JPH02228350A - Resin composition, curable composition, and coating composition - Google Patents

Abstract

PURPOSE:To prepare a resin composition which gives a coating film excellent in the flatness, brightness, and build by compounding a polymer obtd. by the polymerization of radical-polymerizable unsatd. monomers in an org. solvent using a dispersion stabilizer comprising a copolymer which consists of a number of specific polymerizable unsatd. monomers as its essential monomer components. CONSTITUTION:Radical-polymerizable unsatd. monomers (e.g. a mixture of styrene, acrylonitrile, methyl methacrylate, 2-hydroxyethyl methacrylate, and a compd. of formula II) are polymerized in an org. solvent using a dispersion stabilizer comprising a copolymer consisting of, as its essential monomer components, a fluorinated polymerizable unsatd. monomer (e.g. CH2=CFCl), a hydroxylated polymerizable unsatd. monomer [e.g. CH2=CHO(CH2)4OH], a polymerizable unsatd. monomer with a hydoxyl or hydrolyzable group directly attached to silicon [e.g. CH2=CHSi(OH)(OCH3)2], and an epoxidized polymerizable unsatd. monomer (e.g. the compd. of formula I). The resulting polymer particles, which are insoluble in said org. solvent, are compounded to give a resin compsn.

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

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

As a one-component, non-toxic, low-temperature curable composition, for example, Japanese Patent Application Laid-open No. 1983-1999. No. 67553 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane.

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

Means for Solving the Problems The present inventor has conducted extensive research in order to solve the above-mentioned problems. As a result, a fluorine-containing polymerizable unsaturated monomer, a hydroxyl group-containing polymerizable unsaturated monomer, a polymerizable unsaturated monomer having a hydroxyl group and/or a hydrolyzable group directly bonded to silicon, and an epoxy group-containing A copolymer containing a polymerizable unsaturated monomer as an essential monomer component is used as a dispersion stabilizer, and the radically polymerizable unsaturated monomer is polymerized in an organic solvent in the presence of the dispersion stabilizer. By using a resin composition containing polymer particles insoluble in organic solvents, a high-finish coating film with excellent texture can be obtained, and when combined with a specific curing catalyst, it can be cured at low temperatures of 140°C or less. It has been discovered that the coating film obtained by the curing reaction progressing at a sufficient rate exhibits excellent properties such as weather resistance, acid resistance, scratch resistance, stain resistance, and mechanical properties. I was able to complete it.

Instant odor, the present invention uses a fluorine-containing polymerizable unsaturated monomer (A)
, a hydroxyl group-containing polymerizable unsaturated monomer (B), a polymerizable unsaturated monomer (C) having a hydroxyl group and/or a hydrolyzable group (hereinafter referred to as "silane group") directly bonded to silicon (hereinafter referred to as "silane group") A copolymer containing as essential monomer components a "silane group-containing polymerizable unsaturated monomer") and an epoxy group-containing polymerizable unsaturated monomer (D) is used as a dispersion stabilizer, and the dispersion is A resin composition characterized by containing polymer particles insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of a stabilizer; The present invention relates to a curable composition containing a metal chelate compound as a curing catalyst, and a coating composition containing the resin composition or curable composition as an essential component.

The copolymer used as a dispersion stabilizer in the resin composition of the present invention includes a fluorine-containing polymerizable unsaturated monomer (A), a hydroxyl group-containing polymerizable unsaturated monomer (B), and a silane group-containing polymerizable unsaturated monomer. Saturated monomer (C), epoxy group-containing heavy metal-free monomer (D
) and other polymerizable unsaturated monomers (E) as necessary
This is a copolymer obtained by copolymerizing.

Fluorine-containing polymerizable unsaturated monomer (A) A monomer containing a radically polymerizable unsaturated group and a fluorine atom in one molecule.

Representative examples of the fluorine-containing polymerizable unsaturated monomer (A) include monomers represented by the following formulas (1) and (2).

-Formation (1) % formula % (1) In the formula, X is the same or different and is H, CQ.

Br5F represents an alkyl group or a haloalkyl group.

However, the formula contains at least one F.

- Formation (2) % Formula % In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a fluoroalkyl group, and n represents an integer of 1 to 10.

The "alkyl group" in general formula (1) has 6 carbon atoms, preferably 01 to 4 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, and pentyl groups. Further, the "haloalkyl group" has 01 to 6 groups, preferably 01 to 100 m groups. Specifically, for example, CF3, CHF2, CH2P 5C
CI3, CHCl2, CH2CI, CH2CI, C
FCl2, (CF2) 2 CF3, (CF2)
3 CF3, CF2 CH3, CF2 CIIP 2
, CF2BrsCH2Br, and the like.

Examples of the monomer represented by general formula (1) include CP
2=CF2, CHF-CF2, CH2=CF2
, CH2-CHF, CCIF=CF2, CHCl=
CF2, CCI 2=CP2, CCIF”CCIF,
CHF-CCl2, CH2-CCIF, CCI
2 =CCIPSCF3 CH=CH2,CF3C
H=CH2, CP3 CH2CF2, CF3 CF=
CH2, CHF2 CH=CH2, CH3CH=CH
2, CH3CF=CH2, CF2 CHCl=CF2
, CF30CI=CF2, CF3 CP-CPCISC
P2 CICCl = CF2, CP2CICP”CF
CISCFC12CH=CH2, CF2 CCI=C
C.I.F.

CF3 CCI=CC12, CCIF2 CH=CH
22, CCI 3CP=CF2, CP2 CICCl
= CCl 2 , CFCl2 CCI = CCl 2
, CP3 CH=CH2I, CClF2 CF=C
HC1゜CP3CCI=CHCl, CHP2CC
I = CCl2, CF2CICH-CCI2
, CF2CICCl=CHCl, CCI3C
F=CHC1゜CF21CF=CF2, CF2 B
rCH=CF2, CF3 CBr=CHBr5CF
2 CICBr=CH2, CH2BrCP=CC12
, CP3CBr=ClI2, CF2 CH=CHBr
, CF2BrCH=CHF.

CP2 BrCP=CF2, CF3 CP2 CF=
CP2, CF3 CH=CHCF3, CP3 CH
=CH3F3, CF2 =CPCF2 CHF2
, CF3 CF2 CF=CH2, CF3 CH=C
HCF3, CF2 = CFCF2 C)13,
CF2=CFCH2CH3, CF3CH2CH=
CH2, CF3 CH=CHCH3, CP2=CH
Cl(2CH3, CH3CF2 CH=CH2, CFH
2CH=CHCFH2, CH3CP2 CH=CH3,
CH2=CFCH2CH3, CF3 (CP2)
2 CF=CP2, CP3 (CF2), 3CF
=CF2 etc. can be mentioned.

