JPH02251274A - Film forming method - Google Patents

Abstract

PURPOSE:To improve the acid resistance and finish apparent of a top coat film by forming a top coat composite-layer film constituted of a colored top coat film, the first clear film and the second clear film based on a base resin having a specific composition and a curing agent to a surface to be painted. CONSTITUTION:The second crosslinkable and curable clear paint is prepared by compounding a resin, which has a hydroxyl group and/or hydrolysable group directly bonded to a silicon atom and an epoxy group therein, or a resin mixture, which consists of a resin having a hydroxyl group and/or hydrolyzable group directly bonded to a silicon atom and a resin having an epoxy group, with a curing agent. A top coat composite-layer film constituted of a film composed of colored top coat, a clear film composed of the first clear paint and a clear film composed of the aforementioned second clear paint is formed to a surface to be coated.

Description

[Detailed Description of the Invention] The present invention provides a novel method for forming a coating film, and more specifically, provides a coating film that has an excellent finished appearance and excellent resistance to environmental pollution such as acid rain. Regarding the method.

In order to improve the appearance of the paint, applying a pigment-free clear paint as a top coat to the top coated surface has become popular as a painting method, especially for the outer panels of automobile bodies. In this case, from the viewpoint of productivity, it is usual to apply a pigment-containing paint (base coat), then apply the clear paint, and then bake and harden both the base coat and clear coat at the same time. In the industry, this is called a two-coat-one-bake (hereinafter referred to as 2CIB) method.

Although the 2CIB painting finishing method has a finished appearance that is superior to a single-coat finish using a paint containing pigment, recent market demands require an even further improvement in the finished appearance.

In particular, due to acid rain, which has recently become a social problem, 2CIB
The coating surface of this method is easily deteriorated (this is one of the causes of deterioration in the appearance of automobile exterior panels painted using this method, and there is a strong demand for improved acid resistance of top clears).

0 The inventors of the present invention have been working diligently to achieve a drastic improvement in the appearance and acid resistance of the paint finish using the 2CIB method without impairing the light resistance, mechanical properties, etc. of the paint film. conducted research. As a result, it was discovered that the above object could be achieved by further coating the above clear coated surface with a clear paint having a specific composition, and the present invention was completed.

That is, the present invention provides a colored top coat film, a clear coat film (
In the top coat multi-layer coating film consisting of the first) and the clear Ill (second), the clear coating film (second) contains a base resin and a curing agent as main components.

and the base resin has a hydroxyl group directly bonded to the silicon atom and/or
Or a resin (1) having a hydrolyzable group and an epoxy group in the same resin, or a resin (1) having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom, and a resin (2) having an epoxy group. The present invention relates to a coating film forming method characterized in that the coating film is formed based on a crosslinked curable coating material which is a mixed resin (b) formed by mixing the following.

The present inventors initially varied the Tg point (glass transition temperature), molecular weight, styrene content, etc. of conventional acrylic resins and amino resin-based acrylic resins in order to improve the acid resistance of the clear coating film (second). Although a certain degree of effect was observed by using these methods, it was observed that due to changes in test conditions, particularly temperature, acid concentration, etc., there were cases in which significant deterioration occurred in all of these, with no significant difference from conventional methods. Furthermore, since there are various possible situations in which automobiles are actually placed, the above-mentioned improvements have not been able to fundamentally solve the problem.

Therefore, further deterioration due to acid rain etc. is caused by the N of amino resin.
We presume that the basic cause is that the ether bond created by the reaction between the methylol group directly bonded to the acrylic resin and the hydroxyl group of the acrylic resin is highly susceptible to hydrolysis, and we have developed a crosslinking method using bonding points that are more resistant to hydrolysis. We conducted research on

Currently, one of these is a two-component urethane paint that uses a cross-linked polyisocyanate resin with urethane bonds and a hydroxyl group-containing resin mixed before painting, but due to the toxicity of the isocyanate and the process of heating the two components, It has problems such as being complicated.

Therefore, in consideration of the various situations described above, the present inventors conducted further research and found that crosslinking through the reaction between hydroxyl groups and/or hydrolyzable groups directly bonded to silicon atoms and epoxy groups has excellent acid resistance. It has been found that this method also improves the finished appearance of the paint film.

Next, the method of the present invention will be specifically explained.

Colored topcoat film: In the present invention, the colored topcoat film contains a colored topcoat paint (containing a colored pigment and/or a metallic pigment).
It includes coating films formed by so-called solid color paints or metallic paints. As the paint,
Used in the coating of automobile exterior panels, etc. For example, finished appearance (sharpness, smoothness, gloss, etc.), weather resistance (glossy retention, color retention, chalking resistance, etc.), J4 chemical resistance, water resistance. , metallic paints and solid color paints that use known plastic or metal paints that can form coating films with excellent moisture resistance, hardening properties, etc. Specifically, amino-acrylic resins are used. Examples include paints whose vehicle main components are amino-alkyd resins, amino-polyester resins, and the like. The form of these paints is not particularly limited, and may include organic solvent type, non-aqueous dispersion type, water-soluble (dispersion) wave type,
Any form such as powder type or high solid type can be used. Pigments to be contained in the paint include aluminum powder, mica powder, organic colored pigments, inorganic colored pigments,
Examples include titanium white and extender pigments.

Clear paint (first): A transparent paint film formed on the surface of the colored paint film, which can be formed by applying a clear paint (1) containing little or no color pigment or metallic pigment. Clear paint (
As 1), a conventionally known clear paint composition for the 2CIB coating method can be used. For example, JP-A-53
Clear coating compositions described in JP-A-126040, JP-A-53-149063, JP-A-52-71540, JP-A-54-73835, etc. can be used.

The basic composition is, for example, a coating composition that uses a hydroxyl group-containing acrylic resin or oil-free polyester containing 0 to 30% by weight of styrene and an amino resin as a crosslinking agent.

The properties of the clear coating film (first) are as follows:
It is desirable that the adhesion with the (second) material is good. Therefore, the hydroxyl value of the resin (mainly acrylic resin or polyester resin) used for preparing the clear paint (1) should be about 100 to 250 mgKOH/g, preferably about 12
It is desirable to keep it at 0 to 200 mgKOH/g.

This paint can be applied in organic solution type, non-aqueous dispersion type, high solid type, aqueous dispersion type, aqueous solution type, etc.

Clear paint film (second): A transparent paint film formed on the coated surface of the clear paint film (first), which can be formed by applying clear paint 2 that contains no or almost no color pigments or metallic pigments. .

One of the features of the present invention is that the base resin of the clear paint 2 is a resin (a
), or a mixed resin (■) formed by mixing a resin (1) having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom and a resin (2) having an epoxy group. , the resin (1) and the mixed resin (2) will be explained below.

In Resin 1 and Resin 2-1, the hydrolyzable group directly bonded to the silicon atom is a group that is hydrolyzed by water or moisture to produce a silanol group. Examples of the group include those represented by the following general formula.

-0-R' (I)R
"" / -0-N=C \ (nr) R#" \ R"" (Vl) In the formula, R' is a C1-4 alkyl group, and R" to R" are the same or different and are CI-# Alkyl group, aryl group,
Indicates an aralkyl group.

In the general formula, the alkyl group of rC is 11 such as methyl, ethyl, n-propyl, isopropyl,
Examples include n-butyl, isobutyl, SeG butyl, tertbutyl, n-pentyl, isopentyl, n-octyl, isooctyl, and the like. Examples of the "aryl group" include phenyl, tolyl, xylyl, and the like. Examples of the "aralkyl group" include benzyl and phenethyl.

Further, in addition to the above-mentioned hydrolyzable groups bonded to silicon atoms, examples of hydrolyzable groups include 5i-H groups.

In resins (a) and (b-1), the hydroxyl group and/or hydrolyzable functional group (hereinafter sometimes abbreviated as "silane group") include the above from the viewpoint of storage stability, curability, etc. Silane groups represented by general formulas (I) and (II) are preferred.

Next, the above-mentioned base resin will be explained.

Examples of methods for introducing epoxy groups and silane groups into the resin skeleton include the following methods.

