JPH02232280A - Paint composition for automobile - Google Patents

Abstract

PURPOSE:To improve uniform curability and smoothness of a coating film by incorporating a specified base resin as an essential component. CONSTITUTION:One or a plurality of base resins selected from a reaction product (A) obtd. by reacting a functional resin (a), a functional group (b) complementarily reacting with said functional group, and a compd. (c) having both a functional group complementarily with the functional group of the component (a) and a silane group (a hydroxyl group and/or a hydrolyzable group directly bound to Si), a mixture (B) of a reaction product (d) obtd. by reacting the components (a) and (b) and a reaction product (e) obtd. by reacting the components (a) and (c) and a copolymer (C) consisting of an epoxy group-contg. polymerizable unsatd. monomer (f), a silane group-contg. polymerizable unsatd. monomer (g) of formulas I-X (wherein R<6> is H or a methyl; R<9> is a 1-20C divalent hydrocarbon group; Y is H, a hydroxyl group, a hydrolyzable group, a 1-8C alkyl, aryl or aralkyl and at least one of Y is H, a hydroxyl group or a hydrolyzable group) and, if necessary, another polymerizable unsatd. monomer (h), and a curing catalyst (e.g. aluminum trimethoxide) are compounded.

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION This invention relates to automotive paint compositions. Conventional technologies and their problems In automobile body paints, there are demands for improvements in finished appearance, coating performance, etc., as well as for the purpose of reducing energy costs and for automobile exterior panels where thin plate base materials and plastic base materials are integrated. There is a strong demand for the development of low-temperature curing paints with the aim of making it possible to apply an integral coating with the same paint. The paints that currently dominate as top coats for automobiles are: , polyester resin/melamine resin (solid color)
, thermosetting acrylic resin/melamine resin system (metallic color and 2 coats, 1 and bake top clear coat)
However, these paints are close to the limit in pursuit of high level of smoothness, and there is also room for improvement in various coating film properties. Further, the low temperature curability is limited to about 120°C, and it is difficult to harden or harden at lower temperatures. Low-temperature curable top coatings include polyester resin/aliphatic or alicyclic polyisocyanate, thermosetting acrylic resin/aliphatic or cycloaliphatic polyisocyanate. Two-component paints such as alicyclic polyisocyanate-based paints are known, but with such two-wave paints, it is necessary to mix both components immediately before use, and special paints for two-component paints are required. Painting machines and painting equipment are required. Furthermore, isocyanate curing agents have the problem of being highly toxic. Also,
When using aliphatic isocyanates, there are also problems such as yellowing due to decomposition of residual isocyanate groups due to moisture and generation of primary amines. On the other hand, in the case of intermediate coatings for automobiles, there is a strong desire to develop paints that cure at low temperatures, as well as to improve the smoothness of the coating film, the roughness hiding ability of the undercoat coating, and to make it highly solid. The current mainstream paints for automobiles are polyester resin/melamine resin-based paints, but it is difficult to improve the surface smoothness of these paints or to make them ultra-high solid paints. Further, the low temperature curability is limited to about 120°C. For intermediate coatings, low-temperature curing is possible by using polyisocyanate-curing two-component paints, but like topcoats, specialized coating machines and painting equipment are required, and there are problems with the toxicity of the curing agent. There is also. Means for Solving the Problems The present inventor has conducted extensive research in order to solve the problems of the prior art as described above. As a result, a resin having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom and an epoxy group in the same resin, or a resin having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom, In a coating composition containing a specific resin composition containing a resin mixed with a resin having an epoxy group, silanol groups and oxirane groups generated by hydrolysis of silanol groups and alkoxyl groups become crosslinking functional groups, Even at low temperatures of 100°C or lower, the curing reaction proceeds simultaneously on the surface and inside, and there is little difference in the degree of curing between the surface and inside of the cured product, making it difficult to cause distortion, making it suitable for automotive top coats and intermediate coats. It has been found that it can be suitably used as a paint or the like. Further, the above coating composition further contains at least two oxirane groups in one molecule and has a number average molecular weight of 200.
It has been found that by blending a low molecular weight compound of 0 or less, a high solid paint with good uniform curing properties and smoothness can be easily obtained. In the present invention, a resin having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom and an epoxy group in the same resin, or a resin having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom, A specific resin composition containing a resin mixed with a resin having an epoxy group may contain one type or two or more selected from the following (1) to (8), and the composition of the present invention The feature of the product is that it contains the above resin composition as a base resin. In this specification, the above-mentioned "hydroxyl group and/or hydrolyzable group directly bonded to a silicon atom" may be referred to as a "silane group." That is, the present invention provides the following advantages: (1) A resin (A) having a functional group is converted into a compound (B) having a functional group and an epoxy group that react complementary to the functional group.
and a reactant (D) obtained by reacting with a compound (C) having a functional group that reacts complementary to the functional group of the resin (A) and a silane group (hereinafter referred to as "(1) resin composition") ) (2) A reactant (F) obtained by reacting a resin (E) having a functional group with a compound (B) having a functional group and an epoxy group that reacts complementary to the functional group, and a resin having a functional group. A mixture with a reactant (H) obtained by reacting the resin (G) with a compound (C) having a functional group and a silane group that reacts complementary to the functional group (hereinafter referred to as "(2) resin composition") (3) Epoxy group-containing polymerizable unsaturated monomer (J), silane group-containing polymerizable unsaturated monomer CK) and, if necessary, 1 liter of the polymerizable unsaturated monomer CM) Copolymer (L) as polymer component (hereinafter referred to as "(3) resin composition") (4) Homopolymer (N) of the monomer (J) or the monomer (J) A copolymer (N) with other polymerizable unsaturated monomers (M), and a homopolymer (P) of the monomer (K) or the monomer (
K) and a copolymer (P) of other polymerizable unsaturated monomers (M) (hereinafter referred to as "(4) resin composition"). However, in (3) and (4) above, Monomers listed (K)
is the following general formula T CHI-CHCHmQ-R”-S5-T(94》Y [wherein R represents a hydrogen atom or a methyl group, R9 represents a divalent hydrocarbon group having 1 to 20 carbon atoms] , the three Y's are the same or different, hydrogen atom, hydroxyl group, hydrolyzable group, C1
-8 Indicates an alkyl group, an aryl group, and an aralkyl group. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] It is selected from the compounds represented by. (5) A copolymer (R) containing a functional group-containing polymerizable unsaturated monomer (Q) and the epoxy group-containing polymerizable unsaturated monomer (J) as essential components; ) A reaction product with a compound (S) having a functional group and a silane group that reacts complementary with the functional group derived from A copolymer (V) containing an unsaturated monomer (.U) and the silane group-containing polymerizable unsaturated monomer (K) as essential components, and a functional group originating from the monomer (U). Reactant (X) with a compound (W) having a complementary reacting functional group and an epoxy group (hereinafter referred to as "(6) resin composition") (7) the homopolymer (N) or copolymer A mixture (Y) of (N) and the reactant (H) (hereinafter referred to as "(
7) Resin composition) and (8) a mixture (Z) of the homopolymer (P) or copolymer CP) and the reactant (F) (hereinafter referred to as "(8) Resin composition J The present invention provides an automotive coating composition containing as an essential component one or more base resins selected from Or, it is a group that generates a silanol group when hydrolyzed by moisture. Examples of the group include those represented by the following general formula: -O-R' CI) 10-C-R
'(If) In the formula, R' is a C, ~4 alkyl group, and R' to R IN are the same or different. C
The alkyl group, aryl group, and aralkyl group of I to 8 are shown. In the general formula, "as the alkyl group J of CI to B,
For example, methyl, ethyl, n-propyl, lso-propyl, n-butyl, lso-butyl, see-butyl, t
ert-butyl, n-bentyl, lso-bentyl, n
-octyl, Iso-octyl and the like. Examples of the "aryl group" include phenyl, tolyl, xylyl, and the like. Examples of the "aralkyl group" include benzyl and phenethyl. Furthermore, in addition to the above-mentioned hydrolyzable groups bonded to silicon atoms, examples of hydrolyzable groups include -3Si-H radical numbers. As the above-mentioned hydrolyzable group, silane groups represented by the above general formulas (I) and (n) are suitable from the viewpoint of storage stability, curability, etc. Next, the above resin compositions (1) to (8) used in the present invention will be specifically explained. In the resin compositions (1) to (8) above, the complementary reacting groups are groups that can react with each other, and can be appropriately selected, for example, from the table below. Table 1 Table 1 (Continued) Complementary reacting groups can be selected and combined as appropriate from the above table, and the following combinations are preferred. Resin (A)/Compound (B) [or Resin (E)/Compound (
B)] functional group combinations: (1)/(5), (2)/(4), (3)/(3)
(5) / (1) etc. Resin (A) / Compound (C) [or Resin (G) / Compound (
C)] combination of functional groups: (1)/(5). (2)/(3), (2)/(
4) (2)/(5), (3)/(3). (4)
/(2). (4)/(6), (4)/(7).
(5)/(1), (5)/(2), (5)/(
6), (5)/ (7), (6)/ (4),.
