JPH02232251A - Resin composition, curable composition and paint composition - Google Patents

Abstract

PURPOSE:To form a compsn. with excellent storage stability and curability and to make it possible to form a coating film with excellent weatherability, acid resistance and abrasive damage resistance using this compsn. by compounding a specified curing catalyst in a resin compsn. contg. a fluorinated resin having three specified functional groups in the same molecule. CONSTITUTION:A resin compsn. contg. a resin having a silanol group and/or a hydrolyzable group directly bound to a silicon atom, an epoxy group and a hydroxyl group in the same molecule is obtd. by reacting a fluorinated resin A having functional groups (e.g. hydroxyl, carboxyl, isocyanate or silane group) with a compsn. B having a functional group complementarily reactive with the functional groups of the resin A and a compd. C having a functional group complementarily reactive with the functional groups of the resin A, a silanol group and/or a hydrolyzable group directly bound to a silicon atom. A curable compsn. is formed by compounding said resin compsn. with a metal chelate compd. as a curing catalyst.

Description

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

BACKGROUND ART 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 resin composition has a short bottle life and there are also problems with the toxicity of diisocyanates.

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

As a one-component, non-toxic, low-temperature curable composition, for example, Japanese Patent Application Laid-Open No. 60-67,553 describes a method in which an aluminum chelate compound is added to a vinyl polymer containing an alkoxysilane such as methacrylatetrimethoxysilane. Formulated compositions are disclosed.

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

The present inventor has conducted extensive research in view of the problems of the prior art described above. As a result, when a metal chelate compound is blended as a curing catalyst into a resin composition containing a fluororesin that has a silanol group and/or a hydrolyzable group, an epoxy group, and a hydroxyl group directly bonded to a silicon atom in the same resin. Even in a one-component type, a composition with excellent storage stability, no toxicity concerns, and excellent curability can be obtained, and if this composition is used, it has excellent weather resistance, acid resistance, scratch resistance, and stain resistance. They discovered that it is possible to form a coating film with excellent properties, and completed the present invention.

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

■Fluororesin (A) having a functional group is added to (i) resin (
A. ) Compound (B) having a functional group and an epoxy group that react complementary with the functional group of resin (A) and a functional group and a silanol group and/or silicon that react complementary with the functional group of resin (A) A resin having a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, an epoxy group, and a hydroxyl group in the same resin, obtained by reacting a compound (C) with a hydrolyzable group directly bonded to an atom. A resin composition containing (I).

■ A fluororesin (D) having a functional group and an Epoquine group has (i>a functional group that reacts complementary to the functional group of the resin (D) and a silanol group and/or a hydrolyzable group directly bonded to a silicon atom). obtained by reacting a compound (C) having
A resin composition containing a resin (II) having a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, an epoxy group, and a hydroxyl group in the same resin.

■ A fluororesin (E) having a functional group and a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, (i) a functional group and an epoxy group that react complementary to the functional group of the resin (E); A resin composition containing a resin (III) having a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, an epoxy group, and a hydroxyl group in the same resin, obtained by reacting a compound (B) having the following.

(2) A curable composition obtained by adding a metal chelate compound as a curing catalyst to the compositions (1) to (2) above.

(2) A coating composition containing the compositions (1) to (2) above as active ingredients.

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

-O-R, . (1
)-O-C-R2 [In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms.

R2, R3 and R4 are the same or different and have 1 to 1 carbon atoms;
8 shows an alkyl group, an aryl group, or an aralkyl group.

] Examples of the alkyl group having 1 to 8 carbon atoms include methyl,
Examples include ethyl, n-propyl, isobrobyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-bentyl, isobentyl, n-octyl, and isooctyl groups. Examples of the aryl group include phenyl, tolyl, and xylyl groups. Examples of the aralkyl group include benzyl and phenethyl groups.

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

In the resin composition of the present invention, the silane group has the above general formulas (1) and (2) from the viewpoint of storage stability, curability, etc.
and silane groups represented by silanol groups are preferred.

In the present invention, a complementary reactive functional group is a group that can react with the functional group of the other party. Specifically, for example, the combinations shown in the table below can be mentioned.

Complementarily reactive groups can be selected and combined as appropriate from the table above, but among them, the following combinations are preferred.

Resin (A)/Compound (B) [or Resin (E)/Compound (
B)] functional group combinations (1)/(5), (2)/(4), (3)/(3)
, (5)/(1) etc.

Resin (A)/Compound (C) [or Resin (D)/Compound (
C)] functional group combinations (1)/(5), (2)/(3), (2)/(4)
, (2)/(5), (3)/(3) , (4)/(2
), (4)/(6), (4)/(7), (5)/(
1) , (5)/(2) , (5>/(6) , (5)
/(7), (6)/(4), (8)/(8), (7
)/(4), (7)/(8), (7)/(5), etc.

Next, the resin compositions (I) to (m) used in the present invention will be explained.

Resin Composition (I) As a method for introducing a hydroxyl group into resin (I), for example, a compound having a hydroxyl group (for example, a hydroxyl group-containing polymerizable unsaturated monomer) may be used as a raw material to introduce the hydroxyl group into the resin (A) in advance. Method for introducing hydroxyl groups into resin (A), functional groups in resin (A) and compounds (
B) or a method of newly generating a hydroxyl group by reaction with a functional group possessed by the compound (C) (for example, reaction between an epoxy group and a carboxyl group), a method of producing a new hydroxyl group, a resin (A), a compound (
A group that reacts with a hydroxyl group (such as an isocyanate group) is introduced in advance into the reaction product of B) and compound (C), and a polyhydric alcohol compound (such as (poly)ethylene glycol, (
Examples include a method of introducing a hydroxyl group by blending and reacting an excess of poly(propylene glycol, neobentyl glycol, etc.) with a hydroxyl group.

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

When the functional groups in the resin (A) are the same, for example, the resin (A) having an average of two or more hydroxyl groups, the compound (B) having an isocyanate group (5), and the compound having an isocyanate group (5) A resin (A
) can be reacted with a compound (B) having a hydroxyl group (1) and a compound m (C) having an incyanate group (5).

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

The functional group in the compound (B) that reacts with the functional group in the resin (A) may be the same as the epoxy group that the compound (B) has. Similarly, the functional group in the compound (C) that reacts with the functional group in the resin (A) may be the same as the silane group that the compound (C) has.

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.

[Hydroxyl group-containing resin]

Typical examples of the resin include the following hydroxyl group-containing polymerizable unsaturated monomer (a), fluorine-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomers as necessary. Polymers having C. mer (C.) as a monomer component can be mentioned.

Examples of the hydroxyl group-containing polymerizable unsaturated unit (a) include compounds represented by the following general formulas (7) to (10).

[In the formula, R5 represents a hydrogen atom or a hydroxyalkyl group. ] [In the formula, R5 is the same as above. ] [In the formula, R6 represents a hydrogen atom or a methyl group, and m is 2 to
p is an integer of 2 to 18, and q is an integer of 0 to 7. ] CH2-CR6! [In the formula, R6 is the same as above. T1 and T2 are the same or different and represent a divalent hydrocarbon group having 4 to 20 carbon atoms. S and V each represent an integer of 0 to 10. however,
The sum of S and V is 1-10. ] In the general formulas (7) and (8), the hydroxyalkyl group is a hydroxyalkyl group in which the alkyl moiety has 1 to 6 carbon atoms. Specifically, for example, 1C2}140H,
-C3H60H, -C4H80H, etc. can be mentioned.

The divalent hydrocarbon group having 4 to 20 carbon atoms in general formula (10) is, for example, -CH2 -- (CH2
) 2 -, - (CH2 冫 3
-CH3 CH3CHa CH2 CH2 C CH2 CH2 - (C
H2) io-CH3 - (CH2) +2-, - (CH2) +a-
, ÷, -e, -CH2beZhiC112, etc. can be mentioned.

As the monomer component of general formula (8), for example, CI12
=CHCHII2 011 CH2 =CHCH2 0 CH2 CH2 0HC
H2 = CHCH2 0 {CH2CH2 0h mouth HC
112 -CIICH2 0{CHz CH2 0}r
ll etc. can be mentioned.