(1) A resin (A) having a functional group, and a compound (B) having a functional group and an epoxy group that react complementary to the functional group.
and a reactant (D) obtained by reacting a compound (C) having a functional group that reacts complementarily with the functional group of the resin (A) and a silane group, (hereinafter referred to as r(1) I!l fat composition )
, (2) a resin (E) having a functional group, and a compound having a functional group and an epoxy group that react complementary to the functional group (
A mixture of the reaction product (F) with B) and the reaction product (H) with a compound (C) having a functional group and a silane group that reacts complementary to the functional group on the resin CG) (I ), (hereinafter referred to as "(2) resin composition"), (3) Epoxy group-containing polymerizable unsaturated monomer (J), silane group-containing polymerizable unsaturated monomer (K), and as necessary A copolymer (L) containing another polymerizable unsaturated monomer (M) as a monomer component (hereinafter referred to as "(3) resin composition")
, (4) a homopolymer (N) of the monomer (J) or a copolymer (N) of this and another polymerizable unsaturated monomer (M), and the monomer (K) ) homopolymer (P) or a mixture of this and a copolymer (P) with other polymerizable unsaturated monomers (M) (hereinafter referred to as "(4) resin composition"), (5 ) A copolymer (R) containing a functional group-containing polymerizable unsaturated monomer (Q) and the epoxy group-containing polymerizable unsaturated monomer (J) as essential components, and a monomer (Q) A reaction product (T) with a compound (S) having a silane group and a functional group that reacts complementarily with the functional group due to (hereinafter referred to as "(5) resin composition"), (6) Functional A copolymer (V) comprising as essential components a polymerizable unsaturated monomer (U) having a group and the above-mentioned silane group-containing polymerizable unsaturated monomer (K), and the monomer (tJ) A reaction product (X) of a compound (W) having an epoxy group and a functional group that reacts complementary to the contributing functional group (hereinafter referred to as "(6) resin composition").

(7) A mixture (Y) of the homopolymer (N) or copolymer (N) and the reactant (H) (hereinafter referred to as "(7) resin composition").

(8) The homopolymer (P) or copolymer (,P)
A mixture (Z) of and the reactant (F) (hereinafter referred to as "(8)
(referred to as "resin composition").

In the resin compositions (1) to (8) above, the complementary reacting groups are groups that can react with each other,
For example, you can select from the table below as appropriate.

The two complementary reacting groups in Table 1 can be selected and combined as appropriate from the table above, and the following combinations are preferred.

Resin (A)/Compound (B) (or Resin (E)/Compound (
B)] functional group combination m/+5) , +2)/+4) , +3)/(31
, '(5) / (1) etc., resin (A) / compound (C)
Combination of functional groups of [or resin (G)/compound (C)] 1 /+51 , (2)/(31, (2+/(41), (
2)/(5), 3/31, (4)/(2),
(4)/(6), [4)/+7).

51/11, (51/(21, (51/(61,
(5)/(7), 6)/+41, (6)/(81,
(7)/(4), (7)/(81.

71/+5 etc., Monomer (Q)/Compound (S) functional group combination (1)/+51, [41/+21, +
43/+6), (4)/(7), (51/(
11, (5)/(2), (5)/<31,
(51/(6), (51/(71, etc.) Combination of functional groups of monomer (U)/compound (W) (1)/
+5), (2)/(4), +2)/(5)
, (3)/(1).

(51/(11, (61/(4), (61/(5)
, (6)/(8).

(7)/(4), (71/(5), (7)/(8)
)etc.

The Yuyuyu m-based resin (A) can be suitably selected from conventional resins without any particular limitations as long as it has the above-mentioned functional group. Specifically, resins such as vinyl resin, fluororesin, polyester resin, alkyd resin, silicone resin, urethane resin, and polyether resin can be mentioned.

The resin (A) contains the compound (B) and the compound (
The resin has an average of two or more functional groups that react with the functional group in C), but the functional groups in the resin may be the same or different.

When the functional groups in the resin (A) are the same, 1, for example, 2 on average.
The resin (A) having at least 1 hydroxyl group is combined with the compound (B) having an incyanate group (5) and the incyanate group (
5), or
Resin having an average of 2 or more isocyanate groups (5) (
A) can be reacted with a compound (B) having a hydroxyl group (1) and a compound (C) having an isocyanate (5).

In addition, when the functional groups in the resin (A) are different, for example, the resin (A) having an average of one or more hydroxyl groups (1) and carboxyl groups (2) is replaced with an isocyanate group (5
) with compound (C) and compound CB) with epoxy (4).

There is no problem even if the functional group in the compound (B) that reacts with the functional group in the resin (A) is the same as the epoxy group possessed by the compound (B). There is no problem even if the functional group in compound (9) to be reacted is the same as the silane group possessed by compound (C).

As the resin (A), resins having functional groups such as a hydroxyl group, a carboxyl group, an isocyanate group, a silane group, and an epoxy group will be explained.

[Hydroxy group-containing resin] The following items can be mentioned.

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

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

General formula (1) In the formula, R' represents a hydrogen atom or a hydroxyalkyl group.

General formula (2) In the formula, R1 has the same meaning as above.

General formula (3) In the formula, Z represents a hydrogen atom or a methyl group, m represents an integer of 2 to 8, P represents an integer of 2 to 18, and q represents an integer of 0 to 7.

General formula (4) % formula % In the formula, Z has the same meaning as above, T and T are the same or different and represent a divalent hydrocarbon group of 01 to t0, and S and U are each An integer from 0 to 10, with S and U
The sum is 1 to 10.

The "hydroxyalkyl group" in general formulas (1) and (2) is 01 to 6. Specifically, 1 for example -
CJ40H1-CIH60H1-(:, H, OH, etc. can be mentioned.

01-. in general formula (4). . As the divalent hydrocarbon group, for example, =CH,-, -CHa-C1,-1-CH
, -CH, -CH, -1 As a monomer component of the general formula (4), for example, -CHx-CHz-CHx-CH-CH*-CHa-C
Hx-1-Cr. Examples include R2°-1CHa -C+tHt4-5-C+Jas-10,0, -CHbe>cn, -, and the like.

As the monomer component of general formula (2), for example, CHz"C
HCHJH CH,=CHCH10CH,CH,DHCH*”CHC
HtQ(CHtCHtO)yHCHx=CHCHaO(
Examples include CHtCHtO)yH.

As the monomer component of general formula (3), for example, CHa;
H(CHs) C00CJ40HC1,=CH(CH,
l coocsHson■ CH,=CH(C1,) C00-C,H,-0(C-
Examples include CH, -CHt-CH, -CL-GHz-Oh, and the like.

CHa”CH((:Hsl C0Q(CHzCHCHs
QhπHCH1=CH(cns) Coo(CH2CH
10h-g-HCH,=CH(CHI) C00(CH
aCH,0)ydCH*=CH(CHs) C00(C
H*CH*CHzCHtOh)dCI.

CH*=CI(CHsl COO ctt*ctr*o
Examples include hτ;■-CH YOcHoHτ;τR, and the like.

Furthermore, in addition to the above, the general formulas (1) to (4).

Adducts of the hydroxyl group-containing unsaturated monomer represented by the formula and lactones such as ε-caprolactone and γ-valerolactone can be used.

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

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

(b-2) Vinyl ether and allyl ether: e.g. ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, te
Chain alkyl vinyl ethers such as rt-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-pentyl vinyl ether,
Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, 0-m-, p-trivinyl ether, and aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether.

(b-3) Vinyl esters and propenyl esters: for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl incaproate, vinyl parsitate, vinyl caprate, and isopropenyl acetate. Propenyl esters such as isopropenyl propionate, etc.

(b-4) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate , ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, and other alkyl esters of acrylic acid or methacrylic acid having 1 to 1.8 carbon atoms; methoxy acrylate Alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as butyl, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate.

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

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

■ Hydroxyl group-containing fluororesin Hydroxyl group-containing polymerizable unsaturated monomer (a), fluorine-containing polymerizable unsaturated monomer (c), and other polymerizable unsaturated monomers (b) as necessary. A polymer as a monomer component.

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

General formula (5) %Formula %(5) In the formula, X is the same or different and represents H, (1, Br, F,
Indicates an alkyl group or a haloalkyl group, provided that the formula contains at least one F.

General formula (6) %Formula% In the formula, Z has the same meaning as above, R2 represents a fluoroalkyl group, and n represents an integer of 1 to 1O.

The "alkyl group" in general formula (5) has 3 to 6 carbon atoms, preferably 01 to 4@. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl groups, and the like. Further, the "haloalkyl group" has from C+ to 6, preferably from C1 to 4.

Specifically, for example, CF, CHF*, CHJ, CI
Mu, CH-Ch, CH, CI, CFC1'x, [CF
a) *CFs, (CFzls(:Fs, CFt
Examples include Hz, CFiCHFz, CFJr, CHJr, etc.