(6)/(8)(7)/(4). (7)/(8
). (7)/(5) Combinations of functional groups of monomer (Q)/compound (S): (1)/(5), (4)/(2), (4)/(
6) (4)/(7), (5)/(1), (5)
/(2). (5)/ (3). (5) / (6
). ．． (5)/(7) Combinations of functional groups of monomer (U)/compound (W): (1)/(5), (2)/(4). (2)/(
5) (3)/(1), (5)/(1), (6)
/(4), (6)/(5), (6)/(8),
(7)/(4), (7)/(8), (7)/(
5) Etc. IM fat (A) can be appropriately selected from conventional fats without any particular limitations as long as it has the above-mentioned functional group. ．．
Specifically, examples include opening resins such as vinyl IA resins, fluorine resins, polyester resins, alkyd resins, silicone resins, urethane resins, and polyether resins.Resin (A) {:! : It has an average of two or more functional groups that react with the functional groups of compound (E) and compound (C) in one molecule, but even if the functional groups in the resin are It does not matter if the functional groups are different from each other.If the functional groups in the marsh fat (A) are the same, for example, the average
A resin (A) having at least 3 water M groups. A compound (B) having an isocyanate group (5) and an isocyanate group (
5) or react with a compound (C) having
A resin (A) having an average of 2 or more isocyanate groups (5) can be reacted with a compound (B) having a hydroxyl group (1) and a compound (C) having an incyanate (5). , When the functional groups in the resin (A) are different, for example, the resin (A) has an average of one or more hydroxyl groups (1) and carboxyl groups (2), and isocyanate groups (5). The functional group in compound (B) that reacts with the functional group in resin (A) that can be reacted with compound (C) having There is no problem even if the functional group in the compound (C) that reacts with the functional group in the resin (A) is the same as the epoxy group.
) is the same as the silane group possessed by, and is not prohibited. As the resin (A), resins having functional groups such as a hydroxyl group, a carboxyl group, an isocyanate group, a silane group, and an epoxy group will be explained. C* Acid group-containing resin] The following can be mentioned. ■ Hydroxyl group-containing vinyl resin A polymer containing the following hydroxyl group-containing polymerizable unsaturated monomer (a) and, if necessary, other ■ polymerizable unsaturated monomers (b) as monomer components. ．． Hydroxyl group-containing polymerizable unsaturated monomer (a) Compounds represented by the following general formulas (1) to (4) can be mentioned.General formula (1) In the formula, Rl- represents a hydrogen atom or a hydroxyalkyl group. General formula (2) In the formula, . and lull have the same meanings as above.General formula.
(3) In the formula, Z represents a hydrogen atom or a methyl group, m represents an integer of 2 to 8, p represents an integer of 2 to 18, and q represents an integer of 0 to 7. General formula (4) CH2=CZ ``CO-{-T+-0 juice 1 → T2-0+-Hq
In the formula, Z is the same as above, T
1 and T2 are the same or different and represent a divalent hydrocarbon group having 4 to 20 carbon atoms, and S and U each represent an integer of 0 to 10. However, the sum of S and U is 1 to 10. The "hydroxyalkyl group" in general formulas (1) and (2) has 1 to 6 carbon atoms, specifically, 1c2H40
Examples include H1-c, H60H, -C4H80H, and the like. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in general formula (4) include 10H2- (CH2 ) 2
(CI2) 3-CH3 -CH2CH2 C CH2 CH2 - (C
H2) lo CH3 - (CH2) t2-, (CH2) ta-,
÷, -CH2R, CH2, etc. can be mentioned. -a As the monomer component of formula (2), for example, 1:1'CI
lx'CIICHtOI+ (:H!-CMCI.OCH.CIl.OI+CHC(
:H(:II*O{(HtCIlfOh-HC}1n”
(: IICH
．． (CHs)Coo(:xll40HCHz”CH
COOCsH-゛(Hln CLIIC; ((:Ils) C00-Cs11g
=04G-(:}r-CIl-Cliz-CH*-C Summer t.-ohτ publication 1 etc. As the monomer component of the general formula (4), for example, CH1C (CHs ) COO {CH2Cl{CH
J}-T-TIIC}+. -C}{ -(:00{(:
lI. cIl. o｝〒Jl! CM/CG/(CHs)
Coo{C,]I. CHtQFr-rllCH2hcH
cOO-4 CH2CH2CH2CH2 Choguchi H etc. can be mentioned. Furthermore, in addition to the above, monounsaturated monomers containing filtrate M group represented by the general formulas (1) to (4), εcabrolactone, γ
- Adducts with lactone neck such as valerolactone can be used. Other conformal unsaturated monomers (b) The following (b.-1) to (b-.6) can be mentioned. (b-1) Lefin compounds: for example, ethylene, brobylene, butylene, isobrene, chlorobrene, etc. (・b-2)'l? Nyl ether and allyl ether: ethyl vinyl ether, proyl vinyl ether, isobrobyl vinyl ether, butyl vinyl ether. tert-butyl vinyl ether, benzyl vinyl ether, hex. Silvinylethe. isohexyl vinyl ether, isohexyl vinyl ether, 4-
Chain alkyl vinyl ethers such as methyl-1-bentyl vinyl ether, cyclobentyl vinyl ether,
Cycloalkylvinyl binary ethers such as cyclohexyl vinyl ether. Phenyl vinyl ether, 〇1m+,p
Aryl vinyl ethers such as Itto ribinyl ether,
Aralkyl vinyl ethers such as penzyl vinyl ether and phenethyl vinyl ether, etc. (b-,3), vinyl ester and propenyl ester: for example, beer acetate, vinyl lactate, vinyl n8 acid,
Vinyl esters such as vinyl isobutyrate, vinyl cabroate, vinyl incabroate, vinyl bicarbonate, vinyl cabrate, and brobenyl esters such as isobrobenyl acetate and isobrobenyl phosphate. (b-4) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, probyl acrylate, isobrobyl acrylate, butyl acrylate, hexyl acrylate, lactyl acrylate, lauryl acrylate, meccrylic acid Methyl, ethyl mecrylate, probyl mecrylate, isobrobyl mecrylate, butyl mecrylate, hexyl mecrylate, probyl mecrylate. Alkyl esters of acrylic acid or meccrylic acid having 1 to 18 carbon atoms such as lauryl meccrylate: 7'cryl methoxybutyl, methoxybutyl meccrylate, methoxyethyl acrylate, methoxyethyl acrylate, ethoxybutyl acrylate, (bs) Vinyl aromatic compounds such as acrylic acid such as ethoxybutyl meccrylate or alkoxyalkyl esters having 2 to 18 carbon atoms; such as styrene, α
- Methylstyrene, vinyltoluene, p. Lorstyrene et al. (b-s) Others: acrylonitrile, methacrylonitrile,
Terephthalic acid, (anhydrous) maleic acid, (anhydrous) biromellitic acid, (anhydrous) succinic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dimethyl isophthalate, dimethyl terephthalate, etc. contain 2 to 20% in one molecule. compounds having four carboxyl groups or carboxylic acid methyl ester), polyhydric alcohols (e.g., ethylene glycol, polyethylene glycol, propylene glycol, neobentyl glycol, 1,6-hexanediol, trimethylolbroban, pentaeryth) 2 to 6 in 1 molecule of lithol, glycerin, tricyctodecanedimethanol, etc.
It can be obtained by carrying out an ester reaction or an ester conversion reaction with an alcohol having 2 hydroxyl groups. In addition to the above, monobasic acids (e.g. castor oil fatty acids, soybean oil fatty acids,
Fatty acids such as tall oil fatty acids and linseed oil fatty acids, benzoic acid, etc.) can be used as necessary. ■Polyurethane resin containing hydroxyl groups Contains isocyanate groups obtained by modifying hydroxyl group-containing vinyl resins, hydroxyl group-containing polyester resins, etc. with polyisocyanate compounds (for example, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.). No resin. ■ Hydroxyl group-containing silicone resin Hydroxyl group-containing vinyl resin, hydroxyl group-containing polyester resin, etc.
8 (all Dow Corning products), SH5050, S
A resin having no alkoxysilane group or silanol group obtained by modification with H6018, SH6188 (all products of Toray Silicone Co., Ltd.). ■Vinyl alcohol-styrene copolymer. [Carboxyl group-containing resins] Below, the following can be mentioned. ■ Carboxyl group-containing vinyl; sealant carboxyl group (polymerizable unsaturated monomer cd) and essential. A polymer containing other polymerizable unseasoned monomers {b) as a monomer component as required. Carboxyl group-containing polymerizable unsaturated monomer (d) Examples include compounds represented by the following general formulas (7) and (8). General formula (7) In the formula. R1 represents a hydrogen atom or a lower alkyl group, and tR
' represents a water atom, a lower alkyl group, or a carboxyl group, and R1 represents a hydrogen atom, a lower alkyl group, or a carboxy lower alkyl group. General formula (8) In the formula. Rs represents a hydrogen atom or methyl, and m has the same meaning as above.゜In the above formula (ff), the lower alkyl group is 0
Those with 4 or less groups, especially methyl groups, are preferred. General formula (7
) Examples include acrylic vi, meccrylic acid,
Kuro}';Ivi. Itaconic acid, maleic acid, maleic anhydride, fumaric acid, etc. can be used. Further, examples of general formula [8) include Ffq such as 2-carboxyethyl (mec)acrylate, 2-carpoxybrobyl (meth)acrylate, etc. In addition to the above, hydroxyl group-containing polymerizable unsaturated monomers (a
) and 1 mole of a polycarboxylic anhydride (eg, maleic anhydride, iconic anhydride, succinic anhydride, fucuric anhydride, etc.) compound can also be used. (2) Resins for carboxyl group-containing polyesters Examples include resins obtained by esterifying the polybasic acid and the polyhydric alcohol. [Incyanate group-containing resin] The following may be mentioned. (2) Isocyanate group-containing vinyl resin A polymer containing an isocyanate group-containing polymerizable unsaturated monomer (C) and, if necessary, other polymerizable unsaturated monomers (b') as monomer components. Isocyanate group-containing ortholytic unsaturated monomers (e) Examples include monomers represented by the lower general formulas (9) and (10). General formula [9] In the n formula, R'' and n have the same meanings as above. Examples include JJAn bodies represented by. For example, isocyanate ethyl (meth)acrylate is included. Monoacid formula (JO ') n1 In the formula, R@right and n have the above meanings respectively.L, .R
, is a water "fi: H atom or C, the following argyl group. For example, α.α-dimethyl-m-isobro, benylbenzyl isocyanate is included. In addition to the above, .Momohydric M group-containing dish-forming unsaturated monomer (b) 1
mol and 1 mol of a polyisoleanate compound can be used. ．． Examples of the polyisocyanate compound include toluene diisocyanate, 1.6-
Hexamethylene diisocyanate. 4.4'-Diphenylmekunjii. Sosi, Anate. 4,4'-diphenyl ether diisocyanate, phenylene diisocyanate, naphcline diisocyanate, biphenylene diisocyanate, 3,3'-dimethyl-4,4'-piphenylene diisocyanate, dicyclohexylmethane,
4,4"-diisocyanate, P-xylene diisocyanate, m-xylene diisocyanate, bis(4-
Examples include isocyanate phenyl) sulfone, isobropylidene bis(4-phenyl isocyanate), lysine isocyanate, inborondiyne cyanate, and their polymers and burettes. Wear. Furthermore, as an isocyanate group-containing fluorine-based resin, water r! One obtained by reacting, for example, the above-mentioned polyisocyanate compound with an 11-group-containing fluorine-based open resin. A resin obtained by adjusting the content of the hydroxyl group-containing polyester resin and the polyisocyanate compound so that the isocyanate component is in excess. ■ Isocyanate group-containing polyurekne resin said water aI&
Contains Borie. Garden resin obtained by adjusting the terrestrial resin and the polyisocyanate compound so that the isocyanate component is in excess. [Silane group-containing resin J: An open fat obtained by reacting the above-mentioned water U group-containing store fat with the isocyanate group-containing silane compound; The obtained Ia4 fat is the silicone resin used in the hydroxyl group-containing silicone resin. [Author by Eyakishi, Female Filler Resin: An open resin obtained by reacting the water rJ1 group-containing garden resin described above with the isocyanate group-containing epoxy compound described below. (1) The compound (B) used in the resin composition contains a functional group that reacts with the functional group in the resin (A) and an ebo-ox group.
