JPH02228352A - Resin composition, curable composition, and coating composition - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. which gives a coating film excellent in the flatness and brightness by compounding a copolymer which comprises essential monomers consisting of a number of specific polymerizable unsatd. monomers. CONSTITUTION:A copolymer comprising essential monomers consisting of a polymerizable unsatd. monomer having a fluorine (e.g. CH2=CFCl), a polymerizable unsatd. monomer having a hydroxyl group [e.g. CH2=CHO(CH2)4 OH], a polymerizable unsatd. monomer having a hydroxyl and/or hydrolyzable group directly attached to silicon [e.g. CH2=CHSi(OH)(OCH3)2], and a polymerizable unsatd. epoxidized monomer (e.g. the compd. of the formula) is compounded.

Description

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

BACKGROUND ART Conventional techniques and their problems Conventionally, a method of curing a hydroxyl group-containing resin with a crosslinking agent such as diisocyanate or melamine has been employed. However, when diisocyanates are used, the resulting film has insufficient weather resistance and is susceptible to yellowing.

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

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

As a one-component, non-toxic, low-temperature curable composition, for example, a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane is disclosed in JP-A No. 60-67553. things are disclosed.

However, in the above-mentioned conventional composition, since the silanol group produced by hydrolysis of alkoxysilane is the only crosslinking functional group, a large amount of water is required for curing, and a large amount of alcohol etc. produced during this hydrolysis is required. Disadvantages include that the physical properties of the cured product are not sufficient due to the by-products, and that when cured with only moisture in the air, it hardens from the surface, making it difficult to harden the inside and causing stiffness in the cured product. There is.

Means for Solving the Problems The inventors of the present invention have conducted extensive research in order to solve the above-mentioned problems. As a result, a fluorine-containing polymerizable unsaturated monomer, a hydroxyl group-containing polymerizable monounsaturated monomer, a polymerizable unsaturated monomer having a hydroxyl group and/or a hydrolyzable group directly bonded to silicon, and an epoxy group A curable composition in which a metal chelate compound is blended with a resin containing a polymerizable unsaturated monomer as an essential monomer component has excellent storage stability even in a corrugated form, and is curable without worrying about toxicity. The present inventors have discovered that it is possible to form a coating film with excellent weather resistance, acid resistance, scratch resistance, and stain resistance, and have completed the present invention.

That is, the present invention provides a fluorine-containing polymerizable unsaturated monomer (A)
, a hydroxyl group-containing polymerizable unsaturated monomer (B), a polymerizable unsaturated monomer (C) having a hydroxyl group and/or a hydrolyzable group (hereinafter referred to as "silane group") directly bonded to silicon (hereinafter referred to as "silane group") (referred to as "silane group-containing polymerizable unsaturated monomer"), and a copolymer having an epoxy group-containing polymerizable unsaturated monomer (D) as an essential monomer component. A composition, a curable composition characterized by blending the resin composition with a metal chelate compound as a curing catalyst, and a paint characterized by containing the resin composition or curable composition as an essential component. Regarding the composition.

The resin composition of the present invention contains a fluorine-containing polymerizable unsaturated monomer (
A), hydroxyl group-containing polymerizable unsaturated monomer (B), silane group-containing polymerizable unsaturated monomer (C), epoxy group-containing polymerizable unsaturated monomer (D), and other as necessary. It contains a copolymer obtained by copolymerizing the polymerizable unsaturated monomer (E).

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

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

-Formation (1) % formula % (1) In the formula, X is the same or different, and H, Cβ, 8 atoms,
F., alkyl group or halo. Indicates an alkyl group, provided that it contains at least one F in the formula.

General formula (2) %Formula% In the formula, R1 represents a hydrogen atom or a methyl group, and R''!17
J.

It represents an oloalkyl group, and n represents an integer of 1 to 1O.

It is preferably C8-4. in particular.

Examples include methyl, ethyl, propyl, isopropyl, butyl, and pentyl groups. Further, the "haloalkyl group" is a group having 3 to 6 carbon atoms, preferably 8 to 4 carbon atoms. Specifically, for example, CF, CHF*, CH, F,
CC, CB, Nimu, CH2Cl, CH2Cl
.

CFCl, , ((:Fi) lCF3 , (CFx
) 5CF21. CFxCHs, (:FiCHFi,
Examples include CFtBr and CHJr.

Examples of monomers represented by the general formula (1) include CF, =CF2, CHF=(:F, , CI(2
=CF2, CH2=CHF, CC1niCF,,
CC1=CC1, cC12=cF2, CGIF=CCI
F.

CHF=(:C12, CH, 2CCIF, CC12=C
(1; IFCF, (:F CF, , CF, CF2C
IC, CFICH CF, CF, (:F=CH,
1, CHF2CF=CHF, CH,CF=CF,,C
M, CF=CH2, CF2CICF=CF2, CF, C
C1=CF,.

CF, CC=CC1, CF2ClCC1=CF2, CF
, CICF-=CFCI.

CFCl, CF=CF, CF2CC1=CCLF
%CF, CC1=CC12.