Examples of the monomer represented by formula (5) include GFt=GFt, CHF"Ch, CHi"CFg
, CHa”CHF.

CGIP=Ch, CHCl:CFa, CC1z"Ch,
CGIF”CGIF, (:HF:CClt%C)1.
=cclF, CC1, =CCIFChCF=CF*
, CFsCF=CHF, CF-CH2CF-1CF
,CF=CH,,CF,CF=CHF,CHF,C
F=CHF.

CF, CF-CH,, CFsCF=CF, , cus
cp=cpa, CHsCF=CHz, ChCICF”
CFx, CF-CC1=CFl, CF, CF=CFC
1%ChCICCCCCF*, CFiCICF”CPC
l, CFCI□cp=cF*, CF2CC4=CG
IF, CF, CC1=CC11,,ccip*cp
=cc1*,CC1,CF=CF,, CFICICC
l-CCII, CFCI□CC1=CC1□, CF,
CF=CHC1, CGIF, CF=CHC1, CFsC
Cl"CHCl, CHF-CC1:CC1*, C
FtCICH”CCb, CFtCICCl”CHClo
, CC15CF=CHC1, CF! 1cF=cF, ,C
F, BrCH=CF*, CFsCBr=C) (Br
, CF*CICBr=CL, CIJrCF=CC1
,,CFsCBr”CHz, CF*CH=CHBr,C
FJrCH”CHF, CFJrCF”Ch, C
FsCF-CF"CFx, CF8CF=CFCFs,
CFaCH”CFCFs, CF,=CFCF,CH
,F,,CFICFIC,F=CH! , ChCH=CH
CFs, CFyo=CFCFtCHs, CF,=C:F
CH2CH,, CF, CH1CH=CI! , CFsCH
”CHClko, CFt=CHCHiCHs, CHsCF
tCH"CHa,cFH,cH=cHcFHi,CHs
CFtCH"CHs, CH!=CFCIICHI, CF
s((:FtltCF=CFt, CFs[CFtl
Examples include sCF=CFz.

-119 The "fluoroalkyl group" in formula (6) is C
1-t1 items. Concrete number two, for example C
4F*. (Ch) sCF (CFs) *. , C
sF+-, C1. Fat, CaF+y, (CFs
)ycFa, etc.

Examples of the monomer represented by general formula (6) include CH1 CH. =C-COO-CIH4-C. F.

\ C.F.

H8 CH*=C-COO-CI4-C-F+tCH.

CH,=C-Coo-CI4-CI. Fat etc. can be mentioned.

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

■ Hydroxyl-containing polyurethane resin Hydroxyl-containing vinyl resin, hydroxyl-containing fluororesin, hydroxyl-containing polyester resin, etc. are modified with polyisocyanate compounds (e.g., tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.). A resin that does not have isocyanate groups.

■Hydroxyl group-containing silicone resin Hydroxyl group-containing vinyl resin, hydroxyl group-containing fluororesin, hydroxyl group-containing polyester resin, etc.
-6018, Z-6188 (all products from Dow Corning Co., Ltd.), SH5050, SH6018, SH6188 (all products from Toshi Silicone Co., Ltd.)), and is obtained by modifying the resin without alkoxysilane groups and silanol groups.

■Vinyl alcohol-styrene copolymer.

E carboxyl group-containing resin] Below, items Φ to ■ can be mentioned.

(2) Carboxyl group-containing vinyl resin A polymer containing a carboxyl group-containing polymerizable unsaturated monomer (d) and, if necessary, other polymerizable unsaturated monomers (b) as monomer components.

Carboxyl group-containing polymerizable unsaturated monomer (d) Compounds represented by the following general formulas (7) and (8) can be mentioned.

General formula (7) R' C0OH In the formula, R-rich represents a hydrogen atom or a lower alkyl group, and R
4 represents a hydrogen atom, a lower alkyl group or a carboxyl group, and R5 represents a hydrogen atom, a lower alkyl group or a carboxy lower alkyl group.

General formula (8) In the formula, R6 represents a hydrogen atom or a methyl group, and m has the same meaning as above.

In the above formula (■), the lower alkyl group is preferably 04 or less, particularly a methyl group.

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

Furthermore, examples of general formula (8) include 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and the like.

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

■ Carboxyl group-containing fluororesin fluorine-containing polymerizable unsaturated monomer (C), carboxyl group-containing polymerizable unsaturated monomer (d), and other polymerizable unsaturated monomers (b) as necessary. ) as a monomer component, and the same monomer components as mentioned above can be used.

In addition to the above resins, resins obtained by reacting the fluoropolyol resin and the polycarboxylic anhydride compound can also be used.

(2) Carboxyl group-containing polyester resin Examples include resins obtained by esterifying the polybasic acid and the polyhydric alcohol.

[Isocyanate group-containing resin] The following items can be mentioned.

(2) Isocyanate group-containing vinyl resin A polymer containing an isocyanate group-containing polymerizable unsaturated monomer (c) and, if necessary, other polymerizable unsaturated monomers (b) as monomer components.

Isocyanate group-containing polymerizable unsaturated monomer (e) Monomers represented by the following general formulas (9) and (10) can be mentioned.

General formula (9) In the formula, R@ and n have the same meanings as above.

Examples include monomers represented by the following formulas, including inocyanate ethyl (meth)acrylate.

General formula (10) In the formula, R6 and n each have the above meanings, and R1 is a hydrogen atom or an alkyl group of Cs or less. For example, α,α-dimethyl-m- Included are isopropenyl benzyl isocyanate.

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

Furthermore, as the isocyanate group-containing fluororesin, in addition to those mentioned above, those obtained by reacting a hydroxyl group-containing fluororesin with, for example, the polyisocyanate compound can also be used.

(2) Inocyanate group-containing fluororesin A resin obtained by adjusting the hydroxyl group-containing fluororesin and the polyisocyanate compound so that the isocyanate component is in excess.

(2) Isocyanate group-containing polyester resin A resin obtained by adjusting the hydroxyl group-containing polyester resin and the polyisocyanate compound so that the inocyanate component is in excess.

(2) Incyanate group-containing polyurethane resin A resin obtained by adjusting the hydroxyl group-containing polyether resin and the polyisocyanate compound so that the isocyanate component is in excess.

[Silane group-containing resin] A resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing silane compound described below, a resin obtained by reacting the isocyanenite group-containing resin with the hydroxyl group-containing silane compound described below, and the hydroxyl group-containing silicone. Silicone resin etc. used in resin.

[Epoxy group-containing resin] A resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing epoxy compound described below.

(1) The compound (B) used in the composition is the resin (A
) has one or more functional groups and one or more epoxy groups in one molecule, each of which reacts with the functional groups in (2). The resin (A)
There is no problem even if the functional group that reacts with the functional group inside is the same as the epoxy group.If the functional group is the same as the epoxy group, it is necessary to contain two or more epoxy groups in one molecule. be.

Next, a representative compound (B) will be described below.

[Hydroxyl group-containing epoxy compound] Compounds represented by the following general formulas (11) to (21) can be mentioned.

In each formula, R6 and n have the same meanings as above, and R1 is C
The divalent hydrocarbon group represented by +-a and R''G are the same or different and represent a divalent hydrocarbon group represented by C and o.

In general formulas (11) to (21), the divalent hydrocarbon group of C- is the above-mentioned C-. The divalent hydrocarbon group can be appropriately selected from the following. Moreover, as the C5-1o divalent hydrocarbon group, the same groups as mentioned above can be mentioned.

Specific examples of the compounds represented by general formulas (11) to (21) include CHz-C-CHz-OH \1 \1.

(Silane group-containing epoxy compound) Compounds represented by the following general formulas (22) to (25) can be mentioned.

In each formula, R6 and R@ have the same meanings as above, R1
may be the same or different, Y may be the same or different and may be a hydrogen atom, a hydroxyl group, a hydrolyzable group, Ct~,
It represents an alkyl group, an aryl group, or an aralkyl group, provided that at least one Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

In the general formulas (22) to (25), the hydrolyzable groups include the groups of the above general formulas (I) to (Vt). Also,
The alkyl group, aryl group and aralkyl group of C3~ can be the same as those mentioned above.

Specific examples of the compounds represented by formulas (22) to (25) include CRs.

In addition to the above, compounds obtained by condensing compounds represented by general formulas (22) to (25) with polysilane compounds described below (for example, compounds represented by general formulas (38) to (40)) can also be used. . Specifically, the following can be mentioned, for example.

[Polyepoxy compound] Compounds represented by the following general formulas (26) to (33) can be mentioned.