One or more of each in the molecule. Applicable. Resin (A
・) It is acceptable even if the functional group that reacts with the functional group in ) is the same as the epoxy group. The functional group is an epoxy group. If they are the same, they must contain 29 or more epoxy groups in each molecule. Next, one representative compound (B) will be described below. [゜Hydroxy group-containing epoxy compound J Compounds represented by the following general formulas ('Il) to (21) can be mentioned.\/ In each formula, R' and n have the same meanings as above, and R8 is carbon A divalent hydrocarbon group having numbers 1 to 8, R9 is the same or different and represents a divalent ° hydrocarbon group having 1 to 20 carbon atoms. In general formulas (11) to (21), 8-2
The monovalent hydrocarbon group can be appropriately selected from the above divalent hydrocarbon groups having 1 to 20 carbon atoms. Also, carbon number 1
-20 divalent hydrocarbon groups include the same groups as mentioned above. Specific examples of compounds represented by general formulas ('11) to (2B) include the following. [Silane group-containing epoxy compound] In each formula, R1, R, and a have the same meanings as above, and IR
” may be the same or different.Y may be the same or different and may be a hydrogen atom, water, Ill!
．． C+- represents an alkyl group, an aryl group, or a 7largyl group. However, at least one of Y is a water atom, water IX
It is an i2 group or a hydrolyzable ゜ group. General formula (22》~(
In 25), the hydrolyzable group has the above general formula (1) ~'
(v+) groups are included. Also, C1. ．． ．． Examples of the alkyl group, aryl group, and aralkyl group in 8 are the same as those mentioned above. 6 -! Specific examples of the compounds represented by formulas (22) to (25) include the following. [Polyepoxy Compound] Compounds represented by the following general formulas (26) to (33) are listed below. LC In the formula, RA and R″ have the same meanings as above, and R6 and R′ may be the same or different.
10 is the same or different and is a C+-m alkyl group, phenyl group, aryl group, alanolekyl group, or between- or different is a hydroxyl atom, ni, -4 alkyl group, W is O and T! of 1 to 1O! As specific examples of the compounds represented by the general formulas (26) to (3'3), in addition to the above, the following can be used. etc.: Can be done. Adducts with aneneto compounds (Polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; hydrogenated xylylene diisocyanate, isocyanate, or isophorone diisocyanate; Cycloaliphatic diisocyanates such as diisocyanate or aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, or each of these organic diisocyanates together with polyhydric alcohols, low molecular weight polyesters; Additions with resins or water, etc., polymers of organic diisocyanates as described above, and diisocyanates, etc. For example, [
Burnock D-750. -800.0N-950, -9
70 or is-455J ゛[' or above, products from Dainippon Ink and Chemicals]% r Desmodule L. NHL%
IL or N3390J[. West Germany/Country Bayer product], “Takenate D-402.-202.-”1
10N or -123NJ r Takeda Pharmaceutical Company product], “Coronate L.} {L.EH or 203J
[Japan Polyurethane Industries A-gradation products] Ma. [Duranate 24A-90CXJ II! l chemical industry w jr
product A], etc.}: adducts of and polybasic acids; esterified products having, for example, Kasa unsaturated groups in the molecule (e.g., tetrahydrophthalic anhydride, trimethylolbrobaso, and 1,4- Number-average molecules obtained by esterification reaction of butanediyl, etc. [9
Examples include those obtained by oxidizing an esterified product of 00) with peracetic acid or the like. [Isocyanate group-containing epoxy compound] The hydroxyl group-containing epoxidized food and the polyisocyanenite compound.
Examples include those obtained by reacting with other substances in such a way that a hydroxyl group and an incyanate group remain. Specifically, for example, the reaction product of the compound represented by the general formula [1' 1 ．．．）． And Kishi. The reactant of diisosidenate is represented by the general formula (18). Reaction products of the compound represented by formula (20) and isophorone diisocyanate, and the like can be mentioned. (1) The compound (C) used in #f composition has in one molecule a functional group that reacts with the functional group in the 184 fat (A) and a silane group, respectively. ．．
There is no problem even if the functional group that reacts with the functional group in the resin (A) is the same as the silane group. If the functional group is the same as a silane group, it is necessary to contain two or more silane groups per molecule. Next, typical compounds (C゜) are described below. [Hydroxyl group-containing silane compound] The following general formulas (34) to (36). Able to lift tables and objects. General formulas (34) to (36) represented by. As a specific example of the compound represented by, for example, 0CHs In each formula, R a , R16 and Y have the same meanings as above, and SR "lR" and Y may be the same or different. However, if any one of Y is depleted, water T. These are atoms, hydroxyl groups, and hydrolyzable groups. [Hoori Shiran Ikoi Town] Hydrolyzable groups directly bonded to silicon and Si
It is a compound containing two or more groups selected from OH. Compounds represented by the following general formulas (3'8) to (40) can be mentioned. In each formula, Y' is the same or different and is a hydrogen atom, a hydroxyl group, or a hydrolyzable group, and RI° is has the same meaning as above;
Ft I@ may be the same or very different. Specific examples of the compounds represented by (3F3) to (40) include dimethyldimethoxysilane and dibutyldimethoxysilane. Gen, iso-probilge. Proboxysilane, diphenyldibutoxysilane, diphenyldiethoxysilane, diethyldisilanol, dihe-xyldisilanolmethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyl! J ethoxysilane, phenyltributyrosilane, hexyltriacetoxysilane, methyltrisilanonyl, phenyltrisilanol, tetramethoxysilane,
Tetraethoxysilane, Tetrabutyloxysilane, Tetraacetoxysilane, G. Condensates of iso-probioxysilane and tetrasilanol can be used. [Epoxy group-containing silane compound] The above-mentioned silane group-containing epoxy compounds can be mentioned. [Isocyanate group-containing silane compound] The following general formula (4
0) and (4l). Furthermore, in addition to the above-mentioned polysilane compounds, R
' and Y have the same meaning as above, and Y'' may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. Specific examples of the compound represented by 41) include OCR(:-11-Si(OCillsl s, oc
Ncl}14siIOcIIs)s,C}! −
(:-Hy OCN(:3HISi [OCtHI+2,l CI{s OCN(:J-SL (QC}+31 *-CI{s 0.CNCHiSt [DC-Ha) 3,](:NC
HiSi tocH. ) s-? CNCI (zsL (
QC-Hsl■Clls OCNet(*Si(OCR-)s. OH. Calls CI{, 0CN-Gills-SLON [c, I++1CL n O(1:N-CJ6-Si (OCC+{31 1n O(:N- SL Toccl131 s0-CC}l.In addition to the above, compounds obtained by reacting the hydroxyl group-containing silane compound with the polyisocyanate compound can be used.Specifically, the following compounds can be used. Examples include reaction products of the formula (34) with hexamethylene diisocyanate or tolylene diisocyanate, such as 7.Furthermore, the reaction products of the epoxy group-containing silane compound and, for example, the polysilane compound A condensation product with can also be used. An example of such a compound is ゛. [Merkabuto group-containing silane compound] A compound represented by the following general formula (42) can be mentioned. has the same meaning as in Book liii, Y
may be the same or different. However, at least one of Y is a water atom, a hydroxyl group, or a hydrolyzable group. A compound represented by the formula (42). Examples include 0 C's 11 m HS-C. II. -Si-OC411.0C. H
1 Ro. ) can be mentioned, specifically, for example, etc. Furthermore, condensates of the mercabutosilane compounds and, for example, vorisilane compounds can also be used. [NHW or NH
*Group-containing silane compound] The following general formulas (43) and (4
Examples include compounds represented by 4). I can list things like... In addition to the above, the hydroxyl group-containing silane compound may be added to the polyisocyanate compound and the silane compound (for example, II
s-C. I+. ．． -011. ．． has the same meaning as above. In each formula, Rg, Rll1 and Y have the same meaning as above.
11”R”. Y may be the same or different. However, at least one of Y is a water atom, a hydroxyl group, or a hydrolyzable atom. -jllt Specific examples of compounds represented by formulas (43) and (44) include OCI+3 H. N-(CI+21,-St-0(:11,oc
n* OCsHa 1(: IItl 3-Si-OCJi 0(:. A condensate with a vorisilane compound can also be used.