CGIP, CC=CC1□, C(:1.CF=CF,,
CF2CIC(:1=(:C12, CFCl, CC1
=CC1,,CF,CF=CHC1,CCIF,CF=
CHC1:CF, (:Cl=CHC1, CHF2CC1
=CC12,CF-CICH:CCIt,CF,CI
C(J=(:HCI, CCl5(:F=CHC1,
CF, ICF=CF2゜CFJr(:I("CFz,
CF=CBr=C1(Br%CF2CICBr=C
Hz, CHzBrCF=CC12, CF-CH=CH1
, CF2cH=cHBr, CFz°BrCH=CHF
, CFzBrCF=CF4 , CF3CF2CF=
CFz, to F3CF=CF(:F, , CF, CC=C
C1,,CF,=CFCF,CHF2,CF,CF,,
CF=CH2, CF, CC=CC1,, CC1=CC1
,CH,,CC1=CC1,CH,,CF,CH,CH
=CH2, cF3cH=cHc)+3°(,F1=CH
CH2CHs, CHjCF2CH=CH2, CF2CI
C1(CFH!, CIICF, CH=CH1, CH
,=CFCH2CH3,cFs (CF,) ICFHarukaCF, ,CF,(,CF,)s(:F=CF.

etc. can be mentioned.

The "fluoroalkyl group" in general formula (2,) is Cx
-z+ items. Specifically, for example, C, F,
(CFri8CF(CF,)!, C,F,, ,
C. Fil, etc. can be mentioned.

42 As the monomer represented by formula (2), for example, CH.

CH2=C-C0O-C2H4-Cd.

\ CF. CH3 CH,=C-Coo-C,H4-C,F,.

Examples include CH□ CH2=C-Coo-C'2H-C1CF21.

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

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

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

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

-Formation (3) General formula (4) In the formula, R3 has the same meaning as above.

-Formation (5) In the formula, R1 has the same meaning as above, m is an integer of 2 to 8, P is an integer of 2 to 18, and q is an integer of 0 to 7.

General formula (6) In the formula, R1 has the same meanings as I and η as above, and in T1 and the formula, R is a water atom or a hydroxyalkyl group, and T2 is the same or different, and Represents a divalent hydrocarbon group, S and U are each integers of 0 to 10, provided that S
The sum of and U is 1 to 10.

- The "hydroxyalkyl group" in formations (3) and (4) is 01 to 6. Specifically, for example -
Examples include C2H40H, C3Ha OH%-c, and H80H.

- The C7-π divalent hydrocarbon group in formation (6) is, for example, CI.

-C,,H,,-1-C,LH,-1-C,,)l,6
7, -0-10-1-CHyo=C)-CH,7 and the like.

As the monomer component of general formula (3), for example, 0H2-C
Examples include HOH CH2-CHOC, H, OH.

As the monomer component of general formula (4), for example, CH! =C
HCH,0H CH,=C)ICH,0CH2C1,0HCH*=CH
CHzO(CHzCHiO)THCl, =CHC:H,
It is possible to list OiCHRCH*OtrH, etc.

As the monomer component of general formula (5), for example, CH,
=C”-(CL) C00C2H40)ICH1=CH
C00C,H,OH ■ ctti=c-(ctts) C0O-C3H,-0-
Examples include EC-C1, -CH, -CH, t-CH, -CL-0tr=yH, and the like.

As the monomer component of general formula (6), for example, CHx:C-(CHx) COO(CH-CMCM-0
)T=TC00(CH-C--COO(CHzCHiO
)T-rHCHz:C' (CH3)COO(CM-C
Examples of H-0)7=yH include those represented by the following - formation.

-0-R+ (7,) -0-C-R.

I am able to list things like this.

Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the above-mentioned -formations (3) to (6) and ε-caprolactone, γ-
Adducts with lactones such as valerolactone can be used. Polymerizable unsaturated monomer (C) having a silane base is a monomer containing a hydroxyl group and/or a hydrolyzable group directly bonded to silicon and a radically polymerizable unsaturated group in one molecule. A hydrolyzable group directly bonded to a silicon atom is a group that is hydrolyzed by water or moisture to produce a silanol group. As a go game, in the example formula, R4 is an alkyl group of 01 to 4, R5-R7
are the same or different and represent an alkyl group, an aryl group, or an aralkyl group of 01 to 8.

In the general formula, the "alkyl group of CI-8" is:
For example, methyl, ethyl, n-propyl, 1sopropyl, n-butyl, 1sobutyl, secbutyl, tert
Examples include butyl, n-pentyl, isobentyl, n-octyl, isooctyl, and the like.

Examples of "aryl group" include phenyl, tolyl,
Examples include xylyl. Examples of the "aralkyl group" include benzyl and phenethyl.

Also, the hydrolyzable compound bonded to the silicon atom described above.

In addition to the groups, a --)Si-H group can be mentioned as a hydrolyzable group.

In the composition of the present invention, silane groups represented by the above general formulas (7) and (8) and silanol groups are suitable from the viewpoint of storage stability, curability, etc.

In addition, as a radically polymerizable unsaturated group, for example, CH or -
Examples include C-Cl+2-C1[()-CH□-CHCHp- (R4 has the same meaning as above).

Examples of the silane group-containing polymerizable unsaturated monomer (C) in which the radically polymerizable unsaturated group is CH, -CC(X)- include a compound represented by the following general formula (13).