In the formula, R@ and R" have the same meanings as above, R6 and R- may be the same or different, and RIO
are the same or different CI~. alkyl group, phenyl group, aryl group, aralkyl group, or the same or different hydrogen atoms, C1-4 alkyl group, W is 0 and 1-
Indicates an integer of 10.

Specific examples of the compounds represented by formulas (26) to (33) include ON, 1 tC and the like.

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

etc, . Adducts of 9cH,OH and the polyisocyanate compounds listed below (polyisocyanate compounds that can be used include 1) aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; hydrogenated xylylene diisocyanate or isophorone diisocyanate Organic diisocyanates such as cycloaliphatic diisocyanates, nitolylene diisocyanate or aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, or each of these organic diisocyanates and polyhydric alcohols.

Examples of typical commercially available products include low molecular weight polyester resins or adducts with water, polymers of each organic diisocyanate as described above, and isocyanate-biuret bodies. Burnock D-750°-800, DN-950, -970
Or 15-455J [products of Dainippon Ink Chemical Industries], "Desmodule% NHL, IL or N3390J [products of Bayer AG, West Germany],
Takenate D-102, -202, -IION or 1123NJ [Takeda Pharmaceutical Flavor Products], Coronate L, ) (L, E) (or 203J [Japan Polyurethane Industries ■Products] or Duranate 24A-
90CXJ [Asahi Kasei Kogyo ■ product], etc.); Esterified products having an unsaturated group such as α in the molecule (e.g., esterification reaction of tetrahydrophthalic anhydride, trimethylolpropane, 1°4-butanediol, etc.) Examples include those obtained by oxidizing an esterified product (with a number average molecular weight of 900) with peracetic acid or the like.

[Isocyanate group-containing epoxy compound] Examples include those obtained by reacting the hydroxyl group-containing epoxy compound with the polyisocyanate compound so that the epoxy group and the isocyanate group remain. Specifically, for example, a reaction product of a compound represented by general formula (11) and hexamethylene diisocyanate, a reaction product of a compound represented by general formula (20) and inphorone diisocyanate, a reaction product of a compound represented by general formula (15), and toluene. Reaction products of diisocyanate General formula (21) and xylene diisocyanate reaction products Reaction products of the compound represented by General formula (18) and isophorone diisocyanate, etc. can be mentioned.

(1) The compound (C) used in the composition has one or more functional groups that react with the functional groups in the resin (A) and one or more silane groups in one molecule. The functional group that reacts with the functional group in the resin (A) may be the same as the silane group, and if the functional group is the same as the silane group, there may be two or more silane groups in one molecule. Must be included.

Next, a representative compound (C) will be described below.

[Hydroxyl group-containing silane compound] Compounds represented by the following general formulas (34) to (36) can be mentioned.

child, hydroxyl group, and hydrolyzable group.

Specific examples of compounds represented by general formulas (34) to (36) include, for example, OCHs HO-(CH,) 5-5i-OCHsOCHs Ha CH3 In each formula, R"%R" and Y are the same as above. has a meaning, R
", R" and Y may be the same or different, provided that any one of Y can be a hydrogen source.

In addition to those mentioned above, for example, condensates of compounds represented by general formulas (34) to (36) and polysilane compounds described below can also be used. As an example of the condensate, the following can be exemplified.

[Polysilane compound] Hydrolyzable group directly bonded to silicon and 5iO in one molecule
It is a compound having two or more groups selected from H.

Compounds represented by the following general formulas (38) to (4o) can be mentioned.

In each formula, Y' is the same or different and is a hydrogen atom, a hydroxyl group, or a hydrolyzed group, Rlo has the same meaning as above,
R10 may be the same or different.

Specific examples of the compounds represented by the general formulas (38) to (40) include dimethyldimethoxysilane, dibutyldimethoxysilane, diso-pyldibutoxysilane, diphenyldibutoxysilane, diphenyljethoxysilane, diethyldibutoxysilane, Silanol, dihexyldisilanol methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyltributyloxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol,
Tetramethoxysilane, tetraethoxysilane, tetrapropioxysilane, tetraacetoxysilane, G1
so-probyloxydivaleroxysilane, tetrasilanol [Epoxy group-containing silane compound] The above-mentioned silane group-containing epoxy compounds can be mentioned.

[Isocyanate group-containing silane compound] The following general formula (4
Examples include compounds represented by 0) and (41).

can be mentioned.

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

In each formula, R'' and Y have the same meanings as above, and Y may be the same or different.

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

Specific examples of compounds represented by general formulas (40) and (41) include 1 such as 0CNCJaSl (OCJsl s, 0CNCJ4S
l (OCHsl s.

0jNCsHsSi (QCyoR5)3. Hs OCNCsHJi (OCHs) t, Hs OCNCH*Sl (OCJ@) s, 0CNCH*S
i (OCHs) s, 0CNCH! Si (OCJs
l t, Hs OCNCH*Si (OCHs) s,” 0CN-CJs-Si (OCCHs) 5OCN-S
i(OCHals 0CN-Si (OCCHsl s -CCHI), etc. can be mentioned.

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

Specifically, the following can be mentioned.

Examples of the reaction products of general formula (34) and hexamethylene diisocyanate or tolylene diisocyanate can be mentioned.

Furthermore, condensates of the epoxy group-containing silane compounds and, for example, the polysilane compounds can also be used. Examples of such compounds include:

[Mercapto group-containing silane compound] Compounds represented by the following general formula (42) can be mentioned.

In the formula, R1 and Y have the same meaning as above, Y may be the same or different, provided that at least one of Y
Individuals are hydrogen source, child, hydroxyl group, and hydrolyzable group.

Specific examples of the compound represented by -fi formula (42) include CJs HS-CsHs-3i-OCJ* (CJs HI).

Furthermore, condensates of the mercaptosilane compounds and, for example, polysilane compounds can also be used.

[NH group or NH, group-containing silane compound] The following general formula (
Compounds represented by (43) and (44) can be mentioned.

etc. can be mentioned.

In addition to the above, the hydroxyl group-containing silane compound may be added to the polyisocyanate compound and thiocol compound (for example, HS
-CJ! , -OH, have the same meaning as above. ), specifically, for example, in each formula, R', R'' and Y have the same meanings as above, and R@, R16, and Y may be the same or different, provided that Y At least one of these is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of the compounds represented by general formulas (43) and (44) include CH8HJ-(CHil5-5i-OCHsOCHs0.0JaCJs).

In addition, in addition to the above, general formulas (43) and (44)
) and the above-mentioned polysilane compounds can also be used. An example of the condensate can be exemplified.

[Unsaturated group-containing silane compound] The same compounds as the silane group-containing polymerizable unsaturated monomer (10) described later can be used.

Resin (A) can have a number average molecular weight of about 3000 to 200000, preferably about 5000 to 5000.

Compound (B) and compound (C) are about 120 to 1000
0, preferably 120 to 3000.

The reactant CD) obtained by reacting the resin (A) with the compound (B) and the compound (C) each has an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in one molecule. can have. This reaction product (D) corresponds to the resin (2).

11 Engineering J-Ro 11 Clothes resin (E) has on average one or more functional groups in one molecule that react with the functional group of compound (B), and specifically, the above (1) resin composition. You can select and use them as appropriate.

Compound (B) has on average one or more functional groups in one molecule that react with the functional groups of resin (E), and has on average one or more epoxy groups. The functional group in the compound (B) may be the same as the epoxy group, and the same compounds as those described in (1) resin composition can be used as the compound (B).

The resin (G) has on average one or more functional groups in one molecule that react with the functional groups of the compound (C), and specifically, it is appropriately selected from the resin compositions (1) above. It can be used as

Compound (C) has on average one or more functional groups in one molecule that react with the functional groups of resin (G), and also has one or more silane groups on average. The functional group in the compound (C) may be the same as the silane group, and the same compounds as those described in (1) resin composition can be used as the compound (C).

Resins (E) and (G) are about 3,000 to 200,000,
Preferably, it can have a number average molecular weight of 5,000 to 80,000.

The reactant (F) obtained by reacting the resin (E) and the compound (B) has an average of 1 or more, preferably an average of 2 per molecule.
1 reactant (which can have ~40 epoxy groups)
F) corresponds to the resin ①-2.

The reactant (H) obtained by reacting the resin (G) and the compound (C) has an average of 1 or more, preferably an average of 2 per molecule.
6 reactants (H
) corresponds to the resin ■-1.

Reactant (F) and reactant (H) can be blended so that the ratio of epoxy group to silane group is usually 1/99 to 99/l. Equivalent to mixed resin ■.

