JPH02232250A - Resin composition, curable composition and paint composition - Google Patents

Abstract

PURPOSE:To obtain a non-aqueous dispersion curable with a sufficient speed at low temp. and providing a coating film with excellent weatherability, abrasive damage resistance, stain resistance, mechanical characteristics, etc., by polymerizing a radical-polymerizable unsatd. monomer in the presence of a specified fluorinated resin having three specified functional groups in the same molecule as a dispersion stabilizer in an org. solvent. CONSTITUTION:Using a resin having both 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 obtd. by reacting a fluorinated resin A having functional groups with a compd. B having a functional group complementarily reactive with the functional groups of the resin A (e.g. hydroxyl, carboxyl, silane or isocyanate group) 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 as a dispersion stabilizer, a radical-polymerizable unsatd. monomer is polymerized in the presence of said dispersion stabilizer in an org. solvent to form a resin compsn. (a non- aqueous dispersion) contg. polymer particles insoluble in said org. solvent.

Description

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

Conventionally, a method of curing a hydroxyl group-containing resin with a crosslinking agent such as diisocyanate or melamine has been adopted as a method of curing the resin. However, when diisocyanates are used, there are disadvantages in that the weather resistance of the resulting coating film is insufficient and, moreover, the coating film is susceptible to yellowing. Additionally, the pot life of the resin composition is short, and there are also problems with the toxicity of the diisocyanate.

On the other hand, when using a melamine resin, 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. 60-67553 discloses an aluminum chelate compound blended with a vinyl polymer containing an alkoxysilane such as methacrylate trimethoxysilane. Compositions are disclosed.

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 curing with only moisture in the air, it hardens from the surface, making it difficult to harden the inside and easily causing stiffness in the cured product. There are drawbacks such as insufficient sensitivity.

Means for Solving the Problems The present inventor has conducted extensive research in view of the problems of the above-mentioned prior art. As a result, a fluororesin 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 was used as a dispersion stabilizer, and in the presence of the dispersion stabilizer, it was If a resin composition containing polymer particles insoluble in the organic solvent obtained by polymerizing a radically polymerizable unsaturated monomer is used, it is possible to form a coating film with excellent texture and high finish properties. Moreover, by adding a specific curing catalyst to the resin composition, the curing reaction proceeds at a sufficient speed even at low temperatures of 140°C or lower, and the resulting cured coating film has excellent weather resistance.
The present invention was completed based on the discovery that the material has properties such as acid resistance, scratch resistance, stain resistance, and mechanical properties.

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 (
Compound (B) having a functional group and an epoxy group that react complementary to the functional group of A) and (i1) a functional group and a silanol group and/or silicon that react complementary to the functional group of the 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 containing polymer particles insoluble in the organic solvent, obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer using (I) as a dispersion stabilizer. Composition.

■ A fluororesin (D) having a functional group and an epoxy group is combined with (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 (n) 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 is used as a dispersion stabilizer, and radicals are generated in an organic solvent in the presence of the dispersion stabilizer. A resin composition containing polymer particles insoluble in the organic solvent, obtained by polymerizing a polymerizable unsaturated monomer.

■ 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 that reacts complementary to the functional group of the resin (E) and an epoxy As a dispersion stabilizer, 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 is obtained by reacting a compound (B) having a group with A resin composition containing polymer particles insoluble in the organic solvent, obtained by polymerizing a radically polymerizable unsaturated monomer in an organic solvent in the presence of the dispersion stabilizer.

(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.

0-R. (i)N-
C-R3 (6) [wherein, R
, 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 =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 (i) and (2) from the viewpoint of storage stability, curability, etc.
and silane groups represented by silanol groups are preferred.

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

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

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

Resin (A)/Compound (C) [or Resin (D)/Compound (
C)] functional group combinations (i)/(5), (2)/(3), (2)/(4)
, (2)/(5), (3)/(3) , (4)/(2
), <4)/(8), (4)/(7), (5)/(
i) , (5)/(2) , (5)/(6) , (5)
/(7), (8)/(4), (6)/(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 for producing a new hydroxyl group, a method for producing a new hydroxyl group by a reaction with a functional group possessed by the resin (A), or the compound (C).
A group that reacts with a hydroxyl group (e.g., isocyane-1 group, etc.) is introduced in advance into the reaction product of B) and compound (C), and a polyhydric alcohol compound (e.g., (poly)ethylene glycol,
(poly)propylene glycol, neobentyl glycol, etc.) and hydroxyl groups are blended in excess and reacted to introduce hydroxyl groups.

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 is replaced by a compound having an isocyanate group (CB) and a compound having an isocyanate group (5). (C) or a resin (A) having an average of two or more isocyanate groups (5)
) can be reacted with a compound (B) having a hydroxyl group (i) and a compound (C) having an isocyanate group (5).

In addition, when the functional groups in the resin (A) are different, for example, an average of one or more hydroxyl groups (i) 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 containing functional groups such as hydroxyl group, carboxyl group, isocyanate group, silane group, and epoxy group will be explained.

[Hydroxy 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. Examples include polymers containing the mer (c) as a monomer component.

Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a) include compounds represented by the following general formulas (7) to (i0).

OR5 [In the formula, R5 represents a hydrogen atom or a hydroxyalkyl group. ] [In the formula, R5 is the same as above. ] [In the formula, REI represents a hydrogen atom or a methyl group, and m is 2
An integer of ~8, . p represents an integer of 2 to 18, and q represents an integer of 0 to 7. [In the formula, R8 is the same as above. TI and T2 are the same or different and represent a divalent hydrocarbon group having 4 to 2 o carbon atoms. S and V are each an integer of 0 to 1 o is shown. 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, -C2 HA OH
−． C3 H6 0H, -c, H80H, etc. can be mentioned.

The divalent hydrocarbon group having 4 to 20 carbon atoms in general formula (i0) is, for example, -C}{2-(CH2)
2 (CH2) 3-- (CH2) 1
Examples include 2-, (CH2) ta-, tai, sha, -CH2 sha CH2, etc.

As the monomer component of general formula (8), for example, CH2
=CHCH2 04! CH2 -CHCH2 0 CH2 CI12 0}
ICH2-CHCH20fCh CH2■-roCH2
-CHCH2 0{CH2 CH2, etc. can be mentioned.

As the monomer component of general formula (9), for example, CH2
=C(CH3) COOC2 H4 0HCH2 −
As a monomer component of CHCOOC3 Hs OH general formula (i0), for example, CH2 -C(CH3 )Co
o-(CI2 CHCH3 咋rτdingHCH2 -CH
COO(CH2CH20)4~5HCH2-C
(CH3) COO- (CH2 CH2 0 catties τ”
THC2=CHCOO(CH2C82 CH2C
I2 0h: CorrHCH2 -C(CH3)COO-
(CI2 Cl{2 0)s~6-(CH2 CHC
H3 Kui ``7 ding l{'' etc. can be mentioned.

Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (7) to (i0) 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 (i1) and (i2).

CX2-CX2 (i1) [wherein X is the same or different and represents H, CQ, Br, F, an alkyl group or a haloalkyl group. However, the formula contains at least one F. ] C H2 ”” C R I C-0 (i2)0-Cn
H2o-R7 [wherein R1 is the same as above. R7 represents a fluoroalkyl group, and n represents an integer of 1 to 10. ] General formula (i1)
What is the alkyl group in carbon? It has 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, CF,
,CHF2,CH2F,CCAl3,CHC(i2
,CH2CQ,CFCl22(CF2)2
CF3, (CF2) 3CF3, CF2 CH3
, CF2CHF2, CF2Br, CH2Br, and the like.

Examples of the monomer represented by general formula (i1) include:
CF2=CF2, CHF=CF2, CH2=CF
2, CH2 = CHP, CCQ P = CF2, C
tlCQ=CP2, CCQ2-CF2, CCQP
=CC■ P SCHP =CCQ 2,C}! 2
-CC9 F N CC9 2 = CCQ F N C
P3 CF=CP2, CFs CF-CHF SCI'
3 Cl-CP2, CF3 CF-Ch, CHF2
CF-CHF, CH3 CF=CF2, CH3
CP=CI+2, CF2 CQ CF=CF2, C
P3C(,9 = CF2, CF3 CF= CFCG
! , CF2 CQ CCQ = CP2 , CF2
CQ CF=CP-CQ S CPCQ2 CF=
CP2, CP2 CCQ - CCQ P, CP3
CC&! -CCQ2, CCQP2 CP=CCQ
2, CC9 3 CF=CF2, CF2 C
Q CCQ = CC9 2 , CFCQ 2 CCQ
=CC9 2 , CF3 CF- CHC'Q SC
Ci2 F2 CF= CHC9 , CF3 CCQ
=CH-CG! SCHF 2 CCG! =CC(
2 2 , CF2 CQ CH=CCQ2 , CP2
CQ CCQ = CHCG! ,CC9 3
CF=CHCQ, CF2Q CF=CP2
, CF2 BrC}l=cF2, CF3 CBr=
Cl-IBr, CF2CQCBr=CH2,
CH2BrCP-CCQ2, CF3-CBr=C
Il2, CF2 CB=CHBr, CF2 BrCH
=C}IP%, CF2 BrCF=CP2, CP
3 CP2 CF=CF2, CP3 CF=CFCF
3, CP3 CH=CPCF3, CP2=C
FCP2 CHF 2 , CP3 CF2 CF=C
H2, CP3CH=CHCP3, CI'2=C
FCF2 CI+3, CP2=CPCI12
CH3, CF3 Cl{2 CH=CH2, CF3
CH=CHCH3, CP2 “CIICH2CH
3, CH3 CF2 CI=CIi2, CFH 2 C
H=CHCFH 2 , CH3 CP2 CH=CH3
, CH2 -CFCH2 CH3 , CF3 (CP
2) 2 CF=CF2, CF3 (CF2)
3CP-CF2 etc. can be mentioned.

The fluoroalkyl group in general formula (i2) has 3 to 21 carbon atoms. Specifically, for example, C, F9
, (CF2)s CF (CF3)2, C8F+7
, CIO F2 1, etc.

Examples of the monomer represented by general formula (i2) include: CH3 CH2 =C-COO- C2 HA -CA
P9CH3 G! 12 =C-COO-C2! Ia-C8Pr
ICH3 CH2 =C-COO- C2 H▲-C sister F2
+The above monomers can be used alone or in combination of two or more.

When the monomer represented by the general formula (i) is used, a coating film with particularly excellent acid resistance and weather resistance can be formed, and the monomer represented by the general formula (i) can be formed.
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, brobylene, butylene, isobrene, chloroprene, etc.

(c-2) Vinyl vinyl ether and allinol vinyl ether = e.g. ethyl vinyl ether, probyl vinyl ether, isobrobyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, benzyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4 -Methyl-
Chain alkyl vinyl ethers such as 1-bentyl 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-}rivinyl ether, penzyl vinyl ether, phenene Aralkyl vinyl ethers such as chill vinyl ether, etc.

(c-3) Vinyl esters and propenyl esters: For example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocabroate, vinyl bivaric acid, vinyl cabrate, and isobrobenyl acetate. Brobenyl esters such as isobrobenyl luprobionic acid.

(c-4): Acrylic acid or methacrylic acid ester: For example, methyl acrylate, ethyl acrylate,
Probyl acrylate, isobrobyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, probyl methacrylate, methacrylic acid-f
C1-18 alkyl esters of acrylic acid or methacrylic acid such as soprovir, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate: methoxybutyl acrylate, methoxyethyl methacrylate, methoxyethyl acrylate , C2-18 alkoxyalkyl esters of acrylic acid or methacrylic acid, such as methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate.

(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 monomers (C).

Examples of the carboxyl group-containing polymerizable unsaturated monomer (d) include compounds represented by the following general formulas (i3) and (i4).

R 3 R 5 ν′; cc. . . H (i3) [wherein, R
3 represents a hydrogen atom or a lower alkyl group. R 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. ]R8 0 [In the formula, R8 and m are the same as above. ] In the general formula (i3), the lower alkyl group is:
Those having 4 or less carbon atoms, especially methyl group, are preferred.

Examples of the compound of general formula (i3) 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 (i4), for example, 2-
Examples include carboxyethyl (meth)acrylate, 2-carpoxybrobyl (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 (i6) and (i7).

Re ■ CB2 -C-Coo (CnH2,)NGO (i
6) [In the formula, R8 and n are the same as above. ] The monomer of general formula (i6) 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 (i7) 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, and biphenyl diisocyanate. Enylene diisocyanate,
3,3'-dimethyl-4,4'-biphenylene diisocyanate, dicyclohexylmethane, 4,4'-diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, bis(4-isocyanate phenyl) sulfone, isobropylidene Examples include 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.

[Epoxy 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, CH2 = CHCH2 -0- CH2 = CHO-, CH2 = CH- [wherein Rθ is the same as above. ] Examples of the epoxy group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is Rθ carbon dioxide CH2-CCOO- include, for example, compounds represented by the following general formulas (i8) to (30).

[In each of the above formulas, R6 is the same as above. R9 has 1 to 8 carbon atoms
represents a divalent hydrocarbon group. Rlo represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Re, R9 and R may be the same or different.

W represents an integer from 0 to 10. ] As the divalent hydrocarbon group having 1 to 8 carbon atoms, the above-mentioned examples have 1 to 8 carbon atoms. -20 divalent hydrocarbon groups.