[Unsaturated group-containing silane compound] The same compounds as the silane group-containing polymerizable unsaturated monomer (10) described below can be used. The resin (A) has a number average molecular weight of about 3,000 to 200,000, preferably about 5,000 to soooo. Compound (E) and compound (C) can have about 120 to 1000
0. It preferably has a number average molecular weight of 120 to 3000. Reactants obtained by reacting 1M fat (A) with compound (.B) and compound (C) (DJ is an epoxy group and a silane group with an average of 1 g or more each, preferably an average of 2 to 40 f solids per molecule) Yuyuyu' mouth 11 Boso resin (E) has on average one or more functional groups in one molecule that react with the functional groups of compound (B), and specifically, The compound (B) can be used by appropriately selecting from the resin compositions (1) above. The compound (B) has an average of one or more functional groups in one molecule that react with the functional groups of the 1M resin (E), and has an average amount of 1 g or more of epoxy groups.There is no problem even if the functional group in the compound (B) is the same as the epoxy group.
As the compound (B), the same compounds as those described in (1) Resin composition can be used. The resin (G) has on average one or more functional groups in one molecule that react with the functional groups of the compound (C), and specifically, it is appropriately selected from the resin compositions (1) above. It can be used as Compound (C) has on average one or more functional groups in one molecule that react with the functional group of t,'IJIW (G), and has on average one or more silane groups. The compound (C
) may be the same as the silane group. As the compound (C), the same compounds as those described in (1) Resin composition can be used. Resin (E) and CG) are approximately 3,000 to 200,000.
Preferably, it can have a number average molecular weight of 5,000 to soooo. The reactant (F) obtained by reacting the resin (E) and the compound (B) has an average of 1 or more per molecule, preferably an average of 2 per molecule.
It can have ~40 epoxy groups. The reactant (H) obtained by reacting the resin (G) and the compound (C) has an average of 1 or more per molecule, preferably an average of 2 per molecule.
~40g of silane groups. Reactant (F) and reactant (H) can usually be mixed so that the ratio of epoxy group/silane group is 1/99 to 99/1.
．． Epoxy group-containing polymerizable unsaturated monomer (J) This is a compound that has an epoxy group and a radically polymerizable unsaturated group in one molecule. The epoxy group may be aliphatic or alicyclic. Examples of radically polymerizable unta groups include, for example, CH2-C(R')COO- Cl12"'i=gC-0H2"2,"g-N"" CH2°CHCH2-0-CH2-CHO-, R6 is the same as above.
As the epoxy group-containing polymerizable unsaturated monomer of OO-,
Examples include compounds represented by the following general formulas (45) to (57). (56》 In each formula, R''.R@.R'' and W have the same meanings as above, and R'', R1 and R1 may be the same or different. -nq Formulas (45) to (57 ) is displayed in the table J'tl;
As an example of +ζ, we can cite the reward given by the following Ippuka-shiki ~ (60). In each formula, R4 and R1 have the same meanings as above, R@ and R1 may be the same or different, and the radically polymerizable unsaturated group is co. =cn(R) C-N
- Pickles. Examples of epoxy-containing synthetic unsaturated monomers include compounds represented by general formula (58), and specific examples of compounds represented by formula (61) below. In each formula, R" and R1 have the same meanings as above, and R6 and R" may be the same or different.1,X, -JQ Specific examples of compounds represented by formulas (6l) to (63) Examples include epoxy-containing targeted unsaturated monomers. R6 radically polymerizable unsaturated group is CI1. Examples of the polymerizable unsaturated monomer containing -C-C epoxy include compounds represented by the following general 2 (64) to (69). In each formula, R6, R8, R9 and W are the same as above. R1·R and R9 may be the same or different. - Specific examples of compounds represented by Takeshi formulas (64) to (69) include, for example, compounds represented by the following general formulas (70) to (73) as xyl group-containing polymerizable unsaturated monomers. Can you name it? can be mentioned. The radically polymerizable unsaturated group is Cl1. =CH(:11.0
- In each formula, R6 and R1 have the same meaning as above, and R ball may be the same or different. General formulas (70) to (7)
3). As a specific example of the compound represented, for example, as a group-containing unsaturated monomer, for example, the following general formula (74
) to C76). can be mentioned. The radically polymerizable unsaturated group is Cl1. =CIIO- epoxy In each formula, R6 and R@ have the same meanings as above. have a taste, and R'' may be the same or different. Specific examples of the compounds represented by the general formulas (74) to (76) include the following. As the epoxy group-containing unsaturated monomer whose saturated group is cHz*cn-, for example, the following general formula C77
) to (79) can be mentioned. In each formula, R" and R" have the same meanings as above, and tR'
may be the same or different. Specific examples of compounds represented by one-shell formulas (77) to (79) include, for example, compounds represented by the following general formulas (80) to (84) as the epoxy M-containing Fujafa monomer. In each formula, .R'.R'' and R@ have the same meanings as above, and %R'' and R'' may be the same or different. Specific examples of the compounds represented include, for example, examples of the silane Go-containing polymerizable unsaturated monomer include compounds represented by the following general formula (85). Silane group-containing subpolymerizable unsaturated compound (K) is a compound that has at least one silane group and a radically polymerizable unsaturated group in one molecule. (
As the 7 groups, Example A. C}Im-CIIO-coz=cnCII*O- etc. R6 radically polymerizable unsaturated group is CI. =(, - COO-
In the formula, R1., 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 hydroxyl group, or a hydrolyzable group. Specific examples of compounds represented by general formula (85) include:
For example, γ-acryloxib-methyltrimethoxysilane, γ-acryloxib-biltriethoxysilane, γ-acryloxib-tribboxysilane, γ-acryloxib-methyldimethoxysilane. γ-1(mec)acryloxibu-methyldiethoxysilane, γ-1(meth)acryloxibu-methyldibroboxysilane, γ-1(meth)acryloxybutylphenyldimethoxysilane, γ-1(mec)acryloxybutylphenyldimethoxysilane Ethoxysilane, γ-(meth)acryloxybutylphenyldipboxysilane, γ
1 (meth)acryloxib-based bilphenylmethylmethoxysilane, γ-1 (meth)acryloxib-based bilphenylmethylethoxysilane, γ-1 (meth)acryloxib-based bilphenylmethylmethoxysilane, γ-1 (meth)acryloxibu-based bilphenylmethylethoxysilane, γ -(Mek)Acryloxib-methyldihydroxysilane, γ-(Mek)Acryloxib-methyldihydroxysilane, γ-(Mek)Acryloxybutyl phenyldihydo-oxysilane, γ
-(meth)acryloxib-bildimethylhydroxysilane, γ-(meth)acryloxibu-bilphenylmethylhydroxysilane, 0CCHs Silane group-containing polymerization. As a sexually unsaturated monomer. For example, compounds represented by the following general formulas [86] to (88) can be mentioned. In each formula, R'' Re and Y have the same meanings as above,
Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. Specific examples of the compounds represented by the general formulas (86) to (88) include R' Y, etc., where the radically polymerizable unsaturated group is CH.=C+Sifun group-containing synthetic unsaturated monomer For example, the following general formula (89)
The compounds represented by (90) and (90) can be mentioned. Wear. In each formula, R @,, p @ and Y have the same meanings as above, and Y may be the same or different. At least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. Specific examples of compounds represented by general formulas (89) and (90) include 082 -CHSi (OCH3) CHz =CHS1 (OC2H sCH2-CHS
1 (OCR 3) CI+2 - CHS1 (CH3) 2CH2 -
CHCH2 S1 (OCR2CH3 0CH 3 ■ CH2 -CIIS1 (OCCI13) 3C}1
2-CHCH2Sl (OCCI13) 3el
f2-cHsi(CH3)2N(CH3)
2Y may be the same or different. At least l' of Y (IJ is a water atom, a hydroxyl group, or a hydrolyzable group. Specific examples of the compounds represented by the general formulas (91) and (92) include the following. Radical polymerization Examples of the silane group-containing polymerizable unsaturated monomer in which the unsaturated group is (:H.=CHO-) include compounds represented by the following general formulas (91) and (92), for example, Clls C }l*=CHO- (CHtl Ji-OCIIsi OCIIs each, in the formula, R1 and Y have the same meaning as above, CH
sC. lI1 I can raise a hat. Radical heavy. The synthetic unsaturated group is CI+! =CllCH20
- Shira. Examples of the unsaturated Za monomer containing M include compounds represented by the following general formulas (93) and (94). In each formula, R" and Y have the same meanings as above, and Y may be the same or different. Any one of Y" is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. Specific examples of the compounds represented by formulas (93) and (94) include OCJh “CHi”(:lI(:HJ- (Cllsl x-Si
-OCzH*GHs. Other properly polymerizable unsaturated monomers (M) A radically polymerizable unsaturated group that does not have an active group with the epoxy group of the monomer (J) and the silane group of the monomer (K). You can use compounds that have Specifically, the hydroxyl group-containing unsaturated monomer (a), the orthotropic unsaturated monomer (b)
Examples include -1) to (b-6) 1 carboxyl group-containing polymerizable unsaturated monomers. A co-positive polymer (L) obtained by a radical reaction of monomer (J), monomer (K), and one other necessary monomer (M) is obtained by Average of 1 or more each,
Preferably, it has an average of 2 to 40 epoxy groups and silane groups. Monomer (J), monomer (K) and monomer (M) are the same monomers as described in the above (3NN fat composition).