As the monomer component of general formula (9), for example, CH2
-C(CH3) COOC2 H4 0HCH2
=CHCOOC3 Hs OH Ol1? can be mentioned.

As the monomer component of general formula (10), for example, CH2
-C(CH3)Coo-(CH2CHCH3 0
}T27HCH2 ”C}ICOO(C}12 0H2
0■}ICl{2 -C(CH3)Coo-(CH
2 CH2 0 catty-TI{CH2 =CHCOO(CH
z CH2 CH2 CH2 0 effect-]HCH2 -C
(C}la)COO-(CH2CH20h-1-(CH2CHClh05-r7110), etc. can be mentioned.

Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (7) to (10) and ε-cabrolactone,
Adducts with lactones such as γ-valerolactone can be used.

Examples of the fluorine-containing polymerizable unsaturated monomer (b) include compounds represented by the following general formulas (ii) and (12).

CX2=CX2 (ii) [In the formula, X is the same or different and represents HSCQ, BrSF, an alkyl group, or a noroalkyl group. However, the formula contains at least one F. ] C H 2 - C R + C=0 (1 2) 0-CnH2n
-R7 [In the formula, R1 is the same as above. R7 represents a fluoroalkyl group, and n represents an integer of 1 to 10. ] General formula (ii)
The alkyl group in is one having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.

Specific examples include methyl, ethyl, probyl, isopropyl, butyl, and bentyl groups.

Further, the haloalkyl group is one having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, CF3,
CHF2, CH2F-, CCQ3, CHCQ2, CH2
CQ, CFCQ2 (CF2 )2 CFa, (CF2
)a CF3, CF2 CH3, CF2 CHF2
, C.F. ．． 2Br, CH2Br, etc. can be mentioned.

Examples of the monomer represented by general formula (ii) include:
CF'2-CF2, CHF-CP2, CH2-CF2
, CH2-CHF, CCQF-CF2, CHCQ
-CP2, CCQ 2 -CF2, CCR F =C
CΩF SCHF-CCQ2, CH2 = CCQ P
% CC(2 2 -CCR P .. CP3 CF
=CF2, CF3 CF=CHF, CFa CH=
CP2, CFa CF 1,000 CH2, C}iF 2 CF
=CHP, CH3CF=CP2, CH3CF
=CH2, CF2 CQ CF-CF2, CF3
CCQ=CF2, CF3 CP=CFCI2, C
P2 CQ CC (2 = CF2, CF2 CF2 CCQ CF2 CF3 CP3 CF2 CCQ CF2 CF2 CF3 CF2 CF3 CF3 CP3 CP2 CF3 CF2 CQCF=CF-CQ, CFCQ 2 CF-CF
2, CCQ. -CCQ F, CP3 CCQ
-CCQ2,P2CP''-CCQ2,CC
Q3 CP-CF2, CQ CCQ-CCl2 2
, CFCQ 2 CCR = CCQ2 , CF=
CHCQ,CCQ F2 CF=CHCQ,CC
Q-CH-CQ SCHP 2 C(12 -CCQ
2, C9CH-CCR2, CF2CI2C
CQ"CHCR,3 CP=CHCQ,CF
2 ΩCF=CF'2, BrCHT=CP2, C
F3 CBr=CHBrsCQ CBr=CH2
, CH2 BrCF=CC2 2 , -CBr=
CHz, CF2 CH=CHBr, BrCH-CH
F, CF2 BrCF-CF2, CF2 CF=C
F2, CP3 CF=CFCP3, CH=CFC
F3, CP2 = CFCF2 CHF 2, CF
2 CF±CH2, CF3 CH=CHCF3
, = CFCF2CH3 , CP2 = CPCIL2C
H3, C}h CH-CH2, CF3 CH=C
IC! h ,=CHCIh CH3 ,CH3 CF2
C) l=cH2, CFH2CH Showa CIICPH
2, CH3 CF2 CH attack CH3, CH2 −
CFCH2 CH3, CP3 (CP2) 2
CF=CP2, CF3 (CF2) a CF-C
Examples include F2.

The fluoroalkyl group in general formula (12) has 3 to 21 carbon atoms. Specifically, for example, C4F,
, (CF2)s CF-(CF:i)2, CBF1
7.C. Examples include F2 t.

Examples of the monomer represented by general formula (12) include CH3 f CH2 ""C-COO- C2 HA -C4
F9CHa CH2 ”C-COO- C2 H4 -Cs F
lyCH3 CH2 =C-COO- C2 H4-C+. P2
1 The above-mentioned monomers can be used alone or in combination of two or more.

By using the monomer represented by the general formula (1), it is possible to form a coating film with particularly excellent acid resistance, weather resistance, etc.
When the monomer represented by 2) is used, a coating film particularly excellent in water repellency can be formed.

Other polymerizable unsaturated monomers (C) include, for example:
The following (c-1) to (c-6) can be mentioned.

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

(c-2) Vinyl ethers and allyl ethers: e.g. ethyl vinyl ether, probyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t
Chain alkyl vinyl ethers such as ert-butyl vinyl ether, benzyl 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, phenyl vinyl ether , o-, m+, p-} aryl vinyl ethers such as ribinyl ether, aralkyl vinyl ethers such as penzyl vinyl ether, phenethyl vinyl ether, and the like.

(c-.3) Vinyl ester and propenyl ester:
For example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl caprate, and propenyl esters such as isobrobenyl acetate, isopropenyl propionate, etc. .

(c-4): Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, probyl acrylate, isobutyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, probyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate,
Alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms such as octyl methacrylate and lauryl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, methacryl Alkoxyalkyl esters having 2 to 18 carbon atoms of acrylic acid or methacrylic acid such as ethoxybutyl acid, and the like.

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

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

[Carboxy group-containing resin]

Typical examples of the resin include the fluorine-containing polymerizable unsaturated monomer (b), the carboxyl group-containing polymerizable unsaturated monomer (d), and optionally the hydroxyl group-containing polymerizable unsaturated monomer. Examples include polymers obtained by copolymerizing the monomer (a) and the other polymerizable unsaturated monomer (e).

Examples of the carboxyl group-containing polymerizable unsaturated monomer (d) include compounds represented by the following general formulas (13) and (14).

[In the formula, R3 represents a hydrogen atom or a lower alkyl group. R
4 represents a hydrogen atom, a lower alkyl group or a carboxyl group. R5 represents a hydrogen atom, a lower alkyl group or a carboxy lower alkyl group. ] [In the formula, R6 and m are the same as above. ] In the general formula (13), the lower alkyl group is:
Those having 4 or less carbon atoms, especially methyl group, are preferred.

Examples of the compound of general formula (13) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and the like.

Further, as an example of the compound of general formula (14), for example, 2-
Examples include carboxyethyl (meth)acrylate, 2-carboxyprobyl (meth)acrylate, and the like.

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

Furthermore, in addition to the above, resins obtained by reacting the hydroxyl group-containing resin with carboxylic anhydride (eg, maleic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride, etc.) can also be used.

[Isocyanate group-containing resin]

Typical examples of the resin include an isocyanate group-containing polymerizable unsaturated monomer (e), a fluorine-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomers as necessary. Examples include polymers having body (C) as a monomer component.

Examples of the isocyanate group-containing polymerizable unsaturated monomer (e) include monomers represented by the following general formulas (16) and (17).

R6 CH2-C-COO-eCnH2n+-NGO (1
6) [In the formula, R6 and n are the same as above. ] The monomer of general formula (16) above includes, for example, isocyanate ethyl (meth)acrylate.

or an alkyl group having 5 or less carbon atoms. ] The monomer of the above general formula (17) includes, for example, α,α-dimethyl-m-
Included is isobrobenyl benzyl isocyanate.

In addition to the above, a reaction product of 1 mol of the hydroxyl group-containing polymerizable unsaturated monomer (a) 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
Examples include -xylene diisocyanate, bis(4-isocyanate phenyl) sulfone, isobropylidene bis(4-phenyl isocyanate), lysine isocyanate, isophorone diisocyanate, and polymers and bullets 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.

