 70% by weight. The resulting-mixture was cooled to 1000C and maintained at the same temperature. Thereafter 12.3 parts by weight of hexamethylene diisocyanate was added thereto and the mixture was reacted at 1000C for 1 hour for introduction of urethane linkage. The reaction mixture was diluted with a solvent mixture of xylene/n-butanol (50/50, part by - 122 - weight) to produce a solution of a resin (compound (F)) having a solids content of 50% by weight. The compound (F) had a number-average molecular weight of 12,000 and an acid value of 22.

Preparation Example 3 Using the copolymers and nonaqueous dispersions prepared in Preparation Examples given hereinbefore, the curable compositions of the invention containing a carboxylic acid compound as a crosslinking agent were prepared as solid color (white) coating compositions and clear topcoating compositions for use in the two-coat onebake coating method. Preparation of solid color (white) coating composition Table 1 below shows the components and the amounts thereof used for preparaing the solid color (white) coating compositions (Nos. S-1 to S-6). In Table 1, the values indicate the amounts in part by weight and the amounts of copolymers and nonaqueous dispersions are shown in terms of part by weight of the resin solids (these definitions are the same in subsequent tables). Titanium dioxide (Titan White CR-95, trade name for a rutile titanium white, product of Isihara Sangyo Kaisha, Ltd.) was used as a white pigment. Before use, titanium dioxide was dispersed in the copolymer solution for 1 hour using a paint shaker. The coating composition No. S-4 was 2 - 123 - prepared by dispersing titanium dioxide in the copolymer solution similarly, followed by addition of a nonaqueous dispersion. The amount of the pigment used was 80 parts by weight per 100 parts by weight of the resin solids. Table 1 Coating comp. No. S-1 S-2 S-3 S-4 S-5 s-6 Copolymer-2a 40 It 11 11 11 11 so so Nonaqueous disper sion (2) 50 Compound A (1) 20 25 25 40 20 B (2) 25 C (3) 20 Metal chelat compound Compound A (4) B (5) C (6) D (7) e 1 1 0.5 0.5 1 1 0.5 0.5 - 124 Table 1 (continued) Coating comp. No. S-1 S-2 S-3 S-4 S-5 S-6 Carboxylic acid compound Compound A (8) B (9) c 11 D to E to F Preparation of clear coating composition for use in the two-coat one-bake method Table 2 below shows the components and the amounts thereof used for preparation of clear coating compositions (Nos. M-1 to M-7) useful in the two-coat onebake method.

*- 125 - Table 2

Coating comp. No. M-1 M-2 M-3 m-4 M-5 M-6 M-7 Copolymer-la 100 20 100 of 9 f 9 1 11 f ( 9 Nonaqueous dispersion (1) (2) -2a 40 -4 30 -6 30 -9 50 40 30 -10 30 -11 30 so Compound A (1) 11 B (2) Metal chelate compound Compound A (4) 1 It B (5) C (6) Carboxylic acid compound 20 10 20 20 1 0.5 1 1 1 1 0.5 Compound (E) (B) (A) (B) (C) (F) (C) Amount 20 10 10 10 10 10 10 In Tables 1 and 2, the symbols 1 to 9 mean the following.

(1) Compound A: 0 11 (2) Compound B: (D7 Si-(OC2H5)3 (3) Compound C: OZCF CH2-OCONH-C3R6-si(OC2B5)3 (4) Metal chelate compound A: tris(acetylacetonato) aluminum (5) Metal chelate compound B: tris(ethylacetoacetate)aluminum (6) Metal chelate compound C: tetrakis(acetylacetonato)zirconium (7) Metal chelate compound D: diisopropoxy-bis(ethylacetoacetate)titanium (8) Carboxylic acid compound A: trimellitic anhydride (9) Carboxylic acid compound B: methyl-hexahydrophthalic anhydride Examples 1 to 6 The coating compositions S-1 to S-6 were used for Examples 1 to 6, respectively.

Compariso-n Example 1 The same procedure as in preparation of the coating composition S-6 was repeated with the exception of not using the carboxylic acid compound and gave a coating - 127 - composition S-7 for Comparison Example 1.

Com arison Example 2 A coating composition S-8 (Lugabake white, trade name for a coating composition of the polyester/melamine resin type, manufactured by Kansai Paint Co., Ltd.) was used for Comparison Example 2.