You can. The copolymer (N) of the JYi polymer (J) and the monomer (M) can have an average of 1 or more epoxy groups, preferably 2 to 40 epoxy groups in one molecule. The copolymer (P) of monomer (K) and monomer (M) can have an average of 1 or more silane groups, preferably 2 to 40 silane groups, in one molecule. Single or copolymer (N) and single or copolymer C
P) is. Usually the ratio of epoxy group/silane group is 1/99~
It can be blended to give a ratio of 99/1. Polymerizable unsaturated monomer (Q) A compound that has a radically polymerizable unsaturated group and a functional group that reacts with the functional group of compound (S) in one molecule. The functional group of the monomer (Q) is a group inert to the epoxy group, and the functional group may be the same group as the epoxy group. Regarding the copolymer (R) obtained using the monoffi substance (Q), the following examples ① to ② are given below. ■ Water group-containing dicombinant unsaturated monomer (a), epoxy group-containing dicombinant unsaturated monomer (J), and if necessary, a dicombinant unsaturated monomer [e.g. monomer ( b-1) to (b-6), etc.] are subjected to a radical polymerization reaction to produce a copolymer having a hydroxyl group as a functional group. ■Incyanate group-containing polymerizable unsaturated monomer (e), epoxy base polymerizable unsaturated monomer (J), and optionally a polymerizable unsaturated monomer [e.g. monomer (b- 1) ~(b
-6) etc.] is subjected to a radical polymerization reaction to produce a copolymer having incyane 1 group as a functional group. A co-operative combination with. ■ Epoxy group-containing polymerizable unsaturated monomer (J) and, if necessary, a polymerizable unsaturated monomer [e.g. monomer (b-1)]
- (b-6), etc.] by performing a radical polymerization reaction, and having an epoxy group as a functional group. The compound (S) is a compound having a functional group that reacts with the functional group in the conjugate (R) and a silane group, and the compound (c
) can be added as appropriate. The reactant (T) obtained by the reaction of the copolymer (R) and the compound (S) contains an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in each molecule. You can have it. Royal L-shaped polymerizable unsaturated monomer (, ■) This is a compound that has a radically polymerizable unsaturated/Japanese group and a functional group that reacts with the functional group of compound (W) in one molecule. The functional group of the monomer (V) is a group inert to the silane group, and there is no problem even if the functional group is the same group as the silane group. Regarding the copolymer (W) obtained using the monomer (V), list the following Tjll. ■ Hydroxyl group-containing polymerizable unsaturated monomer (a), silane group-containing engineered unsaturated monomer (K), and optionally a polymerizable unsaturated monomer [e.g. monomer (b-1) to (b-6) etc.] is subjected to a radical synthesis reaction to form a hydroxyl group as a functional group. ■ Isocyanate group-containing polymerizable unsaturated monomer (e), silane group-containing polymerizable unsaturated monomer (1), and optionally a polymerizable unsaturated monomer [for example, monomer (b) -1)～(
b-6) etc.] is subjected to a radical polymerization reaction to produce a copolymer having an isocyanate-1 group as a functional group. ■ Carboxyl group-containing polymerizable unsaturated monomer (d), silane group-containing dish-forming unsaturated monomer (1), and if necessary, polymerizable unsaturated monomer [e.g. b-1) ~ (b
-6) etc.] is subjected to a radical polymerization reaction, and the copolymer has a carboxyl group as a functional group. The compound (W) is a compound having an epoxy group and a functional group that reacts with the functional group in the copolymer (V).
B) can be appropriately selected and used. The reactant (X) obtained by the reaction of the copolymer (V) and the compound (W) each has an average of 1 or more, preferably an average of 2 to 40 epoxy groups and silane groups in one molecule. be able to. (7) Resin composition homopolymer (N), copolymer (N) and reactant (H) are the same monomers and reactants as described in the resin compositions of (2) and (4) above. things can be used. The single or copolymer (N) and the reactant (H) can be blended so that the epoxy group/silane group ratio is usually 1/99 to 99/1. (8) The resin composition homopolymer (P), copolymer CP) and reactant (F) are the same monomers and reactants as mentioned in the resin compositions of (2) and (4) above. things can be used. The individual or copolymer (P) and reactant CF) can be blended so that the epoxy group/silane group ratio is usually 1/99 to 99/1. Each of the above ingredients can be obtained by conventionally known methods. That is, the reaction between a hydroxyl group and an incyanate group, the condensation reaction of a silane group, a co-merge reaction, etc. can be carried out based on conventionally known methods. For example, a reaction between a hydroxyl group and an isocyanate group at room temperature to 130°C for about 30 to 360 minutes is sufficient. The condensation reaction of silane groups is carried out in the presence of an acid catalyst (for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.).
Heating for about 1 to 24 hours at a temperature of about 10°C 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 IH 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 a solvent, and the mixture is heated with stirring at a temperature of about 60 to 180°C in the presence of a radical coalescence initiator. Be able to show it. The reaction time is usually 1 to 1
The IJu solvent may be one that is inert to the monomer or compound used, such as an ether solvent, an ester i8 solvent, a hydrocarbon solvent "B", etc. When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility.In addition, as a radical initiator, any commonly used radical initiator can be used. Examples include peroxides such as benzoyl peroxide and t-butylbaroxy-2-ethylhexanoate, and azo compounds such as azoisobutylnitrile and azobisdimethylbaretnitrile. (1) ~(8) Reactant CD of the fat composition), (F).(
H). (L). (N). (P), (T) and (W) are each about 3000 to 200,000, preferably about 50
00 to soooo. In the above resin composition, it is preferable to introduce carboxyl groups and/or hydroxyl groups in addition to the epoxy groups and silane groups because the curability of the coating can be further improved. The carboxyl-containing resin composition can be water-soluble or water-soluble by neutralizing it with a basic compound. In the above resin composition, the above-mentioned resin or copolymer may be combined with other 1″4 resin (e.g. vinyl IH resin, polyester 1 resin, urethane resin, silicone resin, epoxy resin rP).
Modified IH fats chemically bonded with can also be used in the same way. The above resin composition can be used, for example, with 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, dioxane, ethylene glycol diethyl ether, etc. It can be used in the form of a solution or decomposition in an ether solvent, an alcoholic solvent such as Buknol or Probanol, or water, or it can be used in the form of a non-aqueous dispersion containing the resin composition as a dispersion stabilizer component. The above non-aqueous dispersion will be described next. In the presence of the above-mentioned dispersion stabilizer, one or more radically polymerizable unsaturated monomers and a polymerization initiator are dissolved, but the monomer and the dispersion stabilizer are dissolved, but the polymer obtained from the monomer is A non-water-soluble liquid can be produced by adding the particles to an organic solvent in which they cannot be dissolved and carrying out an m-combination reaction. As the monomer fm that can be used to form the polymer that is the particle component of the non-aqueous dispersion, all the monomers already described can be used. 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 IJEi solvent used. Namely, methyl (mec)acrylate, ethyl (meth)acrylate, (mec)acrylonitrile, 2
-Hydroxy(meth)acrylate, Hydroxybuvir(mek)acrylate% (meth)acrylamide,
Acrylic acid, methacrylic acid, itaconic acid, styrene,
It is preferable to contain a large amount of monomers such as vinyltoluene, α-methylstyrene, and N-methylol(meth)acrylamide. Also, the particles of non-water-resolved liquid can be cross-linked if necessary. One example of a method for crosslinking the inside of particles is to copolymerize polyfunctional monomers such as divinylbenzene and ethylene glycol dimethacrylate. Photographic solvent used for non-water-resolved liquid. The dispersion polymer particles produced by the polymerization are not substantially dissolved in the polymer, but the above-mentioned dispersion stabilizer and radically polymerizable unsaturated monoyl compound include substances that serve as good solvents. ．． Single-use liquids include, for example, aliphatic hydrocarbons such as benzene, hexane, hebukun, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols, and ethers. system. Ester and ketone solvents, such as isobrobyl alcohol on butyl alcohol, isobutyl alcohol, lactyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone. Diisobutylketone, ethyl acylketone, methylhexylketone. Examples include ethyl butyl ketone, ethyl acetate, isobutyl fermentate, acyl acetate, 2-ethylhexyl acetate, etc. Each of these may be used alone or in a mixture of two or more, but in general. Mainly composed of aliphatic hydrocarbons, in addition to aromatic hydrocarbons, alcohols and ethers as mentioned above. A combination of ester-based or ketone-based solvents is preferably used. In addition, trichlorotrifluroethane, metaxylene hexaflulide, and tetrac-hexafruide can also be used if necessary. Polymerization of the above monomers is carried out using a radical polymerization initiator. As radical polymerization initiators that can be used for
F4 starter: benzoyl baroxide, lauryl baroxide. Examples include peroxide-based initiators such as tert-butyl bar octoate;
It can be used in a range of 0.2 to 10 parts per 100 parts of the monomer to be subjected to polymerization. The formulation of the dispersion stabilizer resin present during the above processing is based on the fff of the resin.