Epoxy group-containing polymerizable unsaturated monomer (J): A compound having an epoxy group and a radically polymerizable unsaturated group in one molecule. The epoxy group may be alicyclic or alicyclic. Examples of the radically polymerizable unsaturated group include cut-cutcus+ coo- CH2=CH(CHs) CC-1l.

CH,=CH(CHs) C-N- ■ CHffi=CHCH 〇- CH,=CH0- CH2=CH- CH2=CH(C1,)÷ etc. can be mentioned.

The radically polymerizable unsaturated group is CH2=CH (CHsl C
Examples of the epoxy-based polymerizable unsaturated monomer of OO- include compounds represented by the following general formulas (45) to (57).

In each formula, R., R'', R' and W have the same meanings as above, and R6, R'' and R9 may be the same or different.

As specific examples represented by general formulas (45) to (57), examples of epoxy-containing polymerizable unsaturated monomers include those represented by general formulas (58) to (60) below. .

In each formula, Ra and R1 have the same meanings as above, and R6 and Ra may be the same or different.

Specific examples of compounds represented by formulas (58) to (60) include, for example, in each formula, R6 and Ha have the same meanings as above, and R6 and R8 may be the same or different.

Specific examples of compounds represented by general formulas (61) to (63) include, for example, examples of epoxy-containing polymerizable unsaturated monomers include compounds represented by general formulas (61) to (63) below. I can do it.

Examples of the epoxy-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (64) to (69).

In each formula, R6, Ra, R9 and W have the same meanings as above, and R6, Ra and Ra may be the same or different.

Specific examples of the compounds represented by formulas (64) to (69) include the following.

Examples of the epoxy group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2.CHCH*0- include compounds represented by the following general formulas (70) to (73).

In each formula, R6 and R1 have the same meanings as above, and R1
may be the same or different.

Specific examples of the compounds represented by general formulas (70) to (73) include the following.

As the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CHs=CHO-, for example, the following general formula (74
) to (76) can be mentioned.

Specific examples of compounds represented by general formulas (74) to (76) include, for example, in each formula, R6 and R6 have the same meanings as above, and R1
can be the same or different.

Examples of the epoxy group-containing unsaturated monomer whose radically polymerizable unsaturated group is CL/CH- include the following general formulas (77) to
The compound represented by (79) can be mentioned.

stomach.

Examples of the epoxy group-containing unsaturated monomer include compounds represented by the following general formulas (80) to (84).

In each formula, R. and R1 have the same meanings as above, and R'
may be the same or different.

Specific examples of the compounds represented by general formulas (77) to (79) include the following.

The radically polymerizable unsaturated group is cHt・CH(CHs) −
Q-In each formula, R6, R1 and R- have the same meanings as above, and R6 and R@ may be the same or different.

Specific examples of the compounds represented by formulas (80) to (84) include the following.

It is a compound having at least one silane group and a radically polymerizable unsaturated group in one molecule of the silane group-containing polymerizable unsaturated monomer (K). Examples of the radically polymerizable unsaturated group include CH*=CH(CH,)C0O-CHzCus)ζ)-CHgN(:H(CHs)-CHO"CHO-CHOWCHCHJ-, and the like.

The radically polymerizable unsaturated group is CH, ・CH (cns) c
Examples of the oo-silane group-containing polymerizable unsaturated monomer include a compound represented by the following general formula (85).

In the formula, R1, R1 and Y have the same meanings as above,
Y may be the same or different, and at least one Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of the compound represented by general formula (85) include:
For example, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ -(meth)acryloxypropylmethyljethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxy Silane, γ-(meth)acryloxybutylphenyldiethoxysilane, γ-
(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane.

γ-(meth)acryloxypropylphenylmethylmethoxysilane, γ-(meth)acryloxypropylphenylmethylethoxysilane, γ-(meth)acryloxypropyltrisilanol, γ-(meth)acryloxypropylmethyldihydroxysilane, γ -(meth)acryloxybutylphenyldihydroxysilane, γ-(meth)
Acryloxypropyldimethylhydroxysilane, γ-
(Meth)acryloxypropylphenylmethylhydroxysilane.

1! ccHs can be mentioned.

Radically polymerizable unsaturated group is CH2・CI (CHs)
Examples of the silane group-containing polymerizable unsaturated monomer C include compounds represented by the following general formulas (86) to (88).

In each formula, R1, R9 and Y have the same meanings as above,
Y may be the same or different, and at least one Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of the compounds represented by formulas (86) to (88) include the following.

The radically polymerizable unsaturated group is CH, =CH(CH,)-1
17) Examples of the silane group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (89) and (90).

CHx=CH-Si (CHs) *0CHsCH,=
CHCH, Si (OCH8).

CM-=CH-3L (QC:CHs) sCH*=C
HCH*-3L (OCCHs) 5CHi=CHSi
(CHs) tN (CHs) *In each formula, R", R
- and Y have the same meaning as above, Y may be the same or different, at least one of Y is a hydrogen atom,
Hydroxyl group, hydrolyzable group.

Specific examples of compounds represented by general formulas (89) and (90) include Cl-=CH-5i (OCHs) 5CHz=CI-
Si (OCaHsl sCH,=CH-5i (OC
Hll 2CI.

CHs = Cl-5i (a) xON (C; Hl
), etc.

Radical polymerizable unsaturated group is CM! As the silane group-containing polymerizable unsaturated monomer of =CHO-, for example, the following general formula (
Examples include compounds represented by (91) and (92).

CH,=CH0-3i-Y
(92) In each formula, R9 and Y have the same meanings as above, Y may be the same or different, and at least one Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of the compounds represented by general formulas (91) and (92) include the following.

Examples of the silane group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CHs''CHCHJ- include compounds represented by the following general formulas (93) and (94).

In each formula, R@ and Y have the same meanings as above, Y may be the same or different, and any one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of the compounds represented by the general formulas (93) and (94) include, for example, fi3′ Ll! nI 0CJI ■ CHa=CHCHxO-(CHi)O5i-OCtH
sCH.

can be mentioned.

In addition to the silane group-containing polymerizable unsaturated monomer, the silane group-containing polymerizable unsaturated monomer and, for example, a polysilane compound (for example, a compound represented by general formulas (38) to (40)) A polysiloxane unsaturated monomer having a silane group and a polymerizable unsaturated group obtained by reacting the same can also be used.

As a specific example of the polysiloxane unsaturated monomer, for example, the compound of the above general formula (85) and at least one compound of the general formulas (38) to (40) are combined, with 30 to 0.001 mol% of the former; Examples of the latter include polysiloxane macromonomers obtained by reacting 70 to 99.999 mol% (for example, those disclosed in JP-A No. 62-275132) and the compounds listed below.

CCHz Other polymerizable unsaturated monomer (M) A compound having a radically polymerizable unsaturated group that does not have an active group with the epoxy group of the monomer (J) and the silane group of the monomer (K) can be used. Specifically, the hydroxyl group-containing unsaturated monomer (a), the polymerizable unsaturated monomer (b-
1) to (b-6), a fluorine-containing unsaturated monomer (C), a carboxyl group-containing polymerizable unsaturated monomer (d), and the like.

The copolymer (L) obtained by radical polymerization reaction of the monomer (J), the monomer (K), and optionally other monomers (M) has an average of one each in one molecule. As mentioned above, it preferably has an average of 2 to 40 epoxy groups and silane groups, and corresponds to the resin (2).

As the monomer (J), monomer (K), and monomer (M), the same monomers as described in the above (3) resin composition can be used. .

The copolymer (N) of monomer (J) and monomer (M) can have an average of 1 or more epoxy groups, preferably 2 to 40 epoxy groups in one molecule. Equivalent to resin ■-2.

Copolymer (P) of monomer (K) and monomer (R1) is 1
The molecule can have an average of one or more silane groups, preferably 2 to 40 silane groups. Equivalent to resin ■-1.

Single or copolymer (N) and single or copolymer C
P) usually has an epoxy group/silane group ratio of 1/99 to
It can be blended so that it becomes 99/l. Equivalent to mixed resin ■.

Engineering 1L Group 1 Elimination 1 Polymerizable unsaturated monomer (Q) A compound having a radically polymerizable unsaturated group and a functional group that reacts with the functional group of compound (S) in one molecule.

The functional group of the monomer (Q) is a group inert to the epoxy group, and the functional group may be the same group as the epoxy group.

Regarding the copolymer (R) obtained using the monomer (Q), the following examples (1) to (2) will be given.