Specific examples of the compounds represented by the general formulas (i8) to (30) include, for example, those in which the radically polymerizable unsaturated group is CIj2; and monomers such as the following general formulas (31) to (33
) can be mentioned.

The radical polymerizable unsaturated group is [In each of the above formulas, RFI and R9 are the same as above. R8 and R9 may be the same or different. ] General formula (31)
Specific examples of the compounds represented by (33) include the following.

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

etc. can be mentioned.

The radically polymerizable unsaturated group is [In each of the above formulas, Re and R9 are the same as above. R8 and R
9 may be the same or different. ] General formula (34) ~
Specific examples of the compound represented by (36) include, for example, the monomers include the following general formulas (37) to (42).
) can be mentioned.

[In each of the above formulas, R day, R9, RIo and W are the same as above, Re, . R9 and R 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 polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is C H 2 = C H C H 2 0- include compounds represented by the following general formulas (43) to (46). be able to.

[In each of the above formulas, R8 and R9 are the same as above, and R0
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, R8 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, the following can be mentioned.

As the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is C}{2-CH-, for example, the following general formula (50
) to (52) can be mentioned.

[In each of the above formulas, R8 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, Re, R9 and RIo are the same as above, and Rθ and R may be the same or different. ] As specific examples of the compounds represented by general formulas (53) to (57), for example, the compound (B) used in the resin composition (i) is a functional group that reacts with the functional group in the resin (A). group and epoxy group as 1
One or more of each is present in the molecule. The resin (
The functional group that reacts with the functional group in 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.

[Epoxy compound containing hydroxyl group]

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

etc. can be mentioned.

[In each of the above formulas, Re, R9, RIO and n are the same as above, and REI, R9 and R may be the same or different. ] Specific examples of compounds represented by general formulas (58) to (68) include: Ht-G-GH*-OCN- (CH,l .-NC
-0- (CH21 2-OH\/H
}1 [Silane group-containing epoxy compound] For example, compounds represented by the following general formulas (69) to (72) can be mentioned.

It is a D Y group. ] In the general formulas (69) to (72), the hydrolyzable group includes the groups of the above general formulas (i) to (6). Also,
The alkyl group, aryl group, and aralkyl group having 1 to 8 carbon atoms include those exemplified above.

Specific examples of compounds represented by general formulas (69) to (72) include, for example, QCHx [wherein R8 and R9 are the same as above, R8 and R9]
9 may be the same or different. Y is the same or different and represents a hydrogen atom, a hydroxyl group, a hydrolyzable group, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralzyl group. However, at least one of Y can be a hydrogen atom, a hydroxyl group, or hydrolyzable.

[Polyepoxy compound]

The following general formulas (73) to (80) I can list hardware.

Specific examples of compounds represented by the formulas (73) to (80) include: [wherein R'', R9 and W are the same as above, and R6
and R9'- may be the same or different. The R1 groups are the same or different and represent 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. ] Can be used for H2C.

etc. can be mentioned.

In addition to the above, for example, the following are adducts with the anate compound used (polyisocyanate compounds that can be used include, for example, hexamethylene diisocyanate 1.
or aliphatic diisocyanates such as trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate. Organic diisocyanates themselves, adducts of each of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc., polymers of each of the above-mentioned organic diisocyanates, and isocyanade biurets, etc. Examples of typical commercially available products include "Parnock D-750, -8".
00, DN-950, -970 or 15-455"
[The above are Dainippon Ink Chemical Industry products], [Desmodule LSNHLSI L or N3390J [
Product of Bayer AG, West Germany], ``Takene'' D-102
, -202, -LION or -123NJ (Takeda Pharmaceutical Company ■ product), "Coronate L, HL, EH or 203J (Japan Polyurethane Industry ■ product)", "
Adducts of Duranate 24A-90CXJ (products of Asahi Kasei Industries, etc.); esterified products having unsaturated groups such as in the molecule (e.g., tetrahydrophthalic anhydride, trimethylolbroban and 1,4-
Examples include those obtained by oxidizing an esterified product having a number average molecular weight of 900 obtained by esterifying butanediol etc. with peracetic acid etc.

[Incyanate 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, - Reaction product CI+2 -Cl1-Clh -QC-NH-(CHz
10TNCO\0/ ・Reactant of the compound represented by general formula (62) and toluene diisocyanate ・Reactant of general formula (68) and xylene diisocyanate n ・Reactant of the compound represented by general formula (65) and isophorone diisocyanate - A reaction product of the compound represented by the general formula (67) and isophorone diisocyanate, etc. can be mentioned.

Compound (C) used in composition (I). has at least one functional group that reacts with the functional group 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.

HO-R9 -81-Y l Y O HOH CH. C.I. [In each Doki formula, R 9 , R If) 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. ] General formulas (81) to (83
) As a specific example of a compound represented by ? CH3 ``IO- (CM.)■-Si-OCR. ocHa 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.

Rl+ Y'-Sl-Y' Cao Y' Rl+ RuSi-Y'Y' [In each of the above formulas, Rl+ is the same as above, and R11 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 the general formulas (84) to (86) include dimethyldimethoxysilane, dibutyldimethoxysilane, diisobubildipboxysilane, diphenyldibu-1-xysilane, diphenylethoxysilane, diethyldisilanol, dihexyldisilanol methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, probyltrimethoxysilane, phenyltriethoxysilane, phenyltributyroxysilane, hexyltriacetoxysilane,
Medyltrisilanol, phenyltrisilanol, tetramethoxysilane, tetraethoxysilane, tetrabioxysilane, tetraacetoxysilane, diisobutyloxydibaroxysilane, tetrasilanol, OCN-R9 31 Y (
87) Y etc.

In addition to the above-mentioned materials, metal condensates of the polysilane compounds described 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).

[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 Hs S1 (OC2 H5 ) 3
, OCNC2 Ha St (OCH 3 ) 3,
OCNCa Hs Si (OC2 Is) 2
, CHaOCNC2H4Si(OCH3)z,
■ CIl3 OCNCH 2 Sl (OC2 H5) 3, O
CNCH 2 S1 (OCH 3 ) a, OCN
CH2Si(OC2Hs)2, CB3OCNCH2St(OCH3)3, CH
3 CH3 l OCN- C3 H6 -S10N( C3 H7
) 2Cl{ 3 ■ OCN- C3 Is-Si(OCCH3) 3CH
3 0CN- C3 Hs -SIN-( C2 Hs
) 2CH 3 CH a OCN-31 (OCCH3 ) 3 ■ OCN-81 (OCCH3 ) 3 OCN SI OCC4Hg00CH3 J O In addition to the above, compounds obtained by reacting the hydroxyl group-containing silane compound with the polyisocyanate compound are also used. can.

Specifically, the following can be mentioned.

A reaction product of general formula (81) and hexamethylene diisocyanate or tolylene diisocyanate, for example, can be exemplified.