Although it can be selected from a wide range depending on type i, in general, the amount of the radically polymerizable unsaturated j\l polymer is about 3 to 240 parts by weight, preferably 5 to 82 parts by weight, based on the total part of the resin. Appropriate. In the above-mentioned non-aqueous dispersion, the storage stability of the non-aqueous dispersion is improved by combining the dispersion stabilizer resin with polymerizable particles, and the non-aqueous dispersion has excellent transparency, smoothness, and mechanical properties. A cured film can be formed. As a method for bonding the resin serving as the dispersion stabilizer and the polymer particles, it can be carried out by polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable dim bond. As a method for introducing a compounding diffi bond, acrylic acid, methacrylic acid,
It is more convenient to add an α,β monoethylenically unsaturated monocarboxylic acid such as itaconic acid, but it is also more convenient to add an isocyanate group such as isocyanoethyl methacrylate to a hydroxyl group that has been incorporated into the resin in advance. There are methods such as adding a single component containing the material. Furthermore, as a method for bonding the dispersant stabilizer and the polymerizable particles, in addition to the method described above, as a monomer component forming the polymer particles. For example, γ-methacryloxybutyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-acryloxibyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-
Attachment can be achieved by using reactive monomers such as acryloxypyltrisilanol. The coating composition of the present invention is an IF selected from the resin compositions (1) to (8) above. It is a paint containing one or more essential components. Although the coating composition targeted by the present invention may be the resin composition itself, it is preferable to include a curing catalyst in order to accelerate the curing reaction of the coating film. Examples of the curing catalyst include those listed in (1) to (6) below. {1} Metal chelate compounds Aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds are preferred. Among these chelate compounds, chelate compounds containing a compound capable of forming a keto-enol tautomer as a ligand to form a stable chelate are preferred. Compounds that can constitute a keto-enol tautomer include β-dimethones (acetylacetone V?), acetoacetate fl (methyl acetoacetate JLtv?). Malonic acid esters (ethyl malonate, etc.), ketone necks with a hydroxyl group in the β position (diacetone alcohol, etc.), aldehydes with a hydroxyl group in the β position (salicylaldehyde, etc.), esters with a hydroxyl group in the β position ( In particular, acetoacetate esters and β-diketones can be used to obtain suitable aggregation.Aluminum chelate compounds are, for example, monocatalytic E formula, where R. is carbon. represents an alkyl group or an alkenyl group of numbers 1 to 2 o.] A compound capable of forming the above keto-enol tautomer is mixed in a molar ratio of about 3 moles or less per 1 mole of the aluminum alkoxide represented by the following. , can be suitably prepared by heating if necessary. As the alkyl group having 1 to 20 carbon atoms, the above-mentioned alkyl group having 1 to 20 carbon atoms
In addition to the 10 alkyl groups, examples include undecyl, dodecyl, tridecyl, tetradecyl, and tadecyl groups, and examples of alkenyl groups include vinyl and allyl groups. Aluminum alcoholate represented by the general formula (9S); pages include: aluminum trimethoxide, aluminum triethoxide, aluminum triethoxide;
- Proboxide. aluminum triisobroboxide,
Examples include aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec-butoxide, aluminum tri-tart-butoxide, and especially aluminum triisobroboxoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, aluminum tri-sec-butoxide, and aluminum tri-sec-butoxide.
- It is preferable to use butoxide etc. The titanium chelate compound is, for example, in the general formula c, m
is an integer of O-10 +R++ has the same meaning as above. ] For 1 mole of T3 in the ticnates represented by
It can be suitably prepared by mixing the compounds that can constitute the above-mentioned keto-enol tautomer at a molar ratio of about 4 moles or less, and heating if necessary. As a titanate represented by the general formula (9b), m
is 1, tetramethylticunate, tetraethylticunate, tetra-n-provirticunate, tetraisobuvirticunate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert
-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisobutyl titanate, tetra-o-lauryl titanate, etc., especially tetraisobutyl titanate, tetra-n-
Use of butyltichnate, tetraisobutyltitanate, tetratert-butyltitanate, etc. gives favorable results. In addition, for those where m is 1 or more, tetraisobutyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate. etler tert
-butyl titanate dimer to l1mer (general formula (
) with m=1 to 10) gives suitable results. In the zirconium chelate compound, for example, in the general formula C, m and Rl+ have the same meanings as above. ] The compound capable of forming the above-mentioned keto-enol tautomer is mixed with 1 mol of Zr in the zirconates at a molar ratio of usually about 4 mol or less, and is preferably heated if necessary. It can be prepared. As the zirconate neck represented by the general formula (9q),
Tetra tert-butyl zirconate, Tetra n-probyl zirconate, Tetra n-butyl zirconate, Tetra n-butyl zirconate, Tetra 38C-butyl zirconate, Tetra tert-butyl zirconate, Tetra n-bentyl zirconate , Tetler te
rt-bentyl zirconate, Tetler t, ert-hexyl zirconate, Tetler n-heptyl zirconate, Tetler n-cutyl zirconate, Tetler n-
These include stearyl zirconate. In particular, tetraisobutyl zirconate, tetraisobutyl zirconate, tetraisobutyl zirconate, tetra n-butyl zirconate, tetra sec-butyl zirconate,
Good results can be obtained using tetratert-butyl zirconate, etc. In addition, for those where m is 1 or more, tetraisobutyl zirconate, tetra n-probyl zirconate, tetra n-butyl zirconate,
Dimers to 11-mers (m=IA-LO in the general formula ('!'l)) of tetraisobutylzirconate, tetrasec-butyldilphinate, and tetratert-butylzirconate are preferred. gives good results. It may also contain a constituent unit in which these zirconates are associated. Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-pro and ruacetoacetate)aluminum, tris(isobrobylacetoacetate)aluminum. Tris(n-butylacetoacetate)aluminum, isobroboxybis(ethylacetoacetate)aluminum, diisobutylacetoacetatealuminum. Tris(acetylacetonato)aluminum, tris(probioxymethylacetonato)aluminum, diisobutyloxypropyrobinylacetonatoaluminum, acetylacetonatobis(probioxypropyleneacetonato)aluminum, monoethylacetoacetate bis[acetylacetonato)aluminum , Aluminum chelate compounds such as tris(acetylacetonato)aluminum: diisobroboxy bis(ethylacetoacetate) titanate. Titanium chelate compounds such as diisobroboxy bis(acetylacetonato) titanate, diisobroboxy bis(acetylacetonato) titanate: tetrakis. (acetylacetonato) zirconium, tetrakis (n-pro and ruacetoacetate)
Examples include zirconium chelate compounds such as zirconium, tetrakis(Cacetylacetate) zirconium, and tetrakis(ethylacetoacetate)zirconium. Any of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound is lff
You may use l'k, or you may use two or more types in combination. The blending amount of the crosslinking reaction curing agent is 0.01 to 30ff per 1001 Irffi parts of the solid content of the previous i2i coalescence (A).
It is appropriate to set the amount to about i parts. 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 G. The amount is 1 to 10 parts by weight, and the more preferred amount is 1 to 5 parts by weight. (2) Examples include Lewis acid gold dihalides, compounds in which the metal shares a halogen and Ike substituent, and bean pastes of these compounds.Specifically, examples include AIC. Aj'F5
F. ．． AJIF. ．． AfEt(j, . A4E
t, CI. Sn4, TiCI4. TIB+-4.
TiFa, ZrCL. ZrBr i. ZrF4.
SnC1a, FeCum, sbcm. sbcm, PC
h, PCI@. Gacm. GaFi. I'nFs
, BCmu, BBri. B.F. , 11Fs: fOCdl
slx,BF4:(OCzHsls,B'Ci'z:(
OCtHglt, BF Yu: NI+. (1,.+11
．． BFx:NHU(:.H.OH .(3) Protonic acid The protonic acid includes, for example, methanesulfonic acid, ekunesulfonic acid, trifluorotocunsulfonic acid, benzenesulfonic acid, P-toluenesulfonic acid. (4) Metal alkoxides. , Specifically, the above-mentioned aluminum alkoxide, titanium alkoxide, zirconium alkoxide, etc. can be used.Furthermore, in addition to the above, metals such as iron, calcium, and barium may have an alkoxy group, preferably a Cl-1 alkoxy group. Examples of such compounds include bonded compounds.These compounds may be associated. (6) Compounds having Si-0-A! bonds Specific examples of such compounds include frilled aluminum silicate. ,7 In the coating composition of the present invention, the curing catalyst 0.01 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight (solid content) of the resin composition (co) to (8). In addition, the coating composition of the present invention may contain the following as necessary: (1) a hydroxyl group-containing resin and a hydroxyl group-containing compound (2) a carboxyl group-containing resin and a carboxyl group-containing compound ( 3) Silane group-containing resin and silane group-containing compound (4) Epoxy group-containing fat and epoxy group-containing compound (5) Chelating agent (6) Organic solvent and/or water (7) Fighting agent (8) Additive resin (1) Furthermore, the coating composition of the present invention may optionally contain a low-molecular positive compound (C ) can be blended.This low molecular weight compound (C) becomes a reactive diluent, and by adding it to the paint composition, it can lower the viscosity of the paint and increase the solid content, and
Since there are few by-products during curing, it is possible to obtain a high solid paint with excellent uniform curing properties. Also, during curing, there is little sagging, resulting in a coating film with excellent smoothness. Number average molecule ffi20 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 general formula, adducts with nate compounds (polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate) Class: Hydrogenated xylylene diisocyanate is also 1. K is cycloaliphatic diisocyanate such as isophorone diisocyanate; organic diisocyanate itself such as aromatic diisocyanate such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or Examples include adducts of each of these organic diisocyanates with polyhydric alcohols, low-molecular all-polyester resins, water, etc., polymers of each of the above-mentioned organic diisocyanates, and isocyanate biuret bodies, etc., but representative examples thereof include An example of a commercially available product is “Burnock D-750”.
．． -800, DN-950, -970 or 15-4
55J [all products manufactured by Dainippon Ink Chemical Industry Co., Ltd.], "Desmodule L, NILSIL or N3B90J (product of Bayer AG, West Germany),""TakenateD-102,"
-202, -110N or -123N" [Takeda Pharmaceutical Company ■ product], "Coronate L, HL, El {or 203J (Nippon Polyurethane Industry Intermediate Products)] or [Duranate 24A-90CXJ (Asahi Kasei G.
el product); an esterified product with a number average molecular weight of 900 obtained by esterifying hydrophthalic acid, trimethylolbromine, 1,4-butanediol, etc.) is oxidized with peracetic acid, etc. Examples include things that can be obtained. In addition to the compounds having an alicyclic oxirane group as described above, compounds having a non-alicyclic oxirane group such as diglycidyl ether, 2-glycidyl phenyl glycidyl ether, etc. can also be used. It is important that the molecular weight of the compound having two or more oxirane groups in one molecule is less than or equal to the number average molecular ffi2000. 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. It is appropriate to use about 0 to 100 parts by weight, preferably about 5 to 60 parts by weight, based on the base resin 100i1 (based on the weight part). Epoxy group-containing resins such as Shell Chemical *> and hydroxyl group-containing resins such as styrene alinoleanolefur copolymer can be included.