■ Hydroxyl group-containing polymerizable unsaturated monomer (a), epoxy group-containing polymerizable unsaturated monomer (J), and optionally a polymerizable unsaturated monomer [e.g. monomer (b-1) to (b-6) and a fluorine-containing polymerizable unsaturated monomer (C), etc.)] are subjected to a radical polymerization reaction to produce a copolymer having a hydroxyl group as a functional group.

■ Isocyanate group-containing polymerizable unsaturated monomer (e), epoxy group-containing polymerizable unsaturated monomer (J), and optionally a polymerizable unsaturated monomer [e.g. monomer (b-1)] ~(b
-6) and a fluorine-containing polymerizable unsaturated monomer (c), etc.] to a copolymer having an incyanate group as a functional group.

■ Epoxy group-containing polymerizable unsaturated monomer (J) and optionally a polymerizable unsaturated monomer [e.g. monomer (b-1) ~
(b-6) and a fluorine-containing polymerizable unsaturated monomer (c), etc.)] are subjected to a radical polymerization reaction to produce a copolymer having an epoxy group as a functional group.

The compound (S) is a compound having a functional group that reacts with the functional group in the copolymer (R) and a silane group, and the compound (c
) can be selected and used as appropriate.

The reactant (T) obtained by the reaction of the copolymer (R) and the compound (S) each has an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in one molecule. One reactant (T) that can be used corresponds to resin (2).

Polymerizable unsaturated monomer (V) A compound having in one molecule a radically polymerizable unsaturated group and a functional group that reacts with the functional group of the compound (W).

The functional group of the monomer (V) is a group inert to the silane group, and the functional group may be the same group as the silane group.

Regarding the copolymer (W) obtained using the monomer (V), the following examples 1 to 2 are given.

■ Hydroxyl group-containing polymerizable unsaturated monomer (a), silane group-containing polymerizable unsaturated monomer (K), and if necessary, polymerizable unsaturated monomers [e.g. monomers (b-1) to (b-e) and a fluorine-containing polymerizable unsaturated monomer (C), etc., are subjected to a radical polymerization reaction to obtain a copolymer having a hydroxyl group as a functional group.

■Incyanate group-containing polymerizable unsaturated monomer (e), silane group-containing polymerizable unsaturated monomer (K), and optionally a polymerizable unsaturated monomer [for example, monomer (b-1 ) ~ (b-
6) and a fluorine-containing polymerizable unsaturated monomer (c), etc.] are subjected to a radical polymerization reaction to produce a copolymer having an isocyanate group as a functional group.

■ Carboxyl group-containing polymerizable unsaturated monomer (d), silane group-containing polymerizable unsaturated monomer (K), and optionally a polymerizable unsaturated monomer [e.g. monomer (b-1)] ~(b-6
) and a fluorine-containing polymerizable unsaturated monomer (C), etc.] are subjected to a radical polymerization reaction to produce a copolymer having a carboxyl group as a functional group.

The compound (W) is a compound having an epoxy group and a functional group that reacts with the functional group in the copolymer (V).
B) can be appropriately selected and used.

The reactant (X) obtained by the reaction of the copolymer (V) and the compound (W) each has an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in one molecule. The 0 reactant (X) that can be used corresponds to resin ①.

The homopolymer (N), copolymer (N), and reactant (H) are the same monomers and reactants as described in (2) and (4) resin compositions above. things can be used.

The single or copolymer (N) and the reactant (H) can be blended so that the epoxy group/silane group ratio is usually 1/99 to 99/1.

Kou U dish fat phoenix 1 Homopolymer (P) or copolymer (P) and reactant (F)
The same monomers and reactants as described in the resin compositions (2) and (4) above can be used.

Single or copolymer CP) and reactant (F) can be blended so that the epoxy group/silane group ratio is usually 1/99 to 99/1.

Each of the above-mentioned ingredients can be obtained by conventionally known methods. That is, the reaction between a hydroxyl group and an isocyanate group, the condensation reaction of a silane group, a copolymerization reaction, etc. can be carried out based on conventionally known methods. is sufficient. For the condensation reaction of silane groups, heating at about 40 to 150° C. for about 1 to about 24 hours in the presence of an acid catalyst (eg, hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.) is sufficient. In addition, the copolymerization reaction can be carried out using the same method and conditions as those used for general synthesis reactions of acrylic resins, vinyl resins, and the like. An example of such a synthesis reaction is a method in which each monomer component is dissolved or dispersed in an organic solvent, and heated with stirring at a temperature of about 60 to 180°C in the presence of a radical polymerization initiator. The reaction time required to achieve this reaction is usually about 1 to 10 hours.The organic solvent should be one that is inert to the monomer or compound used, such as an ether solvent, an ester solvent, or a hydrocarbon solvent. Solvents etc. can be used.

When using a hydrocarbon solvent, it is preferable to use other solvents together from the viewpoint of solubility.As the radical initiator, any commonly used radical initiator can be used. , peroxides such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate, and azo compounds such as azoisobutyronitrile and azobisdimethylvaleronitrile.

(1) to (6) Reactants (D), (F), (
H), (L), (N), (P), (T) and (W) are each about 3000 to 200.000, preferably about 50
It can have a number average molecular weight of 00 to 80,000.

In the resin composition, it is preferable to introduce a carboxyl group and/or a hydroxyl group in addition to the epoxy group and silane group because the curability of the film can be further improved.

The resin composition having a carboxyl group can be dissolved or dispersed in water by neutralizing it with a basic compound.

In the above resin composition, modified resins in which the above-mentioned resins or copolymers are chemically bonded with other resins (for example, vinyl resins, polyester resins, urethane resins, silicone resins, epoxy resins, etc.) can also be used. .

The resin composition may be used, for example, in a hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as ethyl acetate or butyl acetate, or an ether solvent such as dioxane or ethylene glycol diethyl ether. The resin composition can be used in a dissolved or dispersed form in an alcoholic solvent such as butanol or propatool, or in the form of a non-aqueous dispersion containing the resin composition as a dispersion stabilizer component.

The above non-aqueous dispersion will be described next.

In the presence of the dispersion stabilizer, one or more radically polymerizable unsaturated monomers and a polymerization initiator are eluted from the monomers and the dispersion stabilizer, but the polymer obtained from the monomers is A non-aqueous dispersion can be produced by adding the particles to an insoluble organic solvent and causing a polymerization reaction. All of the monomers described above can be used to form the polymer that is the particle component of the non-aqueous dispersion. Preferably, the polymer serving as the particle component is a copolymer containing a large amount of highly polar monomer, since it must not be dissolved in the organic solvent used. i.e. methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy (meth)
Contains large amounts of monomers such as acrylate, hydroxypropyl (meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, α-methylstyrene, and N-methylol (meth)acrylamide. Preferably, the particles of the non-aqueous dispersion can be crosslinked if necessary.An example of a method for crosslinking the inside of the particles is by copolymerizing a polyfunctional monomer such as divinylbenzene or ethylene glycol dimethacrylate. I can do it.

Although the dispersed polymer particles produced by the polymerization are not substantially dissolved in the organic solvent used for the non-aqueous dispersion, it is a good solvent for the dispersion stabilizer and the radically polymerizable unsaturated monomer. Something is included. Examples of organic liquids that can be used include aliphatic hydrocarbons such as pentane, hexane, heptane, offukun, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene;
Alcohol, ether, ester and ketone solvents, such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol mottyl ether, methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methyl Examples include xyl ketone, ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. Each of these can be used alone or in a mixture of two or more, but in the shell , aliphatic hydrocarbons are used as a main ingredient, and aromatic hydrocarbons and the above alcohol-based, ether-based, ester-based, or ketone-based solvents are preferably used in combination. moreover,
Trichlorotrifluoroethane, metaxylene hexafluoride, tetrachlorohexafluorobutane, etc. can also be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2,2-azoisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile); benzoyl peroxide and lauryl peroxide. Examples include peroxide-based initiators such as oxide and tert-butyl peroctomoth, and these polymerization initiators are generally used within a range of 0.2 to 10 parts by weight per 100 parts by weight of monomers to be subjected to polymerization. can do. The formulation of the dispersion stabilizer resin to be present during the above polymerization can be selected from a wide range depending on the type of resin, but in general, a radically polymerizable unsaturated monomer is added to 100 parts by weight of the resin. A suitable amount is about 3 to 240 parts by weight, preferably 5 to 82 parts by weight.