[Merkabuto group-containing silane compound]

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

(8) etc. can be mentioned.

Furthermore, a condensate of the epoxy group-containing silane compound and, for example, the polysilane compound can also be used. Examples of the compound include: [wherein R and Y are the same as above. Y 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 the compound represented by general formula (88) include: 0C2H, IHS C3 H6 S1-OCa H9QC2 H5 HS-Ca H6-Si (OCCHa)2CH3 (NH group- or NH2 group-containing silane compound) The following general formula (
Compounds represented by (89) and (90) can be mentioned.

Y etc. can be mentioned.

In addition to the above, the hydroxyl group-containing silane compound may be added to the polyisocyanate compound and thiocol compound (for example, HS
-C, H2, -OH and m are the same as above. ),
For example, the following can be mentioned.

[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 Y represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] Specific examples of compounds represented by general formulas (89) and (90) include ocis t 1{*'N- (cl 3-Si-0(;l{30CH
3 0 (i:*Jta I 1・OCxH* 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 the following.

[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 ■ CH2　-CCOO- R5 CH2　-C- CH2 -CHO- CH2-CHCH2 0- [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 radically polymerizable unsaturated group is CH2=CCOO include a compound represented by the following general formula (91).

[In the formula, R6, 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. ] Specific examples of the compound represented by general formula (91) include:
For example, γ-(meth)acryloxypyltrimethoxysilane, γ-(meth)acryloxypyltriethoxysilane, γ-(meth)acryloxypyltributoxysilane, γ-(meth)acryloxypylmethyldimethoxysilane. , γ-(meth)acryloxypylmethyldiethoxysilane, γ-(meth)acryloxypylmethyldipropoxysilane, γ-(meth)
Acryloxybutylphenyldimethoxysilane, γ-(
meth)acryloxybutylphenyldiethoxysilane,
γ-(meth)acryloxybutylphenyldibutyboxysilane, γ-(meth)acryloxybutyldimethylmethoxysilane, γ-(meth)acryloxybutylphenyldimethylethoxysilane, γ-(meth)acryloxybutylphenylmethylmethoxy Silane, γ-(meth)acryloxibulphenylmethylethoxysilane, γ-(
meth)acryloxibyltrisilanol, γ-(meth)acryloxibylmethyldihydroxysilane,
γ-(meth)acryloxybutylphenyldihydooxysilane, γ-(meth)acryloxybutyldimethylhydroxysilane, γ-(meth)acryloxybutylphenylmethylhydroxysilane, CH. 0 0CCH. CH. C. H. 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, 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. ] Specific examples of the compounds represented by general formulas (92) to (94) include 16 Y and the like.

As the silane group-containing polymerizable unsaturated monomer in which the R6 radically polymerizable unsaturated group is CH2-C-, for example, the following general formula (95
) and (96).

Y [In the formula, R6, R, 6 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 (95) and (96) include, for example, CH2-CHSj(OCHs)3CH2=CH
Si (OC2 H 5 ) 3CH2 = CHSi
(OCH3)2CH3CH2-CHS1 (
CH3 ) 2 0CR 3C}12 =CHCH2
Si (OCH 3 ) a■ CH2 =CHSi (OCCH3) a' CHz -Cl{CHz 31 (OCCh) 3C
H2 = CHSi (Cl13) 2
Specific examples of the compounds represented by N(CH3)2 general formulas (97) and (98) include, for example, silane group-containing polymerizable unsaturated monomers in which the radically polymerizable unsaturated group is CH2=CHO-. , for example, the following general formula (
Examples include compounds represented by (97) and (98).

CB2=CHO(Ctb)2CH3HCH3Sl-OCh0CH3CHa [In the formula, 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. ] CHa and the like.

Examples of the silane group-containing polymerizable monomer in which the radically polymerizable unsaturated group is CH2=CHCH20- include compounds represented by the following general formulas (99) and (i00).

[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. ] Specific examples of the compounds represented by the general formulas (9) and (i00) include OC. H, ■ CN*”CHCLO- (CHt) z-Si-OC*
Examples include HsCHs and the like.

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.

OCCHi Resin Composition (II) The hydroxyl groups in the resin composition (n) can be prepared by introducing the hydroxyl groups into the resin (D) in advance in the same manner as in the case of the resin composition (I), or by introducing the hydroxyl groups into the resin (D) in advance. The hydroxyl group can be introduced by generating a hydroxyl group through a complementary reaction between D) and the compound (C), or by reacting a reaction product of the resin (D) and the compound (C) with a polyhydric 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 (b). Examples include copolymers obtained by copolymerizing the unsaturated 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). The resin composition (n) can be obtained by reacting with a silane compound (silane compound, etc.).

Resin composition (III) The hydroxyl groups in the resin composition (m) can be prepared by introducing the hydroxyl groups into the resin (E) in advance in the same manner as in the resin composition (I), or by introducing the hydroxyl groups into the resin (E) in advance. ) and compound (B) to generate a hydroxyl group, or furthermore, it can be introduced by reacting a reaction product of resin (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,
mercapto group-containing silane compound, amino group-containing silane compound, etc.)
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 monomer 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 an average of about 2 to 40 hydroxyl groups, an average of 1 or more epoxy groups, preferably about 2 to 40 epoxy groups, and an average of 1 silane group in one molecule. Above, preferably 2 to 40 or more. If the hydroxyl group, epoxy group, and silane group are below the above range, curing properties will be insufficient, and xylol resistance, hardness,
A coating film with poor mechanical properties is formed, 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 quick 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 general formula (i1) is used as the fluorine-containing polymerizable unsaturated monomer (b), the polymer formed from this monomer has a main chain of 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 (i2) 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, reactions between hydroxyl groups and isocyanate groups, condensation reactions between silane groups, copolymerization reactions, 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 other solvents in view of solubility. Further, as the radical polymerization initiator, any commonly used initiator can be used, and examples thereof include benzoyl peroxide,
Examples include peroxides such as t-butylbaroxy-2-ethylhexanoate, and azo compounds such as azoisobutylnitrile and azobisdimethylvaleronitrile.

The resin compositions (I) to (m) used in the present invention are about 10
00-200000, preferably about 3000-8000
It has a number average molecular weight in the range of 0.

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, a part of the functional groups (e.g., hydroxyl group, epoxy group, silane group, etc.) possessed by the resin compositions (I) to (m) described above can be used to form other resins (e.g., vinyl resins). , polyester resin, urethane resin, silicone resin, etc.) can also be used. The modified resin composition must have an average of one or more hydroxyl groups, epoxy groups, and silane groups in each molecule.

