JPH02240126A - Resin composition, curable composition and coating composition - Google Patents

Abstract

PURPOSE:To obtain a resin excellent in storage stability, curability, weathering resistance and acid resistance and forming a nontoxic coating film by using a resin obtained by reacting a polymerizable unsaturated monomer containing a specified hydrolyzable group with a compound having a specified functional group and an epoxy group. CONSTITUTION:A resin composition containing a polymer containing a polymerizable unsaturated monomer having a silanol group and/or an Si-bonded hydrolyzable group and a resin obtained by reacting a resin having a functional group reactive therewith and an epoxy group. The above Si-bonded hydrolyzable group means a group which can be hydrolyzed with water or moisture to form a silanol group. Examples of such groups include groups of formulas I-IV (wherein R' is a 1-4 C alkyl; and R'', R''' and R'''' are each a 1-8 C alkyl, an aryl or an aralkyl).

Description

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

BACKGROUND OF THE INVENTION Conventional techniques and their problems Conventionally, a method of curing a hydroxyl group-containing resin with a crosslinking agent such as diisocyanate or melamine has been adopted. However, when diisocyanates are used, there are disadvantages in that the weather resistance of the resulting coating film is insufficient and, moreover, the coating film is susceptible to yellowing.

Additionally, the pot life of the resin composition is short, and there are also problems with the toxicity of the diisocyanate.

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

As a one-component, non-toxic, low-temperature curing composition, for example, JP-A No. 60-67553 discloses the method described in JP-A No. 60-67553.
A composition is disclosed in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as trimethoxysilane.

However, since the only crosslinking functional group in this composition is the silanol group produced by hydrolysis of alkoxysilane, a large amount of water is required for curing, and a large amount of by-products such as alcohol are produced during this hydrolysis. Therefore, the physical properties of the cured product cannot be said to be sufficient, and when it is cured only with moisture in the air, it hardens from the surface, so the inside becomes difficult to harden, and the cured product tends to become stiff.

Means for Solving the Problems The present inventor has conducted extensive research in order to solve the above-mentioned problems. As a result, they succeeded in obtaining a composition that has excellent storage stability, no worries about toxicity, has excellent curability, and is capable of forming a coating film with excellent weather resistance and acid resistance, thereby completing the present invention. reached.

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

■ A polymer containing as an essential monomer component a polymerizable unsaturated monomer containing a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, and a resin having a functional group complementary to the functional group. A resin composition (referred to as (1) resin composition) comprising a resin obtained by reacting a reactive functional group with a compound containing an epoxy group.

■ A polymer containing an epoxy group-containing polymerizable unsaturated monomer as an essential monomer component, and a resin containing a functional group containing a functional group and a silane group that react complementary to the functional group. A resin composition (hereinafter referred to as "(2) resin composition") containing a resin obtained by the reaction.

■ Adding at least one curing reaction catalyst selected from the group consisting of organometallic compounds, Lewis acids, protonic acids, and compounds having an Si-0-Al bond to the resin compositions of (1) and (2) above. A curable composition.

(2) A coating composition containing the resin composition and cured composition of (1) and (2) above as essential components.

In this specification, a hydrolyzable group directly bonded to a silicon atom (hereinafter referred to as a silane group) 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) 10-C-
R' (II) [In the formula, R' represents an alkyl group having 1 to 4 carbon atoms.

R#, Rllll and Rlllt are the same or different and represent an alkyl group, an aryl group or an aralkyl group having 1 to 8 carbon atoms. ] In the above general formula, examples of the "alkyl group having 1 to 8 carbon atoms" include methyl, ethyl, n-probyl, iso-
Propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-bentyl, iso-pentyl, n-octyl, 1so-octyl and the like can be mentioned. Examples of the aryl group include phenyl, tolyl, and xylyl groups. Examples of the aralkyl group include benzyl and phenethyl groups.

Further, in addition to the above-mentioned silane group, a =Si-H group can be mentioned as a hydrolyzable group.

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

In the composition of the present invention, an alicyclic epoxy group is preferable as the epoxy group since it improves the curability of the coating.

Next, the resin composition of the present invention will be explained.

(1) Resin composition The resin composition comprises a polymer (polymer (A)) containing a polymerizable unsaturated monomer containing a silanol group and/or a silane group as an essential monomer component, and a functional group. Resin (Resin (
A)) contains a resin (resin (B)) obtained by reacting a functional group that reacts complementary to the functional group with a compound (compound (A)) containing an epoxy group.

The polymer (A) has an average of 1 or more silane groups in one molecule, preferably an average of 2 to 400 silane groups, and a number average molecular weight of about 1,000 to 200,000, preferably about 3,000 to 80.
000. If the number of silane groups is less than one on average, the curability will be poor, which is not preferable. Also, the molecular world is about 10
If it is less than 00, the physical properties and weather resistance of the coating film formed will be poor,
On the other hand, if the molecular weight exceeds about 200,000, the viscosity of the composition increases and coating workability decreases, which is not preferable.

As the polymer (A), for example, a homopolymer of the silane group-containing polymerizable unsaturated monomer (a), a polymer of the monomer (a) and other polymerizable unsaturated monomers (b), etc. Copolymers and the like can be mentioned.

The silane group-containing polymerizable unsaturated monomer (a) is a compound having at least one silane group and a polymerizable unsaturated group in one molecule. Examples of the polymerizable unsaturated group include CH2-C(Rl)COO-CH2-C(Rl)-CH2-CHO-CH2-CHCH20- [wherein R1 represents a hydrogen atom or a methyl group]. ] etc.

Examples of the silane group-containing polymerizable unsaturated monomer having a polymerizable unsaturated group of CH2-C(R')COO include a compound represented by the following general formula (1).

R1 Y Y [wherein R'l is the same as above. R2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Y's are the same or different and represent a hydrogen atom, a hydroxyl group, a hydrolyzable group, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group. However, Y
At least one of these represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

] Examples of divalent hydrocarbon groups having 1 to 20 carbon atoms include -Cl2- -CH2-CH2 -CH2-CM2-
CH2- -CH2-CH-CH2- Cl{3 CH, Black-CM2-CH2-C-CM2-CH2-CH3 -CH2 CH2 CH2 CHCH2 CH2 -C
H3 -C, ●H26 -s CI2 H2 4 - -
One example is cps H3 6.

Specific examples of the compound represented by the general formula (1) include γ-(meth)acryloxib-trimethoxysilane, γ-(meth)acryloxib-piltriethoxysilane, γ-(meth)acryloxib-piltrib Poxysilane, γ-(meth)acryloxybutylmethyldimethoxysilane, γ-(meth)acryloxybutylmethyldiethoxysilane, γ-(meth)acryloxibutylmethyldiproboxysilane, γ-(meth)acryloxybutylph enyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxysilane, γ-(meth)acryloxybutylphenyldimethylmethoxysilane, γ-(meth)acryloxybutylphenyldimethylmethoxysilane, γ-(meth)acryloxib Dimethylethoxysilane, γ-(meth)acryloxib, pylphenylmethylmethoxysilane, γ-(meth)acryloxib, pylphenylmethylethoxysilane, γ-(meth)acryloxib, trisilanol, γ-(meth)acryloxib
Acryloxib-pyrmethyldihydroxysilane, γ-(meth)acryloxybutyl phenyldihydo-oxysilane, γ-(meth)acryloxib-pyldimethylhydroxysilane, γ-(meth)acryloxyp-bylphenylmethylhydroxysilane, occua CI ．． C. ll. can be mentioned.

Examples of the silane group-containing polymerizable unsaturated monomer in which the polymerizable unsaturated group is CH2=C (R+) include compounds represented by the following general formulas (2) to (4).

As specific examples of the compounds represented by general formulas (2) to (4), for example, [wherein Rl, R2 and Y are the same as above. Y may be the same or different. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] RI Y and the like.

Examples of the silane group-containing polymerizable unsaturated monomer having a polymerizable unsaturated group of CH2 = C (R") include the following general formula (
Compounds represented by 5) and (6) can be mentioned.

RI Y CH2 = C-Si-Y (5)
Y Y [wherein Rl, R2 and Y are the same as above. 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 (5) and (6) include CI2-CH-81(OCh)3CI2-CH
Si(QC 2 H s ) 3C}12 = CI
-81(OCIIa) 2 CHaCI{2moCH
Si(CH 3 ) 2 0CH aCH2 child CIC
I2Si(OCh)3OCH2=CHCH2St(OCCH3)
3CH2 -CHS1(CH3)2N(CH3
) One of each of the two is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (7) and (8) include the following.