Examples 7 to 13 The coating compositions M-1 to M-7 were used for Examples 7 to 13, respectively.

Comparison Example 3 The same procedure as in preparation of the coating composition M-7 was repeated with the exception of not using the carboxylic acid compound and gave a coating composition M-8 for Comparison Example 3.

Comparison Example 4 A coating composition M-9 (Magicron #1000 Clear, trade name for a coating composition of the acryl/melamine resin type, manufactured by Ransai Paint Co., Ltd.) was used for Comparison Example 4. Preparation of base coating composition A A base coating composition for use in wet-on-wet coating was prepared from the following ingredients:

Copolymer-la (solution) 200 parts by weight Tris(acetylacetonato)aluminum 2 parts by weight EAB-551-02 (trade name for cellulose acetate butylate, pro- 1 - 128 duct of Eastman Kodak Co.) Toluene Butyl acetate Aluminum paste #4919 (trade name for a product of Toyo Aluminum Co., Ltd.) Aluminum paste #55-519 (trade name for a product of Toyo Aluminum Co., Ltd.) 10 parts by weight The obtained composition was adjusted to a viscosity of 15 seconds (Ford cup #4, 2SOC) with a solvent mixture of toluene/xylene/n-butanol (40/40/20) before application. Production of substrate to be coated Substrates to be coated with coating compositions were produced as follows.

To a dull-finished steel panel treated by zinc phosphate was applied an epoxy resin-type cationic electrodeposition coating composition to a film thickness of about 25 pm and cured by heating at 1700C for 30 minutes. Lugabake AM (trade name for a product of Kansai Paint Co., Ltd.) as an intercoating composition was applied to the primed panel to a dry film thickness of about 30 pm and the coated panel was baked at 1400C for 30 minutes. The coating surface was subjected to wetgrinding with #400 sandpaper, dried and wiped with a piece of cloth saturated with petroleum benzine to give a parts by weight 30 parts by weight 30 parts_ by weight parts by weight t c t - 129 - substrate panel. [Test for properties of coating film) Solid color coating composition The coating compositions obtained in Examples 1 to 6 and Comparison Examples 1 and 2 were adjusted to a viscosity of 22 seconds (Ford cup No. 4, 20IC) with Swasol #1000 (trade name for a product of Cosmo Oil Co., Ltd., petroleum type solvent). Each composition was applied to the substrate panel to a dry film thickness of 40 to 50 pm, set at room temperature for 10 minutes and baked at 1200C for 30 minutes (the substrate panels coated with the coating compositions for Comparison Examples were baked at 1400C for 30 minutes) to produce test coated panels. The test coated panels were tested for properties. Table 3 shows the test results.

Table 3

ExamDle Coating composition State of coating surface (11) Gloss (600) Pencil hardness Water resistance (12) Acid resistance (13) impact resistance (14) Adhesion-1 (15) Adhesion-2 (16) Weatherability (17) JO 0 Comp. Example

S-1 S-2 A A S-3 A 92 9,4 91 H A A A A H F A A 40 40 2 S-4 S-5 A A 93 H A A 40 S-6 A 92 90 H F S-7 S-8 A A 92 B A A A A A A 40 30 100/100 100/100 100/100 100/100 100/100 100/100 50/100 100/100 100/100 100/100 100/100 100/100 100/100 10/100 A A A A A A A 111 92 F B c 30 0/100 0/100 1 W C 1 131 Clear coating composition for use in the two-coat onebake method The base coating composition A was applied to substrate panels. in about 5 minutes the coated substrate panels were coated with each of the coating compositions for Examples 7 to 13 and Comparison Examples 3 and 4 diluted with Swasol #1000 to a viscosity of 22 seconds. The dry thickness of films of the base coating composition was 15 to 20 pm and that of films of'the clear coating composition was 35 to 45 pm. Then the coated substrate panels were left to stand at room temperature for about 10 minutes and baked at 1200C for 30 minutes (the substrates coated with the compositions for Comparison Examples were baked at 1400C for 30 minutes), producing test coated panels. The test coated panels were tested for properties. Table 4 shows the test results.