The resin composition of the present invention is obtained by polymerizing a radically polymerizable unsaturated monopolymer in an organic solvent in the presence of the dispersion stabilizer using resin compositions (I) to (III) as a dispersion stabilizer. It is a non-aqueous dispersion containing polymer particles that are insoluble in organic solvents. The polymer particles can have an average particle diameter of usually about 50 to 1000 μm, preferably about 100 to 500 μm. If the average particle diameter is significantly below the above range, there is a possibility that the characteristics of the dispersion system will not be exhibited. On the other hand, if it greatly exceeds the above range, the storage stability of the composition may deteriorate or the transparency of the coating film may be impaired.

All the monomers already described can be used as the monomers used to form the polymer which becomes the particle component of the above-mentioned non-aqueous dispersion. Preferably, the polymer forming 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)acrylic nitrile, 2-hydroxy (meth)
Contains many monomers such as acrylate, hydroxyl (meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, α-methylstyrene, and N-methylol(meth)acrylamide. Preferably. Also,
The particles of the non-aqueous dispersion can be crosslinked if necessary. Examples of methods for crosslinking the inside of the particles 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 carboxy group-containing monomer. Can be done.

The organic solvent used for the non-aqueous dispersion does not substantially dissolve the dispersed polymer particles produced by the polymerization, but is a good solvent for the dispersion stabilizer and radically polymerizable unsaturated monomer. Included. Specific examples of organic solvents that can be used include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene;
Alcohol, ether, ester and ketone solvents, such as isobrobyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methyl Examples include hexyl ketone, ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. Each of these can be used alone or in a mixture of two or more, but generally , aliphatic hydrocarbons are preferably used in combination with aromatic hydrocarbons and alcohol-based, ether-based, ester-based, or ketone-based solvents such as those mentioned above. Furthermore, halogenated hydrocarbons such as trichlorotrifluoroethane, metaxylene hexafluoride, tetrafluorobutane, etc. can also be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2,2-azoisobutyronitrile, 2,2'-azobis(2,4-dimethylvalenitrile), penzoyl peroxide, and lauryl peroxide. Examples include peroxide-based initiators such as oxide and tert-butyl bar octoate, and these polymerization initiators generally contain 100% of the monomer (radically polymerizable unsaturated monomer) to be subjected to polymerization.
It can be used in a range of about 0.2 to 10 parts by weight. The amount of the dispersion stabilizer resin to be present during the polymerization can be appropriately selected from a wide range depending on the type of resin, but in general, 3 parts by weight of the radically polymerizable unsaturated monomer is used per 100 parts by weight of the resin. About 400 parts by weight, preferably about 10 to 240 parts by weight may be used.

In the present invention, by combining a dispersion stabilizer resin and polymer particles, the storage stability of non-aqueous dispersions is improved, and a cured film with better transparency, smoothness, mechanical properties, etc. is formed. can do. Examples of the method for bonding the dispersion stabilizer resin and the polymer particles include a method of polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable double bond. can.

The most effective method for introducing polymerizable double bonds is to add α,β monoethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid to a portion of the oxysilane groups in the resin. Although convenient, there are other methods such as adding an incyanate group-containing monomer such as isocyanoethyl methacrylate to hydroxyl groups that have been incorporated in the resin in advance, and adding glycidyl methacrylate to some of the carboxyl groups in the resin. There are methods such as adding a monobase of .

Furthermore, as a method for bonding the dispersion stabilizer and the polymer particles, in addition to the above-mentioned method, as a monomer component forming the polymer particles, for example, γ-methacrylate trimethoxysilane, γ-methacrylate trimethoxysilane, etc. γ-acryloxybutyltriethoxysilane, γ-acryloxybutyltriethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-
There are methods that use reactive monomers such as acryloxib-biltrisilanol.

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 may be such that the non-aqueous dispersion accounts for about 1 to 100% by weight, preferably about 10 to 80% by weight, based on the total resin solid content of both.

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 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.

Aluminum chelate compounds can be prepared, for example, by the general formula [wherein Rl3 is the same or different and has 1 to 1 carbon atoms]
20 alkyl or alkenyl groups are shown. ] 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 (i 0 1) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisobroboxide, aluminum tri-n-butoxide, aluminum triisobutoxide, Examples include aluminum tri-sec-butoxide, aluminum tri-tert-butoxide, etc., and it is particularly preferable to use aluminum triisopropoxide, aluminum tri-secC-butoxide, aluminum tri-n-butoxide, and the like.

The titanium chelate compound has, for example, the general formula [wherein W and RI3 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 general formula (i02) include:
In those where W is 1, tetramethyl titanate, tetraethyl titanate, tetra n-probyl titanate, tetraisobutyl titanate, tetra n-butyl titanate, tetraisobutyl titanate, tetra ter
Examples include t-butyl titanate, tetra-n-bentyl titanate, tetra-n-hexyl titanate, tetra-isooctyl titanate, tetra-n-lauryl titanate, and especially tetraisobutyl titanate, tetra-n-butyl titanate, and tetra-isobutyl. titanate,
Suitable results are obtained using tetratert-butyl titanate and the like. Also, for those where W is 1 or more,
Tetraisobutyl titanate, Tetra n-butyl titanate, Tetra lysobutyl titanate, Tetra t
A dimer to a 11-mer (w=1 to 10 in general formula (i02)) of ert-butyl titanate gives preferable results.

The zirconium chelate compound has, for example, the general formula [wherein W and Rl3 have the same meanings as above]. ] For each mole of Zrl in the zirconates represented by
It can be suitably prepared by mixing at a molar ratio of less than 1 molar and heating if necessary.

Examples of the zirconates represented by the general formula (i03) include tetraethyl zirconate, tetra n-propyl zirconate, tetraisopropyl zirconate, tetra n-butyl zirconate, tetrasee-butyl zirconate, and tetratert-butyl zirconate. Nate,
Tetra n-pentyl zirconate, Tetra tert
-bentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, etc., especially tetra-tert-tert-hexyl zirconate, tetra-tert-probyl zirconate, and tetra-tert-hexyl zirconate. Suitable results are obtained using esters such as ester, tetraisobutyl zirconate, tetra n-butyl zirconate, tetra sec-butyl zirconate, tetra tert-butyl zirconate, and the like. In addition, for those where W is 1 or more, tetraisobutyl zirconate, tetra n-probyl zirconate, tetra n-butyl zirconate, tetra isobutyl zirconate, tetra sec-butyl zirconate, tetra tert-butyl zirconate 2
From the whole, 11-mer (W in general formula (i03) = 1 ~
10) gives suitable results. Also, these. It may also contain a constituent unit in which zirconates are associated with each other.

Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, and tris(n-butylacetoacetate)aluminum. , Isoproboxybis(ethylacetoacetate)aluminum, Diisobutyboxyethylacetoacetatealuminum, Tris(acetylacetonato)aluminum, Tris(probionylacetonato)aluminum, Tris(ethylacetonate)aluminum, Diisobutyboxypboxypropylaluminum nylacetonatoaluminum,
Acetylacetonate bis (probionyl acetonate)
Aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(isobrobylate)aluminum, tris(see-butyrate)
Aluminum, diisobutyrate mono-see-butoxyaluminum, aluminum chelate compounds such as tris(acetonatoacetone)aluminum; diisobroboxyφbis(ethylacetoacetonato)titanate,
Diisopropoxy bis(acetylacetonato) titanate, diisopropoxy bis(acetylacetonato)
Titanium chelate compounds such as titanates; tetrakis(acetylacetone) zirconium, tetrakis(n-
Examples include zirconium chelate compounds such as propylacetoacetate) 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.
Heavy! 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 view part.

To the curable composition of the present invention, the above-mentioned chelating agent, preferably a compound such as acetic acid esters and β-diketones, can be added 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 contain at least two oxirane groups in one molecule and have a number average molecular weight of 20.
A low molecular weight compound of 0.00 or less can be blended. This low molecular weight compound acts as a reactive diluent, and by adding it to the paint composition, it can lower the viscosity of the paint and increase the solid content.It also produces less byproducts during curing, so it can be used uniformly. 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.

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 with nate compounds (polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; xylylene diisocyanate) or cycloaliphatic diisocyanates such as isophorone diisocyanate; organic diisocyanates themselves such as tolylene diisocyanate, aromatic diisocyanates such as 1, or 4,4'-diphenylmethane diisocyanate, or polyhydric diisocyanates with each of these organic diisocyanates. Examples of typical commercially available products include adducts with alcohol, low molecular weight polyester resins or water, polymers of each organic diisocyanate as described above, and isocyanate Q biuret. Parnock D-750, -800
, DN-950, -970 or 15-455J
[The above are products of Dainippon Ink and Chemicals], "Desmodule LSNHL, IL or N3390J [product of Bayer, West Germany],""Takenate D-102, -2"
02, -110N or -123N" [Takeda Pharmaceutical Co., Ltd. product], "Coronate L1HLSEH or 20
3J (Japan Polyurethane Industrial Product) or “Duraney” 24A-90CXJ [Asahi Kasei Product]
(e.g., tetrahydrophthalic anhydride, trimethylolpropane and 1.4
Examples include those obtained by oxidizing an esterified product with a number average molecular weight of 900 obtained by esterifying -butanediol etc. with peracetic acid etc.

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.

The molecular weight of compounds with two or more oxirane groups in one molecule is the number average molecule! It is important that the number is 2000 or less. Number average molecule! If it 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 an oxirane group is preferably about 0 to 100 parts by weight, preferably 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 Epicor 1001 (manufactured by Shell Chemical) or a hydroxyl group-containing resin such as styrene allyl alkote 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 1-bake coating or a top clear paint for 3-coat/2-bake coatings, approximately 100 parts by weight of the base resin, 0.1 to 30 parts by weight of the chelate compound, and 0 to 100 parts by weight of the coloring pigment are used. Appropriate. As the coloring pigment, 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-type titanium oxide or carbon black, and quinacridone. Organic pigments such as quinacridone-based pigments such as red, azo-based pigments such as pigment red, and phthalocyanine-based 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,
Usually used without the addition of colored pigments.

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.

When the coating composition of the present invention is used as an intermediate coating for automobiles, the composition includes 100 parts by weight of the base resin and 0.0 parts by weight of the chelate compound. Approximately 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 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, it is appropriate to apply for about 12 to 30 seconds (Ford Cup NQ.4, 20°C), and it may be selected appropriately 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, those having a boiling point of about 150° C. or lower are preferable, but are 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).
Intermediate paint and / 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 determined based on the film thickness after drying. fee,
Metallic color paint for 1 coat/1 bake coat, 2
Coat/1 bake top clear paint, 3 coats/2
When used as a top clear paint for baking, etc.
About 20 to 60 μm, preferably about 30 to 40 μm,
When used as a 2-coat/1-bake metallic base coat paint, the thickness is about 10 to 25 μm, preferably 1
Approximately 0 to 20 μm is appropriate.

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.

Doctor A. Q -0-Si- Next, this bond coordinates to the silanol group (for alkoxysilane groups, aceticoxysilane groups, etc., it becomes a silanol group due to moisture in the air), and polarizes the silanol group. . 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
−c 0H. 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.
It can exhibit excellent curability. 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.

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. It contains a chelate compound. From this, the workability when painting the composition is improved, and the coating has a good texture.
A film with excellent finished appearance can be formed. Furthermore, the formed film has a continuous phase of siloxane bonds and C-F.
It is a photo- and chemically stable coating with bonding, and the polymer particle component in the coating is stabilized by the continuous phase, and the coating is reinforced by the particle component, so it is photo- and chemical-resistant. It has excellent properties and mechanical properties such as impact resistance.

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

(i) A coating film having a high degree of smoothness, sharpness, and texture 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 since it is a dispersed resin composition, the volumetric shrinkage during the coating film curing process is small. It is possible to obtain a highly smooth coating film with excellent durability and no slight unevenness (chirpy skin). Therefore, the image clarity is also excellent.

■ 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.

(4) Very 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, problems such as stains, dullness, and etching caused by acid rain etc. do not occur at all.

0 Strong stain resistance. That is, it has high 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.

0 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.

(7) Good scratch resistance. Good scratch resistance is achieved 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. In other words, 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 and curing, there is little difference in curability between the surface and inside 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
In a stainless steel autoclave with a stirrer (No. 0011112), CH2 = CHOC4 Hs OH 40 parts by weight Methyl isobutyl ketone 200 parts by weight Azobisisobutyronitrile 2 parts by weight Sodium borate 0
．． After charging 2 parts by weight, purging with nitrogen, solidifying by cooling, and degassing, 50 parts by weight of CF2=CFCQ was introduced into the autoclave, and the autoclave internal temperature was 60°C.
The temperature was gradually increased until reaching . Thereafter, the reaction was continued with stirring for more than 16 hours, and the internal pressure of the autoclave was reduced to 1 kg/kg.
When the temperature decreased to below c&, the autoclave was cooled on ice to stop the reaction. The obtained resin solution was poured into excess hebutane to precipitate the resin, followed by washing and drying to obtain 92 g of resin (a). Yield 92%. The number average molecular weight by GPC was 5,500. The obtained resin,
It was dissolved in the same amount of xylene to obtain a resin solution containing 50% non-volatile components.

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

Table 1 shows the amount of monomer charged (parts by weight) and the number average molecular weight (Mn) of the copolymer.

In addition, the production example of macromonomer A is listed below: Methyltrimethoxysilane H3 CS i (OCH3 ) a2720g (20) Vinyltrimethoxysilane 148gCH2 =C
HS i (OCH3)3 (i 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-based macroheptanomer 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 (e) and (f)] An acrylic copolymer varnish having the composition (parts by weight) shown in Table 2 was obtained using a conventional acrylic copolymer face synthesis recipe. Both are xylene solutions containing 50% non-volatile components. Table 2 also lists the number average molecule i (Mn) determined by GPC.