By combining the dispersion stabilizer resin and polymer particles, it is possible to improve the storage stability of the non-aqueous dispersion and form a cured film with excellent transparency, smoothness, and mechanical properties. The dispersion stabilizer resin and the polymer particles can be bonded by polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable double bond.

A method for introducing a polymerizable double bond is to add α,β-ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, or itaconic acid to a part of the oxirane group in the resin. Although most convenient, other methods include adding an isocyanate group-containing monomer such as isocyanoethyl methacrylate to a hydroxyl group that has been previously incorporated into the resin.

Furthermore, as a method for bonding the dispersion stabilizer and the polymerizable particles, in addition to the above-mentioned method, monomer components forming the polymer particles such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxy Silane, γ-acryloxypropyltrimethoxysilane,
Bonding can be achieved by using reactive monomers such as γ-methacryloxybutyltriethoxysilane and γ-acryloxypropyltrisilanol.

Next, the curing catalyst used in the resin (1) and mixed resin (2) of the clear paint 2 will be explained.

(1) Metal chelate compounds Aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds are preferred. Among these chelate compounds, compounds that can form a keto-enol tautomer are used to form a stable chelate ring. Chelate compounds contained as ligands are preferred.

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

For example, the aluminum chelate compound is prepared by adding the above keto-enol tautomer to 1 mol of aluminum alcoholade i represented by the general formula [wherein Ro represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms]. It can be suitably prepared by mixing the constituent compounds in a molar ratio of usually about 3 moles or less and heating if necessary.

As the alkyl group having 1 to 20 carbon atoms, the above-mentioned alkyl group having 1 to 20 carbon atoms
In addition to the 10 alkyl groups, examples include undecyl, dodecyl, tridecyl, tetradecyl, octadecyl, etc., and examples of alkenyl groups include vinyl, allyl, etc.

The aluminum alcoholades represented by the general formula (95) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-5ec-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-5e
Preferably, c-butoxide, aluminum tri-n-butoxide, etc. are used.

The titanium chelate compound has 1, for example, the general formula [in the formula 1m
is an integer from 0 to 10, and Ro has the same meaning as above.] For 1 mole of Ti in the titanates,
It can be suitably prepared by mixing compounds that can constitute the above-mentioned keto-enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary.

Titanates represented by the general formula (96) include m
is 1, tetramethyltichnate, tetraethyltitanate, tetra-n-propyltitanate, tetraisopropyltitanate, tetra-n-butyltichnate, tetraisobutyltitanate, tetra-tert
-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetra-isooctyl titanate, tetra-n-lauryl titanate, etc., especially tetra-isopropyl titanate, tetra-n-
Suitable results are obtained using butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, and the like. In addition, if m is 1 or more, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-ter
Dimer to decamer of t-butyl titanate (general formula (
96) where m=1 to 10) gives suitable results.

The zirconium chelate compound is, for example, a compound capable of forming the above keto-enol tautomer per 1 mole of Zr in the zirconates represented by the general formula c, where m and R11 have the same meanings as above. It can be suitably prepared by mixing them at a molar ratio of usually about 4 moles or less and heating if necessary.

As the zirconates represented by the general formula (97),
Tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-
n-butylzirconate, tetra-8ec-butylzirconate, tetra-tert-butylzirconate, tetra-n-pentylzirconate, tetra-tert-
Pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-hebutyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, etc., especially tetraisopropyl zirconate, tetra-n- -propyl zirconate, tetra-isobutyl zirconate, tetra-n-butyl zirconate, tetra-5ec-butyl zirconate, tetra-tert-butyl zirconate and the like are used to give suitable results. In addition, for those where m is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetra-isobutyl zirconate, tetra-5ee-butyl zirconate, tetra-tert-butyl Zirconate 2
mer to 11-mer (m=1 to 1 in general formula (97)
0) gives suitable results. Further, it may contain a structural unit in which these zirconates are associated.

Particularly preferred chelate compounds in the present invention include tris(ethyl acetoacetate)aluminum, tris(n-pro and ruacetoacetate)aluminum, tris(isopro and ruacetoacetate)aluminum, and tris(n-butylacetoacetate)aluminum. acetate) aluminum, isopropoxybis(ethylacetoacetate) aluminum, diisopropoxyethylacetoacetate aluminum, tris(acetylacetonato) aluminum, tris(propionyl acetonato) aluminum, diisopropoxypropionyl acetonato aluminum, acetylacetonato Aluminum chelate compounds such as bis(propionylacetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisopropoxy bis(ethylacetoacetate) titanate, diisopropoxy bis [Acetylacetonatocotitanate, diisopropoxy bis(
Titanium chelate compounds such as acetylacetonato) titanate: Zirconium chelates such as tetrakis(acetylacetonato)zirconium, tetrakis(n-pro and ruacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate)zirconium, etc. Compounds can be mentioned.

The aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used alone or in combination of two or more thereof.The amount of the crosslinking reaction curing agent is 1. Solid content of the polymer (A) 1
It is appropriate to set the amount to about 0.01 to 30 parts by weight based on the weight part of oo.If it is less than this range, the crosslinking curability tends to decrease, and if it is more than this range, it may remain in the cured product. Undesirable as it tends to reduce water resistance.
The preferred amount is 0.1 to 10 parts by weight, and the more preferred amount is 1 to 5 parts by weight.

(2) Lewis acid metal halides, compounds in which the metal shares a halogen and other substituents, and complex salts of these compounds can be mentioned. Specifically, for example, A7C, A4BF,
, A7F3, A7EtCj proverb, A7EtICj
.

5nCJ4, T1Cf4. TiBr4. TiF4.
ZrCl4. ZrBr4, ZrF<, SnC<
, FeC, sbcm, sbcm, PC, PC, GaC, GaFs, InFs, OC, BBrs,
BF,, BFs: (0(:J-) *, BF4:
(OC,H,l l,OCmu: (OCJs) *,B
Fs:NHzCJs, BFs:NH*CJ<0H1
BFs: NHCH*CH*CHiCHt, PFaS-
+c>) 5(3) Protonic acid The protonic acid specifically includes organic protonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and P-toluenesulfonic acid; Examples include inorganic protonic acids such as phosphoric acid, phosphorous phosphinic acid, phosphonic acid, sulfuric acid, and perchloric acid.

(4) Metal alkoxides As the metal alkoxides, specifically, the aforementioned aluminum alkoxides, titanium alkoxides, zirconium alkoxides, and the like can be used.

Furthermore, in addition to the above, metals such as iron, calcium, and barium may have an alkoxy group, preferably C3-1. Examples include compounds to which an alkoxy group is bonded. These compounds may be associated.

(5) Organometallic compound Specific examples of the compound include triethylaluminum, diethylzinc, and the like.

(6) Compound having Si-0-Aβ bond A specific example of this compound is aluminum silicate.

The following materials can be blended into the clear paint 2 as required.

(1) Hydroxyl group-containing resin and hydroxyl group-containing compound (2) Carboxyl group-containing resin and carboxyl group-containing compound (3) Silane group-containing resin and silane group-containing compound (4) Epoxy group-containing resin and epoxy group-containing compound (5) Chelate (6) Organic solvent (7) Pigment (to the extent that it does not impede transparency) (8) Additive resin (CAD, etc.) or compound (9) Polyepoxy compound Pigment: For example, inorganic pigments, organic pigments, etc. can be blended. Inorganic pigments include oxides (titanium dioxide, red iron oxide, chromium oxide, etc.), hydroxides (alumina white, etc.), sulfates (precipitated barium sulfate, etc.), carbonates (
(precipitated calcium carbonate, etc.), sulfate (clay, etc.),
Examples include carbon-based powders (carbon black, etc.) and metal powders (aluminum powder, bronze powder, zinc powder, etc.). Examples of organic pigments include azo pigments (Lake Red, Fast Nilo-I, etc.) and phthalocyanine pigments (Fuclocyanine Blue, etc.).

The clear paint 2 is a paint that forms a transparent coating film mainly composed of the above-mentioned resin (1) or mixed resin (2) as a base resin and the above-mentioned hardening agent, and is dispersed or dissolved in an organic solvent and/or water. Become.

Explanation of the coating film forming method of the present invention 1 The main object to be coated by the present invention is an automobile body, and the coating of an automobile body is usually performed by electrodeposition coating on a chemically treated steel plate. Or, a step is taken to form a top coat on the intermediate coat.