Examples of the silane group-containing polymerizable unsaturated monomer whose polymerizable unsaturated group is CH2-CHO- include compounds represented by the following general formulas (7) and (8).

CH3 CH3H Y CH2 = CHO-Si-Y (8)
l Y [In the formula, R2 and Y are the same as above. Y may be the same or different. However, CH, etc. with less Y can be mentioned.

As the silane group-containing polymerizable unsaturated monomer whose polymerizable unsaturated group is CH2-CHCH20-, for example, the following general formula (9
) and (10).

CH2-CHCH20-St-Y (9)Y [wherein R2 and Y are the same as above. Y may be the same or different. However, any one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (9) and (10) include OC. H. ■CH! =CHCH10- (CI!)yo-Si-QCyoH,CH, can be mentioned.

In addition to the silane group-containing polymerizable monomer, the silane group-containing polymerizable unsaturated monomer and, for example, a polysilane compound (
For example, compounds represented by general formulas (87) to (89))
A polysiloxane unsaturated monomer having a silane group and a polymerizable unsaturated group, which is obtained by reacting the above, can also be used.

Specific examples of the polysiloxane unsaturated monomer include compounds of the general formula (1) and general formulas (87) to (8).
9) and at least one compound of the former 30 to 0.00
Examples include polysiloxane macromonomers obtained by reacting 1 mol %, the latter, 70 to 99.999 mol % (for example, those disclosed in JP-A-62-275132), and the following compounds.

OH" OCH3 OCCI1. Examples of other polymerizable unsaturated monomers (b) include the following (b-1) to (b-9).

(b-1) Hydroxyl group-containing polymerizable unsaturated monomer with the following general formula (
Compounds represented by 11) to (14) can be mentioned.

[In the formula, R3 represents a hydrogen atom or a hydroxyalkyl group. ] [In the formula, R3 is the same as above. ] [In the formula, R1 is the same as above. m represents an integer of 2 to 8.

p represents an integer of 2 to 18. q represents an integer from 0 to 7.

] CH2 -CR' 澹O [In the formula, R1 is the same as above. T1 and T2 are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms.

S and V each represent an integer of 0 to 10. However, S
The sum of V and V is 1 to 10. ] The hydroxyalkyl group in general formulas (11) and (12) has 1 to 6 carbon atoms. Specifically, for example, -c2H,OH,-c,H60H,-CaH60
Examples include H.

As the monomer component of general formula (11), for example, CM2
-CHOH CH2-CHOC4H8 0I{ etc. can be mentioned.

As the monomer component of general formula (12), for example, CI2
-C}ICH 2 0HCH2 -CICI 2
0CH 2 CH2 0HCH2 -CHC}I
2 0 + CI2 CH2 0 +2HCII2 −
CICI 2 0÷CH2 CH2 0 +3H, etc. can be mentioned.

As the monomer component of general formula (13), for example, C}+2
-CCH3 COOC2 H 40HCH2 -CH
COOCH2 C}12 CH2 0HOH CH2 -CCH3 COOCH 2 CHC}13C
H2-CCH3COO (CH2) 4 0H0
H CH2 -CCH3 COOCI{ 2 C82 CH
CHaO CH2 -CCH3 Coo-C 3H s -0÷C
-CB2 -CI2-CH2-CH2-CH
2-0+* to 7H, etc. can be mentioned.

As the monomer component of general formula (14), for example, Cl{2 CH2 CII2 CH2 CI2 -CCHa Coo +CH2CHCHa O +s
=C}ICOO +Ch CH2 0 +a~5-CCH3COO÷CI{2 CH2 0 +y~-C
HCOO ÷ CH2 CH2 C}12 Cll2
0=CCh COO÷CH2 CH2 0 +s~+C
Examples include H2CIICIla O +s~s II~6H 8H +4~5 l1.

Furthermore, in addition to the above, adducts of hydroxyl group-containing unsaturated monomers represented by the general formulas (11) to (14) and lactones such as ε-cabrolactone and γ-valerolactone can be used.

(b-2) Carboxyl group-containing polymerizable unsaturated monomer Compounds represented by the following general formulas (15) and (16) can be mentioned.

[In the formula, R4 represents a hydrogen atom or a lower alkyl group. R
5 represents a hydrogen atom, a lower alkyl group or a carboxyl group. R6 represents a hydrogen atom, a lower alkyl group or a carboxy lower alkyl group. ]CH2=C-C-0-Cm
H2mCOOH [wherein R1 and m are the same as above. ]
In the above general formula (15), the lower alkyl group has 4 or less carbon atoms, and is particularly preferably a methyl group.

Specific examples of the compound of general formula (15) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.

Further, as specific examples of the compound of general formula (16), for example, 2-carboxyethyl (meth)acrylate, 2-
Examples include carboxyprobyl (meth)acrylate and 5-carboxypentyl (meth)acrylate.

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

(b-3) Fluorine-containing polymerizable unsaturated monomer of the following general formula (
Compounds represented by (17) and (18) can be mentioned.

CX2 -CX2 (17) [wherein X is the same or different and represents H, Cl, Br, F, an alkyl group or a haloalkyl group. However, at least one of X represents F. ]CH2! CR1 C=0 (18)0-C nH2
n-R7 [In the formula, R1 is the same as above. R7 represents a fluoroalkyl group. n represents an integer of 1 to 10. ] General formula (17)
The alkyl group in has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
belongs to. Specific examples include methyl, ethyl, probyl, isobrobyl, butyl, and pentyl groups. Further, the haloalkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, C
F3, CHF2, CH2FSCC! ! 3.CHC/! ,
CH2 CIS CFCl2, (CF2)2CF3,
(CF2)s CF3, CF2 CH3, CF2
Examples include CHF2, CF2Br, CH2Br, and the like.

Examples of the monomer represented by the general formula (17) include CF2 = CF2, CHP CF2, CH2-CP2
, CH2 -CHP , CCf F CF2, CHC
J-CF2, CCI 2 =CF2, CCJ! F=C
ClF SCHF = CCl2, CH2 -OR F
, OR 2 −C(/! F SCF3 CP=CP
2, CF3CF=CHF, CF3CH-CF2,
CFa CF=CI2, CHF2CF-CHPSC
H3 CF-CP2, CHa CF-CH2, CF2
CICF-CF2, CFa CCJ2-CF2, C
F3CF= CFCj! SCF2 Cj'CCJ=
CF2, CP2 0-poor CF Hatake CF-CJl, C
FCl2 CP=CP2, CF2 CCj' -CCI
F, CFa CCl=CCl2, ccJ! P2
CF=CCl2, CCJ! 3CP=CP2, CP2
Cl ccl-ccz 2, CFCl 2 ccz
=ccz 2, CF3 CF= CHClSCCI
F2 CF= CHCl, CF3 CC/! =CH
Cl! , CHF 2 CC/! =CC Shiba 2, C
P2 CfCH-C(/! 2, CF2 CI!
ccJ = CHCJ, CC! ! 3 CF-CHC
lSCF2 1cP-CF2, CP2 BrCH=CF
2, CPa CBr = CHBr, CF2 CI C
Br=CH2, CH2 BrCP=CCf 2, C
F3 CBr-Clh, CP2 CH=C}]Br
, CF2BrCH-CHF, CF2BrCF=
CP2, CF3 0F2 CF"CF2, CF3 0F
-CFCF3,CFa CH=CFCF3,CP2=
CFCF2 CHF 2, CF3 0P2 CP-CH
2, CF3CH=CHCF3, CF'2 -CFCF
2 Ch, CF2-CPCI! 2 (Jla, CF
3CH2 CI=CH2, CP3 C}l=cHcH
3, CF2 = CHCH2 CH3, CHa CF2
CH=CH2, CP}l2ell-C}IcPH
2, CI{3 CP2 1”cth, CI12 =
CFCH2 CH3, CF3 (CF2) 2
CP=CF2, CP3 (CP2) 3 CP=
Examples include CF2.

The fluoroalkyl group in general formula (18) has 3 to 21 carbon atoms. Specifically, for example, 04F9,
(CF2)s CF (CFa)2, C8F+7, C,
. Examples include F2+.

Examples of the monomer represented by general formula (18) include CH3 -C-COO- 02 Ha -C4
P9CH3 CH2 =C-COO- C2 H4-Cs Fl
7CH3 CH2 =C-COO- C2 H4-C+● F2
+, etc. can be mentioned.

(b-4) Olefin compounds; for example, ethylene, brobylene, butylene, isobrene, chloroprene, etc.