Table 4

Example

7 8 9 10 11 12 13 coating composition M-1 M-2 M-3 m-4 M-5 M-6 m-7 State of coating A A A A A A A surface (11) Gloss (601) 91 93 92 93 94 92 92 Pencil hardness F F F F F F F water resistance (12) A A A A A A A Acid resistance (13) A A A A A A A Impact resistance 35 35 40 35 40 40 40 (14) Adhesion-3 (18) 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Weatherability (17) A A A A A A A k 4 0, 1 - 133 - Table 4 (continued) Comparison Example Coating composition State of coating surface (11) Gloss (600) Pencil hardness Water resistance Acid resistance Impact resistance Adhesion-3 Weatherability (12) (13) (14) (18) (17) 3 M-8 A 93 B A A 30 20/100 4 M-9 B 92 p B 10/100 In Tables 3 and 4, the symbols 11 to 18 indicate the following.

(11) State of coating surface The test coated panels were observed with the unaided eye to evaluate the appearance according to the following criteria:

A: Excellent B: Slightly unsatisfactory in surface smoothness C: Poor in surface smoothness (12) Water resistance 1 - 134 - The test coated panel was immersed in a thermostatic water bath at 400C for 240 hours. After withdrawal, the water resistance of the test coated panel was evaluated in terms of loss of gloss, blistering and like change according to the following ratings: A: No change B: Slight loss of gloss caused C: Loss of gloss and blistering caused (13) Acid resistance The test coated panel was immersed in 40% by weight H2S04 at 400C for 5 hours, withdrawn and washed with water after which the acid resistance was evaluated according to the following criteria: A: No change B: Slight loss of gloss caused C: Loss of gloss and blistering caused (14) Impact resistance The impact resistance of the test coated panel was determined using a Du Pont impact tester (l/2 inch diameter of impact load element, 0.5 kg weight). The impact resistance was assessed in terms of the maximum height (cm) at which the dropping of the weight caused no cracking on the coating surface. (15) Adhesion-1 Panels of polished mild steel were used as sub- - 135 - strates to be coated. After degreasing, the mild steel panel was coated with the coating composition by spraying and baked at 1201C for 30 minutes. Then the coated panel was immersed in hot water at 800C for 5 hours, withdrawn, and dried at room temperature for 1 hour. The surface of the coated panel was cut crosswise to the substrate at a spacing of 1 mm to form 100 squares. Cellophane adhesive tape was applied over the cut surface and removed. The adhesion was evaluated in terms of a value given by: (the number ofsquares remaining adhered)/100.

(16) Adhesion-2 Test coated panels were produced in the same manner as those prepared for testing the solid color coating compositions. The obtained test coated panel was further baked at 1400C for 30 minutes, thereafter coated with the same solid color coating composition to a dry film thickness of 40 pm and baked at 1200C for 30 minutes. The test coated panels were immersed in hot water at 800C for 5 hours, dried at room temperature for 1 hour and subjected to the same cross-cut test as above in Adhesion-l.

(17) Weatherability Using an accelerated weathering tester (manufactured by Q Panel Co., Ltd. ), a QUV accelerated exposure test was carried out under conditions of one - 136 cycle comprising:

UV irradiation 16 hr/600C water condensation 8 hr/500C After conducting 125 cycles (3000 hours), the weatherabiiity was evaluated according to the following ratings. A: Retaining substantially the same gloss as in initial stage. B: Slightly reduced in gloss but free of cracking, blushing and the like. C: Significantly reduced in gloss and marked in cracking and chalking. (18) Adhesion-3 Substrate panels were prepared in the same manner as done for the clear coating compositions useful for the two-coat one-bake method and further baked at 1400C for 30 minutes. The base coating composition and the clear top coating composition of the types as used above were applied to the substrate panels in the same manner and the coated panels were baked at 1200C for 30 minutes. The coated panels were thereafter immersed in hot water at 800C for 5 hours, withdrawn from the hot water and dried at room temperature for 1 hour. Then the same cross-cut adhesion test as above was conducted. Preparation Example 4 137 - Using the copolymers and nonaqueous dispersions prepared in Preparation Examples given hereinbefore, the curable compositions of the invention containing a polyisocyanate compound as a crosslinking agent were prepared as solid color coating compositions (white) and clear top coating compositions for the two-coat and onebake method. Preparation of solid color coating composition (white) Table 5 below shows the components and amounts thereof for preparing solid color (white) coating compositions (coating compositions Nos. S-9 to S-14). Titanium dioxide was used as a white pigment as in Preparation Example 3.