[Silane group-containing resin]

Representative examples of the resin include, for example, a resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing silane compound described below, and a resin obtained by reacting the isocyanate group-containing resin with the hydroxyl group-containing silane compound described later. can be mentioned.

[Eboxy group-containing resin]

Typical examples of the resin include the fluorine-containing polymerizable unsaturated monomer (b), the epoxy group-containing polymerizable unsaturated monomer (f), and, if necessary, the other radically polymerizable monomers. Examples include a copolymer obtained by copolymerizing the saturated monomer (C), and a resin obtained by reacting the hydroxyl group-containing resin with the isocyanate group-containing epoxy compound described below.

As the epoxy group-containing polymerizable unsaturated monomer (f), 1
It is a compound containing an epoxy group and a radically polymerizable unsaturated group in its molecule. As a radically polymerizable unsaturated group,
For example, R6 CH2 -CC-N-CH2-CHCH2-0- CH2-CHO-, CH2-CI{- [wherein R6 is the same as above. ] Examples of the epoxy group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is R6 g CH2-CCOO- include compounds represented by the following general formulas (18) to (30). .

and Rgo may be the same or different.

W represents an integer from 0 to 10. ] The divalent hydrocarbon group having 1 to 8 carbon atoms can be selected from the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms.

Specific examples of the compounds represented by general formulas (18) to (30) include, for example: [In each of the above formulas, R6 is the same as above. R9 has 1 to 8 carbon atoms
represents a divalent hydrocarbon group. RI5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of monomers in which R6 and R9 are radically polymerizable unsaturated groups include the following general formulas (31) to (33).
) can be mentioned.

The radical polymerizable unsaturated group is CH2 [the above formula widths, R6 and R9 are the same as above. R6 and R
9 may be the same or different. ] General formula (31) ~
Specific examples of the compound represented by (33) include the following.

Examples of monomers include the following general formulas (34) to (36).
) can be mentioned.

[In each of the above formulas, R6 and R9 are the same as above. R6 and R
9 may be the same or different. ] General formula (34) ~
Specific examples of the compound represented by (36) include the following.

Examples of monomers in which the radically polymerizable unsaturated group is represented by the following general formulas (37) to (42)
) can be mentioned.

[In each of the above formulas, R6, R9, R10 and W are the same as above, and R6, R9 and RIG may be the same or different. ] Specific examples of the compounds represented by general formulas (37) to (42) include the following.

Examples of the epoxy group-containing unsaturated monomer having a radically polymerizable unsaturated group of cu, -CHCH20- include the following general formulas (43) to (4).
Examples include compounds represented by 6).

[In each of the above formulas, R6 and R9 are the same as above, and R6
and R9 may be the same or different. ] General formula (4
Specific examples of compounds represented by 3) to (46) include:
For example, the following can be mentioned.

As the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CHO-, for example, the following general formula (47
) to (49) can be mentioned.

[In each of the above formulas, R6 and R9 are the same as above, and R6
and R9 may be the same or different. ] General formula (4
Specific examples of compounds represented by 7) to (49) include:
For example, H etc. can be mentioned.

Examples of the epoxy group-containing unsaturated monomer having a radically polymerizable unsaturated group of CH2-CH1 include the following general formula (50):
Compounds represented by (52) can be mentioned.

R6 CH2=CH Rg C CH2
(50)\ / [In each of the above formulas, R6 and R9 are the same as above, and R9
may be the same or different. ] General formula (50) ~ (
Specific examples of the compound represented by 52) include the following.

Examples of radically polymerizable unsaturated groups include compounds represented by the following general formulas (53) to (57).

[In each of the above formulas, R6, R9 and RIG are the same as above, and R6 and R1. may be the same or different. ] Specific examples of the compounds represented by general formulas (53) to (57) include the following.

The compound (B) used in the resin composition (I) has one or more epoxy groups and one or more functional groups that react with the functional groups in the resin (A.) in one molecule. The functional group that reacts with the functional group in the resin (A) may be the same as the epoxy group.

When the functional group is the same as an epoxy group, it is necessary to contain two or more epoxy groups in one molecule.

Next, a representative compound (B) will be explained.

[Eboxy compound containing hydroxyl group]

Examples of the compound include the following general formulas (58) to (6).
Compounds represented by 8) can be mentioned.

Specific examples of the compounds represented by the general formulas (58) to (68) include: [R6, R9, R1 in each of the above formulas. and n are the same as above, R6, R9 and R1. may be the same or different. ] etc.

[Silane group-containing epoxy compound]

For example, compounds represented by the following general formulas (69) to (72) can be mentioned.

Represented by Y [wherein R6 and R9 are the same as above, and R9 may be the same or different.

Y is the same or different, a hydrogen atom, a hydroxyl group, a hydrolyzable group,
It represents an alkyl group, an aryl group, or an aralkyl group having 1 to 8 carbon atoms. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] In the general formulas (69) to (72), the hydrolyzable group includes the groups of the above general formulas (1) to (6). Also,
The alkyl group, aryl group, and aralkyl group having 1 to 8 carbon atoms include those exemplified above.

Specific examples of the compounds represented by formulas (69) to (72) include Sono OCHI OCHz and the like.

[Polyepoxy compound]

Compounds represented by the following general formulas (73) to (80) can be mentioned.

R6 C R1 H x C [In the formula, R6, R9 and W are the same as above, and R6 and R9 may be the same or different. R11 is the same or different and represents an alkyl group, an aryl group, or an aralkyl group having 1 to 8 carbon atoms. R 12 is the same or different and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] Specific examples of the compounds represented by general formulas (73) to (80) include H. Examples include C.

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

Adducts with anate compounds (polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate; Organic diisocyanates themselves such as aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or adducts of each of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc.; Polymers of each organic diisocyanate as mentioned above, as well as isocyanade-Bauret bodies, etc., can be mentioned, and representative examples of commercially available products include "Parnock D-750",
-800, DN-950, -970 or 15-45
5" [The above are Dainippon Ink & Chemicals ■ products], [Desmodule L, NHL, I L or N3390J
(Product from Bayer, West Germany), [Takenate D-1]
02, -202, -110N or -123NJ
(Product adopted by Takeda Pharmaceutical Company), “Coronate LSMLSEH
Or 203J (Japan Polyurethane Industries ■product)
, "Duranate 24A-90C Number average molecular weight 90 obtained by esterification reaction of broban and 1,4-butanediol etc.
Examples include those obtained by oxidizing an esterified product of 0) with peracetic acid or the like.

[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 the compound represented by the general formula (58) and hexamethylene diisocyanate - A reaction product of the compound represented by the general formula (65) and isophorone diisocyanate - A reaction product of the compound represented by the general formula (67) and isophorone diisocyanate Reactant/Reactant of general formula (68) and xylene diisocyanate n HO-R9 -si-y I Y etc. can be mentioned.

The compound (C) used in the composition (I) 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. When the functional group is the same as a silane group, it is necessary to contain two or more silane groups in one molecule.

Next, a representative compound (C) will be explained.

[Hydroxyl group-containing silane compound]

Compounds represented by the following general formulas (81) to (83) can be mentioned.

[In each of the above formulas, R9, R,. and Y are the same as above, and R9, RIO 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 compounds represented by general formulas (81) to (83) include OCH3 HO (CH2 ) 3 Si OCH30
C H 3 Y'Y'-81-Y'Y' CH. C.I. etc. can be mentioned.

[Polysilane compound]

Hydrolyzable groups directly bonded to silicon and Si
A compound having two or more groups selected from OH groups, specifically, for example, the following general formulas (84) to (86)
Compounds represented by can be mentioned.

Y' R1+ I R++ 81-Y'[Y' (86.) [In each of the above formulas, Rl+ is the same as above, and Rl1 may be the same or different. Y′ are the same or different;
Indicates a hydrogen atom, hydroxyl group, or hydrolyzable group. ] Specific examples of the compounds represented by general formulas (84) to (86) include dimethyldimethoxysilane, dibutyldimethoxysilane, diisopropoxysilane, diphenyldibutoxysilane, diphenylethoxysilane, diethyldisilanol, dihexyldisilanol methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol, tetra Examples include methoxysilane, tetraethoxysilane, tetrabioxysilane, tetraacetoxysilane, diisopyroxydibareoxysilane, and tetrasilanol.