(b-5) Vinyl ethers and allyl ethers: e.g. ethyl vinyl ether, probyl vinyl ether, isobrobyl 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 cyclobentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, o1, m-p-}rivinyl ether, and aralkyl vinyl ethers such as penzyl vinyl ether and phenethyl vinyl ether.

(b-6) Vinyl esters and propenyl esters: for example, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate,
Vinyl esters such as vinyl bivaric acid and vinyl caprate, and propenyl esters such as isopropenyl acetate and isopropenyl propionate.

(b-7) Esters of acrylic acid or methacrylic acid; for example, methyl acrylate, ethyl acrylate, probyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methacrylate Alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms, such as methyl acid, ethyl methacrylate, probyl methacrylate, isoprobyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, and lauryl methacrylate: acrylic acid Alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as methoxybutyl, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate.

(b-8) Vinyl aromatic compound: for example, styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene, etc.

(b-9) Others: acrylonitrile, methacrylonitrile, etc.

Among the monomers (b) described above, it is preferable to use monomers (b-1) or (b-2) containing a hydroxyl group or a carboxyl group because they form a coating film with excellent curability.

The amount of monomer (b-1) and/or monomer (b-2) used is about 50% or less of the total amount of monomer components in polymer (A), preferably about The content may be 5 to 30% by weight.

The resin (B) has an average of 1 or more epoxy groups in one molecule, preferably an average of 2 to 400 epoxy groups, and a number average molecular weight of about 1000 to 200000, preferably about 3000 to 80.
000. If the number of epoxy groups is less than one on average, the curability will be poor, which is not preferable. Also, the molecular weight is about 1
If the molecular weight is less than about 200,000, the physical properties and weather resistance of the formed coating film will be poor. On the other hand, if the molecular weight is more than about 200,000, the viscosity of the composition will increase and the coating workability will decrease, which is not preferable.

Resin (B) consists of resin (A) having a functional group and resin (A).
) is a resin obtained by reacting a compound (A) containing an epoxy group with a functional group that reacts complementary to the functional group in (A).

Examples of the functional groups in the resin (A) include hydroxyl groups, carboxyl groups, silane groups, phenolic hydroxyl groups, and isocyanate groups.

Further, examples of the functional group in the compound (A) include a hydroxyl group, a silane group, an epoxy group, and an isocyanate group.

Groups that react complementary to each other can be selected and combined as appropriate from the above groups, and the following combinations are preferred.

Resin (A)/compound (A): hydroxyl group/isocyanate group, carboxyl group/epoxy group, silane group/silane group,
Phenolic hydroxyl group/epoxy group, phenolic hydroxyl group/isocyanate group, isocyanate group/hydroxyl group, etc.

The resin (A) has on average one or more functional groups that react with the functional group of the compound (A) in one molecule, and the resin can be any conventional resin without any particular restriction as long as it has the above-mentioned functional group. You can select and use them as appropriate. in particular,
Examples include resins such as vinyl resin, fluororesin, polyester resin, alkyd resin, silicone resin, urethane resin, and polyether resin.

There is no problem even if the functional group in the compound (A) that reacts with the functional group in the resin (A) is the same as the epoxy group that the compound (A) has.

Next, the resin (A) containing a hydroxyl group, a carboxyl group, a silane group, a phenolic hydroxyl group, or an isocyanate group will be explained.

[Hydroxy group-containing resin]

The following items can be mentioned.

■ Hydroxyl group-containing vinyl resin The hydroxyl group-containing polymerizable unsaturated monomer (b-1) and, if necessary, other polymerizable unsaturated monomers (b-3) to (b
- A polymer obtained by subjecting 9) to a radical polymerization reaction.

■ Hydroxyl group-containing polyester resin polybasic acids (e.g. (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) maleic acid, (anhydrous) biromellitic acid, (anhydrous) trimellitic acid, (anhydrous) succinic acid, sebacic acid , azelaic acid, dodecanedicarboxylic acid, dimethyl isophthalate, dimethyl terephthalate, etc., compounds having 2 to 4 carboxyl groups or carboxylic acid methyl ester groups in one molecule), and polyhydric alcohols (e.g., ethylene glycol, Polyethylene glycol, propylene glycol, neopentyl glycol, 1.6-
It is obtained by an ester reaction or transesterification reaction with alcohols having 2 to 6 hydroxyl groups in one molecule, such as hexanediol, trimethylolpropane, pentaerythritol, glycerin, and tricyclodecane dimethanol. In addition to the above, monobasic acids (e.g. castor oil fatty acids,
Fats such as soybean oil fatty acids, tall oil fatty acids, and linseed oil fatty acids. fatty acids, benzoic acid, etc.) and monohydric alcohols (eg, oleyl alcohol, 12-hydroxystearic acid, etc.) can be used as necessary.

■ Hydroxyl group-containing polyurethane resin A hydroxyl group-containing polyurethane resin obtained by modifying a hydroxyl group-containing vinyl resin, a hydroxyl group-containing fluororesin, a hydroxyl group-containing polyester resin, etc. with a polyisocyanate compound (for example, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.) A resin without 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 C or higher (Dow Corning product), SH5050, SH6018, SH6188
(The above are products of Toray Silicone Co., Ltd.)), and is obtained by modifying the resin with no alkoxysilane group or silanol group.

(2) A hydrolyzate obtained by hydrolyzing a part or all of polyvinyl acetate or a copolymer of vinyl acetate and other polymerizable unsaturated monomers.

(2) Vinyl alcohol-styrene copolymer (carboxyl group-containing resin) The following may be mentioned.

■ Carboxyl group-containing resin The carboxyl group-containing polymerizable unsaturated monomer (b-
Homopolymers of 2) and copolymers of monomer (b-2) and other polymerizable unsaturated monomers (b-3) to (b-9) can be used.

■ Carboxyl group-containing fluorine-containing resin fluorine-containing polymerizable unsaturated monomer (b-3), carboxyl group-containing polymerizable unsaturated monomer (b-2), and other polymerizable unsaturated monomers as necessary Monomers (b-1) and (b-3) to (b
-9) can be used as a monomer component.

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

■ Carboxyl group-containing polyester resin A resin obtained by ester-reacting the polybasic acid (or its anhydride) and the polyhydric alcohol, and a resin obtained by adding an acid anhydride to the hydroxyl group-containing polyester resin. can be mentioned.

[Isocyanate group-containing resin]

The following items can be mentioned.

■ Isocyanate group-containing vinyl resin Inocyanate group-containing polymerizable unsaturated monomer (C) and other polymerizable unsaturated monomers (b-2) to (
A polymer having b-9) as a monoplane component.

Isocyanate group-containing polymeric unsaturated monomer (c) Monomers represented by the following general formulas (19) and (20) can be mentioned.

RI CH2-C-Coo-+CnH2n+NCO (19
) [wherein R1 and n are the same as above. ] The monomer represented by these is mentioned. The monomer includes, for example, isocyanate ethyl (meth)acrylate.

or an alkyl group having 5 or less carbon atoms. ] Examples include monomers represented by the following. The monomer includes, for example, α, α-
Dimethyl-m-isobropenylbenzyl isocyanate is included.

In addition to the above, hydroxyl group-containing polymerizable unsaturated monomer (b-1)
A reaction product of 1 mol and 1 mol of 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, isobropylidene bis(
(4-phenyl isocyanate), lysine isocyanate, isophorone diisocyanate, and their polymers and purets.

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) Isocyanate 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 isocyanate component is in excess.

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

[Silane group-containing resin]

Used in the resin obtained by reacting the hydroxyl group-containing resin with the isocyanate-1 group-containing silane compound described below, the resin obtained by reacting the isocyanate group-containing resin with the hydroxyl group-containing silane compound described later, and the hydroxyl group-containing silicone resin. silicone resin etc.

[Epoxy group-containing resin]

(2) A polymer containing an epoxy group-containing unsaturated monomer (d) described below as an essential monomer component.

■ Glycidyl etherified products of phenol or cresol type resins (for example, phenol type novolak resins, etc.).

(2) A resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing epoxy compound described below.

[Phenolic hydroxyl group-containing resin]

The following items can be mentioned.

■ Phenol or cresol type resin (for example, phenol type novolac resin, phenol type resol resin, cresol type novolac resin, etc.).

(2) A polymer containing a phenolic hydroxyl group-containing polymerizable unsaturated monomer (for example, p-vinylphenol, etc.) as an essential monomer component.

■ Epoxy group-containing resin (for example, the above polymer (A), etc.)
and a polyhydric phenol compound (for example, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyhydroquinone, etc.) are adjusted so that the polyhydric phenol compound is in excess.