138 - Table 5

Coating composition No.

Component S-9 S-10 S-11 S-12 S-13 S-14 Copolymer -2a 40 -3 so -5 50 -7 25 -8 so 11 -12 80 80 Nonagueous dispersion (2) Compound A 11 B 19 c Metal chelate Compound II 99 11 (1) (2) (3) compound A (4) B (5) C (6) D (7) SUMIDUL N (1-9) TAKENATE B- 815N (20) Dibutyltin dilaurate 25 25 40 20 1 1 0.5 1 1 1 0.5 - 139 - Preparation of clear coating composition for use in the two-coat one-bake method Table 6 below shows the components and amounts thereof for preparing clear coating compositions useful for the two-coat one-bake method (coating compositions Nos. M-10 to M-16).

- 140 - Table 6

Component Copolymer -1b 91 f 1 11 11 11 19 -2a -4 -6 -9 -10 -11 Nonaqueous dispersion (1) (2) Compound A (1) B (2) C (3) Metal chelate compound Compound A (4) to B (5) C (6) SUMIDUL N (19) TAKENATE B-815N (20) Dibutyltin dilaurate 11 Coating composition No.

M-10 M-11 M-12 M-13 M-14 M-15 M-16 20 100 40 30 - - - 30 - 20 10 20 20 1 1 0.5 1 1 1 1 0.5 5 10 5 10 5 - - - - - -10.

0.1 The symbols 1 to 7 are as described above.

The symbols 19 to 20 mean the following.

A - 141 - (19) SUMIDUL N: product of Sumitomo Bayer Urethane Co., Ltd., biuret type polyisocyanate (active ingredient 75 wt.%, NCO content 16.5 wt.%) (20) TAKENATE B-815N: product of Takeda Chemical Industries, Ltd. Non- yellowing type blocked polyisocyanate Examples 14 to 19 The coating compositions S-9 to S-14 were used for Examples 14 to 19, respectively.

Comparison Example 5 The coating composition S-15 identical with the coating composition S-14 but free of TAKENATE B-815N and dibutyltin dilaurate was used for Comparison Example 5. Examples 20 to 26 The coating compositions M-10 to M-16 were used for Examples 20 to 26, respectively.

Comparison Example 6 The coating composition M-17 identical with the coating composition M-16 but free of TAKENATE B-815N and dibutyltin dilaurate was used for Comparison Example 6.

Comparison Example 7 The coating composition M-18 (tradename, Magicron #1000 Clear, product of Kansai Paint Co., Ltd., - 142 - acryl/melamine resin-type coating composition) was used for Comparison Example 7. Preparation of base coating composition B using azobisisobutyronitrile as a polymerization initiator, the following monomer mixture was subjected to radical polymerization in a solvent mixture of xylene/nbutanol (80/20, part by weight), giving a solution of vinyl copolymer. The vinyl copolymer had a number-average molecular weight of 18,000. The vinyl copolymer solution had a nonvolatile content of 50% by weight and a viscosity of Z1 (as determined by Gardner-Holdt bubble viscometer).

Methyl methaerylate 40 parts by weight Ethyl acrylate 20 parts by weight n-Butyl acrylate 20 parts by weight 2-Hydroxyethyl methacrylate 18 parts by weight Acrylic acid 2 parts by weight A base coating composition B for wet-on-wet coating was prepared from the following components.