In the formula, R+ has the same meaning as above, R8 represents a divalent hydrocarbon group of C9 to +, and Y is the same or different and represents a hydrogen atom, a hydroxyl group, a hydrolyzable group, C, ~8 Indicates an alkyl group, an aryl group, or an aralkyl group. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Hydrolyzable groups, C4-8 alkyl groups, aryl groups, aralkyl groups, and C,202-valent hydrocarbon groups include 1 as mentioned above, such as 1 (meth)acryloxypropyltrimethoxysilane, γ- (meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyljethoxysilane, γ-( Meta)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldiethoxysilane, γ-(meth)acryloxybutylphenyldiethoxysilane , γ−
(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane.

γ-(meth)acryloxypropylphenylmethylmethoxydisilane, γ-(meth)acryloxypropylphenylmethylethoxysilane, γ-(meth)acryloxypropyltrisilanol, γ-(meth)acryloxypropylmethyldihydroxysilane, γ-(meth)acryloxybutylphenyldihydroxysilane, γ-(meth)acryloxyprobyldimethylhydroxysilane, γ
-(meth)acryloxypropylphenylmethylhydroxysilane, C) 130 occtt.

Hn 2Hs Silane group-containing polymerizable unsaturated monomer? For example, compounds represented by the following formulas (14) to (16) TC can be mentioned.

In each formula, R, R1, and y have the same meanings as above, and Y may be the same or different. At least one of Y is a hydrogen atom, a tetrahydroxyl group, or a hydrolyzable It is the basis.

Specific examples of compounds represented by formulas (14) to (16) include 1, for example, CHi"CSI Examples of saturated monomers include the following -formation (
Compounds represented by (17) and (18) can be mentioned.

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

Specific examples of compounds represented by the general formulas (,17.) and (18) include, for example, CH-=CHSi (OCH3) 5 CHi=CH-Sl (OCJi) sCH,=CH-
, --Si (OCH3) 2C)lUCH2=CI
','5l(CH3)20CHyuCH2"C'H
-CL-5L(OCHiliCH,=CH-5i (0
(1:(:H, l.

CI(,=C■-CHtSi(OCCH3)
5CH1CH,'Si (CHsl zNlcH31x
Y may be the same or different, and at least one Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group.

Specific examples of compounds represented by general formulas (19) and (2o゛) include, for example, CHl=CH---Sit-Ql, ON (CII
l* etc. can be mentioned.

Examples of the silane group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH=CHD- include compounds represented by the following formulas (19) and (20).

CH,H C3 CHt”CHO-(CH-1-5i-OCH-0CH.

In each formula, R2 and Y has the same meaning as above, cow C, H.

I can raise a hat.

The radically compatible unsaturated group is C)(2.CHCl1.O-
Examples of the silane group-containing normally unsaturated monomer include compounds represented by the following formulas (21 and (2)).

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

Specific examples of compounds represented by general formulas (21) and (22) include CH,=C)[CH,0-(CI21, -5i-occ
zHs0CCH.

Recommended C-Hl CH2=CHCH,O-(CHI) z-Si-OCJ
sCHl can be mentioned.

In addition to the silane group-containing polymerizable unsaturated monomer, the silane group-containing polymerizable unsaturated monomer is reacted with, for example, a polysilane compound (for example, a compound represented by formulas (23) to (25)). Similarly, a polysiloxane unsaturated monomer having a silane group and a polymerizable unsaturated group obtained by this process can be obtained at a cost of 3.

[Polysilane compound]

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

Compounds can be mentioned.

Y.

In each formula, Y's are the same or different hydrogen atoms.

The hydroxyl group or hydrolyzable group, R9, is the same or different and represents an alkyl group, an aryl group, or an aralkyl group.

Specific examples of compounds represented by general formulas (23) to (25) include dimethyldimethoxysilane, dibutyldimethoxysilane, di-1so-propyldibroboxysilane, diphenyljethoxysilane, and diphenyljetoxysilane. Toxysilane, diethyldisilanol, dihexyldisilanol methylmethoxysilane, methyltriethoxysilane, disilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane.

Phenyltributyloxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol, tetramethoxysilane, tetraethoxysilane, tetrapropioxysilane, tetraacetoxysilane, di-1so-probioxydiparellooxy, silane,
A polysiloxane macromonomer obtained by reacting 99.999 mol% of tetrasilanol (for example, JP-A-6
2-275!32) and the compounds listed below.

CI”　OCH.

can be mentioned.

In addition to the above, it is also possible to use a condensate of two poly-IJ silane compounds.

As a specific example of the polysiloxane unsaturated monomer, for example, the compound represented by the formula (1 color) and at least one compound represented by the general formulas (23) to (25) may be combined in an amount of 30 to 0.001 mol% of the former. , the latter 70~OH'OC
R.

CCHs (R1 has the same meaning as above.9 etc. can be mentioned.

Examples of the epoxy group-containing polymerizable unsaturated monomer include compounds represented by the following formulas (26) to (38).

Epoxy group-containing polymerizable unsaturated monomer (D) A monomer containing a radically polymerizable unsaturated group and an epoxy group in one molecule. The epoxy group may be alicyclic or aliphatic, but the alicyclic epoxy group has the effect that the addition reaction of the epoxy group to the hydroxyl group is fast, and the curability of the coating film is further improved. demonstrate.