■ A resin obtained by reacting an epoxy group-containing resin with a phenolic hydroxyl group-containing compound (such as hydroxybenzoic acid).

Next, the compound (A) containing a hydroxyl group, a silane group, an epoxy group or an isocyanate group will be described.

[Epoxy compound containing hydroxyl group]

Compounds represented by the following general formulas (21) to (31) can be mentioned.

[In the formula, Rl, R2 and n are the same as above. R9 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. ] General formula (21) ~
Specific examples of the compound represented by (31) include l CH. -C-C}l. -OH \/ etc. can be mentioned.

[Silane group-containing epoxy compound]

For example, compounds represented by the following general formulas (32) to (35) can be mentioned.

Represented by 0 Y Y [wherein Rl, R9 and Y are the same as above. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (32) to (35) include QC}I. Otori et al.

In addition to the above-mentioned compounds, compounds represented by general formulas (32) to (35) may also be used with polysilane compounds described below (for example, general formula (
Compounds obtained by condensation with the compounds represented by (87) to (89)) can also be used.Specifically, the following can be mentioned.

[Boreepoxy compound]

Compounds represented by the following general formulas (36) to (43) can be mentioned.

HiC [wherein R1 and R9 are the same as above. RIG is the same or different and represents an alkyl group, an aryl group, or an aralkyl group having 1 to 8 carbon atoms. Rl+ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , W is 0
and an integer from 1 to 10. ] Specific examples of the compounds represented by formulas (36) to (43) include LC.

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

Adducts with nate compounds.

Examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate and inphorone diisocyanate, tolylene diisocyanate, and 4,4'-diphthalate. Organic diisocyanates themselves such as aromatic diisocyanates such as enylmethane diisocyanate, adducts of each organic diisocyanate with polyhydric alcohol, low molecular weight polyester resin or water, polymers of each organic diisocyanate,
Examples include isocyanate biuret and the like. An example of a typical commercially available product is “Burnock D-750
, -800, DN-950, -970 or 15-4
55" [The above are Dainippon Ink & Chemicals ■ products], "Desmodule%N'HL, IL Moshi《N3390J
[Manufactured by Bayer, West Germany] "Takenate D-10"
2, -202, -110N or -123N" {Takeda Pharmaceutical ■product], [Coronate L,}IL,E}I
Or 203J (Japan Polyurethane Industries ■product)
, [DURANATE 24A-90CXJ [Asahi Kasei Kogyo ■ product], etc.].

Furthermore, adducts of and polybasic acids, esterified products having unsaturated groups in the molecule (e.g., tetrahydrophthalic anhydride, trimethylolpropane, 1,4-butanediol, etc.) The number average molecular weight obtained by
Those obtained by oxidizing an esterified product of 0) with peracetic acid etc. can also be used.

[Isocyanate group-containing epoxy compound] Examples include those obtained by reacting the hydroxyl group-containing epoxy compound and the polyisocyanate compound so that the epoxy group and the isocyanate group remain. in particular,
For example, a reaction product of a compound represented by general formula (21) and hexamethylene diisocyanate, a reaction product of a compound represented by general formula (28) and isophorone diisocyanate, a reaction product of a compound represented by general formula (30) and isoporone diisocyanate. Reaction products of the compound represented by the general formula (25) and toluene diisocyanate, and reaction products of the general formula (31) and xylene diisocyanate-1.

The copolymer (A) and resin (B) are usually blended so that the silane group/epoxy group ratio is 1/99 to 99/1.

(2) Resin composition The resin composition is a polymer (polymer (B)) containing an epoxy group-containing polymerizable unsaturated monomer as an essential monomer component.
and a compound containing a silane group and a functional group that reacts complementary to the functional group (resin (C)).
Resin obtained by reacting compound (B)) (resin (D)
).

The polymer (B) has an average of 1 or more epoxy groups in one molecule, preferably an average of 2 to 400 epoxy groups, and a number average molecular weight of about 1,000 to 200,000, preferably about 3,000 to
It's from soooo.

If the number of epoxy groups is less than one on average, the curability will be poor, which is not preferable. In addition, when the molecular weight is less than about 1000, the physical properties and weather resistance of the coating film formed are poor;
If it exceeds 00,000, the viscosity of the composition increases and coating workability decreases, which is not preferable.

The polymer (B) is a homopolymer of the epoxy group-containing polymerizable unsaturated monomer (d) or a copolymer of the monomer (d) and the other polymerizable unsaturated monomer (b). Combination can be used.

Epoxy group-containing polymerizable unsaturated monomer (d) A compound having an epoxy group and a polymerizable unsaturated group in one molecule. The epoxy group may be alicyclic or aliphatic. Examples of polymerizable unsaturated groups include, for example, CH2=C (R')COO-CH2=C (R'')CC- l1 CH2 -Rl Rl O (in the formula, R1 is the same as above), and the like.

Examples of the epoxy group-containing polymerizable unsaturated monomer whose polymerizable unsaturated group is CH2-C(Rl)COO- include compounds represented by the following general formulas (44) to (56).

Rl [In the formula, Rl, R2, R9 and W are the same as above.

Rl, R2 and R9 may be the same or different. ] As specific examples of the compounds represented by general formulas (44) to (56), for example, as the epoxy group-containing polymerizable unsaturated monomer of CH2 C- (R t C-N-, for example, the following General formula (5
7) to (59) can be mentioned.

etc. can be mentioned.

The polymerizable unsaturated group is [wherein R1 and R9 are the same as above]. R1 and R9 may be the same or different. ] General formula (57) ~ (
Specific examples of the compound represented by 59) include RI O and the like.

Examples of the polymerizable unsaturated monomer containing an epoxy group in which the polymerizable unsaturated group is CM2-C (R') are represented by the following general formula (60):
Compounds represented by (62) can be mentioned.

υ (In the formula, Rl and R9 are the same as above. R1 and R9 may be the same or different.) General formula (60) ~ (
Specific examples of the compound represented by 62) include the following.

Examples of the epoxy group-containing polymerizable unsaturated monomer in which the polymerizable unsaturated group is CH2 -C- (Rl C-N-) include the following general formula (6
Compounds represented by 3) to (68) can be mentioned.

Rl R1 [In the formula, RI SR2, R9 and W are the same as above.

RISR2 and R9 may be the same or different. ] Specific examples of the compounds represented by formulas (63) to (68) include the following.

Examples of the epoxy group-containing polymerizable unsaturated monomer in which the polymerizable unsaturated group is CH2=CHCH20- include the following general formula (
Compounds represented by (69) to (72) can be mentioned.

OH (72) [In the formula, R1 and R9 are the same as above. R9 may be the same or different. ] Specific examples of the compounds represented by the general formulas (69) to (72) include, for example, CH3. Specific examples of the compounds represented by the general formulas (73) to (75) include, for example.

Examples of the epoxy group-containing unsaturated monomer whose polymerizable unsaturated group is CH2-CHO- include the following general formulas (73) to (7).
Compounds represented by 5) can be mentioned.

etc. can be mentioned.

Examples of the epoxy group-containing unsaturated monomer in which the polymerizable unsaturated group is CH2=CH1 include the following general formulas (76) to (78).
) can be mentioned.

[In the formula, R1 and R9 are the same as above. If R9 is the same《
may be different. ] Examples of the boxy group-containing unsaturated monomer include compounds represented by the following general formulas (79) to (83).

In each formula, Rl and R9 have the same meanings as above; R9
may be the same or different.

As specific examples of the compounds represented by the general formulas (76) to (78), for example, [wherein Rl, R2 and R9 are the same as above. R1 and R2 may be the same or different. ] General formula (7
Specific examples of the compounds represented by 9) to (83) include the following.

Among the above-mentioned monomers, monomers containing an alicyclic epoxy group are preferably used because they form a coating film with excellent curability.

As the other polymerizable unsaturated monomer (b), the same monomers as mentioned above can be used.

The resin (D) has an average of 1 or more silane groups in one molecule, preferably 2 to 400 on average, and the total number average molecule is about 1
000-200000, preferably about 3000-800
00. If the number of silane groups is less than one on average, the curability will be poor, which is not preferable. Also, the molecular world is about 100
If the molecular weight is less than 0, the physical properties and weather resistance of the formed coating film will be poor. On the other hand, if the molecular weight exceeds about 200,000, the viscosity of the composition will increase and the coating workability will decrease, which is not preferable.

The resin (D) is a resin obtained by reacting the resin (C) with a compound (B) containing a silane group and a functional group that reacts complementary to the functional group in the resin (C).