% or less is preferable. The automotive coating composition of the present invention can be used as a top coating and/or intermediate coating for personal use by blending various known additives as required. The coating composition of the present invention can be used as a top coat, such as a base coat and/or top clear coat for finishing solid color two coats. When the fish food composition of the present invention is used as a top coat (for example, as a top solid color paint, a two-coat, one-bake coating, and a clear paint), 1 part of the base resin, Approximately 0 to 3 parts of curing catalyst o.oi, 0 to 100 parts by weight of a low molecular weight compound (c) having two or more oxirane groups in one molecule, and 0 to 100 parts by weight of coloring pigment. As pigments, both inorganic and organic highly weather-resistant coloring pigments used in conventional top coatings for automobiles can be used, such as inorganic pigments such as rutile titanium oxide or carbon black, and quinacridone red-based pigments. Organic pigments such as quinacridone pigments such as quinacridone pigments, azo pigments such as pigment red, and phthalocyanine pigments such as phthalocyanine blue and lid cyanine green can be used.
When used as a clear paint for a bake coat, it is usually used with little or no addition of colored pigments. Among the above paints, when used as a 2-coat/1-bake base coat paint or a 1st-coat 1-bake metallic paint, the composition is based on 100 mff of base resin.
llm, curing catalyst o. 01 to 36 parts by weight of a metallic pigment, 0 to 100 parts by weight of a low molecular weight compound (c) having two or more oxysilane groups in one molecule, and about 0 to 40 parts by weight of a colored pigment. Appropriate. Known metallic pigments can be used, including scale-like metallic pigments such as aluminum, copper, iron matrix oxide, iron oxide or titanium oxide coated matrix, titanium oxide coated mica iron oxide, bronze, and stainless steel. Powder etc. can be used, and as for 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, acrylic dispersions with core crosslinking obtained by heterogeneous polymerization obtained by known methods, cellulose acetate butyrate, etc. It is also possible to mix up to about 20 tnffi parts. Furthermore, when the coating composition of the present invention is used as an intermediate coating for automobiles, the composition is as follows: 100 parts by weight of base resin, 0.01 to 30 parts by weight of curing catalyst, and 5 to 150 parts by weight of pigment.
About 0 to 100 parts by weight of the low-molecular positive compound (C) having the fi part and two or more oxirane groups in one molecule is suitable. Pigments include titanium oxide, barium sulfate, calcium carbonate, clay, etc. U-colorants 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, RE
Type A), air spray painting, etc., and conventionally used paint machines and painting equipment can be used as they are. The viscosity of the paint during 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 No. 4.20''C), and it may be selected appropriately depending on the coating machine, type of solvent, coating conditions, etc. . As the solvent for diluting the paint, all solvents used in conventional acrylic resin/melamine resin paints can be used. Examples include ketone solvents, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether, alcohol solvents such as butanol and propanol, and water. These solvents can be used alone or in an appropriate mixture, but when using an alcoholic solvent, it is preferable to use it in combination with another solvent from the viewpoint of solubility of the resin. Also, from the point of view of curing speed,
Those having a boiling point of about 150° C. or lower are preferred, but are not limited to this. The coating composition of the present invention can be prepared, for example, by electrodepositing a primer on a chemically treated copper plate, and then 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 80 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: solid color paint for 1 coat/1 bake, metallic color paint for 1 coat/1 bake, top clear paint for 2 coats/1 bake. etc., 2
About 0 to 100 μm, preferably about 30 to 70 μm,
When used as a 2-coat/1-bake metallic base coat paint, the thickness is about 10 to 50 μm, preferably 1
Approximately 0 to 40 μm is appropriate. Furthermore, two coats of the aqueous rice coating composition of the present invention were applied.
It can be used as a base coat for one bake. The baking conditions for coated rice are 80 to 200°C and 30°C.
The drying time may be about 40 minutes, but by extending the drying time, the crosslinking reaction can be carried out even at room temperature to about 80°C.
For example, it can be cured in about 3 days at room temperature. It is thought that the curing of the coating composition of the present invention by the above-mentioned curing catalytic action causes various curing reactions such as those described below. (A) Condensation of silanol groups (B) Condensation of silanol groups with hydroxyl groups generated from oxirane groups (C) Addition of silanol groups to oxirane groups (D) Addition of hydroxyl groups to oxirane groups (E) Combination of oxirane groups In addition, in the coating composition of the present invention, when it contains an alkoxyl group (that is, when it contains an alkoxysilane group), hydrolysis is required to generate a silanol group, but this hydrolysis reaction The process is sufficient to occur even in the presence of a small amount of moisture, such as that in the air. In the coating composition of the present invention, in the vinyl copolymer used,
There are functional groups such as silanol groups and oxirane groups derived from vinyl monomers containing oxirane groups. For this reason,
Various curing reactions as shown in (A) to (E) above occur in parallel. As a result, curing proceeds simultaneously on the surface and inside of the cured product, and the degree of curing is small on the surface and inside of the cured product, making it difficult to cause distortion. Effects of the Invention When the coating composition of the present invention is used as an intermediate 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 ionic polymerization reaction and addition reaction, and the generation of reaction by-products is extremely small, so volume shrinkage during the coating H curing process is small, and the product is highly smooth with no microscopic unevenness (chirpy skin). A coating film can be obtained. Therefore, the sharpness of the top coat after the top coat 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. Therefore, it can also be used as an intermediate coating for plastic substrates where the baking temperature cannot be raised above 120°C. ■ Single wave paint has good paint stability and low toxicity. ■ It is easy to design ultra-high solid intermediate coatings. By combining the molecular weight adjustment of the base resin and a low molecular weight compound (CC) containing two or more oxirane groups in one molecule with a molecular weight of less than The coating composition of the present invention is a high solid coating system and has good uniform curing properties because the low molecular weight compound (C) functions as a reactive diluent, lowering the viscosity of the coating and reducing the solid content. In addition, as a crosslinking reaction of the base resin, 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 simultaneously, resulting in by-products during curing. This is presumed to be because there is little difference in hardenability between the surface and the interior, and almost no uncured material remains.In addition, when used as a top coat for automobiles, the above
In addition to the effects of ~■, the following excellent effects are also achieved. ■ Extremely good acid resistance. There are no problems with stains, dullness, or etching caused by acid rain. ■ Strong stain resistance. It has good resistance to various types of contaminants due to its dense crosslinking density and water repellency based on the polysiloxane present in the base resin. ■ Good scratch resistance. Good scratch resistance is achieved due to the synergistic effect of the fine crosslinking density and the frictional resistance reducing effect based on the H-lysiloxane present in the base resin. ■ Obtains a coating film with high weather resistance (no gloss, cracking, cracking, blistering, etc.). 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 simultaneously, and because there are few byproducts during curing, there is a difference in curability between the surface and inside. Since there is little uncured material remaining, it has a high degree of weather resistance. Examples Production examples and examples are shown below. In the example, “
Unless otherwise specified, "%" and "%" refer to
Means "parts by weight" and "% by weight" respectively. Production example 1 ■. Production of silane group- and epoxy group-containing resin ■Si-1 Glycidyl methacrylate 14.2 parts Butyl methacrylate} 44.2 parts 2-Hydroxydiethyl acrylate 11.6 parts Styrene 30.0 parts A 50% xylene solution of an acrylic resin with a peak molecular weight (as determined by mutation chromatography) of 20,000 was obtained. ■Si-2 γ-methacrylate trimethoxysilane
23.6 parts n-butyl methacrylate 46.4 parts Styrene 30.0
A 50% xylene solution of an acrylic resin having a molecular fi20,000 was obtained. ■S i-3 Trimethylolbroban 40.95 parts Adivic acid
87.6 parts neobentyl glycol
73.5 parts Phthalic anhydride 44.4
75% of polyester with an acid value of 2.2 obtained using
131 parts of succinic anhydride was reacted with 1746 parts of the xylol solution. To 313 parts of the obtained high acid value polyester,
129 parts of the following compound P was added and an addition reaction was carried out until the acid value reached 6. Compound P: 26.0 parts of Si-4 2-hydroxyethyl methacrylate 7.2 parts of acrylic acid 66.8 parts of methyl methacrylate was added to an acrylic resin (molecule ffi4 0 0 00), and the following compound Q was added to it.
and 10 parts of compound R were subjected to an addition reaction (50 parts
% xylol solution). Compound Q2 Compound R: CON CH2 CH2 -SI (OC2
Hs)3Si-5 In the above Si-1, the entire amount of n-butyl methacrylate and styrene was replaced with n-butyl acrylate to obtain an acrylic resin. (2) Si-6 In the above St-2, the entire amounts of n-butyl methacrylate and styrene were replaced with n-butyl acrylate to obtain an acrylic resin. Examples 1 to 5 Using the resins obtained in the above production examples, intermediate coatings for automobiles having the formulations shown in Table 2 were produced (paints Nos. 1 to 5). For each paint, the pigment was dispersed with the resin and solvent using a Bain 1 shaker for 1 hour. As a comparative product, oil-free polyester resin/melamine resin (
Trademark: Rugabake AM, manufactured by Kansai Bain 1-Aji, Comparative Example 1, Paint No. S-6), and acrylic boriol/boryson anate-based low-temperature curing resin (trademark: Rethane PG)
80, manufactured by Kansai Paint Aji, Comparative Example 2, Paint Na. s-7
), 60 parts by weight of titanium oxide was mixed with 100 parts by weight of resin solid content. In Table 2, Ebicoat #8 is the epoxy resin.
28 (manufactured by Ciel Chemical), and titanium oxide J as the pigment.