The "fluoroalkyl group" in general formula (2) is 03-
There are 21 items. Specifically, for example, CaF2, (
CF2 ) s CP (CF3 ) 2, C3F17
, C1oF21, and the like.

Examples of the monomer represented by general formula (2) include CH3 CH2-C-Coo-C2HA -Ct F 9H3 CH2=C-Coo-C2HA Ca P + y
H3 CH2=C-Coo-C2H4-c+ o P 2
.

etc. can be mentioned.

The above-mentioned monomers can be used alone or in combination of two or more.

When the monomer represented by general formula (1) is used, acid resistance,
A coating film with particularly excellent weather resistance is formed, and the general formula (2
) can form a coating film with particularly excellent water repellency.

Hydroxyl group-containing polymerizable unsaturated monomer (B) A monomer containing a radically polymerizable unsaturated group and a hydroxyl group in one molecule.

Representative examples of the hydroxyl group-containing polymerizable unsaturated monomer (B) include monomers represented by the following general formulas (3) to (6).

General formula (3) In the formula, R3 represents a hydrogen atom or a hydroxyalkyl group.

General formula (4) In the formula, R3 has the same meaning as above.

General Formula (5) In the formula, R1 has the same meaning as above, m is an integer of 2 to 8, P is an integer of 2 to 18, and q is an integer of O to 7.

General formula (6) CH2CH2 I In the formula, R1 has the same meaning as above, T1 and I2 are the same or different and represent a divalent hydrocarbon group of 01 to 2o, and S and U are each 0 to An integer of 10, where S
The sum of and U is 1 to 10.

The "hydroxyalkyl group" in general formulas (3) and (4) has 1 to 6 carbon atoms. Specifically, for example -
C2HAOH, C3H60H.

-C4H80H etc. can be mentioned.

CI in general formula (6), the divalent hydrocarbon group at 2° is, for example, =CH2--CH2CH2-CH2-C) (2CH2CH2CH2CH2-嘗CH3 CH3 CH2CH2CCH2CH2- CH3 =CH2-CH2-CH2-CH-CH2- CH2-C
Examples include H2-CH3-CIIH20Cl2H24C5aH3s-.

As the monomer component of general formula (3), for example, CH2=C
Examples include H0H CH2-CHOCt Ha OH and the like.

As the monomer component of general formula (4), for example, CH2''=
CHCH20H CH2=CHCH20CH2CH2oHCH2= CH
CH20(CH2CH20h-HCH2=CHCH20
(CH2CH20 squares "H etc. can be mentioned.

As the monomer component of general formula (5), for example, CH2=C
-(CH3)cooc2H40HCH2=CH-COO
C3H60H CH2=C(CH3) C00-C3Hs -0(C-
C) +2-CH2-CH2CH2CH2-0-H
I-+7 etc. can be mentioned.

As the monomer component of general formula (6), for example, CH2-C
(CH3)COO(CH2CHCh OH--H5~
6 CH2-CHCOO-(-CH2CH20F-m-H4
~5 CH2-C(CH3)Coo(CH2CI20-
T! 7-8 CH2-CI(COO(CH2C82CH2C)+20
L---H4~ 5 CH2=C(CH3)Coo(CH2CH2■-m-5
- 6 (CH2CHCH30←-H 5+6 etc. can be mentioned.

Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (3) to (6), ε-caprolactone, γ-
Adducts with lactones such as valerolactone can be used.

The silane group-containing polymerizable unsaturated monomer (C) is a monomer containing a hydroxyl group and/or a hydrolyzable group directly bonded to silicon and a radically polymerizable unsaturated group in one molecule. A hydrolyzable group directly bonded to a silicon atom is a group that is hydrolyzed by water or moisture to produce a silanol group. Examples of the groups include those represented by the following general formula.

OR & (7)
-N-C-R6 In the formula, R4 represents a CI-4 alkyl group, and R5-R7 are the same or different and represent a C1-8 alkyl group, aryl group, or aralkyl group.

- In the formation, the "alkyl group of 01 to B" is:
For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, SeC butyl, tert
Mention may be made of butyl, n-pentyl, isopentyl, n-octyl, isooctyl, and the like. Examples of the "aryl group" include phenyl, tolyl, xylyl, and the like. Examples of the "aralkyl group" include benzyl and phenethyl.

Furthermore, in addition to the above-mentioned hydrolyzable groups bonded to silicon atoms, examples of hydrolyzable groups include -98i-H groups.

In the composition of the present invention, the silane groups represented by the above-mentioned -formations (7) and (8) and silanol groups are preferred from the viewpoint of storage stability, curability, etc.

Examples of the radically polymerizable unsaturated group include l CH2=CCOO- CH2=C CH2=CHO- CH2=CHCH20- (R+ has the same meaning as above).

Examples of the silane group-containing polymerizable unsaturated monomer (C) in which the radically polymerizable unsaturated group is CH2=CCOO include the following -
Compounds represented by the formula (13) can be mentioned.

In the formula, R has the same meaning as above, and R8 is 01-2
o represents a divalent hydrocarbon group, and Y is the same or different and represents a hydrogen atom, a hydroxyl group, a hydrolyzable group, a C1-8 alkyl group, an aryl group, or an aralkyl group. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. Hydrolyzable groups, C,~8 alkyl groups, aryl groups, aralkyl groups and C1. As the divalent hydrocarbon group,
The same ones as above can be mentioned.

- Specific examples of compounds represented by formation (13) include:
For example, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ -(meth)acryloxypropylmethyljethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxy Silane, γ-(meth)acryloxybutylphenyldipropoxysilane, γ
-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane, γ(meth)acryloxypropylphenylmethylmethoxysilane, γ-(meth)acryloxypropylphenylmethylethoxysilane, γ- (meth)acryloxypropyltrisilanol, γ-(meth)acryloxypropylmethyldihydroxysilane, γ-(meth)
Acryloxybutylphenyldihydroxysilane, γ-
Examples include (meth)acryloxypropyldimethylhydroxysilane and γ-(meth)acryloxypropylphenylmethylhydroxysilane.

Examples of the silane group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (14) to (16).

In each formula, R1, RB and Y have the same meanings 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 (14) to (16) include C112-C-(CH30C28t 51(OCH3)
3 etc. can be mentioned.

As the silane group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2=C-, for example, the following general formula (17
) and (18).

CH2=C-8i -Y CH2 CH2 CH2 CH2 CH2 CH2 =CH81 =CH31 =CH81 =CH8i CHCH2 =CH81 (OCH3)3 (OC2Hs ) 3 (OCH3) 2 CHs (CH3) 2 0 CH3 Si ('0CR 3) 3 (oCCH3)3 CH2=CHCH2S i (OCCH3) 3CH
2-CH8i (CH3)2 N (CH3)2, in each formula, R1, R8 and Y have the same meanings as above, Y
may be the same or different. at least 1 of Y
Each is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of the compounds represented by formulas (17) and (18) include the following.