Examples of the functional group in the resin (C) include a hydroxyl group, a carboxyl group, a carbon group, an epoxy group, an isocyanate group, a mercabuto group, an amino group (NH, NH2), a phenolic hydroxyl group, an acid anhydride group, etc. can be mentioned.

In addition, examples of functional groups in compound (B) include hydroxyl group, carboxyl group, silane group, epoxy group, isocyanate group, mercabuto group, and amino group (NH, NH2').
, unsaturated groups, etc.

Groups that react complementary to each other can be selected and combined as appropriate from the above groups, and the following combinations are preferred.

Resin (C)/compound (B): hydroxyl group/isocyanate group, carboxyl group/silane group, carboxyl group/epoxy group, carboxyl group/isocyanate group, silane group/
Silane group, silane group / carboxyl group, epoxy group / carboxyl group, epoxy group / mercapto group, epoxy group / amino group, isocyanate group / hydroxyl group, isocyanate group / carboxyl group, isocyanate group / mercabuto group, isocyanate group / amino group, Mercapl/epoxy group, mercabuto group/unsaturated group, amino group/epoxy group, amino group/unsaturated group, amino group/isocyanate group, phenolic hydroxyl group/carboxyl group, phenolic hydroxyl group/epoxy group, phenolic Examples include hydroxyl group/isocyanate group, unsaturated group/mercapto group, unsaturated group/amino group, acid anhydride group/hydroxyl group, acid anhydride group/epoxy group, and acid anhydride group/amino group.

The resin (C) has on average one or more functional groups that react with the functional group of the compound (B) in one molecule, and the resin can be any conventional resin without any particular restriction as long as it has the above-mentioned functional group. You can select and use them as appropriate. in particular,
For example, vinyl resin, fluororesin, polyester resin,
Examples include resins such as alkyd resins, silicone resins, urethane resins, and polyether resins.

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

As the resin (C), which contains a hydroxyl group, a carboxyl group, a silane group, a phenolic hydroxyl group, and an isocyanate group, the same resin as the resin (B) can be used.

Moreover, as resins having groups other than those mentioned above, the following can be mentioned.

[Mercapto group-containing resin]

The following items can be mentioned.

(2) A resin obtained by reacting the isocyanate group-containing resin with a mercabutane compound (for example, a hydroxyl group-containing thiol compound, a polymercabutane compound, etc.) so as to have a mercabutan group.

(2) A resin obtained by reacting the epoxy group-containing resin with a polymercabutane compound so as to have a mercapto group.

(2) A resin obtained by reacting the silane group-containing resin with the merkabutosilane compound described below so as to have a merkabuto group.

[Amino group-containing resin]

A resin obtained by reacting the hydroxyl group- or silane group-containing resin with the amino group-containing silane compound described below so as to have an amino group.

[Unsaturated group-containing resin]

The following items can be mentioned.

(2) A resin obtained by reacting the carboxylic group-containing resin with the epoxy group-containing polymerizable unsaturated monomer (d) so as to have an unsaturated group.

(2) A resin obtained by reacting the epoxy group-containing resin with the carboxyl group-containing polymerizable unsaturated monomer (b-2) so as to have an unsaturated group.

(2) A resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing polymerizable unsaturated monomer (C) so as to have an unsaturated group.

(2) A resin obtained by reacting the isocyanate group-containing resin with the hydroxyl group-containing polymerizable unsaturated monomer (b-1) so as to have an unsaturated group.

[Acid anhydride group-containing resin]

The carboxyl group-containing polymerizable unsaturated monomer (b-
2) A homopolymer of an unsaturated monomer containing an acid anhydride group selected from ) copolymer with

As the compound (B) containing an epoxy group and an unsaturated group, the same compounds as the silane group-containing epoxy compound and the silane group-containing polymerizable unsaturated monomer (a) can be used.

Moreover, the following can be mentioned as a compound (B) which has a functional group other than the above.

[Hydroxyl group-containing silane compound]

Compounds represented by the following general formulas (84) to (86) can be mentioned.

[In the formula, R2, R9 and Y are the same as above. R2R9 and Y may be the same or different.

However, any one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (84) to (86) include OCHs IO- (CH.). -St-OCH. Metal condensates of compounds represented by 0CRs to (86) and polysilane compounds described below can also be used. An example of the condensate is CH, HO (CH2) s + Si
-0) 竃●OCH3l CH, can be exemplified.

(Polysilane compound) A compound having two or more groups selected from a silane group and a SLOH group in one molecule, for example, the following general formula (8
Compounds represented by 7) to (89) can be mentioned.

one 〇 can be mentioned.

Further, in addition to the above, for example, general formula (84) R1● Y' -81 -Y'Y' RIO R1 -81 -Y'Y' [wherein Ril1 is the same as above. R1● may be the same or different. Y' are the same or different and represent a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] General formula (87)
Specific examples of the compounds represented by (89) include dimethyldimethoxysilane, dibutyldimethoxysilane, di-1so-propyldibropoxysilane,
Diphenyldibutoxysilane, diphenyldiethoxysilane, diethyldisilanol, dihexyldisilanol methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, probyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane , hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol, tetramethoxysilane, tetraethoxysilane, tetrapoxysilane, tetraacetoxysilane, di-1go-propyloxydivaleroxysilane, and tetrasilanol.

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

[Epoxy group-containing silane compound]

The above silane group-containing epoxy compounds can be mentioned.

[Isocyanate group-containing silane compound] The following general formula (9
Examples include compounds represented by 0) and (91).

Y 0CN-R9 -81 -Y (90)Y As a specific example of the general formulas (90) and (91), the compound OCNC38s S1 (OC2 H s ) 3, O
CNC2 H4 St (QC H3) a, OCN
Ca Hs St (OC2 H5) 2, CH
3 OCNC2 ) Ia Si (OCR 3 ) 2,
CH3 OCNCI{ 2 Si (Oe2} is ) 3, O
CNCII 2 Si (QC) I a ) a, OC
NCH 2 St (OC2 H5 ) 2, CH3 0CNCH 2 Si (OCH a ) 3, [wherein R9 and Y are the same as above. Y may be the same or different. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] CH 3 OCN- C3 }16 -SIN-( C2 H
5) 2CH3OCN-Si (OCCl13) 3OCN-C
3 OCN- C3 H6 H6 CH 3 CH 3 -SiON( C}l 3 C3 I1 -Si (OCCH3 C}l H7 OCN Si OCCA H90CCH3 etc.).

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.

A reaction product of general formula (84) and hexamethylene diisocyanate or tolylene diisocyanate, such as OCN-31 (OCfh), can be mentioned.

Furthermore, a condensate of the isocyanate group-containing silane compound and, for example, the polysilane compound. Examples can be given.

[Merkabuto group-containing silane compound]

Examples include compounds represented by the following general formula (92).

HS-R9-81-Y
(92)Y [wherein R9 and Y are the same as above. Y may be the same or different. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] As a specific example of the compound represented by general formula (92),
Examples include 0C2 H5 HS C3 Hs Si OC4 Hgl OC2 H5.

In addition to the above, the hydroxyl group-containing silane compound may be added to the polyisocyanate compound and thiocol compound (for example, H
SC, H2, -OH, m are the same as above. ) can be used, specifically, for example, etc.

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

[NH group- or NH2 group-containing silane compound] The following general formula (
Examples include compounds represented by (93) and (94).

Y l H2N-R9 -S1 -Y (9
3) Y HN-eR9-Si-Y)2 (94)i Y [wherein R9 and Y are the same as above. R9 and Y may be the same or different. However, at least 1 of Y
is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (93) and (94) include H2N - (CH2 ) 3 St (OCH3
) 3HN[(CH2)3 81(OC2Hs)3)
2nd place can be mentioned.

In addition, in addition to the above general formulas (93) and (94),
) and the above-mentioned polysilane compounds can also be used. Examples of the condensate include the following.

The polymer (B) and resin (D) are usually epoxy 1&/
The silane group ratio is blended to be 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-1 group, the condensation reaction of a silane group, a copolymerization reaction, etc. can be carried out based on conventionally known methods. For example, the reaction between a hydroxyl group and an isocyanate group is sufficient for about 30 to 360 minutes at room temperature to 130°C. The condensation reaction of silane groups is carried out in the presence of an acid catalyst (e.g. hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.) with a
Heating at about 0°C for about 1 to 24 hours is sufficient. In addition, for the copolymerization reaction, the same method and conditions as those for general synthesis reactions of acrylic resins, vinyl resins, etc. can be adopted. As an example of such a synthesis reaction, each monomer component is dissolved or dispersed in an organic solvent, and 6
A method of heating while stirring to a temperature of about 0 to 180°C can be shown. The reaction time may normally be about 1 to 10 hours. Further, as the organic solvent, one that is inert with the monomer or compound used, such as an ether solvent, an ester solvent, a hydrocarbon solvent, etc., can be used.