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

Table 2 Production Example 3 [Production of copolymer (i)] In a glass flask with a capacity of 400 and equipped with a stirrer, 200 parts by weight of copolymer (a) solution (non-volatile content 50%) (C H30) 3S i 03 Hs N C 02
5 parts by weight H3 C CH2Nco 50 parts by weight xylene 75 parts by weight were charged, 9
The reaction was continued under stirring at 0° C. for 5 hours.

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

Production Example 4 [Production of copolymer (2)] In a glass flask with a capacity of 400 and equipped with a stirrer, 200 parts by weight of copolymer (b) solution (non-volatile content 50%) (C2 85 0>2 (H3C) SIC 3H
s Neo 15 parts by weight xylene 55 parts by weight were charged, 9
The addition reaction of the 10H group and the -NGO group was continued under stirring at 0°C for 5 hours. In the infrared absorption spectrum, the absorption of the NOC group disappears, indicating that -OH group, -S i (C
It was confirmed that H3) (OC2 HU (2)) was obtained.

Production Example 5 [Production of copolymer (3)] In a glass flask with a capacity of 400 and equipped with a stirrer, 200 parts by weight of copolymer (C) solution (non-volatile content 50%) (Cl 3COO) 3 SiC a 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 group and -N
The addition reaction of CO groups was continued. In the infrared absorption spectrum, the absorption of -NCO group disappears, so 10H
group, -Si(OCHa)3- group, was confirmed.

Production Example 6 [Production of copolymer (4)] In a glass flask with a capacity of 400 nl2 equipped with a stirrer, 200 parts by weight of copolymer (d) solution (non-volatile content 50%), total 40 parts by weight, and 40 parts by weight of xylene were charged.
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 (4) were obtained.

Production Example 7 [Production of copolymer (5)] In a glass flask with a capacity of 400111I2 and equipped with a stirrer,
Copolymer (e) solution (nonvolatile content 50%) 200 parts by weight 15 parts by weight (C2 H5 0) 3 S i C3 H6 NCO
Add 5 parts by weight of xylene and 20 parts by weight, and
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 (5), was obtained.

Production Example 8 [Production of copolymer (6)] 200 parts by weight of copolymer (f) solution (non-volatile content 50%) (CH3Coo)2 SICa Hs SH! CH3 20 parts by weight xylene Add all 20 parts by weight, 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 10H group was obtained because the absorption of -SH group disappeared.

Production Example 9 [Production of dispersion stabilizer (i)] Introducing double bonds into copolymer (i) A solution of copolymer (i) (nonvolatile content 50%) was placed in a glass flask equipped with a stirrer with a capacity of 400. 200 parts by weight CH2 -C (CH3)COOC2 H4NCO2.
8 parts by weight Hydroquinone 0.02 parts by weight Xylene
Add 2.8 parts by weight and add 110 parts by weight while stirring.
The addition reaction was carried out at ℃ for 5 hours, and the isocyanate value was 0.
I confirmed that it was below 001. This means that an average of 1.0 copolymerizable double bonds were introduced per molecule of the copolymer.

Production Example 10 [Production of dispersion stabilizer (2) (2'') < 5)] Double bonds were introduced into the copolymer in the same manner as Production Example 9. Table 3 shows the copolymer, added isocyanate The average number of copolymerizable double bonds per molecule of monomer and copolymer is listed.The number of copolymerizable double bonds was adjusted by the amount of isocyanate monomer charged.

Production Example 11 [Production of dispersion stabilizer (3)] Copolymer (3)
) Into a glass flask equipped with a stirrer with a capacity of 400, 200 parts by weight of copolymer (3) solution (non-volatile content 50%), 2 parts by weight of H2C=C(CH3)COOH, 4-
tert-butyl virocateur 0.02 parts by weight dimethylaminoethanol 0.1 parts by weight xylene
Add 2 parts by weight and add 120 parts by weight while stirring.
Addition reaction was carried out at ℃ for 5 hours, and the resin acid value was 0.001m.
It was confirmed that the concentration was below gKOH/g. Copolymer 1
per molecule, average 0. This means that six copolymerizable double bonds have been introduced.

Production Example 11 [Production of Dispersion Stabilizers (3'), (4), and (6)] Double bonds were introduced into each copolymer in the same manner as in Production Example 10. Table 4 lists the copolymer, the added α,β-ethylenically unsaturated monocarboxylic acid, and the average number of copolymerizable double bonds per molecule of the copolymer. The number of copolymerizable double bonds was adjusted by the amount of α,β monoethylenically unsaturated monocarboxylic acid charged.

Table 4 [Example 1 [Production of dispersed polymer liquid (i)] Hebutane
80 parts by weight n-butyl acetate
10 parts by weight dispersion stabilizer (i) solution (non-volatile content 50%)
200 parts by weight was charged into a flask, heated under reflux, and the following monomers and polymerization initiator were added dropwise into the flask over a period of 3 hours. After further aging for 2 hours, 10 parts by weight of n-butyl acetate was added.

CH2-CH@10 parts by weight CH2-OH
-CN 10 parts by weight CH2-C (CH3
) COOCH338 parts by weight CH2 -. C (CH3) COOC2 H4 0H1
0 parts by weight 15 parts by weight CH2 -C(CH3) COOC a H s S1
(OCR3) 315 parts by weight C H 2 = C H + C H = C H 2
2 parts by weight tert-butyl baroxy-2-ethylhexanoate 1.5 parts by weight (total of particle forming monomer components 100 parts by weight, particle components/dispersion stabilizer (solid content ratio) -50/50) The nonvolatile components of the dispersant were adjusted to 50% with n-butyl acetate, if necessary. It was a milky white stable dispersion in which the particle size of the polymer particles (average particle size according to Coulter N4 (Coulter)) was 0.15 μm. No precipitation or coarse particles were observed in this product even after it was allowed to stand at room temperature for 3 months.

Examples 2 to 11 [Production of dispersed polymer liquids (2) to (i1)] Dispersed polymer liquids were produced in the same manner as in Example 1. Table 5 shows the content of the dispersion stabilizer in the total resin (solid content weight %), the monomer composition ratio of the particle forming components (weight total %), and the average particle size of the produced polymer particles.

■) Copolymer (i).

2) Copolymer (6).

3)...Made by Daicel Kagakubun, hydroxyl group-containing cabrolactone modified methacrylic ester 4)...Average particle size by Coulter N4 (Coulter) Example 13 Copolymer obtained in the above production example and copolymer obtained in Example A top coating for automobiles was prepared using a dispersed polymer liquid. As the top coat, a solid color (white) and a 2-coat, 1-bake clear coat were prepared.