Examples of radically polymerizable unsaturated groups include CH2=C-
COO- I CH2= C, -CC- CH2=C=C-N- CH2=CHCH2-0- CH2=C=C- CH2=CH In each formula, R3 and R8 have the same meaning as above, and R3 and R8 may be the same or different.

W represents 0 and an integer from 1 to 10. RIG is the same or different and represents a C3-82 valent hydrocarbon group.

- Specific examples represented by the grain formulas (26) to (33) are 1. For example, epoxy-containing polymerizable unsaturated monomers are 1. For example, the following - Formulas (39) to (41) are can be mentioned.

In each formula, R2 and R1 have the same meanings as above, and R and R may be the same or different.

Specific examples of the compounds represented by the general formulas (39) to (41) include compounds represented by the following formulas (102) to (+lf) as epoxy-containing polymerizable unsaturated monomers. Can be done.

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

Specific examples of the compounds represented by the 10Ω formula (, qz ) to (71-1) include the following.

Examples of the epoxy-containing polymerizable unsaturated monomer in which the radical macrounsaturated group is CH, =C-5C-N- include compounds represented by the following formulas (It5) to (5Q). can.

In each formula, *R(-Rto, Ry and W have the same meanings as above, and R,, R, and R1 may be the same or different.

Specific examples of the compounds represented by the general formulas (↑5) to (5o) include one example.

Examples of the epoxy group-containing polymerizable unsaturated monomer having a radically polymerizable unsaturated group of C1, .CHCH, O- include compounds represented by the following formulas (51) to (5,000S).

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

Specific examples of compounds represented by formulas C, 51) to (5f) include 1, such as CH.

can be mentioned.

Examples of epoxy group-containing unsaturated monomers in which the radically polymerizable unsaturated group is CH2/Ct (O-) include compounds represented by the following formulas (5) to r, 5-7. .

In each formula, R2 and R1 have the same meanings as above, and R
7 and 7 may be the same or different. Specific examples of the compounds represented by the general formulas (Kinut) to (5) include Fuki.

As an epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2/C1 (-, for example, the following formula (53
) to (60) can be mentioned.

In each formula, R and R7o have the same meanings as above, and R
7° may be the same or different.

Specific examples of the compounds represented by the two RQ formulas (,3f) to (6ρ) include the following epoxy group-containing unsaturated monomers:
Examples include compounds represented by formulas (6t) to (65).

In each formula, R1, Rlo and Rg have the same meanings as above, and 1. R1 and Rg may be the same or different.

Specific examples of the compounds represented by R';= Formulas (61) to (65) include examples.

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

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

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

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

(E-3) Vinyl esters and propenyl esters: for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl paricate, vinyl caprate, and isopropenyl acetate. Propenyl esters such as impropenyl propionate, etc.

(Sen-4) Esters of acrylic acid or methacrylic acid: For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate , ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, methyl methacrylate, etc.The original text is an alkyl ester of methacrylic acid having 1 to 18 carbon atoms: methoxybutyl acrylate. Methoxydibutyl acrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylic acid, ethoxybutyl methacrylate with 2 to 2 carbon atoms in acrylic acid or methacrylic acid
18 alkoxyalkyl esters, etc.

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

(E-6) Others: acrylonitrile, meth (E-1
) to (E-6), a carboxyl group-containing polymerizable unsaturated monomer (E-7) can be used. Use of this monomer has the effect of improving the curability of the film.

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

- Formula (66) In the formula, R represents a hydrogen atom or a lower alkyl group, R represents a hydrogen atom, a lower alkyl group, or a carboxyl group, and R and 3 represent a hydrogen atom, a lower alkyl group, or a carboxy lower Indicates an alkyl group.

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

In the formula (66), the low alkyl group is 04
methyl groups are preferred, especially methyl groups. Delicious.

- Examples of formula (66) include acrylic acid, methacrylic acid, crotonic acid, ibuconic acid, maleic acid, maleic anhydride, and fumaric acid.

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

In addition to the above, hydroxyl group-containing polymerizable unstructured fO monomers (
e) A combination of 1 mole of a polycarboxylic anhydride (eg maleic anhydride, iconic anhydride, conoctate anhydride, phthalic anhydride, etc.) compound can also be used.

The blending ratio of the monomer components may have the following range based on 48 weight h1 of the monomer.

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

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

Hydroxyl group-containing polymerizable unsaturated mono-noble (B.): about 0, 1~
50% by weight, preferably about 3-30% by weight. Approximately 0
．． If it is less than 1% by weight, the curing properties will be insufficient, resulting in a coating film inferior in pheasant roll resistance, hardness, mechanical properties, etc. On the other hand, if it is more than about 50% by weight, it will be inferior in water resistance, weather resistance, mechanical properties, etc. This is not preferable because it forms a coating film.

Silane group-containing polymerizable unsaturated monomer (C): about 1 to 60% by weight, preferably about 5 to 50% by weight. Approximately 1% by weight
If the amount is less than 60 wt.
If the amount is more, the coating film will have a poor appearance (coating surface gloss, etc.), which is not preferable.