R-602 (manufactured by Teikoku Kakokan) and the following compound as oligomer S were used. Furthermore, the following metal chelate compounds were used. Chelate compound...}・Lisu (acetylacetona)
Aluminum chelate compound ■...Tetrakis(ethyl acetoacetate) zirconium Test Example 1 (Coating film performance test) A chemical conversion treated dull steel plate was coated with an epoxy resin-based cationic electrodeposition paint (film thickness 25 μrn) and heated at 170°C for 30 minutes. The intermediate coating compositions of the present invention and comparative products were applied to the heat-cured plates so that the thickness of the cured coating was 40 ± 5 μm.
It was spray painted and cured by baking in two ways: 100°C for 30 minutes and 140°C for 30 minutes. Furthermore, this. E was coated with 40 μm of a polyester resin/melamine resin automotive top coat (white color, manufactured by Kansai Paint ■, Rugabake AM) and baked at 140° C. for 30 minutes to prepare a test plate. Using the test plates thus obtained, various coating film performance tests were conducted. The results are shown in Table 3. Note that the pencil hardness and xylene resistance tests were conducted without applying a top coat. Test method 4) Pencil hardness: Scratch the surface of the coating film with the lead of a Mitsubishi Yuni pencil,
The maximum hardness of the core that will not scratch the painted surface is indicated by a symbol. 5) Xylol resistance Hold the gauze impregnated with xylol with your fingers and strongly rub the painted surface back and forth 10 times. The degree of melting of the painted surface, scratches and swelling is between good (◎) and markedly poor (×): ◎, ○, ■, Δ
Judgment was made on a 5-level scale of , x. 6) IMAGE CLARITY METE
R: Measured with Suga Test Instruments Co., Ltd.). The numbers in the table are IC
The M value takes a value in the range of 0 to 100%, and the larger the value, the better the image clarity, and the ICM value of 80 or more indicates extremely excellent image clarity. 7) Make 100 cross-cuts by making incisions on the painted surface at intervals of 1 square in each direction to reach the adhesive substrate. A cellophane adhesive tape was pasted on top of this, and the condition was evaluated after it was rapidly peeled off. Display: Number of stitches without peeling/1008) 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. 9) Pitting resistance A flying stone tester [Suga Test Instruments ■, JA-400 type] was used. Attach the painted test plate vertically to the sample holder of the testing machine and load 50g of No. 7 crushed stone at 4kg/c using the pressure gauge of the testing machine.
The crushed stone is injected at an air pressure of J at right angles to the test plate. At that time, the degree of peeling scratches was evaluated as good (◎) to poor (×
) Judgment was made on a five-point scale. 10) Heating residue during painting (%) Heating residue of paint diluted with Swazol #1000 (trade name, manufactured by Maruzen Sekiyu ■, petroleum-based mixed solvent) to a coating viscosity of 20 seconds (Ford Cup No. 4/20℃) %(flffff
i). Those with a high value also had good base hiding properties. 11) Storage stability Paint diluted with 10) above (20 seconds/Food Cup N
o. 4) Cover with a lid to prevent contact with outside air and heat at 40℃.
It was stored for 5 days. ◎...Viscosity increase for less than 5 seconds. ■...Viscosity rises for 10 to 15 seconds. Evaluation was made on a five-point scale: x: gelation. Exam f! +1 2 Apply 15 to 20 μm of Soflex Nα2500 (trade name, manufactured by Kansai Paint ■, urethane-modified chlorinated polypropylene resin) as a brimer to polypropylene resin. After baking at 80°C for 20 minutes, apply the intermediate coating (S-
1 and s-6) were applied to a thickness of 40±5 μm, respectively, and heated at 80°C.
Baked for 0 minutes. After that, as a top coat, Soflex N
α200 (trade name, manufactured by Kansai Paint ■, polyester resin/aliphatic polyisocyanate type) of 30 to 40 μm
Apply and bake at 80℃ for 30 minutes to form a topcoat film.
A test plate was obtained. The test plate thus obtained was subjected to the same coating film performance test as in Test Example 1. The results are shown in Table 4 below. Table Example 2 Using the resin obtained in the above production example, the compositions shown in Table 5 were used for automotive top coats [■Colored paint (white), ■2 coat/1 bake (2CIB) base coat (metallic paint), and ■2Clear coat for CIB] were manufactured. The titanium oxide was dispersed in a paint shaker for 1 hour. In the case of solid color paints, 80 parts by weight of titanium oxide per 100 parts by weight of resin solids, and in the case of base metallic paints for 2 coats and 1 bake, aluminum per 100 parts by weight of resin solids. The amount was 13 parts by weight. Comparative Example 3 is a 1-coat/1-bake method of Luga Bake AM White, and Comparative Example 4 is a 2-coat/1-bake method, using Magikron #1000 Base Coat (Silver) (trade name, manufactured by Kansai PE India ■, acrylic). melamine resin)
was used. Test Example 3 An epoxy resin-based cationic electrodeposition paint (25 μrr+) was applied to a chemically treated dull steel plate, and after heating and curing at 170°C for 30 minutes, Lugabeke AM was applied as an intermediate coat to a dry film thickness of 30 μm. It was painted as follows and baked at 140°C for 30 minutes. Next, the painted surface was water-sanded with #400 sandpaper, drained and dried, and the painted surface was wiped with petroleum benzene to prepare a material. For colored topcoat paint (white) and clear paint, use Swasol #1000 for 22 seconds (Ford Cuff No.4,
For metallic topcoat (silver), use toluene/swasol #1500 (20°C).
The viscosity was adjusted to 13 seconds (Ford cup Nα4, 20°C) with a mixed thinner of 80/20 (trade name, manufactured by Maruzen Oil Co., Ltd.). The viscosity-adjusted paint was air-sprayed. The colored top coat (white) was applied so that the dry film thickness was 40 to 50 μm. In the case of a 2-coat, 1-bake metallic finish, the metallic top coat was left at room temperature for 3 minutes, and the clear coat was immediately applied. The film thicknesses were 15 to 20 μm and 35 to 45 μm in dry film thickness, respectively. Then, it was left at room temperature for 10 minutes and then heated at 100°C for 30 minutes and 14 minutes.
Two batches of 30 minutes of baking were carried out at 0°C. The formed coating film was subjected to the same performance test as Test Example 1 and the following performance test. The results are shown in Tables 6 and 7. 12) Acid 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. Depending on the degree, there is no abnormality at all (◎), and abnormalities such as noticeable glossiness and erosion (×).
Judgment was made in five stages: O, ■, △, and ×. 13) Scratch resistance A dyeing abrasion fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho) was used. Harden polishing powder (Daruma Cleanser) with water, place it on the painted surface, press it with the terminal of the testing machine, apply a load of 0.5 kg, and rub it back and forth 25 times. After washing with water, the degree of scratches was evaluated on a five-point scale: ◎% O% ■, △, and ×. 14) Water resistance After immersion at 40° C. for 10 days, the state of the painted surface was evaluated. 15) Weather resistance A QUV accelerated weather test was conducted using an accelerated weather resistance tester manufactured by Q Bunnell. Test conditions: UV irradiation 16H/60℃ water condensation 9H/
After testing at 50°C for 3000 hours (125 cycles), the condition of the coating film was evaluated. In Table 6, * indicates chalking, and ** indicates cracking. (that's all)

Claims (1)

[Scope of Claims] [1] (1) A resin (A) having a functional group is mixed with a compound (B) having a functional group and an epoxy group that react complementary to the functional group and the resin (A). A functional group that reacts complementary to the functional group and a silane group (a hydroxyl group directly bonded to a silicon atom and/or
or a hydrolyzable group) (C)
Reaction product (D) obtained by reacting (2) A reaction obtained by reacting a resin (E) having a functional group with a compound (B) having a functional group and an epoxy group that reacts complementary to the functional group. A mixture of a compound (F) and a reactant (H) obtained by reacting a resin (G) having a functional group with a compound (C) having a functional group and a silane group that reacts complementary to the functional group ( 3) Epoxy group-containing polymerizable unsaturated monomer (J), silane group-containing polymerizable unsaturated monomer (K), and if necessary, other polymerizable unsaturated monomers (M) as monomers Copolymer (L) as a component (4) A homopolymer (N) of the monomer (J) or a copolymer of the monomer (J) and another polymerizable unsaturated monomer (M) a polymer (N), and a homopolymer (P) of the monomer (K) or the monomer (
A mixture of a copolymer (P) of K) and another polymerizable unsaturated monomer (M), provided that the monomer (K) described in (3) and (4) above
is the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (85) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (86) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (87) ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ (88) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (89) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (90) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (91) ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ (92) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (93) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (94) [In the formula, R^6 represents a hydrogen atom or a methyl group, R^9 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and the three Y's are the same or different and represent a hydrogen atom, a hydroxyl group, a hydrolyzable group,
C_1_-_8 Indicates an alkyl group, aryl group, or aralkyl group. However, at least one of Y is a hydrogen atom, a hydroxyl group, or a hydrolyzable group. ] It is selected from the compounds represented by. (5) A copolymer (R) containing a functional group-containing polymerizable unsaturated monomer (Q) and the epoxy group-containing polymerizable unsaturated monomer (J) as essential components; ) Reaction product (T) with a compound (S) having a functional group and a silane group that reacts complementary with the functional group derived from (6) a polymerizable unsaturated monomer (U) having a functional group and the silane A copolymer (V) containing a group-containing polymerizable unsaturated monomer (K) as an essential component, and a functional group and an epoxy group that react complementary with the functional group originating from the monomer (U). Reactant (X) with compound (W) (7) A mixture (Y) of the homopolymer (N) or copolymer (N) and the reactant (H), and (8) the homopolymer ( Automotive coating composition containing as an essential component one or more base resins selected from P) or a mixture (Z) of copolymer (P) and the reactant (F) [2] Automotive The coating composition according to claim 1, which is an intermediate coating. [3] The coating composition according to claim 2, which is a top coating for automobiles.