Examples of the silane group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CHo- include the following -formation (
Compounds represented by (19) and (20) can be mentioned.

CH2=CH0-R8-8i -Y CH2=CH0-8L -Y (20)
In each formula, R and Y have the same meanings as above, and Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of compounds represented by general formulas (1) and (20) include, for example, CH3H CH3 CH2=CHO(CH2)2 S L OCH3
CH3 CH3 etc. can be mentioned.

As the silane group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CHCH20-, for example, the following -
Compounds represented by the formations (21) and (22) can be mentioned.

CH2=CHCH20-3i-Y(21) CH2=CH
CH20Rs S i -YY (22) In each formula, Rs and Y have the same meanings as above, and Y may be the same or different. Any one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of compounds represented by general formulas (21) and (22) include, for example, CH2=CHCH20(,CH2) 3 Si
0CC2H5CCH3 C2H5 CH2=CHCH20(CH2) 2 S i O
C2HsH3 can be mentioned.

In addition to the silane group-containing polymerizable unsaturated monomer, the silane group-containing polymerizable unsaturated monomer is reacted with, for example, a polysilane compound (for example, a compound represented by -formation (23) to (25)). A polysiloxane unsaturated monomer having a silane group and a polymerizable unsaturated group obtained by this method can also be used.

[Polysilane compound]

Hydrolyzable group directly bonded to silicon and 5i in one molecule
It is a compound having two or more groups selected from OH.

Compounds represented by the following general formulas (23) to (25) can be mentioned.

In each formula, Y' is the same or different and is a hydrogen atom, a hydroxyl group, or a hydrolyzable group, R9 is the same or different and is CI,
8 Indicates an alkyl group, an aryl group, and an aralkyl group.

Specific examples of compounds represented by general formulas (23) to (25) include dimethyldimethoxysilane, dibutyldimethoxysilane, diiso-propyldipropoxysilane, diphenyldibutoxysilane, diphenyljethoxysilane, diethyldisilanol. , dihexyldisilanol, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyltributyloxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol , tetramethoxysilane, tetraethoxysilane,
Tetrapropioxysilane, tetraacetoxysilane,
Examples include di-1so-propioxydivaleroxysilane and tetrasilanol C2H5.

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

Specific examples of the polysiloxane unsaturated monomer include compounds of the general formula (13) and general formulas (23) to (2).
5), and the former 30 to 0.0
01 mol % of the latter, and 70 to 99.999 mol % of the latter, polysiloxane-based macrosiloxanes (for example, those disclosed in JP-A No. 62-275132) and the following compounds can be mentioned.

C3H7CH3 H3 CR3 R1 CH2=C-CC- A monomer containing a radically polymerizable unsaturated group and an epoxy group in one molecule. The epoxy group may be alicyclic or aliphatic, but the alicyclic epoxy group has the effect that the addition reaction of the epoxy group to the hydroxyl group is fast, and the curability of the coating film is further improved. demonstrate.

Examples of the radically polymerizable unsaturated group include R.

CH2=C-COO- CH2=CHCH2-○- CH2=CHO CH2=CH (R1 has the same meaning as above), and the like.

For example, as a whole saturated radical polymerizable unsaturated group, the following -formation (26) to (3)
Compounds represented by 8) can be mentioned.

In each formula, R1 and R8 have the same meanings as above, and R7 and R8 may be the same or different.

W represents 0 and an integer from 1 to 10. R10 is the same or different and represents a 01-82 valent hydrocarbon group.

As specific examples represented by general formulas (26) to (38), for example, H H30 The radical polymerizable unsaturated group is f CH2=C-C-N- As the epoxy-containing polymerizable unsaturated monomer, for example, the following Those represented by general formulas (3) to (41) can be mentioned.

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

As specific examples of the compounds represented by the general formulas (39) to (41), for example, the radically polymerizable unsaturated group is CH2, and R1 and RIo may be the same or different.

As specific examples represented by general formulas (42) to (44), for example, as a Japanese monomer, for example, the following general formulas (42) to (44) are used.
) can be mentioned.

R.

etc. can be mentioned.

In the radically polymerizable unsaturated groups, R1 and Rlo have the same meanings as above, and examples of the monomer include compounds represented by the following general formulas (45) to (50). .

R+ OR.

In each formula, R1, R, , R8 and W have the same meanings as above, and R1, RIOi and R8 may be the same or different.

Specific examples of compounds represented by general formulas (45) to (50) include (J t, R3 CH2-CHCH2 0-R, -C-CH2 \1 ).

Examples of epoxy group-containing polymerizable unsaturated monomers in which the radically polymerizable unsaturated group is CH2=CHCH20- include the following general formulas (51) to (54).
) can be mentioned.

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

Specific examples of compounds represented by formulas (51) to (54) include CH.

CH2=CHCH2O-CH2-C-CH2\1 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 (55
) to (57) can be mentioned.

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

Specific examples of compounds represented by general formulas (55) to (57) include CH2-CHO-(CH2)3C-CH2\1.

Examples of the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CH- include the following -formation (58)
Compounds represented by (60) can be mentioned.

Rto may be the same or different.

Specific examples of the compounds represented by -formations (58) to (60) include the following.

In each formula, R and R1° have the same meanings as above, and examples of the epoxy group-containing unsaturated monomer include compounds represented by the following -formations (61) to (65). .

Specific examples of compounds represented by general formulas (61) to (65) include, for example, in each formula, R,, R, and R8 have the same meanings as above, and R and R8 are the same or different. You can.

can be mentioned.

Other polymerizable unsaturated monomers (E) Depending on the required coating performance, conventionally known monomers containing radically polymerizable unsaturated groups can be used as appropriate.

Representative examples of the other polymerizable unsaturated monomers (E) include the following monomers (E-1) to (E-6).

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

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

(E-3) Vinyl esters and propenyl esters: for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl bivaric acid, vinyl caprate, and isopropenyl acetate propionic acid. Propenyl esters such as isopropenyl.

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

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

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

Furthermore, the other polymerizable unsaturated monomers (E-1) described above
In addition to ~(E-6), a carboxyl group-containing polymerizable unsaturated monomer (E-7) can be used. Use of this monomer has the effect of improving the curability of the film.

Examples of the carboxyl group-containing polymerizable unsaturated monomer (E-7) include monomers represented by the following general formulas (66) and (67).

General formula (66) In the formula, RI 1 represents a hydrogen atom or a lower alkyl group, R12 represents a hydrogen atom, a lower alkyl group, or a carboxyl group, and R13 represents a hydrogen atom, a lower alkyl group, or a carboxy lower alkyl group.

General formula (67) In the formula, R has the same meaning as above, and m has the same meaning as above.

In the above formula (66), the lower alkyl group is preferably a C4 or less group, particularly a methyl group.