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

[Epoxy group-containing silane compound]

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

[Isocyanate group-containing silane compound] Examples include compounds represented by the following general formulas (87) and (88).

OCNCH 2 81 (OC2 H5) 3,
OCN-R9-81-Y (87)
Y Y OCN-Si-Y (88)
Y [In each of the above formulas, R9 and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (87) and (88) include OCNC3 H6 Si (OC2 H5 ) 3
, OCNC2 114 31 (OCH 3 ) 3
, OCNC3 H6 Si (OC2 Is)
2, C}+3 0CNC2. lI4St (OCII 3) 2
, CH3 OCNCH 2 Si (OCH 3 ) 3 , OC
NCH281 (OC2Hs)2, CH
3OCNCH2Si(OCH3)3,C
H3 I OCN- C3 lb; -SIN-( C2 H
s) 2CH3CH3CH3''OCN-C3Is-SiON(C3Hv
) 2CH 3 0CN- C3 1{s -SiOCCH 3CH
3 The resulting compound can be used.

Specifically, the following can be mentioned.

A reaction product of general formula (81) and hexamethylene diisocyanate or tolylene diisocyanate, for example, OCN-Si(OCH3) 3 0CN-S1 (OCCH3 ) 3 OCN St OCC4H9OCCib In addition to the above, the silane compound containing a hydroxyl group may also be used. Examples include reacting with the polyisocyanate compound.

Furthermore, a metal condensate of the epoxy group-containing silane compound and, for example, the polysilane compound can also be used. Examples of the compound include:

[Merkabuto group-containing silane compound]

Compounds represented by the following general formulas (8) can be mentioned.

(8) [In the formula, R9 and Y are the same as above. Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compound represented by general formula (88) include OC2 H5 HS C3 H6 -Si-OC4 H90C2
H, Is-C3 Hs 81. (OCCHa) 2
CH3 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, Is
-C, H2, -OHSm are the same as above. ), for example, and the like.

[NH group- or NH2 group-containing silane compound] The following general formula (
Examples include compounds represented by (90) and (91).

Y H2N-R9-Si-Y (90)
Y Y HN (R9 Si Y) 2
(9 1)Y [In each of the above formulas, R9 and Y are the same as above. Y and R9 may be the same or different. However, at least one of Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (90) and (91) include 0CH3H2N(CH2)3St-OCH3
CH. 0 O.C. H, `` I OC, H, etc.

In addition, in addition to the above, general formulas (89) and (90
) and the above-mentioned polysilane compounds can also be used. . Examples of the condensate include oCH3.

[Unsaturated group-containing silane compound]

It is a compound having at least one silane group and a radically polymerizable unsaturated group in one molecule.

As the radically polymerizable unsaturated group, for example, R6 l C. H2　-CCOO- R6 [ C}{2g=. C1 CH2-CHO- CH2 - CHCH2 01 [In the formula, R6 is the same as above. ] etc. can be mentioned.

Examples of the silane group-containing polymerizable unsaturated monomer in which the R6 l radically polymerizable unsaturated group is CH2=CCOO- include a compound represented by the following general formula (91).

[In the formula, R6, R, and Y are the same as above, and Y may be the same or different. However, at least 1 of Y!
represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compound represented by general formula (91) include:
For example, γ-(meth)acryloxypyltrimethoxysilane, γ-(meth)acryloxypyltriethoxysilane, γ-(meth)acryloxypyltripboxysilane, γ-(meth)acryloxypylmethyldimethoxysilane, γ- -(meth)acryloxypyrumethyldiethoxysilane, γ-(meth)acryloxypyrumethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxysilane , γ
-(meth)acryloxybutyl phenyldibutylpoxysilane, γ-(meth)acryloxib-pyrphenylmethylmethoxysilane, γ-(meth)acryloxib-pyrphenylmethylethoxysilane, γ-(meth)acryloxib-pyrphenylmethylmethoxysilane , γ-(meth)acryloxib-bilphenylmethylethoxysilane, γ-(meth)acryloxib-biltrisilanol, γ-(meth)acryloxib-pyrmethyldihydroxysilane, γ
-(meth)acryloxybutylphenyldihydroxysilane, γ-(meth)acryloxybutylphenyldihydooxysilane, γ-(meth)acryloxybutylphenylmethylhydroxysilane, CHI 0 0CCH. CHs, CJs, etc. can be mentioned.

Examples of the silane group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (92) to (94).

[In the formula, R6, R,. and Y are the same as above, and Y
may be the same or different. However, at least 1 of Y
Each represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of the compounds represented by general formulas (92) to (94) include the following.

As the silane group-containing polymerizable unsaturated monomer in which the R6 l radically polymerizable unsaturated group is CI{2=C1, for example, the following general formula (9
Compounds J represented by 5) and (96) can be mentioned.

R6 Y C H 2 = C - St - Y heat Y CH2 = C-RIG -81-Y
(96)Y [wherein R6, R,. and Y are the same as above, and Y
may be the same or different. However, at least 1 of Y
Each represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (95) and (96) include, for example, CH2 = CHSi (OCH 3) 3CH2 =C
HS1 (002 H s ) 3CH2 =CHSi
(OCH 3) 2 CH3CH2 =C}ISI
(CH3) 2 0CH 3CH2 =CHCH2
Si (OCR 3 ) 3CH2 =CHSi (
OCCH3 ) 3CH2 =CHCH2 81 (
OCCH3 ) 3 radically polymerizable unsaturated group is cH2=
As the silane group-containing polymerizable unsaturated monomer of CHO-,
For example, compounds represented by the following general formulas (97) and (98) can be mentioned.

Y CH2 =CHO-R,. -Si-Y (97
)Y [wherein, R1. and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] CH2 = CIISj (CHh) 2 N(CI
-13) 2 Specific examples of compounds represented by general formulas (97) and (98) include: CH3HCH3CH2=CHO(CH2)2Si-OCH3
CH3 CH3 CH3 etc. can be mentioned.

Examples of silane group-containing polymerizable monomers in which the radically polymerizable unsaturated group is CH2=CHCH20- include CH2-CHCH20 represented by the following general formulas (99) and (100).
-Si-Y (99)l Y [In the formula, RIG and Y are the same as above, and Y may be the same or different. However, at least one Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] As a specific example of the compound represented by the general formulas (99) and (100), for example, OCJm "CHx"CHCH*0- (CHJ*-Si-OC2H
*l CH. etc. can be mentioned.

In addition to the silane group-containing polymerizable unsaturated monomer, the silane group-containing polymerizable unsaturated monomer may be reacted with, for example, a polysilane compound (for example, a compound represented by general formulas (84) to (86)). A polysiloxane unsaturated monomer having a silane group and a polymerizable unsaturated group obtained by this method can also be used.

Specific examples of the polysiloxane unsaturated monomer include the compound of the general formula (91) and the general formulas (84) to
(86) and the former 30 to 0
．． 001 mol% of the latter and 70 to 99.999 mol% of the latter (such as those described in JP-A-62-275132) and the following compounds.

CI” OCI{. Alternatively, a hydroxyl group can be generated through a complementary reaction between the resin (D) and the compound (C), or a polyvalent reaction product between the resin (D) and the compound (C) can be generated. It can be introduced by reacting with alcohol.

The resin (D) has a functional group that reacts with the compound (C) and an epoxy group, and it is desirable that the functional group has poor reactivity with the epoxy group in the resin (D). It may be the same as the group. Representative examples of the resin (D) having the functional group include the fluorine-containing polymerizable unsaturated monomer (b), the epoxy group-containing polymerizable unsaturated monomer (f), and the hydroxyl group-containing polymerizable monomer (f). Examples include copolymers obtained by copolymerizing the saturated monomer (a) and, if necessary, other polymerizable unsaturated monomers (C). Since the copolymer contains a hydroxyl group and an epoxy group, some of the functional groups are used to form a compound (C) (for example, the above-mentioned isocyanate group-containing silane compound, mercabuto group-containing silane compound, amino group-containing silane compound, respectively). Resin composition (II) can be obtained by reacting with a silane compound (silane compound, etc.).