Vinyl copolymer solution obtained above (nonvolatile -content 50 wt.%) 160 parts by weight U-Van 28SE-60 (tradename, Mitsui Toatsu Chemicals Inc., melamine resin, nonvolatile content 60 wt.%) 33.3 parts by weight EAB-551-2 (tradename, Eastman Kodak Co., cellulose acetate butyrate) 20 parts by weight - 143 - Toluene Butyl acetate Aluminum paste #4919 (tradename for product of Toyo Aluminum Co., Ltd.) 5 parts by weight Aluminum paste #55-519 (tradename for product of Toyo Aluminum Co., Ltd.) 5 parts by weight Using a solvent mixture of toluene/xylene/nbutanol (40/40/20, part by weight), the coating compositions were adjusted to a viscosity of 15 seconds (Ford Cup No.4/25OC). Production of substrate to be coated A dull finished steel panel treated by zinc phosphate was further treated in the same manner as above to give a substrate panel. [Test for properties of coating film] Solid color coating composition The coating compositions prepared in Examples 14 to 19 and Comparison Example 5 were adjusted to the same viscosity as above and applied to substrate panels, and the coated substrate panels were similarly set and baked to give test coated panels. The test coated panels were tested for properties. Table 7 shows the test results.

parts by weight parts by weight - 144 - Table 7

Example

Coating composition S-9 State of coating surface A (11) Gloss (600) Pencil hardness Water resistance (12) Acid resistance (13) Impact resistance (14) Weatherability (17) 14 15 16 17 18 19 S-10 S-11 S-12 S-13 S-14 A A A A A 94 94 H H A A A A 50< 50 A A Clear coating composition for use in the two-coat one-bake method The base coating composition B was applied to the surface of substrate panels and the coated panels were allowed to stand for 5 minutes. Thereupon the coating compositions of Examples 20 to 26 and Comparison Examples 6 and 7 diluted to a viscosity of 22 seconds with Swasol #1000 (tradename for product of Cosmo Oil Co., Ltd.) were applied to the coated substrate panels and the coated panels were allowed to stand and baked in the same manner as above to give test coated panels. The test coated panels were tested for properties. Table 8 shows the test 91 H H A A A A 50< 50< A A Comparison - - Example - S-15 A 92 2H A A 45 A 91 p A A 45 A F B B A M, - 145 - results.

0 Table 8

1 Coating composition State of coating surface Gloss (600) Pencil hardness Water resistance (12) Acid resistance (13) Impact resistance (14) Weatherability (17) Adhesion-4 (21) Example

A H A A 50< Comp.

Example

21 22 23 24 25 26 6 7_ M-10 M-11 M-12 M-13 M-14 M-15 M-16 M17 M-18 A A A A A A A A 93 96 H 19 A A A A 50< 91 94 H H A A A A 50< 94 2B A A 45 94 H A A 45 94 94 H H B A B A A A A A A A A 100/ 100/ 100/ 100/ 100/ 100/ 100/ 25/ 100 100 100 100 100 100 100 100 0/ 100 1 F-i 4th m 1 a 11, - 147 - The symbols 11 to 14 and 17 are as described above. 21 "Adhesion-4" means the following. (21) Adhesion-4 Urethane resin panels cut from an automotive bumper made of urethane resin were degreased with trichloroethane vapor. The coating compositions were applied to the degreased panels to a dry thickness of about 40 pm and the coated panels were baked at 1200C for 30 minutes. The coated panels were immersed in warm water at 400C for 5 days, withdrawn from the warm water and dried for 2 hours. A lattice pattern with eleven cuts in each direction was made in the coating film to the substrate to form 100 squares (1 mm2). Cellophane tape was applied over the lattice and then removed, and the adhesion was evaluated in terms of a value given by: (the number of squares remaining adhered)/ 100. Preparation Example 5 Using the copolymers and nonaqueous dispersions obtained in Preparation Examples given above, the curable compositions of the invention containing an aminoaldehyde resin as a crosslinking agent were prepared as solid color coating compositions (white) and clear top coating compositions for use in the two-coat and one-bake method. Preparation of solid color (white) coating composition Table 9 shows the components and amounts thereof - 148 for preparing solid color coating compositions (white) (coating composition Nos. S-16 to S-21). Titanium dioxide was used as a white pigment as done in Preparation Example 3.

t Table 9

Coating composition No.