Epoxy group-containing polymerizable unsaturated monomer (D): about 5 to 80
% polymerization, preferably about 10-60% by weight. If the polymerization amount is less than about 5% by weight, the curability will be insufficient, resulting in a coating film with poor pheasant roll resistance, hardness, and mechanical properties.On the other hand, if it exceeds about 80% by weight, the coating film will have poor mechanical properties, which is not preferred.

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

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

The copolymerization reaction of each of the monomer components described above can be carried out in the same manner and under the same conditions as those used for general synthesis reactions of acrylic resins, vinyl resins, and the like. An example of such a synthesis reaction is a method in which each monomer component is dissolved or dispersed in an organic solvent, and heated with stirring at a temperature of about 40 to 180°C in the presence of a radical polymerization initiator. Can be done. The reaction time may normally be about 1 to 24 hours. Furthermore, as the organic solvent, one that is inert to the monomer or compound used, such as an ether solvent, an ester solvent, a hydrocarbon solvent, etc., can be used. When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility.

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

The copolymer in the resin composition of the present invention has a molecular weight of about 1,000 to 200
000, preferably from about 3,000 to 80,000.

When the number average molecular weight is less than about 1000, scratch resistance,
The result is a coating film with poor stain resistance, weather resistance, acid resistance, etc.
If the number average molecular weight is greater than about 200,000, the storage stability of the composition, coating workability, II: L appearance, etc. will be poor, so it is not preferable.

In the resin composition of the present invention, a part of the functional groups (e.g., hydroxyl group, epoxy group, silane group, etc.) possessed by the above-mentioned resin components can be used to form other resins (e.g., vinyl resin, polyester resin, urethane resin, silicone resin). etc.) can also be used. The modified resin is
Each molecule must have an average of one or more hydroxyl group, epoxy group, or silane group.

The resin composition of the present invention can be used, for example, in hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as dioxane and ethylene glycol diethyl ether. Can be used with solvents, Buknol, propa tools, etc.

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

The metal chelate compound is preferably an aluminum chelate compound, a titanium chelate compound, or a zirconium chelate compound. Among these chelate compounds, chelate compounds containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring are preferred.

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

The aluminum chelate compound has, for example, the general formula % formula % [wherein R14 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 alcoholades represented by the general formula (68) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-5ee-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-5ee-butoxide, etc.
Preferably, ee-butoxide, aluminum tri-n-butoxide, etc. are used.

The titanium chelate compound has, for example, the general formula [wherein W and R14 have the same meanings as above]. ] Preferably prepared by mixing a compound capable of forming the above-mentioned keto-enol tautomer at a molar ratio of usually about 4 moles or less with respect to 1 mole of Ti in the titanates represented by the formula, and heating as necessary. can do.

Titanates represented by the general formula (6) include W
is 1, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert
-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, etc., especially tetraisopropyl titanate, tetra-n-
Suitable results are obtained using butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, and the like. In addition, for those where W is 1 or more, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert
- 11-mer from all 2 of butyl titanate (general formula (6
9), W-1 to W-10) give preferable results.

The zirconium chelate compound has, for example, the general formula [wherein W and R14 have the same meanings as above]. ] Preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of usually about 4 moles or less with respect to 1 mole of Zr in the zirconates represented by the formula, and heating as necessary. can do.

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

Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, Impropoxybis(ethylacetoacetate)aluminum, diisopropoxyethylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(propionylacetonato)aluminum, diisopropoxyprobionylacetonatoaluminum, acetylacetonato bis(propionyl) Aluminum chelate compounds such as monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisopropoxy bis(ethylacetoacetate) titanate, diisopropoxy bis(acetylacetonate) titanate, diisopropoxy bis(nato) titanate, diisopropoxy bis(
titanium chelate compounds such as acetylacetonato) titanate; zirconium chelate compounds such as tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate)zirconium, etc. can be mentioned.

Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or two or more types may be used in combination as appropriate. The blending Ω of the crosslinking reaction curing agent is based on the solid content of the resin composition: 100
It is appropriate to add about 0.01 to 30 parts by weight based on the weight of the heavy firefly.

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

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

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

The coating composition of the present invention may optionally contain a number average molecule ff1 containing at least two oxirane groups in one molecule.
A low molecular weight compound of 2000 or less can be blended. This low-molecular compound becomes a reactive diluent, and by adding it to a paint composition, it can lower the viscosity of the paint and increase the solid content, and also produces fewer byproducts during curing, so It is possible to obtain a high solid paint with excellent uniform hardening properties. Also, during curing, there is little sagging, resulting in a coating film with excellent smoothness.

Number average molecule ff120 containing at least two oxirane groups in one molecule that can be used in the present invention
00 or less, for example, compounds represented by the following formula, 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 or aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, or each of these organic diisocyanates, polyhydric alcohols, and low molecular weight polyester resins. or adducts with water, etc., polymers of each organic diisocyanate as described above, and isocyanate biuret bodies, etc. Typical commercial products thereof include [Parnock D-750, - 800,
DN-950, -970 or 15-4554 (
The above are products of Dainippon Ink Chemical Industry ■, Desmodur L, NHLSIL or N3390J [product of Bayer, West Germany], [Takenate D-102, -202]
, -11ON or -123N" [Takeda Pharmaceutical Company ■
Product], [Coronate L1HLSEH or 203J
(Nippon Polyurethane Kogyo product) or Duranate 24A-90CXJ (Asahi Kasei Kogyo product)) Examples include those obtained by oxidizing an esterified product (with a number average molecular weight of 900 obtained by a chemical reaction) with peracetic acid or the like.