Resin composition (III) The hydroxyl group in resin composition (III) is the same as that in resin composition (1).
In the same manner as in the case of (2), the hydroxyl group may be introduced into the resin (E) in advance, or the hydroxyl group may be generated by a complementary reaction between the resin (E) and the compound (B), or furthermore, the hydroxyl group may be generated by a complementary reaction between the resin (E) and the compound (B). It can be introduced by reacting a reaction product of E) and compound (B) with a polyhydric alcohol.

The resin (E) has a functional group that reacts with the compound (B) and a silane group, and it is desirable that the functional group has poor reactivity with the silane group in the resin (E). It may be the same as the group.

Representative examples of the resin (E) having the functional group include the fluorine-containing polymerizable unsaturated monomer (b), the unsaturated group-containing silane compound, and the hydroxyl group-containing polymerizable unsaturated monomer (a).
) and other polymerizable unsaturated monomers (C) as necessary
Examples include copolymers obtained by copolymerizing these. Since the copolymer contains a hydroxyl group and a silane group, a part of the functional group is used to form a compound (B) (for example, the above-mentioned isocyanate group-containing silane compound,
The resin composition (II
I) can be obtained.

The resin composition of the present invention has a fluorine content of 1 to 7, using the fluorine-containing polymerizable unsaturated monomer (b) as a sole component.
It can be contained in a range of about 0% by weight, preferably about 5 to 60% by weight. If the content is less than the above range, the coating film will have poor scratch resistance, weather resistance, stain resistance, acid resistance, etc., while if it exceeds the above range, the unit price of the resin composition will be too high to be practical. .

The resin composition of the present invention has an average of 1 or more hydroxyl groups, preferably about 2 to 40 hydroxyl groups, an average of 1 or more epoxy groups, preferably 2 to 40 hydroxyl groups, and an average of 1 silane group in one molecule. The number can preferably be 2·' to 40 or more. If the hydroxyl group, epoxy group, and silane group are below the above range, the curability will be insufficient and a coating film will be formed that is inferior in xylene resistance, hardness, mechanical properties, etc., which is not preferable.

In the resin composition of the present invention, when a resin composition into which an alicyclic epoxy group is introduced as the epoxy group is used, the addition reaction of the epoxy group to the hydroxyl group is rapid, and the curability of the coating film is improved. It will be done.

In the resin composition of the present invention, when the monomer represented by the general formula (ii) is used as the fluorine-containing polymerizable unsaturated monoprecious substance (b), the polymer formed from this monomer has a main chain Since it has a structure in which fluorine atoms are bonded, it exhibits excellent effects such as weather resistance, and when the monomer represented by general formula (12) is used, fluorine atoms are bonded to the side chain, resulting in water repellency, etc. Demonstrates excellent effects.

Each of the above-mentioned ingredients can be obtained by conventionally known methods. That is, the reaction between a hydroxyl group and a cyanate 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 about 130°C.

For the condensation reaction of silane groups, heating at about 40 to 150° C. for about 1 to 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 40 to 180°C in the presence of a radical polymerization initiator. can. Reaction time is 1 to 24
It may be about an hour. Further, as the organic solvent, one that is inert to the monomer or compound used, such as an ether solvent, an ester solvent, a hydrocarbon solvent, etc. can be used. When using a hydrocarbon solvent, it is preferable to use another solvent in view of solubility. In addition, as the radical polymerization initiator, any commonly used initiator can be used, and examples include peroxides such as benzoyl peroxide, t-butyl baroxy-2-ethylhexanoate, azoisobutyl Examples include azo compounds such as nitrile and azobisdimethylvaleronitrile.

The resin compositions (I) to (m) used in the present invention are about 10
00-200000, preferably about 3000-gooo
It has a number average molecular weight in the range of o.

If the number average molecular weight is significantly smaller than about 1,000, the coating film may have poor scratch resistance, stain resistance, weather resistance, acid resistance, etc., while if it significantly exceeds about 200,000, the resin composition may deteriorate. It is not preferred because storage stability, painting workability, finished appearance, etc. may be poor.

In the present invention, some of the functional groups (e.g., hydroxyl group, epoxy group, silane group, etc.) possessed by the resin compositions (I) to (III) described above are used to create other resins (e.g., vinyl resins). , polyester resin, urethane resin, silicone resin, etc.) can also be used. Each molecule of the modified resin composition contains:
It is necessary to have one or more hydroxyl group, epoxy group, or silane group on average.

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

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

The metal chelate compound is preferably an aluminum chelate compound, a titanium chelate compound, or a zirconium chelate compound. 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.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as diacetone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β
- Favorable results are obtained using diketones.

The aluminum chelate compound has, for example, the general formula RI3 0 A Q O R,3 [wherein RI3
are the same or different and represent an alkyl group or an alkenyl group having 1 to 20 carbon atoms. ] It is suitably prepared by mixing the above-mentioned compound capable of forming the keto enol tautomer at a molar ratio of about 3 moles or less per mole of the aluminum alkoxide represented by the formula, and heating as necessary. be able to.

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

Examples of the aluminum alcoholates represented by the general formula (101) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-proboxide, aluminum tri-isobroboxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec -butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisobroboxoxide, aluminum tri-tert-butoxide, etc.
Preferably, eC-butoxide, aluminumtri-n-butoxide, etc. are used.

The titanium chelate compound has, for example, the general formula [wherein W and Rl3 have the same meanings as above. ] The above-mentioned compound capable of forming the keto enol tautomer is mixed with the mole of Til in the titanates represented by the above formula at a molar ratio of usually about 4 moles or less, and is suitably prepared by heating if necessary. can do.

Titanates represented by the general formula (102) include those in which W is 1, such as tetramethyl titanate, tetraethyl titanate, tetra n-probyl titanate,
Tetraisobutyl titanate, Tetra n-butyl titanate, Tetra isobutyl titanate-1, Tetra t
These include ert-butyl titanate, tetra-n-bentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, and especially tetraisobutyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and tetra-isobutyl titanate. Suitable results are obtained using tert-butyl titanate and the like. In addition, for those where W is 1 or more, tetraisobutyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-t
Dimers to 11-mers (w-1 to w-10 in general formula (102)) of ert-butyl titanate give preferable results.

The zirconium chelate compound has, for example, the general formula [wherein W and RI3 have the same meanings as above. ] Preferably prepared by mixing the above-mentioned compound capable of forming the keto enol tautomer at a molar ratio of about 4 mol or less to the Zrl mole in the zirconate represented by the formula, and heating as necessary. can do.

Examples of the zirconates represented by the general formula (103) include tetraethylzirconate, tetran-propylzirconate, tetraisobutylzirconate, tetran-butylzirconate, tetrasee-butylzirconate, and tetratert-butylzirconate. Tetra n-pentyl zirconate, Tetra ter
t-bentyl zirconate, tetra tert-hexyl zirconate, tetra n-heptyl zirconate,
Tetral n-octyl zirconate, Tetral n-stearyl zirconate, etc., especially Tetral n-probyl zirconate, Tetral n-probyl zirconate,
Suitable results are obtained using tetraisobutylzirconate, tetran-butylzirconate, tetrasec-butylzirconate, tetratart-butylzirconate, and the like. Also, for those where W is 1 or more,
'2-mer to 11-mer (general W-1 to 10) in formula (10B) give suitable results. Also,
It may also contain a structural unit in which these zirconates are associated with each other.

Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(II-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, and tris(II-butylacetoacetate). Aluminum, Isopropoxybis(ethylacetoacetate)aluminum, Diisopropoxyaluminum, Tris(acetylacetonate)
Aluminum, tris(probionyl acetonato)aluminum, tris(ethyl acetonate)aluminum, diisopropoxypoxyprobionyl acetonatoaluminum, acetylacetonatoφbis(propionyl acetonate)aluminum, monoethyl acetoacetate bis(
acetylacetonato)aluminum, tris(isopropylate)aluminum, tris(see-butyrate)aluminum, diisopropyrate mono-SeC
- Aluminum chelate compounds such as butoxyaluminum, tris(acetonatoacetonate)aluminum; diisobroboxy bis(ethylacetoacetonato) titanate, diisopropoxy bis(acetylacetonato)
Titanium chelate compounds such as titanate, diisopoquin bis(acetylacetonato) titanate; tetrakis(acetylacetone)zirconium, tetrakis(II-propylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate) Zirconium chelate compounds such as zirconium 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. The blending amount of the crosslinking reaction curing agent is 100% of the solid content of the resin composition.
It is appropriate that the amount is about 0.01 to 30 parts by weight.

If the amount is less than this range, crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is 0.1 to 10 parts by weight, and the more preferred amount is 1 to 5 parts by weight.
It is a heavy world club.

The curable composition of the present invention contains the above-mentioned chelating agent, preferably acetoacetic esters, β-diketones, etc., in order to improve storage stability. compounds can be added.

The resin composition and curable composition of the present invention can be used widely depending on the purpose. For example, it can be used as a curing agent component in compositions containing itself as a main vehicle component and other resins (eg, hydroxyl group-containing resins or carboxyl group-containing resins).

The coating composition of the present invention may optionally contain a number-average molecule ffi containing at least two oxirane groups in one molecule.
A low molecular weight compound of 2000 or less can be blended. This low molecular weight compound becomes a reactive diluent,
By adding it to a paint composition, it is possible to lower the viscosity of the paint and increase the solid content, and since there are few by-products during curing, it is possible to obtain a high solid paint with excellent uniform curing properties. Can be done. Also, during curing, there is little sagging, resulting in a coating film with excellent smoothness.

A number average molecular weight of 2000 containing at least two oxirane groups in one molecule that can be used in the present invention
Examples of the following compounds include compounds represented by the following formulas, adducts of o -CH20H and the following polyisocyanate compounds (useable polyisocyanate compounds include, for example, hexamethylene diisocyanate or trimethylhexamethylene diisocyanate). aliphatic diisocyanates such as; cycloaliphatic diisocyanates such as xylylene diisocyanate or isophorone diisocyanate; organic diisocyanates such as aromatic diisocyanates such as 1-lylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or each of these organic diisocyanates; Additives of diisocyanates and polyhydric alcohols, low molecular weight polyester resins, water, etc., or polymers of each of the above-mentioned organic diisocyanates, and isocyanates.
Examples of typical commercially available products include “Parnock D-750, -800, D
N-950, -970 or 15. -4554C
The above are Dainippon Ink Chemical Industry Products], ``Desmodule L, NHLSIL or N3390J [West German Bayer product], ``Takenate D-102, -202
, -LION or -123N” [Takeda Pharmaceutical Company ■
Product], [Coronate, HL, EH or 203J
(product of Nippon Polyurethane Industries) or Duranate 24A-90CXJ (product of Asahi Kasei Industries, etc.); Examples include those obtained by oxidizing an esterified product (with a number average molecular weight of 900 obtained by a chemical reaction) with peracetic acid or the like.

In addition to the compounds having an alicyclic oxirane group as described above, compounds having a non-alicyclic oxirane group such as diglycidyl ether, 2-glycidyl phenyl glycidyl ether, etc. can also be used.

It is important that the molecular weight of the metal compound having two or more oxirane groups in one molecule is a number average molecular weight of 2,000 or less. If the number average molecular weight fl exceeds 2000, the compatibility with the base resin used in combination decreases, making it impossible to form a coating film with excellent finish and coating performance.

The compounding amount of the compound having the oxirane group is determined from the above base resin 1. It is appropriate that the amount is about 0 to 100 parts by weight, preferably about 10 to 60 parts by weight.

The coating composition of the present invention may further contain, if necessary, an epoxy group-containing resin such as Ebicor 1001 (manufactured by Shell Chemical Co., Ltd.) or a hydroxyl group-containing resin such as styrene allyl alkote copolymer. The content n of these resins in the coating composition is preferably about 10% by weight or less.

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

When using the coating composition of the present invention as a top coat, for example, when using it as a top solid color paint, a top clear paint for 1 bake coating in 2 coats, and a top clear paint for 3 coats/2 bake coatings, for example, 100 parts by weight of base resin, 0.0 parts by weight of chelate compound. Appropriate amounts are 1 to 30 parts by weight and 0 to 100 parts by weight of the colored pigment. As the coloring agent, both inorganic and organic highly weather-resistant coloring pigments used in conventional top coatings for automobiles can be used, such as inorganic pigments such as rutile titanium oxide or carbon black, Organic pigments such as quinacridone-based pigments such as quinacridone red, azo-based pigments such as pigment red, and phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green can be used.

When used as a 2-coat/1-bake coat clear paint or a 3-coat/2-bake coat clear paint, it is usually used without adding a coloring pigment.

Among the top coat paints, when used as a hair coat paint for 2 coats/1 bake coat or a metallic paint for 1 coat/1 bake coat, the composition is base resin 100%
Suitable parts by weight include 0.1 to 30 parts by weight of the chelate compound, 2 to 36 parts by weight of the metallic pigment, and 0 to 40 parts by weight of the colored pigment. Known metallic pigments can be used, such as aluminum, copper, micaceous iron oxide,
Scale-like metallic powder of bronze, stainless steel, etc. can be used, and as the coloring pigment, any of the above-mentioned ones can be used. In addition, as a modified resin for rheology control to adjust the arrangement of metallic pigments and improve the metallic feel, an acrylic dispersion with a core crosslinked by heterogeneous polymerization obtained by a known method,
Up to about 20 parts by weight of cellulose acetate butyrate and the like can also be blended.

Further, when the coating composition of the present invention is used as an intermediate coating for automobiles, the composition is as follows: 100 parts by weight of the base resin, 0.1 to 30 parts by weight of the chelate compound, and 5 to 150 parts by weight of the pigment.
Fi part and about 0 to 100 parts by weight of a low molecular weight compound having two or more oxirane groups in one molecule are suitable.

As the pigment, inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and clay, and organic pigments for coloring can be used.

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

The coating viscosity at the time of painting is as follows:
About 15 to 35 seconds (Ford Cup No. 4, 20℃)
, when used as a top coat, for about 12 to 30 seconds (
Ford Cup No. 4.20° C.), and may be appropriately selected depending on the coating machine, type of solvent, coating conditions, etc.

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

The coating composition of the present invention can be prepared, for example, by electrodepositing a primer on a chemically treated copper plate, and applying an intermediate coating (sometimes omitted).
, a paint system in which a top coat is applied sequentially, a primer suitable for various plastic materials is applied, and after drying, an intermediate coat (sometimes omitted) and a top coat are applied in sequence, etc. Or it can be used as a top coat.

When used as an intermediate coating, the appropriate film thickness is about 25 to 60 μm based on the film thickness after drying. On the other hand, when used as a top coat, the film thickness is based on the film thickness after drying: 1 coat/1 bake coat solid color paint, 1 coat
When used as a metallic color paint for coat/1 bake coat, top clear paint for 2 coat/1 bake, top clear paint for 3 coat/2 bake, etc.
About 0 to 60 Itrn, preferably 30 to 4
Approximately 0 μm, when used as a 2-coat/1-bake metallic base coat paint, approximately 10 to 25 μm,
A suitable thickness is preferably about 10 to 20 μm.

The coating composition of the present invention can be easily crosslinked and cured at a low temperature of 140°C or lower. For example, when cured at room temperature without any heating, it usually takes about 8 hours to 7 days to fully cure. When heating to about 40 to 100°C, it can be sufficiently cured in about 5 minutes to 3 hours.

Function The reason why the curable composition of the present invention has excellent low-temperature curability is considered to be as follows. That is, as the first reaction, the metal chelate compound reacts with the silane group to form the following bond.