Component S-16 S-17 S-18 S-19 S-20 S-21 Copolymer -2b 40 -3 so -5 50 -7 25 -8 50 -12 80 80 Nonaqueous dispersion (2) Compound A (1) 20 B (2) Metal chelate compound Compound A (4) 1 B (5) C (6) -D (7) CYMEL 235 (22) 10 U-Van 28SE (23) Acid catalyst (24) 0.5 0.2 91 1 so 25 40 20 0.5 0.5 1 1 0.5 - - 0.5 - 5 5 is 0.2 0.2 0.5 - 150 - Preparation of clear coating composition for use in the two-coat one-bake method Table 10 shows the components and amounts thereof for preparing clear coating compositions for use in the two-coat one-bake method (coating compositions Nos. M-19 to M-25).

z c d - 151 Table 10

Coating composition No._ Component M-19 M-20 M-21 M-22 M-23 M-24 M-25 Copolymer -lc 100 20 100 if -2b 40 it -4 30 -6 30 -9 50 40 30 -10 30 -11 30 Nonaqueous dispersion (1) (2) Compound A (1) B (2) c (3) Metal chelate compound Compound A (4) 1 B (5) C (6) D P7) 1 so 20 10 20 20 20 1 0.5 1 1 1 0.5 CYMEL 235 (22) 10 5 10 5 10 5 U-Van 28SE (23) Acid catalyst (24) 0.5 0.2 0.5 0.2 0.5 0.2 - 152 The symbols 1 to 7 are as described above. The symbols 22 to 24 indicate the following.

(22) CYMEL 235: tradename, Mitsui Cyanamido Co., Ltd., methyl/n-butyl etherified monomeric melamine resin (23) U-Van 28SE: tradename, Mitsui Toatsu Chemicals Inc., n-butyl alcohol- modified melamine resin (nonvolatil content 60 wt. %) (24) Acid catalyst: dodecylbenzenesulfonic acid neutralized with dimethyl ethanolamine (to 1.0 equivalent) Examples 27 to 32 The coating compositions S-16 to S-21 were used for Examples 27 to 32, respectively.

Comparison Example 8 The coating composition S-22 identical with the coating composition S-21 but free of U-Van 28SE was used for Comparison Example 8.

Examples 33 to 39 The coating compositions M-19 to M-25 were used for Examples 33 to 39, respectively.

Comparison Example 9 The coating composition M-26 identical with th coating composition M-25 but free of U-Van 28SE was used for Comparison Example 9. Preparation of substrate to be coated A dull finished steel panel treated by zinc - 153 phosphate was further treated in the same manner as above to give a substrate panel. (Test for properties of coating film] Solid color coating composition The coating compositions prepared in Examples 27 to 32 and Comparison Examples 8 were adjusted to the same viscosity as above and applied to substrate panels. The coated substrate panels were similarly set and baked to give test coated panels. The test coated panel were tested for properties. Table 11 shows the test results.

Table 11 coating composition State of coating surface (11) Gloss (60) Pencil hardness Water resistance (12) Acid resistance (13) Impact resistance (14) Adhesion - 5 (25) Adhesion - 6 (26) weatherability (17) w,' Comp.

Example E?l e

28 29 30 31 32 8 S-17 S-18 S-19 S-20 S-21 A A A A 27 S-16 91 H H A A A A A A A 94 H 94 H A A S-22 A 92 91 90 2H F B A A A A B A A 40 40 50 40 40 20 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 10/100 A A A A A A A 0 1.

1 -i (n 11, 1 - Clear coating composition for use in the two-coat one-bake method The base coating composition B was applied to substrate panels and the coated panels were allowed to stand for 5 minutes. Thereupon the coating compositions of Examples 33 to 39 and Comparison Example 9 diluted to a viscosity of 22 seconds with Swasol #1000 were applied to coated panels. The coated panels were allowed to stand and baked in the same manner as above to give test coated panels. The test coated panels were tested for properties. Table 12 shows the test results.

Table 12

Comp.

Example Examp e 33 34 35 36 37 38 39 9 Coating composition M19 M-20 M-21 M-,22 M-23 M-24 M-25 M-26 State of coating surface A A A A A A A A (11) Gloss (600) 95 93 96 91 94 94 94 93 Pencil hardness H H H H H 2H H B Water resistance (12) A A A A A A A B UI Acid resistance (13) A A A A A A A A impact resistance (14) 35 35 35 35 50 45 35 20 Weatherability (17) A A A A A A A A Distinctness-of- 88 89 91 92 91 87 87 68 image gloss -1 (27) Distinctness-of- 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.3 image gloss -2 (28) ki 1 f, 5 - 157 - The symbols 11 to 14 and 17 are as described above. The symbols 25 to 28 indicate the following.