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

It is important that the molecular weight of the compound having two or more oxirane groups in one molecule is no more than number average molecular ff12,000. When the number average molecular weight exceeds 12,000, the compatibility with the base resin used in combination decreases, making it impossible to form a coating film with excellent finish and coating performance.

The compound having an oxirane group is suitably added in an amount of about 0 to 100 parts by weight or about 10 to 60 parts by weight per 100 parts by weight of the base resin.

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

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

When the coating composition of the present invention is used as a top coat, examples of the composition include a top coat solid color paint, a two-coat paint, and a two-coat paint.
When used as a top clear paint for one-bake coating or a top clear paint for three-coat/two-bake coatings, 100 parts by weight of base resin, 0.1 to 30 parts by weight of chelate compound, and 0 to 100 parts by weight of swelling pigment. is appropriate. As the swelling pigment, both inorganic and organic highly weather-resistant swelling pigments used in conventional top coatings for automobiles can be used, such as inorganic pigments such as rutile titanium oxide or carbon black, and quinacridone. Organic pigments such as quinacridone pigments such as red, azo pigments such as pigment red, and phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green can be used.

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

Among the top coat paints, when used as a base coat paint for 2 coats/1 bake coat or a metallic paint for 1 coat/1 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 swelling pigment. Known metallic pigments can be used, such as aluminum, copper, micaceous iron oxide,
A scaly metallic powder of bronze, stainless steel, etc. can be used, and as the swelling pigment, any of the above-mentioned ones can be used. In addition, as modified resins for rheology control to adjust the arrangement of metallic pigments and improve the metallic feel, we also use core-crosslinked acrylic dispersions obtained by heterogeneous polymerization obtained by known methods, and cellulose acetate butyrate. It is also possible to mix up to about 20 parts by weight.

Further, 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, 0.1 to 30 parts by weight of the chelate compound, 5 to 150 parts by weight of the pigment,
and 0 to 100 parts by weight of a low molecular weight compound having two or more oxirane groups in one molecule. As the pigment, inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and clay, and organic pigments for swelling can be used.

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

The coating viscosity at the time of painting is as follows:
About 15 to 35 seconds (Ford Cup No. 64, 20℃)
, when used as a top coat, for about 12 to 30 seconds (
Ford Cup No., 4.20° C.) is appropriate, and may be appropriately selected depending on the coating machine, type of solvent, coating conditions, etc.

All solvents used in conventional acrylic resin/melamine resin paints can be used as paint diluting solvents, such as hydrocarbon solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. , ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether, and alcohol solvents such as butanol and propatool. 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 by, for example, applying a primer to a chemically treated steel plate by electrodeposition, and applying an intermediate coating (which may be omitted in some cases).
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 based on the film thickness after drying.
When used as a metallic color paint for coats/1 bake coat, top clear paint for 2 coats/1 bake coat, top clear paint for 3 coats/2 bake coats, etc., the thickness is about 20 to 60 μm, preferably 30 to 4 μm.
Approximately 0 μm, approximately 10 to 25 μm when used as a 2-coat/1-bake metallic base coat paint,
A suitable thickness is preferably about 10 to 20 μm.

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

Function The reason why the curable composition of the present invention has excellent low-temperature curability is considered to be as follows. That is, in the second reaction, the metal chelate compound polarizes the silanol group in the opposite direction to the silane group. This polarized silanol group reacts with the epoxy group, and this bond then coordinates with the silanol group (alkoxysilane groups, acyloxysilane groups, etc. become silanol groups due to moisture in the air). So, it becomes \AQ-0-8L / \. Next, this reacts with the hydroxyl group to form 10-0-C
-C-H. In this process, the reaction between poxy groups and hydroxyl groups proceeds at relatively low temperatures.

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

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

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

■ A coating film with high level of smoothness and sharpness can be obtained.

The main curing reaction is an ionic polymerization reaction and an addition reaction, and the generation of reaction by-products is extremely small, so the volumetric shrinkage during the coating film curing process is small, and the film is highly smooth without minute irregularities (chirpy skin). A coating film can be obtained. Therefore,
The image clarity is also excellent.

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

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

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

■ Extremely good acid resistance.

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

■ Strong stain resistance.

It has good resistance to various pollutants due to its water repellency based on the dense crosslinking density, polysiloxane bonds present in the base resin, and fluorine components.

■ Good water repellency.

゛Due to the polysiloxane bonds and fluorine components present in the base resin, the resin has high hydrophobicity and good water repellency. In particular, the fluorine component in the side chain of the base resin lowers the surface energy of the coating film, allowing it to achieve high water repellency as a coating film for automobiles.

■ Good scratch resistance.

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

■ Obtain a coating film with high weather resistance (no gloss, cracking, chalking, blistering, etc.).

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

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

An example of producing a copolymer is shown below.