When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility. Further, as the radical polymerization initiator, any commonly used initiator can be used, such as benzoyl peroxide, t-butyl,
{-peroxides such as oxy-2-ethylhexanoate,
Examples include azo compounds such as azoisobutylnitrile and azobisdimethyl/chloronitrile.

In the resin composition of the present invention, the curability of the coating film is further improved by introducing carboxyl groups and/or hydroxyl groups in addition to the epoxy groups and silane groups into the composition components. Introduction of these groups can be carried out according to known methods.

In the resin composition of the present invention, the above-mentioned resin or copolymer may be combined with other resins (e.g. vinyl resin, polyester resin,
Modified resins chemically bonded with urethane resins, silicone resins, epoxy resins, etc. can also be used similarly.

The resin composition of the present invention can be used in a form dissolved or dispersed in a suitable solvent. Examples of the solvent include hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether, Examples include alcoholic solvents such as butanol and propanol, and water.

The curable composition of the present invention includes (1) an organometallic compound, (2) a Lewis acid, (3) a protonic acid, and (
4) S L -0-AJ! It is made by adding at least one type of curing reaction catalyst selected from the group consisting of compounds having bonds.

(1) Organometallic compounds such as metal alkoxide compounds, metal chelate compounds,
Examples include metal alkyl compounds.

(Metal alkoxide compound) Examples include compounds in which an alkoxy group is bonded to metals such as aluminum, titanium, zirconium, calcium, and barium.These compounds may be associated.Among them, aluminum alkoxide, titanium, etc. Alkoxides and zirconium alkoxides are preferred.Specific examples of these metal alkoxide compounds are listed below.

Aluminum alkoxide, for example, has the general formula [wherein R
I2 are the same or different and represent an alkyl group or an alkenyl group having 1 to 20 carbon atoms. ] Aluminum alkoxides can be mentioned.

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 alkyl group of 8, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl groups, etc. can be exemplified, and examples of the alkenyl group include vinyl, allyl group, etc.

Examples of the aluminum alcoholates represented by the general formula (95) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-isoproboxide, aluminum tri-n-butoxide, aluminum tri-isobutoxide, and aluminum tri-isobutoxide. See-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisoproboxoxide, aluminum tri-se
Preferably, e-butoxide, aluminum tri-n-butoxide, etc. are used.

The titanium chelate compound has, for example, the general formula [wherein W and RI2 are the same as above. ] can be mentioned.

Titanates represented by general formula (96) include W
For those with 1, tetramethyl titanate, tetraethyl titanate, tetra-n-probyl titanate, tetra-isobutyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-ter
Examples include t-butyl titanate, tetra n-pentyl titanate, tetra n-hexyl titanate, tetraisooctyl titanate, tetra n-lauryl titanate, and among them, tetraisobutyl titanate, tetra n-butyl titanate, and tetraisobutyl titanate. Particularly preferred are titanates, tetra-tert-butyl titanates, and the like. In addition, for those in which W is 1 or more, dimers to decamers of tetraisobutyl titanate, tetra n-butyl titanate, tetraisobutyl titanate, and tetratert-butyl titanate (
In the general formula (96), w=l to 10) gives preferable results.

The zirconium chelate compound has, for example, the general formula [wherein W and RI2 are the same as above. ] Zirconates represented by the following can be mentioned.

As the zirconates represented by the general formula (97),
Tetra ethyl zirconate, Tetra n-brobyl zirconate, Tetra sobutyl zirconate, Tetra n-butyl zirconate, Tetra see-butyl zirconate, Tetra tert-butyl zirconate, Tetra n-pentyl zirconate, Tetra tert-
Examples include pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, and among these, tetra-tert-tert-hexyl zirconate, tetra-n- Particularly preferred are propylzirconate, tetraisobutylzirconate, tetran-butylzirconate, tetrasec-butylzirconate, tetratert-butylzirconate, and the like. Also, for those where W is 1 or more,
Dimers to 11-mers of tetraisobutyl zirconate, tetra n-propyl zirconate, tetra n-butyl zirconate, tetra isobutyl zirconate, tetra sec-butyl zirconate, and tetra tart-butyl zirconate (general formula ( w=l in 97)
~10) give suitable results.

Further, it may contain a structural unit in which these zirconates are associated with each other.

[Metal chelate compound]

Preferred are aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds. Also. Among these chelate compounds, chelate compounds containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring are preferred.

Compounds that can constitute keto-enol tautomers include β-diketones (acetylacetone, etc.), acetoacetate esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and compounds with a hydroxyl group at the β position. Examples include ketones having a hydroxyl group at the β position (diaheptone alcohols), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), and esters having a hydroxyl group at the β position (methyl salicylate). In particular, acetoacetic acid esters, β-dikel
・Suitable results can be obtained by using the following types.

The aluminum chelate compound is preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of about 3 moles or less per 1 mole of the aluminum alkoxide, and heating as necessary. It can be prepared.

Particularly preferred aluminum chelate compounds include, for example, tris(ethyl acetoacetate) aluminum,
Tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, isoproboxybis(ethylacetoacetate)aluminum, diisobutylacetoacetatealuminum, tris( acetylacetonato)aluminum, tris(probionylacetonato)aluminum, tris(ethylacetonato)aluminum, diisobutoxypionylacetonatoaluminum, acetylacetonatobis(propionylacetonato)aluminum, monoethylacetoacetate bis Examples include (acetylacetonato)aluminum, trisC-(sobropyrate)aluminum, tris(acetylacetonado)aluminum, and the like.

As a titanium chelate compound, a compound capable of forming the above-mentioned K-Nol tautomer is mixed with 1 mole of the titanium alkoxide at a molar ratio of usually about 4 moles or less, and heated if necessary. It can be suitably prepared by doing this. Particularly preferred titanium chelate compounds include, for example, diisobroboxy bis(ethylacetoacetonato) titanate, diisopropoxy bis(acetylacetonato) titanate, diisopropoxy bis(acetylacetonato) titanate, and the like. can.

The zirconium chelate compound is preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer in a molar ratio of about 4 moles or less per 1 mole of the above-mentioned zirconium alkoxide, and heating if necessary. It can be prepared.

Particularly preferred zirconium chelate compounds include, for example, tetrakis(acetylacetonato)zirconium, te1.rakis(n-propylacetoacetate-1.)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate)zirconium, etc. The following zirconium chelate compounds can be mentioned.

Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or two or more types may be used in combination as appropriate.

[Metal alkyl compound]

The compound has an alkyl group, a metal such as aluminum or zinc,
Preferably, an alkyl group having 1 to 20 carbon atoms is bonded thereto. Specifically, for example, triethylaluminum,
Examples include diethylzinc.

(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, Arcom A7 [3F
3. Ai'F,,AIEtCI2. AfEt. C
I! , Sncl4, TIC1'4. TiBy4.
TiF<, ZrC. L. ZrBr. , lrF 4
, SnC4a. FeCmu. sbcm. SbC1
'i. PCIa, PCmu. Gacm. GaF,
, InF. , BCmu, BBrx, BF. , B.F. :
fOc. H. l. , BF4: (QC-Hsl-, BC
Mu: (OC2HBl z -BF3:N}l.C.H
S., Wangyu: NH, C. H. OR, etc. can be mentioned.

(3) Protonic acid The protonic acid specifically includes organic protonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoroethanesulfonic acid, benzenesulfonic acid, p-1-luenesulfonic acid, phosphoric acid, etc. , phosphorous phosphinic acid,
Inorganic compounds such as phosphonic acid, sulfuric acid, and perchloric acid can be mentioned.

(4) Compound having S i -0-AI bond A specific example of this compound is aluminum silicate.

Among the curing reaction catalysts (1) to (4) above, which one? Chelate compounds of the genus chelate can be used particularly preferably because they can form a coating film with excellent curability.

The blend n of the crosslinking reaction curing agent in (1) to (3) above is 0.01 to 3 parts by weight based on 100 parts by weight of the solid content of the resin composition.
Appropriately, the amount is approximately 0 parts by weight. If it is less than this range, the crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is 0.1 to 10
The more preferred amount is 1 to 5 parts by weight.