Examples of general formula (66) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and the like.

Furthermore, examples of general formula (67) include 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, 5-carboxypentyl (
Examples include meth)acrylate and the like.

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

The blending ratio of the monomer components may have the following range based on the total weight of the monomers.

Fluorine-containing polymerizable unsaturated monomer (A): about 1 to 70% by weight, preferably about 5 to 60% by weight.

If it is less than about 1% by weight, the resulting coating film will have poor scratch resistance, stain resistance, weather resistance, and acid resistance, while if it is more than about 70% by weight, the unit price of the resin composition will become high, which is not practical. Moreover, manufacturing becomes difficult.

Water/acid group-containing polymerizable unsaturated monomer (B): about 061-5
0% by weight, preferably about 3-30% by weight. Approximately 0.
If it is less than 1% by weight, the curing properties will be insufficient, resulting in a coating film inferior in pheasant roll resistance, hardness, mechanical properties, etc.;
If the amount is more than 0% by weight, the resulting coating film will have poor water resistance, weather resistance, mechanical properties, etc., which is not preferable.

Silane group-containing polymerizable unsaturated monomer (C): about 1 to 60% by weight, preferably about 5 to 50% by weight. Approximately 1% by weight
If the amount is less than 60% by weight, the curing property will be insufficient and the coating film will be inferior in pheasant roll resistance, hardness, and mechanical suitability.
If the amount is more, the coating film will have a poor appearance (coating surface gloss, etc.), which is not preferable.

Epoxy group-containing polymerizable unsaturated monomer (D): about 5 to 80
% by weight, preferably about 10-60% by weight. If it is less than about 5% by weight, the curing property is not sufficient and the coating film is poor in roll resistance, hardness, and mechanical properties;
If it exceeds % by weight, the resulting coating film will have poor mechanical properties, which is not preferable.

Other polymerizable unsaturated monomers (E-1) to (E-6):
About 0-90% by weight, preferably about 0-50% by weight.

Other polymerizable unsaturated monomers (E-7): about 0 to 20% by weight, preferably about 0 to 5% by weight.

The copolymerization reaction of each of the monomer components described above can be carried out in the same manner and under the same 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 be done. The reaction time may normally be about 1 to 24 hours. Furthermore, as the organic solvent, one that is inert to the monomer or compound used, such as an ether solvent, an ester solvent, a hydrocarbon solvent, etc., can be used. When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility.

As the radical initiator, any commonly used radical initiator can be used, including peroxides such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and azoisobutyl peroxide. Examples include azo compounds such as nitrile and azobisdimethylvaleronitrile.

The copolymer used as a dispersion stabilizer in the resin composition of the present invention has a molecular weight of about 1,000 to 200,000, preferably about 3,000 to 200,000.
It can have a number average molecular weight range of 5oooo. If the number average molecular weight is less than about 1,000, the coating film will have poor scratch resistance, stain resistance, weather resistance, acid resistance, etc., while if the number average molecular weight is more than about 200,000, the storage stability of the composition and coating workability will be poor. , is not preferred because the finished appearance is inferior.

In the copolymer used as a dispersion stabilizer in the resin composition of the present invention, the functional groups (for example, hydroxyl group,
epoxy group, silane group, etc.) to create other resins (
For example, modified resins bonded with vinyl resins, polyester resins, urethane resins, silicone resins, etc. can also be used. The modified resin must each have an average of one or more hydroxyl group, epoxy group, or silane group in one molecule.

The resin composition of the present invention uses the copolymer as a dispersion stabilizer, and is obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer. It is a non-aqueous dispersion containing polymer particles. The polymer particles usually have a diameter of about 50 to 1000 mμ, preferably 10
It can have an average particle diameter of about 0 to 500 mμ. If the average particle diameter is below the above range, the characteristics of the dispersion system will not be exhibited, while if it exceeds the above range, the storage stability of the composition will deteriorate and the transparency of the coating film will be impaired. That's why I don't like it.

As for the types of monomers that can be used to form the polymer serving as the particle component of the above-mentioned non-aqueous dispersion, all the monomers already described can be used.

Preferably, the polymer serving as the particle component is a copolymer containing a large amount of highly polar monomer, since it must not be dissolved in the organic solvent used. Namely, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyl It is preferable that the particles of the non-aqueous dispersion contain a large amount of monomers such as toluene, a-methylstyrene, and N-methylol (meth)acrylamide, and the particles of the non-aqueous dispersion can be crosslinked if necessary. Examples of methods for this include a method of copolymerizing polyfunctional monomers such as divinylbenzene and ethylene glycol dimethacrylate, and a method of simultaneously using an epoxy group-containing monomer and a carboxyl group-containing monomer.

Although the dispersed polymer particles produced by the polymerization are not substantially dissolved in the organic solvent used for the non-aqueous dispersion, it is a good solvent for the dispersion stabilizer and the radically polymerizable unsaturated single N substance. things are included. (Acceptable organic liquids include, for example, aliphatic hydrocarbons such as pentane, hexane, pentane, octane, mineral spirits, naphtha, etc.)
Aromatic hydrocarbons such as benzene, toluene, xylene, etc. Alcohol, ether, ester and ketone solvents, such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl Isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methylhexyl ketone, ethyl butyl ketone, ethyl acetate, isobutyl acetate,
Examples include acyl acetate, 2-ethylhexyl acetate, etc., and these may be used alone or in a mixture of two or more, but in general, aliphatic hydrocarbons are the main component, and in addition to these as appropriate. Combinations of aromatic hydrocarbons and the above-mentioned alcohol, ether, ester, or ketone solvents are preferably used. Furthermore, trichlorotrifluoroethane, metaxylene hexafluoride, tetrachlorohexafluorobutane, etc. can also be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Examples of usable radical polymerization initiators include azo initiators such as 2,2-7zoisobutyronitrile, 2,2'-azobis(2,4-, and dimethylvaleronitrile); Examples include peroxide-based initiators such as lauryl peroxide and tert-butyl peroctoate, and these polymerization initiators are generally in the range of 0.2 to 10 parts by weight per 100 parts by weight of monomers to be subjected to polymerization. The formulation of the dispersion stabilizer resin to be present during the above polymerization can be selected from a wide range depending on the type of resin, but in general, it is possible to use a radical polymerizable resin based on 100 parts by weight of the resin. 3-400 unsaturated monomers
It is appropriate that the amount is about 5 to 240 parts by weight.

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

A method for introducing a polymerizable double bond is to add a, β-ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, or itaconic acid to a part of the oxirane group in the resin. However, there is also a method of adding an isocyanate group-containing monomer such as isocyanoethyl methacrylate to hydroxyl groups that have been incorporated in the resin in advance, and a method of adding methacrylic acid to some of the carboxyl groups in the resin. There is a method of adding a monomer such as glycidyl.