CH2F CH-8i (OH) (OCH3)2 15 in a stainless steel autoclave with a stirrer with a capacity of 400 mQ.
Heavy part CH2=CH0(CH2)A OH10 parts by weight C
H2=CH0-010 each monomer and methyl isobutyl ketone 200 parts by weight of azobisisobutyronitrile 2 parts by weight Sodium borate 0.5 parts by weight were charged,
After nitrogen substitution, cooling solidification, and degassing, CH2=CFC (25
0 parts by weight was introduced into the autoclave, and the autoclave internal temperature was 6.
The temperature was gradually raised until it reached 0°C. After that, the reaction continued with stirring for more than 16 hours, and the internal pressure of the autoclave was 1 kg.
When the temperature decreased to below /c-, the autoclave was cooled with water to stop the reaction. The obtained resin solution was poured into excess hebutane to precipitate the resin, and then washed and dried.
g of resin was obtained. The yield was 92%, and the number average molecular weight by GPC was 7,000. The obtained resin was dissolved in the same amount of xylene to obtain a resin solution with a nonvolatile content of 50%.

'@ 2-4 Polymerization 2-4.

Production was carried out according to the production method of Production Example 1. Table 1 shows the amount of monomer charged and the number average molecular weight.

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

Macromonomer A synthesis example H2OS i (OCH3) a (methyltrimethoxysilane) 2720 g (2
0moQ) CH2=CH8i (OCH3)3 148g (vinyltrimethoxysilane) (1moR) Deionized water 1134g 36% hydrochloric acid
2g hydroquinone
1 g of these mixtures were reacted at 80° C. for 5 hours to remove water and solvent. The obtained polysiloxane macromonomer had a number average molecular weight of 2000, and had on average one vinyl group (polymerizable unsaturated group) and four hydroxyl groups per molecule.

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

Table 1 Table 1 (Continued) Table 1 (Continued) Table 1 (Continued) Production Examples 5 to 11, Comparative Production Example 1.2 The acrylic copolymer of the composition in Table 2 was produced using the usual acrylic copolymer face synthesis method. A polymerized face was obtained.

Both are xylene solutions with a non-volatile content of 50% by weight. In addition, Table 2 shows the number average molecular weight determined by GPC.

The method for producing macromonomer B is shown below.

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

Macromonomer B Synthesis Example esi(OH)3 (phenyltrisilanol) 7800g (5
0moJ2) CH2=CHC00C3Hs S i (OCH3)
3 (γ-Acycloxypropyl 200g trisilanol) (1moρ) Toluene
4500g of these mixtures 117
The mixture was reacted at ℃ for 3 hours and dehydrated. The obtained polysiloxane macromonomer had a number average molecular weight of 7,000, and had on average one vinyl group and 5 to 10 hydroxyl groups per molecule.

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

Preparation of Base Coat A A base coat to be combined with a two-coat, one-bake (2CIB) clear coat was produced using the above polysiloxane macromonomer as follows.

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

The number average molecular weight of the resulting polysiloxane, macromonomonomer, and mer was 2,000, and on average had one vinyl group (polymerizable unsaturated bond) and four hydroxyl groups per molecule.

A copolymer was produced using the obtained macromonomer.

The following copolymer was produced.

Polysiloxane tuna monomer 150g 2-hydroxyethyl acrylate 100gn-butyl acrylate 500g Steel
100g azobisisobutylnitrile
10 g of the mixture was added dropwise to 1000 g of an equal weight mixture of butanol and xylene at 120°C and polymerized to obtain a transparent copolymer. The number average molecular weight was approximately 30,000.

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

The blending amount is indicated by solid weight.

Above copolymer 95 parts Cellulose acetate butyrate 5 parts Aluminum paste #5
5-5.19 (manufactured by Toyo Aluminum ■) 13 parts aluminum trisacetylacetone 1 part This was then mixed with toluene/Sfusol #1500 (trade name, manufactured by Maruzen Sekiyu ■) =
13 seconds with 80/20 mixture thinner (Ford Cup N
The viscosity was adjusted to 0,4,20'C) and used for coating.

Preparation Example A top coating for automobiles was prepared using the copolymer obtained in the above production example. As a top coat, solid color (white)
A clear coat for 2CIB was produced.

Preparation examples 81 to S4 of solid color (white) are shown in Table 3.

Dispersion of titanium oxide was carried out using each copolymer in a paint shaker for 1 hour.

In the case of solid color paint, the pigment has a resin solid content of 100
The amount was 80 parts by weight.

Preparation examples M1 to M9 of 2CIB clear coats are shown in Table 4. As Comparative Preparation Examples, M-10 and M-11 were prepared using the copolymers of Comparative Preparation Examples 1 and 2.

Note that all values for copolymers and oligomers in the preparation examples shown in Tables 3 and 4 are weight % of the active ingredient. Moreover, the numerical values of pigments and metal chelate compounds are weight % (PHR) based on 100 resin content.

Coating film performance test An epoxy resin-based cationic electrodeposition paint (25 μm thick) was applied to the Edal chain plate (chemical conversion treatment) and cured by heating at 170°C for 30 minutes.
A polyester resin/melamine resin automotive paint manufactured by Kansai Paint Fin Co., Ltd. was applied to a dry film thickness of 30 μm and baked at 140° C. for 30 minutes. Next, the painted surface was water-sanded with a #400 sandpaper, drained, dried, and the painted surface was wiped with petroleum benzene to prepare the material.