The amount of the crosslinking curing agent (4) to be blended is preferably about 1 to 100 parts by weight based on 100 parts by weight of the solid resin composition. If the amount is less than this range, the crosslinking curability tends to decrease, and if it is more than this range, the physical properties of the coating film tend to decrease, which is not preferable.

The coating composition of the present invention contains as an essential component at least one composition selected from the resin composition of the present invention and the curable composition.

For example, pigments, pigment dispersants, fluidity regulators, etc. may be added to the coating composition as necessary. Furthermore, the above-mentioned chelating agent and the above-mentioned polyepoxy compound may be added to improve the curability for the purpose of improving storage stability.

As the 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 (Rikiichi Bomb Black, etc.) and metal powders (aluminum powder, bronze powder, zinc powder, etc.). Examples of organic pigments include azo-based pigments (Lakeid, Fast Yellow, etc.) and phthalocyanine-based pigments (Phthalocyanine Blu-1, etc.).

The coating composition of the present invention can be applied, for example, to electrostatic coating (bell type, DEA coating).
The coating can be applied by conventionally used means such as molds, etc.), air spray coating, peel coating, roller coating, and dip coating.

The coating composition of the present invention can be used as a primer for various metals or plastic materials, or as an intermediate coating or top coating.

Function The resin composition of the present invention comprises a polymer into which these groups are introduced using a polymerizable unsaturated monomer containing a silane group or an epoxy group, and a polymer into which these groups are introduced using a compound containing an epoxy group or a silane group. It is a mixture with a resin into which a group of is excellent. In addition, the polymer can be easily obtained by polymerizing a monomer containing a silane group or an epoxy group, or by subjecting a compound containing an epoxy group or a silane group to an addition and/or condensation reaction. By this method, epoxy groups or silane groups can be introduced into a wide range of resins by a reaction mechanism different from the above-mentioned radical polymerization reaction.

Furthermore, since the crosslinking reaction of the epoxy groups and silane groups in the mixture proceeds at a relatively low temperature in the presence of a curing reaction catalyst,
A coating film with excellent curability can be obtained.

Effects of the Invention According to the present invention, a composition that exhibits the following excellent effects can be obtained.

(1) Excellent curability at low temperatures.

■ Can be combined with various resins.

■ A cured coating film with excellent appearance can be formed.

(4) A coating film with excellent acid resistance, water resistance, etc. can be formed.

0 A coating film with excellent weather resistance can be formed.

Example Production examples, working examples, and performance test examples are shown below.

"Part" and "%" are each based on weight.

Production example 1 [Production example of epoxy group-containing polymer] Copolymer (part) Glycidyl methacrylate 568n-butyl acrylate 3202-hydroxyethyl acrylate 112 azobisisobutyronitrile
The mixture of 40 was added dropwise to butyl acetate (667 parts) heated to 110°C over 3 hours, and the mixture was heated to 110°C.
After time aging, non-volatile content is 60%, number average molecular ff
A copolymer with i(Mn) of about 20,000 and 80 epoxy groups/molecule was obtained.

Copolymer ■ (Part) 3,4-epoxy hexylmethane 455 tyl acrylate styrene 200 n-butyl acrylate 2452-hydroxyethyl methacrylate 100 -Topenzoyl peroxide A mixture of 60 and 2-n-butoxy was heated to 110°C. Ethanol (6
67 parts) over 3 hours and aged at the same temperature for 3 hours to obtain a copolymer with nonvolatile content of 60%, Mn of about 15,000, and 37.5 epoxy groups/molecule.

Copolymer ■ 0 (parts) 1 l A mixture of styrene methyl methacrylate azobisisovaleronitrile was added dropwise to xitanol (=500/500 parts) heated to 80°C over a period of 3 hours, and at the same temperature After aging for 3 hours, the non-volatile content was reduced to 50%.
%, Mn about 22000,! A copolymer containing 8 boxy groups/molecule was obtained.

Production example 2 [Production example of silane group-containing polymer] Copolymer ■ (Part) n-butyl methacrylate 300 n-butyl acrylate 200 γ-methacryloxypropyltri 400 methoxysilane 2-hydroxyethyl methacrylate 10 t- A mixture of 50 butyl peroxybenzoates was added dropwise over 3 hours to xylene/2-ethoxyethanol (500/500 parts) heated to 120°C.
Aging was performed at the same temperature for 3 hours, resulting in a non-volatile content of 60% and Mn.
A copolymer having about 8,000 silane groups and 37.5 silane groups/molecule was obtained.

Copolymer■ (Parts) n-butyl methacrylate 400 n-butyl acrylate 200 γ-methacryloxybrobyltri 400 methoxysilane t-butyl baroxybenzoate A mixture of 50 and 50 was heated to 120°C and xylene/2-ethoxyethanol = (500 /500 parts) over 3 hours and aged at the same temperature for 3 hours to obtain a copolymer with nonvolatile content of 50%, Mn of about 80,000, and 37.5 silane groups/molecule.

Copolymer■ (Part) Methyltrimethoxysilane 2720γ-methacryloxypropyltri256methoxysilaneDeionized water 113460% Hydrochloric acid 2hydroquinone
1 These mixtures were heated to 80℃,
Reacted for 5 hours, Mn was about 2000, on average 1 per molecule.
A polysiloxane malomonomer having 2 vinyl groups and 4 silanol groups at the terminal portion was obtained.

(Parts) A mixture of 400 n-butyl methacrylate, 500 2-hydroxyethyl acrylate, and 30 t-butyl peroxyoctoate,
xylene/butyl acetate (÷3
0 0/7 0 0 parts) over 3 hours and aged at the same temperature for 3 hours to obtain a non-volatile content of 50% and a richness of about 15
000, a copolymer containing 24 silane groups/molecule was obtained.

Production Example 3 [Production Example of Functional Group-Containing Resin] Resin ■ (Parts) Styrene 300n-Butyl methacrylate 50Q 2-Hydroxyethyl acrylate 20〇1 Toazobisisobutyronitrile A mixture of 40 and 40 was heated to 110°C to produce butyl Dropped into acetate (667 parts) over 3 hours, aged at the same temperature for 3 hours,
A resin having a nonvolatile content of 60%, an Mn of about 20,000, and 34.5 hydroxyl groups/molecule was obtained.

Resin■ (Parts) A mixture of 38.5 trimellitic anhydride, 117 neopentyl glycol, and 88.5 was subjected to a dehydration condensation reaction at 210°C for 8 hours, and then xylene (70 parts) and propylene glycol monomethyl ether (71 parts) diluted with
．． 5/molecule of resin was obtained.

Resin ■ (Parts) Incyanate Ethyl methacrylate 155 Tobutyl methacrylate 500 Ethyl acrylate 345 Azobisisobutyronitrile A mixture of 60 was added dropwise to butyl acetate (1000 parts) heated to 90°C over 3 hours, and the mixture was heated to 90°C. Aging for 3 hours at 50% non-volatile content, M
A resin having n of about 16,000 and 16 isocyanate groups/molecule was obtained.

Resin [Co., Ltd.] (Department) Glycidyl methacrylate 71 Styrene
300n-butyl methacrylate 629 benzoyl peroxide
The mixture of 60 was added dropwise to butyl acetate (667 parts) heated to 100°C over 3 hours, and the mixture was added at the same temperature for 3 hours.
After time aging, non-volatile content is 60%, Mn is approximately 7500.
, a resin containing 3.8 epoxy groups/molecule was obtained.

Resin ■ (Part) Resin ■ Solution A mixture of 1000 mercaptoethanol 39 methyl ethyl ketone 39 was heated at 80℃ to 4
The reaction was carried out for a period of time to obtain a resin having a non-volatile content of 50%, an Mn of approximately 1700, and 16 mercapto groups/molecule.

Resin 0 (parts) Glycidyl methacrylate 71n-Butyl methacrylate 184 Styrene
300n-butyl acrylate
445t-butyl peroxybenzoate 60
A mixture of butoxyethanol (
367 parts) and butyl acetate (300 parts) over 3 hours, and then cooled to 110°C, 36 parts of acrylic acid, 0.1 part of hydroquinone and 0.5 part of tetraethylammonium bromide were added dropwise for 6 hours. Reacted, nonvolatile content 60%, Mn about 7000, unsaturated group 3.4
A resin containing 3.4 hydroxyl groups/molecule and 3.4 hydroxyl groups/molecule was obtained.