Furthermore, as a method for bonding the dispersant stabilizer and the polymerizable particles, in addition to the method described above, monomer components forming the polymer particles may be used, such as γ-meccryloxypropyl trimethoxysilane, γ-methacryloxy Propyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-
Attachment can be achieved by using reactive monomers such as acryloxypropyltrisilanol.

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

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

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

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

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 diaheptone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β
- Favorable results are obtained using diketones.

The aluminum chelate compound can be prepared, for example, by the general formula [wherein R14 is the same or different and has a carbon number of 1,
~20 alkyl or alkenyl groups. ] For 1 mole of aluminum alkoxide represented by
It can be suitably prepared by mixing at a molar ratio of less than 1 molar and heating if necessary.

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

Examples of the aluminum alcoholades represented by the general formula (68) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-5eC-butoxide, aluminum tri-5e, tart-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-5eC-butoxide, etc.
Preferably, ea-butoxide, aluminum tri-n-butoxide, etc. are used.

The titanium chelate compound is, for example, represented by the general formula [wherein W and R1 have the same meanings as above. ] Preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of usually about 4 moles or less with respect to 1 mole of Ti in the titanates represented by the formula, and heating as necessary. can do.

Titanates represented by the general formula (6) include W
is 1, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert
-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, etc., especially tetraisopropyl titanate, tetra-n-
-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, etc. are used to give suitable results. In addition, for those where W is 1 or more, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-ter
Dimer to decamer of t-butyl titanate (general formula (
W-1 to W-10) in 69) give suitable results.

The zirconium chelate compound is, for example, represented by the general formula [wherein W and R o have the same meanings as above. ] Preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of usually about 4 moles or less with respect to 1 mole of Zr in the zirconates represented by the formula, and heating as necessary. can do.

As the zirconates represented by the general formula (70),
Tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-
n-butylzirconate, tetra-5ee-butylzirconate, tetra-tert-butylzirconate, tetra-n-pentylzirconate, tetra-tert-
Pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-hebutyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, etc., especially tetraisopropyl zirconate, tetra-n- Propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-8ec-butyl zirconate, tetra-
Suitable results are obtained using tert-butyl zirconate and the like. In addition, for those where W is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetra-isobutyl zirconate, tetra-5ec-butyl zirconate, tetra-tert-butyl Zirconate dimer to decamer (- W = 1 to 10 in formation (70)
) gives suitable results. Further, it may contain a structural unit in which these zirconates are associated.

Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, and tris(.h-butylacetoacetate)aluminum. , isopropoxybis(ethylacetoacetate)aluminum, diisopropoxyethylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(propionylacetonato)aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonatobis(propionyl) Aluminum chelate compounds such as monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum diisopropoxy bis(ethylacetoacetate) titanate, diisopropoxy bis(acetylacetonato) ) titanate, diisopropoxy bis(acetylacetonato) titanate, and other titanium chelate compounds: tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)
Examples include zirconium chelate compounds such as zirconium, tetrakis(acetylacetonato)zirconium, and tetrakis(ethylacetoacetate)zirconium.

Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or two or more types may be used in combination as appropriate. The blending amount of the crosslinking reaction curing agent is 100% of the solid content of the resin composition.
It is appropriate to add 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.
Parts by weight.

The chelating agent described above, preferably a compound such as acetoacetate or β-diketone, can be added to the curable composition of the present invention in order to improve storage stability.

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.
, 2000 or less low molecular weight compounds can be blended. This low molecular weight compound acts as a reactive diluent, and by adding it to a paint composition, it can lower the viscosity of the paint and increase the solid content, and also produces less by-products during curing, so it can be used evenly. - A high solid paint with excellent curability etc. can be obtained. Also, during curing, there is little sagging, resulting in a coating film with excellent smoothness.

Number average molecule ff120 containing at least two oxirane groups in one molecule that can be used in the present invention
Examples of compounds of 00 or less include compounds represented by the following formulas, and adducts of (6) -c H20H with the following polyisocyanate compounds (usable polyisocyanate compounds include, for example, hexamethylene diisocyanate or trimethyl aliphatic diisocyanates such as xamethylene diisocyanate; cycloaliphatic diisocyanates such as xylylene diisocyanate or inphorone 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., or polymers of each of the above-mentioned organic diisocyanates, and furthermore, isocyanates.
Examples of typical commercially available products include [Parnock D-750, -800, D
N-950, -970 or 15-455J (all products manufactured by Dainippon Ink Chemical Industry Co., Ltd.), "Desmodur L, NHL, IL or N3390J [products of Bayer AG, West Germany],""Takenate D-102, -202,
-11ON or -123N" [Takeda Pharmaceutical Company ■ product], "Coronate L1HL, EH or 203J
(Nippon Polyurethane Kogyo ■ product) or "Duranate 24A-90CXJ [Asahi Kasei Kogyo ■ product] 1 etc." Examples include those obtained by oxidizing an esterified product (with a number average molecular weight of 900 obtained by an esterification 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-glycidylphenylglycidyl ether, etc. can also be used.

It is important that the molecular weight of the compound having two or more oxirane groups in one molecule is a number average molecular weight of 2000 or less. When the number average molecular weight 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 compound having an oxirane group is suitably added in an amount of about 0 to 100 parts by weight, or about 10 to 60 parts by weight, based on 100 parts by weight of the base resin.

The coating composition of the present invention may further contain an epoxy group-containing resin such as Epicoat 1001 (manufactured by Shell Chemical Co., Ltd.) or a hydroxyl group-containing resin such as styrene allylalcoat copolymer, if necessary. The blending amount 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 the coating composition of the present invention is used as a top coat, examples of the composition include a top coat solid color paint, a two-coat paint, and a two-coat paint.
When used as a top clear paint for one-bake coating or a top clear paint for three-coat/two-bake coatings, 100 parts by weight of base resin, 0.1 to 30 parts by weight of chelate compound, and 0 to 100 parts by weight of swelling pigment. is appropriate. As the swelling pigment, both inorganic and organic highly weather-resistant swelling pigments used in conventional top coatings for automobiles can be used, such as inorganic pigments such as rutile titanium oxide or carbon black, and quinacridone. Organic pigments such as quinacridone pigments such as red, azo pigments such as pigment red, and phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green can be used.

Clear paint for 2 coats/1 bake coat, 3 coats/
2. When used as a clear paint for bake coat,
It is usually used without the addition of swelling pigments.

Among the top coat paints, when used as a base coat paint for 2 coats/1 bake coat or a metallic paint for 1 coat/1 base 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 swelling pigment. Known metallic pigments can be used, such as aluminum, copper, micaceous iron oxide,
A scaly metallic powder of bronze, stainless steel, etc. can be used, and as the swelling 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.