;Aa-o-sx- Next, this bond coordinates to a silanol group (for alkoxysilane groups, aceticoxysilane groups, etc., becomes a silanol group due to moisture in the air), becoming ee and forming a silanol group. polarizes. This polarized silanol group reacts with the epoxy group to form H 2 . This then reacts with the hydroxyl group to form -c-o-c
-cOH. This reaction between the epoxy group and the hydroxyl group proceeds at a relatively low temperature.

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

The fluorine component in the curable composition of the present invention is poorly compatible with components containing alkoxy groups and epoxy groups, and there is no risk of inhibiting the reaction between alkoxy groups and epoxy groups.
Excellent curing properties can be achieved. Moreover, the fluorine atoms chemically bonded to the cured product are chemically stable against external contributions such as light, heat, water, acids, etc., and it is possible to obtain a cured product with low surface energy.

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

(1) A coating film having a high degree of smoothness and sharpness can be obtained. In other words, since the main curing reaction is an ionic polymerization reaction and an addition reaction, the generation of reaction by-products is extremely small, and the volume shrinkage during the coating film curing process is small (and there is no slight unevenness (chirpy skin)). A coating film with a high degree of smoothness can be obtained. Therefore, the image clarity is also excellent.

(2) One-component paint with good low-temperature curing properties. In the case of a baking time of 30 to 40 minutes, a sufficient crosslinking reaction occurs even at a temperature of about 80°C.

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

■ Extremely good acid resistance. That is, the basic resin skeleton has a C-F bond with excellent chemical stability, and the crosslinking points have a structure that is resistant to acids, so the acid resistance is extremely good. Therefore, stains caused by acid rain, dullness, etc.
No problems such as etching occur.

■ Strong stain resistance. That is, it is highly resistant to various pollutants due to its water repellency based on the dense crosslinking density, polysiloxane bonds present in the base resin, and fluorine components.

(6) Good water repellency. That is, due to the polysiloxane bond and fluorine component present in the base resin, the resin has high hydrophobicity and good water repellency.

In particular, the fluorine component in the side chain of the base resin lowers the surface energy of the coating film, and exhibits high water repellency, especially as a coating film for automobiles.

(″f) Good scratch resistance. Good scratch resistance due to the synergistic effect of the frictional resistance reducing effect based on the dense crosslinking density and the polysiloxane bonds and C1F bonds present in the base resin.

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

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

EXAMPLES Production examples, working examples, and comparative examples are given below to make the present invention even clearer.

Production Example 1 [Production of copolymers (a) to (d)] Volume ffi4
001rlQ stainless steel autoclave with a stirrer was charged with 40 parts by weight of CH2-CHOC4H80H 200 parts by weight of methyl isobutyl ketone 2 parts by weight of azobisisobutyronitrile 0.5 parts by weight of sodium borate, followed by nitrogen purging, solidification by cooling, and desorption. After thinking about it,
50 parts by weight of CF2=CFCQ was introduced into the autoclave, and the temperature was gradually raised until the internal temperature of the autoclave reached 60°C. Thereafter, the reaction was continued with stirring for 16 hours or more, and when the internal pressure of the autoclave decreased to below ikg/cJ, the autoclave was ice-cooled to stop the reaction. The obtained resin solution was poured into excess hebutane to precipitate the resin, and then washed and dried.
Resin (a) of g was obtained. Yield 92%. The number average molecular weight by GPC was 5,500. The obtained resin was dissolved in the same amount of xylene to obtain a resin solution containing 50% nonvolatile components.

Copolymers (b) to (d) were obtained in the same manner.

Table 1 shows the amount (parts by weight) of the single n substance and the number average molecular weight (Mn) of the copolymer.

Table 1 Further, a production example of macromonomer A is listed below.

Methyltrimethoxysilane H3 C S i (OC H3 ) 32720
r (20mQ) Vinyltrimethoxysilane 148gCH2 -C
HS t (OCH3)3 (1 mol) deionized water 1134g 36% hydrochloric acid
2g hydroquinone
A mixture of 1 g of the above components was reacted at 80° C. for 5 hours to remove water and solvent. The obtained polysiloxane macromonomer had a number average molecular weight of 2000, and had on average one vinyl group (polymerizable unsaturated group) and four hydroxyl groups per molecule.

The amount blended in the examples is the amount of the active ingredient as a macromonomer.

Production Example 2 [Production of copolymers ce> and (f)] An acrylic copolymer fabric having the composition (parts by weight) shown in Table 2 was obtained by a conventional acrylic copolymer fabric synthesis method. Both are xylene solutions with a non-volatile content of 50% by weight. Table 2 shows the number average molecule m (Mn) determined by GPC.
Also listed.

In addition, the FM-3 monomer is a hydroxyl group-containing cabrolactone-modified methacrylic ester, and has an average molecular weight of ! 472,
The theoretical hydroxyl value is 119 K O Hmg/g [manufactured by Daicel Chemical Co., Ltd.].

Table 2 Production Example 3 [Production of copolymer (1)] In a glass flask with a stirrer having a capacity of 4001 TIf2,
Copolymer (a) solution (nonvolatile content 50%) 200 parts by weight (CH3 0) a SiC3 Hs NCO25 parts by weight 50 polymer parts xylene 75 parts by weight were charged,
The reaction was continued under stirring at 0° C. for 5 hours.

In the infrared absorption spectrum, the absorption of NGO groups disappeared, confirming that -OH groups and polymer (1) were obtained.

Production Example 4 [Production of copolymer (2)] In a glass flask with a capacity of 400 mQ and equipped with a stirrer, 200 parts by weight of copolymer (b) solution (non-volatile content 50%) (C2 H50) 2 (H3 C)SiC 3 H
s NCO 15 parts by weight 200 parts by weight (C}l a COO) 3SiC 3 H s NCO
2 5 parts by weight 25 parts by weight of xylene were charged, and while stirring at 90°C for 5 hours, -OH groups and -
The addition reaction of the NCO group was continued. In the infrared absorption spectrum, the absorption of -NCO group disappears, so -O
H group, S i (OCR3) 3 groups, xylene
55 parts by weight was charged, and the addition reaction of 10H group and 1NGO group was continued at 90°C for 5 hours with stirring. In the infrared absorption spectrum, the absorption of NCO groups disappears,
Therefore, -OH group, S L (CH3)
(OC2H was confirmed.

Production Example 6 [Production of copolymer (4)] In a glass flask with a volume fi of 400 + 112 and equipped with a stirrer,
It was confirmed that 200 parts by weight (2) of copolymer (d) solution (nonvolatile content 50%) was obtained.

Production Example 5 [Production of copolymer (3)] In a glass flask equipped with a stirrer and having a volume of 400 ml,
Copolymer (C) solution (nonvolatile content 50%) 40 parts by weight xylene 40 parts by weight was charged, 9
The reaction was continued under stirring at 0° C. for 5 hours.

In the infrared absorption spectrum, the absorption of -NGO group disappeared, confirming that 10H group, polymer (4), was obtained.

Production Example 7 [Production of copolymer (5)] Volume fl400m! Into a glass flask equipped with a stirrer in Step 2, add 200 parts of copolymer (e) solution (non-volatile content 50%) and 15 parts by weight (C2 H5 0) 3 Si C3 Hs NCO.
Add 20 parts by weight of 5 parts xylene, 9
The reaction was continued under stirring at 0° C. for 5 hours.

In the infrared absorption spectrum, the absorption of the -NGO group disappeared, confirming that -OH group and polymer (5) were obtained.

Production Example 8 [Production of copolymer (6)] In a glass flask with a stirrer and a volume ffi of 400 mQ, 200 parts by weight of copolymer (f) solution (non-volatile content 50%) (CH3 Coo)2 SIC3Hs SHCH3
Prepare 20 parts by weight of xylene, 9
The reaction was continued under stirring at 6° C. for 9 hours.

In the infrared absorption spectrum, it was confirmed that the copolymer (6) having an -OH group, 0 CH3, was obtained because the absorption of one SH group disappeared.

Example 1 A top coating for automobiles was prepared using the copolymer obtained in the above production example. As top coats, solid color (white) and 2CIB (2 coats, 1 bake) clear coats were prepared. In addition, base coat A was manufactured as a base coat for 2CIB.