Resin 0 (parts) Itaconic anhydride 112 Styrene
A mixture of 300n-butyl acrylate, 588t-butylbaroxybenzoate, and 60% was added dropwise over 3 hours to butyl acetate (667 parts) heated to 110°C, and aged at the same temperature for 3 hours to obtain a non-volatile content of 50% and %. n about 6500,
A resin containing 6.5 carboxylic anhydride groups/molecule was obtained.

Production example 4 [Production example of silane group-containing resin] Resin @ (part) Resin ■ Solution 16670CN-
C2Hz-Si(OCH3)3
1 9 1 dibutyltin dilaurylate
A mixture of 0.3 methyl isobutyl ketone 127 was reacted at 60°C for 5 hours, and the nonvolatile content was 60%.
Mn approximately 24,000, 60 silane groups/molecule, 14 hydroxyl groups
．． 5 resins/molecule were obtained.

A mixture of 0 resin and resin solution (parts) was reacted at 100°C for 6 hours to reduce the nonvolatile content to 60
%, Mn approximately 2000, 6 silane groups/molecule, and 1.5 carboxyl groups/molecule.

Resin ■ (Part) Resin ■ Solution 10783-Methoxysilane butyl acetate A mixture of 124 and 124 was reacted at 110°C for 8 hours, and the non-volatile content was 50%, Mn
A resin containing approximately 21,000 silane groups and 48 silane groups/molecule was obtained.

Resin [Phase] (Part) Resin ■ Solution A mixture of 1667 N-methylaminobutyltrimeth 96.5 xysilane butyl acetate 64 was reacted at 50°C for 3 hours to reduce the non-volatile content to 60%.
, Mn about 8000, 10.9 silane groups/molecule, and 3.6 hydroxyl groups/molecule were obtained.

Resin [phase] (parts) Resin 0 solution 16663-Mercaptopyrol 98 Butoxyethanol 65 mixture was heated at 100°C.
was reacted for 8 hours, non-volatile content was 60%, Mn was about 7500,
A resin containing 10.2 silane groups/molecule and 3.4 hydroxyl groups/molecule was obtained.

Resin■ (Parts) A mixture of 1000 resin 0 solution was reacted at 100℃ for 5 hours, non-volatile content 50%, Mn
Approximately 8000, 19 silane groups/molecule, 6.4 hydroxyl groups/molecule
A resin containing 6.4 carboxyl groups/molecule was obtained.

Resin [Phase] (Part) Epicor} 180390 1000 (trade name: manufactured by Yuka Ciel Epoxy Co., Ltd., molecular weight approximately 1000, epoxy toho 219) A mixture of butoxyethanol 1000 was reacted at 120°C for 10 hours, resulting in a non-volatile content of 62%,
Mn about 1600, 7.5 silane groups/molecule, 2 hydroxyl groups.
5 resins/molecule were obtained.

Production Example 5 [Production Example of Epoxy Group-Containing Resin] Resin [Phase] Resin ■ Solution (Part) CH 3 Dibutyltin diacetate 0.5 A mixture of butyl acetate 210 was heated at 80°C.
After 4 hours of reaction, the non-volatile content was 60% and Mn was about 2600.
0, 20 epoxy groups/molecule, and 14.3 hydroxyl groups/molecule were obtained.

Resin [Phase] (Part) Resin ■ Solution A mixture of 1666 ether was reacted at 100°C for 6 hours, and the nonvolatile content was 60
%, Mn about 2600, 3.5 epoxy groups/molecule, and 3.5 hydroxyl groups/molecule.

Resin ■ (Part) Resin ■ Solution tooU Butyl acetate A mixture of 37 was reacted at 50°C for 4 hours, and the non-volatile content was 50%, Mn
A resin containing approximately 17,000 epoxy groups and 15.8 epoxy groups/molecule was obtained.

Resin ■ (Part) A mixture of 2 Epikote 180S90 1000 butoxyethanol 1945υ dibutyltin dilaurate was reacted at 80°C for 5 hours to obtain a resin with nonvolatile content of 50%, Mn of about 1950, and 3 epoxy groups/molecule.

Examples 1 to 13 The above polymers and resins were blended in the proportions (solid content, parts) listed in Table 1 to obtain compositions of Examples 1 to 13.

Table 1 Compound A: Tris(ethylacetoacetate)aluminum compound B: Tris(n-propylacetoacetate)aluminum compound C: Tris(acetylacetonato)aluminum compound D: Tetrakis(acetylacetonato)zirconium Example 14 50 parts of polymer (solid content), 50 parts of resin (solid content), 3 parts of the above compound A, and 4 parts of dimethylaminoethanol were mixed, and while stirring, 100 parts of deionized water was gradually added to form a water dispersion. I got something.

Example 15 20 parts (solid content) of the above copolymer (solid content), 080 parts (solid content) of resin, Compound B and 4.8 parts of N,N-dimethylethanolamine were mixed, and 166 parts of deionized water was added with stirring. It was added gradually to obtain an aqueous dispersion.

Example 16 In Example 2, 65 parts of copolymer (1) was replaced with titanium white CR-
93 (trade name, manufactured by Ishihara Sangyo Co., Ltd., titanium dioxide) was used for ball mill dispersion, but a composition was obtained using the same formulation as in Example 2.

Comparative Example 1 100 parts (solid content) of Copolymer (1) was blended with 3 parts of Compound A.

Comparative Example 2 100 parts (solid content) of copolymer (1) was blended with 1 part of p-}luenesnephonic acid.

Comparative Example 3 2 parts of zirconium isopropoxide was blended with 0.100 parts of resin (solid content).

Comparative Example 4 80 parts (solid content) of resin (1) was blended with 20 parts of hexakinemethoxymethylsilane and 2 parts of p-}luenesulfonic acid.

Comparative Example 5 Takenate D-165N (
Product name, Takeda Pharmaceutical Co., Ltd., isocyanate compound) 30
A combination of parts.

Comparative Example 6 A composition was obtained using the same formulation as in Comparative Example 5, except that 100 parts of titanium white CR-93 was used in Comparative Example 5.

The storage stability and coating film performance of the paints obtained in Examples and Comparative Examples were investigated. The results are shown in Table 2.

Table 2 [Storage Stability Test] The time during which the viscosity did not increase when the sample was left in a container at a temperature of 30° C. and a humidity of 70% was measured.

[Coating film performance test]

After each composition of Examples and Comparative Examples was coated to a dry film thickness of 100 μm (however, water resistance and weather resistance were
μm), cured under the conditions listed in Table 2,
Tested.

Painted surface condition: Mild steel plate was used as the material. The presence or absence of abnormalities in the painted surface condition (blurring, blurring, cracking, peeling, pigment spots, etc.) was examined.

Gel fraction: Peel off the dried coating film from the glass plate,
After extraction with acetone in a Soxhlet extractor at reflux temperature for 6 hours, the residue of the coating was expressed in %.

Impact resistance: The material used is mild steel plate. Using a DuPont impact tester, a 500 g weight was dropped onto the paint, and the maximum drop distance (cm) without cracking or peeling of the paint film was determined.

Water resistance: The material used is mild steel plate. Place the test piece in warm water (40℃
) for 60 days, and then the presence or absence of any abnormalities in the painted surface condition (blistering, whitening, dullness, etc.) was examined.

Weather resistance: The material used is aluminum plate. QU manufactured by The Q Bunnel Co., Ltd.
V-type weather meter (ultraviolet fluorescent lamp rNa.QF
S-40, UV-BJ, wavelength range 320-280nm)
Irradiation (15 minutes) and dew condensation (1
A cycle of 5 minutes) was repeated to determine the time required for defects such as deterioration of coating film gloss and cracking to occur. Note that the values of Example 16 and Comparative Example 6 are acid resistance: a glass plate was used as the material. The test piece was heated to 40% H2
The appearance of the coating film (
(blurring, whitening, etc.) was observed.

(that's all)

Claims (4)

[Claims] (1) A polymer containing as an essential monomer component a polymerizable unsaturated monomer containing a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, and a resin having a functional group that is complementary to the functional group. 1. A resin composition comprising a resin obtained by reacting a compound containing a functional group that reacts with an epoxy group. (2) A polymer containing an epoxy group-containing polymerizable unsaturated monomer as an essential component, a resin having a functional group, a functional group that reacts complementary to the functional group, a silanol group, and/or a silicon atom. A resin composition characterized by containing a resin obtained by reacting a compound containing a directly bonded hydrolyzable group. (3) The resin composition according to claim (1) or (2),
Organometallic compounds, Lewis acids, protonic acids and Si-O-
A curable composition containing at least one curing reaction catalyst selected from the group consisting of compounds having Al bonds. (4) A coating composition containing the composition according to claims (1) to (3) as essential components.