When the coating composition of the present invention is used as an intermediate coating for all automobiles, the composition includes 100 parts by weight of the base resin and 0.0 parts by weight of the chelate compound. 1 to 30 parts by weight, 5 to 150 parts by weight of pigment, and 0 to 100 parts by weight of a low molecular weight compound having two or more oxirane groups in one molecule. Pigments include titanium oxide, barium sulfate, galcium carbonate,
Inorganic pigments such as clay and organic pigments for swelling can be used.

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

The coating viscosity at the time of painting is as follows:
About 15 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) is appropriate, and may be 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 solvents for diluting the paint, such as hydrocarbon solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Solvents, ester solvents such as ethyl acetate and butyl acetate,
Examples include ether solvents such as dioxane and ethylene glycol diethyl ether, and alcohol solvents such as butanol and propatool. These solvents are
They can be used alone or in a suitable mixture, but when using an alcoholic solvent, it is preferable to use it in combination with another solvent from the viewpoint of solubility of the resin. In addition, from the point of view of hardness rate, it is preferable to have a boiling point of about 150"C or less,
It is not limited to this.

The coating composition of the present invention can be prepared by, for example, applying a primer to a chemically treated steel plate by electrodeposition, and applying an intermediate coating (which may be omitted in some cases).
, 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.
When used as a metallic color paint for coat/1 bake coat, top clear paint for 2 coat/1 bake coat, top clear paint for 3 coat/2 bake coat, etc., the thickness is about 20 to 60 μm, preferably 30 to 4 μm.
Approximately 0 μm, approximately 10 to 25 μm when used as a 2-coat/1-bake metallic base coat paint,
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 is usually sufficiently cured in about 8 hours to 7 days. 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, in the -th stage reaction, the metal chelate compound reacts with the silane group to form the following bond.

\Next, this bond coordinates to a silanol group (for alkoxysilane groups, acyloxysilane groups, etc., becomes a silanol group due to moisture in the air), and becomes \AA=O-8i / \ to form a silanol group. polarizes. This polarized silanol group reacts with the epoxy group to form \ 11 . This then reacts with hydroxyl groups to form -c-,o-
It becomes c-c-H. 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 fear of inhibiting the reaction between alkoxy groups and epoxy groups, so it can exhibit excellent curability effects. . Furthermore, the fluorine atoms and molecules chemically bonded to the cured product are chemically stable against external contributions such as light, heat, water, etc., and can provide a cured product with low surface energy.

Furthermore, the composition of the present invention is a non-aqueous dispersion in which a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase in which a dispersion stabilizer resin is dissolved in an organic solvent. contains a chelate compound. This improves the workability of the composition during coating, and allows the formation of a film with good durability and an excellent finished appearance. Furthermore, the formed film is a photo- and chemically stable film in which the continuous phase of the film has a silanobond and a C-F bond, and the polymer particle components in the film are stabilized by the continuous phase. In addition, since the film is reinforced with particle components, it has excellent optical and chemical properties, as well as excellent mechanical properties such as impact resistance.

Effects of the Invention When the coating composition of the present invention is used as a coating for automobiles, the following excellent effects are exhibited.

■ A coating film with a high level of smoothness, sharpness, and texture can be obtained. The main curing reaction is an ionic polymerization reaction and an addition reaction, and the generation of reaction by-products is extremely small.In addition, due to the dispersion resin composition, volumetric shrinkage during the coating film curing process is small, and minute irregularities can be avoided. It is possible to obtain a coating film that is highly smooth and has an excellent long-lasting feel without any scratchy skin. Therefore, the image clarity is also excellent.

■ One-component paint with good low-temperature curing properties.

With a baking time of 30 to 40 minutes, a sufficient crosslinking reaction can be obtained at a temperature of about 80''C.

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

■ Extremely good acid resistance.

The base resin skeleton has a C'-F bond with excellent chemical stability, and the crosslinking points have a structure that is resistant to acids, resulting in extremely good acid resistance. Therefore, there are no problems with stains, gloss, or etching caused by acid rain.

■ Strong stain resistance.

It has good resistance to various pollutants due to its dense crosslinking density, polysiloxane bonds present in the base resin, low surface energy effect based on the fluorine component, and high water repellency.

■ Good water repellency.

Due to the polysiloxane bonds and fluorine components 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, allowing it to achieve high water repellency as a coating film for automobiles.

■ Good scratch resistance.

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

■ Obtain a highly weather-resistant coating (no gloss, cracking, chalking, blistering, etc.).

In addition to the presence of a C-F bond that has excellent chemical stability,
As a crosslinking reaction, the ionic polymerization reaction of epoxy groups, the addition reaction of epoxy groups with silanol groups and hydroxyl groups, and the condensation reaction of silanol groups occur in parallel, and because there are few byproducts during curing, the curability between the surface and inside is improved. Since there is little difference and almost no uncured material remains, it has a high degree of weather resistance.

EXAMPLES The present invention will be explained in more detail with reference to specific examples below.

An example of producing a copolymer is shown below.

In a stainless steel autoclave with a stirrer with a volume of 400 mG CH2 = CHSi (OH) (OCH3)2 15 parts by weight CH2 = CH0 (CH2)t OH 10 parts by weight CH2
= CHO-C) 10 parts by weight of each monomer and methyl isobutyl ketone azobisisobutyronitrile sodium borate were charged, purged with nitrogen, cooled and solidified, and CH2=CFCρ 200 parts by weight 2 parts by weight 0.5 parts by weight were removed. After cooling, 50 parts by weight was introduced into the autoclave, and the temperature inside the autoclave reached 6.
The temperature was gradually raised until it reached 0°C. After that, the reaction continued with stirring for more than 16 hours, and the internal pressure of the autoclave was 1 kg.
When the temperature decreased to below /c♂, the autoclave was cooled with water to stop the reaction. The obtained resin solution was poured into excess hebutane to precipitate the resin, and then washed and dried.
g of resin was obtained. The yield was 89%, and the number average molecular weight by GPC was 7,000. The obtained resin was dissolved in the same amount of xylene to obtain a resin solution with a nonvolatile content of 50%.

Production Examples 2 to 4.12 (Production of Copolymers 2 to 4.12) Production was carried out according to the production method of Example 1. Table 1 shows the amount of monomer charged and the number average molecular weight.

In addition, the manufacturing method of macromonomer A is listed below.

Macromonomer A Synthesis Example H3C8i (OCH3) 3 (methyltrimethoxysilane) 2720g (2
0moρ) CH2=CH8i (OCH3) 3 148g (vinyltrimethoxysilane) (1mof deionized water 1134g 36% hydrochloric acid
2g hydroquinone
1 g of these mixtures were reacted at 80° C. for 5 hours to remove water and solvent. The number average molecular weight of the obtained polysiloxane macromonomer was 2000. On average, each molecule had one vinyl group (polymerizable unsaturated group) and four hydroxyl groups.