In addition, base coat A was produced as a two-coat, one-bake base coat.

Preparation example of solid color (white) (Paint NαS-1 to S-
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. Pigment content is resin/solid content 10
The amount was 80 parts by weight compared to 0 parts by weight. The amounts of the copolymers and dispersion polymers shown in Table 6 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.

Table 6 shows the amount of particle components in the dispersed polymer (disversion degree) in the total resin content in weight %.

Preparation example of clear coat for 2 coats and 1 bake (Paint NaM
-1 to M-17) are shown in Table 7. The meanings of the numbers in the table are the same as for solid colors.

At this time, the following chelate compounds were used.

・Chelate compound■・・・Tris(acetylacetonato)aluminum chelate compound■・・・Tris(ethylacetoacetate), aluminum chelate compound■・・・Tetrakis(acetylacetonato)zirconium chelate compound■・・・Diisobroboxy bis(acetylacetonato) titanate 2 coats below 1 bake base coat
A production example of A) is shown.

A base coat combining a two-coat, one-bake clear coat was produced as follows.

Methyltrimethoxysilane 2720g (20mol) γ-Methyltrimethoxysilane 256g!・Rimethoxysilane (imol) deionized water
1134g 60% hydrochloric acid
2g: Hydroquinone 1g The 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 1.100g 150g n-butyl acrylate 500g styrene 100g azobisisobutyronitrile A mixture of 10g was dropped into 1000g of an equal weight mixture of butanol and xylene at 120°C, and polymerized. A transparent copolymer was obtained. The number average molecular weight was approximately 30,000.

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

The blending amount is shown in terms of solid content weight.

The above copolymer: 95 parts Cellulose acetate butyrate 5 parts Aluminum trisacetylacetone 1 part
The viscosity was adjusted to 3 seconds (Ford cup Nll4, 20°C) and used for coating.

Table 6 [Preparation of coating material] A coating material was prepared as follows.

Preparation of Material (A) A chemical conversion-treated dull steel plate was coated with approximately 25 μm of epoxy resin-based cationic electrodeposition paint, and after curing by heating at 170°C for 30 minutes, Rugabake AM (trade name, manufactured by Kansai Paint ■) was applied as an intermediate coating. , a polyester resin/melamine resin automotive paint] was applied to a dry film thickness of approximately 30 μm and baked at 140°C for 30 minutes.Then, the painted surface was sanded with #400 sand baver, and dried. The material was made by wiping the painted surface with petroleum benzine.

Preparation of Material (B) Solex NG. 2500 was applied to a thickness of 15 to 20 μm and heated at 80°C for 20
The material that was baked for a minute was used as a paint material.

Preparation of test coated plate (I) Apply the topcoat solid color prepared above to the above material A using Swazol #1000 (trade name, Maruzen Sekiyu ■).
manufactured by Petroleum-based mixed solvent] for 22 seconds (Ford Cup Nα4
After adjusting the viscosity to
It was baked at ℃ for 30 minutes and used as a test plate.

In addition, the angle of the coated plate for evaluating the feeling of texture during the above-mentioned standing and baking was set at an angle of about 75° with respect to the horizontal plane.

As a comparison sample, Lugabake AM white (paint NαS-6
), a comparative test board was created in the same manner.

Further, the above material B was coated in the same manner and baked at 80° C. for 30 minutes. As a comparison product, letane PG-80 white [product name,
Kansai Bain}M made, paint No. S-73 was used.

The test results are shown in Table 8. In Table 8, paint No.
S-6 and S-7 are comparative examples.

Preparation of test coated plate (II) Apply base coat A to the above material A, leave it for about 5 minutes, and immediately apply clear coat (paint No. M-1 to M-11) diluted with Swasol #1000 for 22 seconds. Painted. The coating film thickness is 15 to 20 μm based on dry film thickness.
1 clear coat was 35-45 μm. Painting approx. 10
After standing at room temperature for a minute, baking was performed at 100°C and 140°C for 30 minutes.

Here, the angle of the coated plate for evaluating the feeling of texture during the above-mentioned standing and baking was approximately 75° with respect to the horizontal plane.

Also, as a base coat, Magiklon #1000 Silver, as a clear coat, Magiklon #1000 Clear [manufactured by Kansai Paint ■, acrylic/melamine resin paint, No. M-12, Comparative Example] was coated and baked in the same manner. It did not cure at 100°C. The results are shown in Table 9.

3) Pencil hardness: Scratch the coating surface with the lead of a Mitsubishi Yuji pencil,
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 that the image clarity is extremely excellent.

5) Feeling of texture As mentioned above, the feeling of texture of the coated plate which was left and baked at an angle of 75 degrees with respect to the horizontal plane was visually observed and evaluated.

◎...Excellent meatiness.

O...There is sufficient meatiness.

Δ...The finish is poor in texture and is rejected.

×...There is no feeling of meatiness. The finished appearance is particularly poor.

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

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) Weather resistance After immersing in 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. ◎, O, ■, △, × between no abnormalities at all (◎) and abnormalities such as significant shine and erosion (×)
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: ◎, ◯, ■, △, and X.

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 contamination dust on a 5 x 5 cm coated plate.
Spread it evenly by sweeping it 20 times with a brush,
It was left standing 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 According to the QUV accelerated weathering test using an accelerated weathering tester manufactured by Q Bunnell.

Test conditions: UV irradiation 16H/60℃ water condensation 8H/
The coating film was evaluated after being tested for 3000 hours (i25 cycles) at 50°C.

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

○: There is a slight decrease in gloss, but there are no defects such as cracking or whitening.

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

14) Storage Stability A paint diluted to a constant viscosity (22 seconds/Ford Cup No. 4) was stored at 40° C. for one week with a lid on to prevent contact with the outside air.

◎...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 (I) having a hydrolyzable group, an epoxy group, and a hydroxyl group directly bonded to silicon atoms in the same resin is used as a dispersion stabilizer, and radical polymerizable in an organic solvent in the presence of the dispersion stabilizer. A resin composition obtained by polymerizing an unsaturated monomer and containing polymer particles insoluble in the organic solvent. [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 (II) 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 is used as a dispersion stabilizer, and radicals are generated in an organic solvent in the presence of the dispersion stabilizer. A resin composition containing polymer particles insoluble in the organic solvent, obtained by polymerizing a polymerizable unsaturated monomer. [3] Fluororesin having a functional group and a silanol group and/or a hydrolyzable group directly bonded to a silicon atom (
E) is directly bonded to a silanol group and/or a silicon atom obtained by reacting (i) a compound (B) having an epoxy group and a functional group that reacts complementary to the functional group of the resin (E). A resin (III) having a hydrolyzable group, an epoxy group, and a hydroxyl group in the same resin 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 containing polymer particles insoluble in the organic solvent. [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.