(25) Adhesion-5 A substrate coated with Lugabake AM (tradename, Kansai Paint Co., Ltd., polyester resin/melamine resin baking-type coating composition) was baked at 1400C for 30 minutes and further baked at 1601C for 30 minutes. Such treated substrates were used in preparing substrate panels.

A lattice pattern with eleven cuts in each direction was made in the coating film to the substrate to form 100 squares (1 mm2). Cellophane adhesive tape was applied over the lattice and then removed, and the adhesion was evaluated in terms of a value given by: (the number of squares remaining adhered)/100.

(26) Adhesion-6 A test coated panel prepared by the same method as in Adhesion-5 was immersed in hot water at 600C for 3 days, withdrawn from the hot water and dried for 1 hour. The same cross-cut adhesion test as in adhesion-5 was carried out. The values in the table indicate the same evaluation as in Adhesion-5.

(27) Distinctness-of-image gloss -1 The distinctness-of-image gloss was measured with an image clarity meter (manufactured by Suga Tester - 158 Co., Ltd.). The values in the table represent ICM values which vary from 0 to 100%. The larger the ICM value, the higher the distinctness-of-imagegloss. The ICM value not less than 80 represents a high distinctness-ofimage gloss.

(28) Distinctness-of-image gloss -2 The distinctness-of-image gloss was measured with a Gd meter for measuring the distinctness-of-image gloss (JCRI-GGD-166 model manufactured by Nippon Shikisai Kenkyusho) at a fixed angle of 550.

W - 159 -

Claims (11)

CLAIMS:

1. A curable composition comprising: (I) a resin component containing as essential functional groups epoxy group, and silanol group and/or hydrolyzable group directly attached to silicon atom, (II) at least one crosslinking agent selected from the group consisting of carboxylic acid compounds, polyisocyanate compounds and aminoaldehyde resins, and (III) at least one curing catalyst selected from the group consisting of organometallic compounds, Lewis acids, protonic acids and compounds having Si-O-Al bond or bonds.

2. A curable composition according to claim 1 wherein (I) resin component further contains hydroxyl group as essential functional group.

3. A curable composition according to claim 1 wherein the epoxy group contained in (I) resin component is alicyclic.

4. A curable composition according to claim 1 wherein (I) resin component is used as dissolved or dispersed in a solvent or in the form of a nonaqueous dispersion of polymer particles prepared in the presence of said resin component as a dispersion stabilizer.

5. A curable composition according to claim 1 wherein (II) crosslinking agent is a carboxylic acid compound and is used in an amount of about 1 to about 40 - parts by weight per 100 parts by weight of (I) resin component, calculated as solids.

6. A curable composition according to claim 1 wherein (II) crosslinking agent is a polyisocyanate compound and is used in an amount of about 1 to about 30 parts by weight per 100 parts by weight of (I) resin component, calculated as solids.

7. A curable composition according to claim 1 wherein (II) crosslinking agent is an aminoaldehyde resin and is used in an amount of about 1 to about 50 parts by weight per 100 parts by weight of (I) resin component, calculated as solids.

8. A curable composition according to claim 1 wherein (III) curing catalyst is at least one organometallic compound selected from the group consisting of metal alkoxide compounds, metal chelate compounds and metal alkyl compounds.

9. A curable composition according to claim 8 wherein (III) curing catalyst is a metal chelate compound.

1-0. A curable composition according to claim 1 wherein (III) curing catalyst is at least one compound selected from organometallic compounds, Lewis acids and protonic acids, and is used in an amount of about 0.01 to about 30 parts by weight per 100 parts by weight of combined amount of (I) resin component and (II) 0:

161 - crosslinking agent, calculated as solids.

11. A curable composition according to claim 1 wherein (III) curing catalyst is a compound having Si-O-Al bond or bonds and is used in an amount of about 1 to about 100 parts by weight per 100 parts by weight of combined amount of (I) resin component and (II) crosslinking agent, calculated as solids.

Published 1990 at The Patent Office, State House. 66.71 High Holborn, LondonWC1R4TP.Further copies maybe obtainedfromThe Patent Mce. mmn IXPn Ptpd bv MultiDlex techmques ltd. St Mary Cray, Kent, Con. 1187