According to the method of the present invention, the above chemical conversion treatment, electrodeposition coating (known cationic electrodeposition paints can be used as electrodeposition paints, but
Particularly suitable are those whose film thickness is less than 20 μm based on the cured film in the flat area and which forms a single layer film. ), the above-mentioned colored topcoat composition is usually spray-coated onto the object to be coated, which has been coated with an intermediate coat or the like. As a coating machine, a normal air spray gun, air spray one-type electrostatic coating machine, rotary atomization type electrostatic coating machine, etc. can be used.The film thickness of the colored top coat is about 10 to 50μ (after curing). It is preferable to leave the paint at room temperature for several minutes after painting, or
After forced drying at 0 to 80°C for several minutes or heat curing, clear paint (1) is applied. The coating machine can be appropriately selected from among the same types of coating machines as those used for the colored top coating. Clear coating i! (1st) thickness is 20-100
μ (after curing) is preferably 0. Then, the coated object is 60 to 17
It is preferable to heat cure at about 0° C. for about 10 to 90 minutes, but it may be left uncured. The heat curing conditions depend on the paint material of the colored top coat and clear paint (1).

After applying the colored paint and the clear paint (1), the clear paint (2) is applied to the coated surface of the clear paint film (first). As the coating machine, an appropriate coating machine can be selected from those that can be used for coating the clear paint (1). The thickness of the clear coating film (second) is preferably about 10 to 80 u (after curing).

To ensure good adhesion between both clear coatings, if necessary, lightly polish the surface of the pre-cured clear coating (first) with a #400 to #1000 sand vapor. Good, 60~ after applying clear paint (2)
It is preferable to heat and cure at about 170° C. for about 10 to 90 minutes.

(Effects of the Invention) The present invention provides a top coat film that is particularly excellent in acid resistance and finished appearance.

Base materials that require acid resistance, smoothness, scratch resistance, etc.
For example, it is suitable for application to the coating of automobile bodies, architectural exterior materials, etc., and especially to the top coating of automobile bodies.

Furthermore, in the method of the present invention, colored paints and clear paints (
1) was painted using wet-on-wet 2CIB method,
Apply clear paint (
The so-called 3-coat, 2-bake method, in which 2) is applied and heated to form a clear coating film (second), is preferable in order to prevent the occurrence of wrinkles, etc., and also to improve the finished appearance (smoothness,
The film also had good image clarity, gloss, etc.) and scratch resistance.

Examples and comparative examples of the present invention will be described below. In addition, both parts and percentages are based on weight in principle.

1. Sample ■Electrodeposition paint: ED-1 Epoxy resin-based cationic electrodeposition paint.

■Intermediate paint: S-1 ■-Gabeke AM (manufactured by Kansai Paint■, trade name, polyester resin/melamine resin system).

■Metallic paint 2M-1 Magikron #1000 pace coat (Kansai paint■,
Product name: Acrylic resin/melamine resin silver metallic).

■Clear paint (1): C-1 Magikron #1000 Clear (Kansai Paint ■, product name, acrylic resin/melamine resin system) ■Clear paint (2) C-2-1: Molecular weight consisting of (gel permeation chromatography) Acrylic resin with a molecular weight of 20,000 consisting of 100 parts of a 50% solution of acrylic resin-xylol with a peak molecular weight of 20,000 (the same applies hereafter) □100 parts of a 50% solution of xylol with 1 part of tris(acetylacetonato)aluminum was mixed, and further mixed with Swasol. #1000
(Cosmo Oil, trade name) was added to adjust the viscosity to 24 seconds/Ford Cup #4/20°C.

C-2-2: A 60% solution of an acrylic resin with a molecular weight of 7000 made up of Trol/Isobutyl acetate = 1/110
0 part, 0.2 part of tetrakis(ethyl acetoacetate) zirconium, and 1 part of ethyl acetoacetate were mixed, and then the viscosity was adjusted in the same manner as C-2-1.

(Resiloxane macromonomer: Molecular weight 700 obtained by hydrolyzing and condensing methyltrimethoxysilane/γ-methacryloxypropyltrimethoxysilane = 20 mol/1 mol)
0 siloxane macromonomer 〇-2-3: 129 parts of the following compound P was added to 313 parts of a high acid value polyester made by reacting 131 parts of succinic anhydride with 1746 parts of a polyester with an acid value of 2.2 (75% Kizilol solution). The addition reaction was carried out until the acid value reached 6.

Compound P To 100 parts of this polyester having an epoxy group at the end, 5 parts of methylphenyl silicone resin (molecular weight 1000) with a methoxy end, 10 parts of acetylacetone, and 20 parts of fine aluminum hydroxide were added, and further, the above C-2-
The viscosity was adjusted in the same manner as in 1.

C-2-4: Compound Q in an acrylic resin (molecular weight 40,000)
15 parts of Compound R and 10 parts of Compound R were added to perform an addition reaction. □Troll 50% solution Compound Q Compound R OC* Hs 0C*Hs 1 part of tris(acetylacetonato)aluminum was added to 100 parts of this solution, and the viscosity was further adjusted in the same manner as in C-2-1 above.

2. Examples and Comparative Examples Electrodeposition paint E-1 was electrodeposited on a steel plate whose surface had been treated with zinc phosphate, and cured by heating at 170°C for 30 minutes (film thickness 15μ).
Then, the intermediate coating paint S-1 was spray-painted to give a coating of 140
℃ for 30 minutes (II thickness 40μ), apply metallic paint M-1 to the intermediate coated surface at a coating rate of 15 to 2
Paint it to a thickness of 0μ, leave it for 10 minutes at room temperature, then spray paint the clear paint (1) C-1 to a thickness of 35 to 40μ based on the cured film, and heat it at 140℃ for 30 minutes. Both coatings were cured.

Next, clear paint (
2) was spray-coated to a film thickness of 10 to 15 μm based on the cured coating, and the coating was cured by heating at 140° C. for 30 minutes to form the coating film aimed at by the present invention.

Table 1 shows the performance of the coating film formed based on the above coating process.

■ Pencil hardness: Scratch the coating surface with the lead of a Mitsubishi Uni-pencil, and display the hardness symbol of the highest lead that will not scratch the painted surface.

■ Resistance to Kijiroll Hold the gauze soaked in Kijiroll with your fingers and rub the painted surface strongly back and forth 15 times. The degree of dissolution of the painted surface is 0, ○, O1△, and the range between good (0) and markedly poor (×) in terms of scratches and swelling.
Judged on a 5-point scale.

■ Image clarity measuring device (IIIAGE CLARITY MET)
ER: Measured with Suga Test Instruments (manufactured by Suga Test Instruments) 0 The numbers in the table are ICM values in the range of 0 to 100%. This shows that the image quality is extremely good.

■ Make 100 base marks by making incisions at 1 mm intervals in both the vertical and horizontal directions on the painted surface to reach the adhesive base. Cellophane adhesive tape was pasted on top of this and the condition was evaluated after it was suddenly removed.

Display: Number of stitches without peeling/100゜■ Impact resistance: Uses a DuPont impact tester (striking core diameter 1/2 inch, weight 0.5 kg), maximum weight drop height that does not cause cracks on the paint film. Displayed in .

■ Acid resistance 40%H! After immersing the 5O41 sample at 40°C for 7 hours, it was taken out and washed with water, and the condition of the coated surface was evaluated. No abnormalities at all 0),
Judgments were made in five stages: o, O20, Δ, and X, depending on the degree of abnormality (×) such as significant gloss and piquancy, and corrosion.

■ Using a scratch resistance dyeing rub fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho), harden 0M powder (Daruma Cleanser) with water, place it on the painted surface, and press it with the terminal of the tester. 0.70k
Apply a load of g and perform 20 reciprocations of friction. After washing with water, the degree of scratches was evaluated using a 5-level scale of o, 0, ■, Δ, and ×.

■ Water resistance Coated surface evaluation after immersion at 40°C for 10 days.

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

Test conditions: UV irradiation 16H/60℃ water condensation 9H
The coating film was evaluated after testing at 150°C for 3000 hours (125 cycles).

Table 2

Claims (1)

[Claims] In a top coat multi-layer paint film consisting of a colored top coat, a clear paint film (first) and a clear paint film (second), the clear paint film (second) has a base resin and a curing agent as main components,
and the base resin has a hydroxyl group directly bonded to the silicon atom and/or
Or a resin (a) having a hydrolyzable group and an epoxy group in the same resin, or a hydroxyl group and/or a hydroxyl group directly bonded to a silicon atom.
Or a mixed resin formed by mixing resin (b)-1 having a hydrolyzable group and resin (b)-2 having an epoxy group (
A coating film forming method characterized by forming a coating film based on the crosslinked curable coating material according to b).