Top coat solid color (white) S-1 created in the above preparation example
~S-4 was heated with Swasol #1000 (trade name, manufactured by Maruzen Oil Co., Ltd., petroleum-based mixed solvent) for 22 seconds (Ford Cup No.
, 4.20°C).

The viscosity-adjusted paint was applied by air spray painting to a dry film thickness of 40 to 50 μm, allowed to set at room temperature for 10 minutes, and then baked at 140° C. for 30 minutes to prepare a coated board.

A painted board was prepared in the same manner using Rugabeke AM White (S-5 (manufactured by Kansai Peyton Co., Ltd.) as a comparative paint. Table 5 shows the results of the coating film performance test.

Coating film performance test ■ Apply 15 to 20 μm of Soflex Nα2500 as a primer to polypropylene resin, bake at 80°C for 20 minutes, and then apply a top coat of solid color (white) to 40 to 50 μm.
μm was coated and baked at 80° C. for 30 minutes. Rethane PG-80 White (trade name, manufactured by Kansai Paint Co., Ltd.) was used as a comparative product (Paint 5-6). The coating film test results are shown in Table 6.

Paint film performance test■ Apply base coat A to the material treated in the same manner as in paint film performance test I, leave it for 5 minutes after painting, and immediately apply Swasol #
1000 (trade name, manufactured by Maruzen Sekiyu ■, petroleum-based mixed solvent)
Clears M1 to M9 and comparative products MIO to Mll whose viscosity was adjusted were applied for 22 seconds (Ford Cup Nα 4.20°C). The dry film thickness is 15-20 for the base coat.
The thickness of the clear coat was 35 to 45 μm.

Then, it was left at room temperature for 10 minutes and then heated to 100℃ for 30 minutes and 14 minutes.
Two batches of 30 minutes of baking were carried out at 0°C.

Furthermore, as a comparison product, Magiklon #1000 Silver was applied as a base coat, and Magiklon #1000 Clear (acrylic melamine resin system manufactured by Kansai Paint ■, paint No. M-12) was applied in the same manner as a clear coat.

This product was baked at 140°C for 30 minutes. The results of these coating film performance tests are shown in Table 7.

*3) Pencil hardness: Scratch the surface of the paint film with the lead of a Mitsubishi Uni-Pencil, and use the highest hardness symbol of the lead that does not scratch the paint surface. (IMAGE, CLARITY MET
ER: Measured by Suga Test Instruments. The numbers in the table are ICM values in the range of 0 to 100%. The higher the number, the better the image clarity. If the ICM value is 80 or more, the image clarity is extremely excellent. show.

Rice 5) Pheasant roll resistance: Hold gauze impregnated with Shirol with your fingers and rub the coated surface strongly back and forth 10 times. The degree of dissolution of the painted surface is ◎, ○, ■, Δ, with the degree of scratches and swelling being good (◎) and markedly poor (×).
Judgment is made in 5 stages: , intersection.

×6) Make 100 base marks by cutting the painted surface at 1 mm intervals vertically and horizontally to reach the adhesive base. Cellophane adhesive tape was pasted on top of this and the condition was evaluated after it was suddenly removed.

Display, Number of stitches without peeling/100° *7) Impact resistance Using a DuPont impact tester (striking core diameter 1/2 inch, min'MO, 5, kg). Displayed as the highest weight drop height that does not cause cracks in the paint film.

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

*9) Use a scratch resistance dyeing rub fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho). Rinse 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 back and forth 25 times.

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

10) Water resistance The test piece was immersed in a constant temperature water bath at 40°C for 240 hours. After taking it out, make sure there are no abnormalities such as glossy pique or blistering on the paint film ◎
And so.

Brown 11) Contamination Place 1 g of JIS Class 15 contamination dust on a 5 x 5 cm coated plate and spread it evenly by sweeping it 20 times with a brush 2
It was left standing at 0°C for 24 hours. Next, this was washed under running water using a clean brush, and the degree of contamination was examined.

◎ No stains observed at all ○ Slight stains are observed.

Δ Quite dirty and rejected × Significant dirt is observed Thread 12) Water repellency It is expressed as a value obtained by measuring the contact angle of water with the painted surface.

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

Chestnut 13) Weather Resistance According to QUV accelerated Bacro test using an accelerated weather resistance tester manufactured by Q Panel Co., Ltd.

Test conditions: UV irradiation 16H/60°C water condensation 8H
The coating film was evaluated after testing at 150°C for 3000 hours (125 cycles).

◎ Maintains almost the same gloss as the initial level 0 There is a slight decrease in gloss, but there are no defects such as cracking or whitening. Passed *14) Storage stability: Paint diluted to a constant viscosity (22 seconds/Ford Cup No. 4) and kept covered for 40 minutes to prevent it from coming into contact with outside air.
Store at ℃ for 1 week.

◎: Viscosity increase less than 5 seconds ■= 5-10 seconds or less × nigerization (Hereafter Up)

Claims (3)

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