The total formulation in the production examples is the amount of active ingredient as macromonomer.

Production Examples 5 to 11.13, Comparative Production Example 1.2 Acrylic copolymer fabrics having the compositions shown in Table 2 were obtained by a conventional acrylic copolymer fabric synthesis method.

Both are xylene solutions with a non-volatile content of 50% by weight. Table 1 shows the number average molecular weights determined by GPC.

The method for producing macromonomer B is shown below.

The FM-3 monomer is a hydroxyl group-containing caprolactone-modified methacrylic ester, and has an average molecular weight of 472 and a theoretical hydroxyl value of 119 KOHmg/g (manufactured by Daicel Chemical Co., Ltd.).

Macromonomer B Synthesis Example esi(OH)3 (phenyltrisilanol) 7800g (5
0m oΩ) CH2=CHC00C3Is S i (OCH3)
3 (γ-acryloxypropyl 200 g trisilanol) (1 m o , Q ) toluene 4500 g The mixture was reacted at 117° C. for 3 hours and dehydrated. The number average molecular weight of the obtained polysiloxane macromonomer was 700.
0, on average had one vinyl group and 5 to 10 hydroxyl groups per molecule.

The compounding amount in the manufacturing example is as a macromonomer It is the amount of active ingredient.

Table (continued) Table (continued) Table (continued) Table (continued) Synthesis of dispersion stabilizer (1) Introduction of double bond into copolymer (1) Made of glass with a 400aQ stirrer Copolymer (1
) solution (nonvolatile content 50%) 200 parts by weight H2C=C(CH3)COOH 2 parts by weight 4-tert-butylpyrocatechol 0.02 parts by weight Dimethylaminoethanol 0.1 parts by weight Xylene 1.2 parts by weight Preparation stirring 1
The addition reaction was carried out at 20℃ for 5 hours, and the resin acid value was O, OO1.
It was confirmed that the concentration was below mgKOH/g. This means that one copolymerizable double bond is introduced per one copolymer molecule.

Synthesis of Dispersion Stabilizers (3), (4), (5), (8), (9), and (11) Double bonds were introduced into each copolymer in the same manner as in Dispersion Stabilizer (1). Table 3 lists the copolymer name, the monomer volume of the added acid, and the number of copolymerizable double bonds per copolymer molecule. The number of double bonds was adjusted by adjusting the amount of acid type polymer charged.

Synthesis of dispersion stabilizer (2) Introduction of double bond into copolymer (2) 400m! In a glass flask equipped with a Q stirrer, 200 parts by weight of copolymer (2) solution (50% non-volatile content) H2C-CCCH3) COOC2Ht 1.4 parts by weight of NC0 0.02 parts by weight of hydroquinone 1.4 parts by weight of xylene were charged. Under stirring 1
Addition reaction was carried out at 10℃ for 5 hours and the isocyanate value was 0.
．． I confirmed that it was below 001. copolymer molecule 1
This means that 0.5 copolymerizable double bonds were introduced per book.

Double bonds were introduced into each copolymer in the same manner as the dispersion stabilizer (2). Table 4 lists the copolymer name, the added isocyanate monomer volume, and the number of copolymerizable double bonds per copolymer molecule. The number of double bonds was adjusted by adjusting the amount of incyanate monomer charged.

Example 1 Synthesis of dispersed polymer liquid (1) Heptane 80 parts by weight Acetic acid n-
Butyl 10 parts by weight dispersion stabilizer (1)
200 parts by weight of the solution (non-volatile content 50%) was charged into a flask and heated to reflux, the following monomers and polymerization initiator were added dropwise into the flask over 3 hours, and after further aging for 2 hours, 10 parts of n-butyl acetate was added to the flask. Added parts by weight.

CH2=CH- ■ CH2=CHCN CH2=C(CH3)COOCH3 CH2=C(CH3)COOC2H40H 10 parts by weight 10 parts by weight 50 parts by weight 20 parts by weight Tert-butyl peroxy 2 ethylhexanoate 1.5 parts by weight obtained The non-volatile content of the solution was reduced by 50% with n-butyl acetate as necessary.
adjusted to %. Particle size of polymer particles (Coulter N4 (
The dispersion was a milky white stable dispersion having an average particle size of 0.10 μm (as determined by Coulter Co.).

No precipitation or coarse particles were observed even after being left at room temperature for 3 months. The proportion of the dispersion chamber/leg side resin component in the total resin component of the dispersion liquid was 50%.

Examples 2 to 11, Comparative Example 1.2 Dispersed polymer liquids were synthesized in the same manner as in Example 1. 5th content
Shown in the table.

Even after the obtained dispersion was allowed to stand at room temperature for 3 months, no precipitation or coarse particles were observed.

Incidentally, as the dispersion stabilizer in Example 10, Copolymer 10 was used as it was.

An automobile top coat was prepared using the copolymer obtained in the above production example and the dispersed polymer liquid. As the top coat, a solid color (white) top coat and a 2-coat, 1-bake clear coat were prepared. Base coat A was also produced as a 2-coat/1-bake base coat.

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

Preparation example of 2-coat/1-bake clear coat (Paint No.
, M-1 to M-11) are shown in Table 7. The meanings of the numbers in the table are the same as for solid colors. Comparative preparation examples M-12 and M-13 are also shown. M-12 is an example in which there is no epoxy group in the resin, and M-13 is an example in which the resin does not contain a silane group.

In addition, a manufacturing example of a 2-coat, 1-bake base coat (base coat A) used below is shown.

Preparation of Basecoat A A basecoat to be combined with the 2CIB clearcoat was prepared as follows.

Preparation of siloxane macromonomer Methyltrimethoxysilane 2720g (20mo
l) γ-methacryloxypropyl 256g trimethoxysilane (1mol) deionized water
1134g 60% hydrochloric acid
2g hydroquinone 1
g These mixtures were reacted at 80°C for 5 hours.

The obtained polysiloxane macromonomer had a number average molecular weight of 2000, and had on average one vinyl group (polymerizable unsaturated bond) and four hydroxyl groups per molecule.

A copolymer was produced using the obtained macromonomer.

Polysiloxane macromonomer 150g 2-hydroxyethyl acrylate 100gn-butyl acrylate 500g Steel
A mixture of 100g of azobisisobutylnitrile was added dropwise to 1000g of a mixture of equal weights of butanol and xylene at 120°C and polymerized to obtain a transparent copolymer. The average molecular weight for several years was about 3oooo.

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

The blending amount is indicated by solid weight.

Above copolymer 95 parts Cellulose acetate butyrate 5 parts Aluminum paste #55
-519 (manufactured by Toyo Aluminum ■) 13 parts aluminum trisacetylacetone 1 part This was then mixed with toluene/sufuzol #1500 (trade name, manufactured by Maruzen Sekiyu ■) -
13 seconds with 80/20 mixture thinner (Ford Cup N
The viscosity was adjusted to α4.20°C) and used for coating.