Preparation example of solid color (white) (Paint No. S -
1 to S-7) are shown in Table 3. Titanium oxide was dispersed in a copolymer solution for 1 hour using a paint shaker. In the case of a solid color paint, the amount of pigment compounded gold was 80 parts by weight based on 100 parts by weight of resin solid content. The total formulations of the copolymers and dispersion polymers shown in Table 3 are all weight % of the active ingredient (resin content). In addition, the amount of pigment and metal chelate compound is % by weight (p
HR). At this time, the following chelate compounds were used.

・Chelate compound I...aluminum tris (acetylacetone) ・Chelate compound ■...zirconium tetrakis (acetylacetone) ・Chelate compound ■...titanium diisopoxybis(ethyl acetoacetate) Preparation example of clearcoat for 2CIB (Paint No. .M-1
~M-10) are shown in Table 4. The meanings of the numerical values in the table are the same as in the case of solid color.

Furthermore, an example of manufacturing a base coat (base coat A) to be combined with the base coat for 2CIB will be shown.

[Production of siloxane macromonomer]

Methyltrimethoxysilane 2720g (20mol) γ-methacrylicoxypropylene 256grutrimethoxysilane (1mol) Deionized water
1134g 60% hydrochloric acid
2g Hydroquinone 1g A mixture of the above components was reacted at 80'C for 5 hours. The obtained polysiloxane macromonomer had a number average molecular weight of 2,000, with an average of one vinyl group per molecule (
It had a polymerizable unsaturated group) and four hydroxyl groups.

A copolymer was produced using the obtained macromonomer.

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

Using the obtained copolymer, a metallic base for 2CIB coating having the following composition was prepared. The compounded metal is indicated by solid weight.

Above copolymer 95 parts Cellulose acetate butyrate 5 parts Aluminum paste #55-519
13 parts [manufactured by Toyo Aluminum ■] 1 part aluminum/lisacetylacetone] This was then mixed with toluene/Swazol #1500 [trade name, manufactured by Maruzen Sekiyu ■] = 80/20 mixed thinner, 1 part
The viscosity was adjusted to 3 seconds (Ford Cup No. 4, 20°C) and used for coating.

Incidentally, titanium oxide JR-602 (manufactured by Teikoku Kako ■) was used as the titanium white, and the following alicyclic oxirane group-containing compound was used as the oligomer A.

Test Example 1 A chemical conversion treated dull steel plate was coated with approximately 25 μm of epoxy resin-based cationic electrodeposition paint, heated and cured at 170°C for 30 minutes, and then coated with Rugabake AM (trade name, manufactured by Kansai Paint ■, polyester resin) as an intermediate coating. / melamine resin-based automotive paint] was applied to a dry film thickness of approximately 30 μm and baked at 140°C for 30 minutes.
Material A was prepared by water-sanding the painted surface with sandpaper, draining it to dry, and wiping the painted surface with petroleum benzene.

Top coat solid color (white) S-1 created in Example 1
～S-7 was heated with Swazol #1000C (trade name, manufactured by Maruzen Sekiyu ■, petroleum-based mixed solvent) for 22 seconds (Ford Cup No.
．． The viscosity was adjusted to 4.20°C).

The above material A was coated with a paint whose viscosity was adjusted by air spray painting so that the dry film thickness was 40 to 50 μm, and after being left at room temperature for 10 minutes, it was baked at 140° C. for 30 minutes to prepare a test plate.

As a comparison sample, Rugabeke AM white (paint No.S-
8), a comparative test board was prepared in the same manner.

The test results of coating film performance are shown in Table 5.

Test Example 2 Solex No. 2 was added as a primer to polypropylene resin. Apply 15-20μm of 2500,
After baking at ℃ for 20 minutes, topcoat solid color (S-1
and S-6) to a thickness of 40 to 50 μm and baked at 80° C. for 30 minutes to obtain a test plate.

For comparison, lettan PG was used instead of topcoat so/tricolor.
A comparative test panel was obtained in the same manner as above, except that -80 white (manufactured by Kansai Paint ■, S-9) was used.

The results of the coating film performance test are shown in Table 6.

Test Example 3 Base coat A was applied to the above material A, and after leaving it for about 5 minutes, a clear coat (paint NαM-1 to M-10 ) was painted. The dry coating film thickness was 15 to 20 μm for the base coat and 35 to 45 μm for the clear coat. After the coating was left at room temperature for about 10 minutes, it was baked at 100°C and 140°C for 30 minutes in two ways to obtain test plates.

Also, for comparison, I used Magikron #1 as a base coat.
Magiklon # as 000 silver and clear coat
1000 Clear [manufactured by Kansai Paint ■, acrylic/melamine resin paint, paint No. M-11], painted 14
Baking was performed at 0° C. for 30 minutes to obtain a comparative test board.

The coating film performance test results are shown in Table 7.

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

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

5) Xylol resistance Hold the gauze impregnated with xylol with your fingers and strongly rub the painted surface back and forth 10 times. The degree of melting of the painted surface, scratches and swelling is between good (◎) and markedly poor (×): ◎, O, ■, △
Judgment was made on a 5-level scale of , x.

6) In order to reach the adhesive substrate, cuts were made on the coated surface at intervals of mm in length and width to form 100 grids. A cellophane adhesive tape was pasted on top of this, and the condition was evaluated after it was rapidly peeled off.

Display: Number of stitches that did not peel off/100 7) Impact resistance A DuPont impact tester was used (striking core diameter 1/2 inch, weight 0.5 kg). The maximum weight drop height that does not cause cracks in the paint film is indicated.

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

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

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

11) Stain Resistance 1 g of JIS Class 15 Stain Dust was placed on a 5 x 5 cm coated plate, spread evenly by sweeping it 20 times with a brush, and allowed to stand at 20°C for 24 hours. Next, this was washed under running water using a clean brush, and the degree of contamination was examined.

◎...No stains observed at all.

O: Slight stains are observed.

△: Considerable dirt is observed.

×: Significant stains are observed.

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

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

13) Weather resistance QU. By V-promoted back mouth test.

Test conditions: UV irradiation i6H/60℃ water condensation 8H/
The coating film was evaluated after testing at 50° C. for 3000 hours (125 cycles).

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

0: Slight decrease in gloss, but no defects such as cracking or whitening.

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

14) Storage stability The paint diluted to a constant viscosity (22 seconds/Food cup No. 4) was heated for 40 minutes with a lid on to avoid contact with the outside air.
Stored at ℃ for 1 week.

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

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

×...Gelification.

(that's all)

Claims (1)

[Scope of Claims] [1] A fluororesin (A) having a functional group, (i) a compound (B) having a functional group and an epoxy group that reacts complementary to the functional group of the resin (A), and (ii) A silanol group obtained by reacting a functional group that reacts complementary to the functional group of the resin (A) with a compound (C) having a silanol group and/or a hydrolyzable group directly bonded to a silicon atom. and/or a resin composition containing a resin (I) having a hydrolyzable group, an epoxy group, and a hydroxyl group directly bonded to a silicon atom in the same resin. [2] Fluororesin (D) having a functional group and an epoxy group
(i) a compound (C) having a functional group that reacts complementary to the functional group of the resin (D) and a silanol group and/or a hydrolyzable group directly bonded to a silicon atom; A resin composition containing a resin (II) having a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, an epoxy group, and a hydroxyl group in the same resin. [3] A fluororesin (E) having a functional group and a silanol group and/or a hydrolyzable group directly bonded to a silicon atom is added with (i) a functional group that reacts complementary to the functional group of the resin (E); A resin containing a resin (III) containing a silanol group and/or a hydrolyzable group directly bonded to a silicon atom, an epoxy group, and a hydroxyl group in the same resin, which is obtained by reacting a compound (B) with an epoxy group. Composition. [4] A curable composition obtained by further adding a metal chelate compound as a curing catalyst to the composition of claims [1] to [3]. [5] A coating composition containing the compositions of claims [1] to [4] as active ingredients.