(Rice 1) Oligomer A: Alicyclic oxirane group-containing compound: O ゜-o-C-0-CH2te:.

Table (Continued (*1) Oligomer A: Alicyclic oxirane group-containing compound: O's) -C-0-CH2°Cn.

Table (continued) (*1) Oligomer A: Alicyclic oxirane group-containing compound: o': GC-0-CH2'0:.

Adjustment of paint material The coating material was prepared as follows.

Coat approximately 25 μm of epoxy resin-based cationic electrodeposition paint on a dull steel sheet that has been subjected to conditioning chemical conversion treatment as material (A), heat cure it at 170°C for 30 minutes, and then apply Lugabake A/M (trademark product, Kansai Paint Co., Ltd.) as a medium. A polyester resin/melamine resin-based automobile paint manufactured by M. Co., Ltd., was applied to the surface to a dry film thickness of approximately 30 μm, and baked at 140° C. for 30 minutes. The coated surface was then sanded with #400 sandpaper, drained and dried, and the coated surface was wiped with petroleum benzene to prepare a material.

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

Preparation of test coated plate (I) Apply the top coat solid color prepared in the above preparation example to the above material A using Swasol #1000 (trade name, Maruzen Sekiyu ■).
(Ford Cup No., petroleum-based mixed solvent) for 22 seconds (Ford Cup No.
The viscosity was adjusted to 4.20 DEG C.), coated to a dry film thickness of 40 to 50 .mu.m, set at room temperature for 10 minutes, and then baked at 140 DEG C. for 30 minutes to prepare a test plate.

The painted plate for evaluating the texture was set at an angle of about 75 degrees with respect to the horizontal plane during the above-mentioned setting and baking.

As a comparison paint, Rugabeke AM white (paint No.

A coated board was prepared in the same manner using 5-6).

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

The above test results are shown in Table 8.

Preparation of coated plate for test (II) Apply base coat A to the above material A, wait 5 minutes after painting, and immediately apply clear coat (paint No. M-1 to M-13) diluted with Swasol #1000 for 22 seconds. did.

The coating film thickness was a dry film thickness of 15 to 20 μm for the base coat and 35 to 45 μm for the clear coat. Approximately 10 minutes after painting
After standing at room temperature for a minute, baking was performed at 100°C and 140°C for 30 minutes.

Here, the painted plate for evaluation of flesh feeling was set and baked at an angle of 75° with respect to the horizontal plane.

Further, Magiklon #1000 Silver was applied as a base coat, and Magiklon #1000 Clear (manufactured by Kansai Paint ■, acrylic/melamine resin paint No. M-14) was applied as a clear coat, and baked in the same manner.

This product did not cure at 100°C.

The above test results are shown in Table 9.

*3) Pencil hardness: Press and scratch the surface of the paint film with the lead of a Mitsubishi Uni-pencil, and the hardness of the paint surface is indicated by the hardness symbol of the highest lead.

*4) Image clarity measuring device (IMAGE, CLARITY) [E
TER:'';Z, Ga Test 1 Test 1 Tukkan Seisakusei. The numbers in the table are IC?vI values and take values in the range of 0 to 1.00%.
．． The larger the numerical value, the better the image clarity, and an ICM value of 80 or more indicates that the hood image clarity is extremely excellent.

*5) Feeling of texture As mentioned above, set and bake at 75° against the horizontal surface.
The texture of the coated plate was visually observed and evaluated at an angle of .

◎ Very good texture ○ Sufficient texture ∆ The finish is poor in texture and is rejected × There is no texture and the finished appearance is particularly poor *6) Pheasant roll resistance Q: Hold the gauze soaked in Shirol with your fingers and rub the painted surface strongly back and forth 10 times. The condition of the coating surface is ◎, ○ζ■, Δ, with the degree of scratches and swelling being good (◎) and extremely poor (X).
, x, fixed once a year in 5 stages.

×7) Impact resistance: Used a DuPont impact tester (striking core diameter: 2 inches, weight: 0-5.kg).・Displayed at the highest weight drop height that does not cause cracks in the paint film.

*8) Acid resistance After immersing in 40% H2SO4 at 40°C for 5 hours, it was taken out and washed with water, and the condition of the painted surface was evaluated. Judgments were made in five stages: ◎, -〇, o1△, and ×, depending on the degree of abnormality (◎) with no abnormalities at all, and abnormalities (×) such as significant gloss and piqué and erosion.

*9) Use a scratch-resistant dyed product rubbing fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho). Thoroughly scoop polishing powder (Da, Luma Cleanser) with water, place it on the painted surface, press the top with the tester terminal, and test 0.
25 reciprocating friction with a 5 kg load.

After washing with water, the degree of scratches is ◎, 0S0. Evaluation was made using a five-step scale of Δ and ×.

*10) Water resistance: Immerse the test sample in a constant temperature water bath at 40℃ for 240 hours. . After removal, the paint film was rated ◎ if there were no abnormalities such as gloss, piquancy, or blistering.

*11) Place 1 g of JIS Class 15 contaminated dust on a 5 x 5 cm painted plate and spread it evenly by sweeping it 20 times with a brush.
It was left standing at 0°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 ○ Slight stains are observed Δ　Significant dirt was observed and the test was rejected. × Significant dirt is observed X12) Water repellency It is expressed as a value obtained by measuring the contact angle of water with the painted surface.

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

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

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

◎ Maintains almost the same gloss as the initial stage ○ There is a slight decrease in gloss, but there are no defects such as cracking or whitening × Significant decrease in gloss, cracking, and whitening (chalking)
Rejected due to observed phenomenon *14) Storage stability Paint diluted to a constant viscosity (22 seconds/Ford Cup No. 4) was stored at 40℃ for one week with a lid on to prevent contact with outside air.

◎: Viscosity increase less than 5 seconds ■: 5 to 10 seconds or less ×Nigerization (that's all)

Claims (3)

[Claims] (1) Fluorine-containing polymerizable unsaturated monomer (A), hydroxyl group-containing polymerizable unsaturated monomer (B), polymerizable unsaturated monomer having a hydroxyl group and/or hydrolyzable group directly bonded to silicon mer (C), and an epoxy group-containing polymerizable unsaturated monomer (D)
A copolymer having as an essential monomer component is used as a dispersion stabilizer, and a radically polymerizable unsaturated monomer is polymerized in an organic solvent in the presence of the dispersion stabilizer. A resin composition characterized by containing coalesced particles. (2) A curable composition characterized in that a metal chelate compound is blended into the composition according to claim 1 as a curing catalyst. (3) A coating composition comprising the composition according to claim 1 or 2 as an essential component.