JPH06287511A - Paint composition - Google Patents

Abstract

(57) [Summary] [Purpose] A coating composition that can form a coating film that has good adhesion to the surface of the material and that also has excellent water whitening resistance, stain resistance, solvent resistance, chemical resistance, etc. Getting things. A resin composition comprising an acrylic resin having at least one tertiary amino group in one molecule and an acrylic resin having at least one hydroxyl group in one molecule, and (1) an isocyanate compound as a curing agent And a compound containing at least one epoxy group in one molecule, or a compound having both an epoxy group and a hydrolyzable silyl group in one molecule, or (2) an isocyanate compound and one molecule in one molecule. A compound containing at least one epoxy group, or a compound having an epoxy group and a hydrolyzable silyl group together in one molecule, and a compound having a hydrolyzable silyl group and / or a silanol group are added, and further addition is required. A coating composition which is cured by adding a hydrolysis-condensation catalyst depending on the above.

Description

Detailed Description of the Invention

[0001]

[Industrial application] The present invention is made of stainless steel material, aluminum material, alumite material, zinc material, copper bronze material, colored stainless steel material, colored alumite material,
Excellent adhesion to materials such as glass materials, ABS-chrome plating materials, electroless nickel plating materials, aluminum vapor deposition materials, and inorganic-filled plastics whose surface is partly or wholly inorganic or metal, as well as stain resistance and corrosion resistance. The present invention relates to a coating composition capable of forming a coating film having good solvent resistance and chemical resistance.

[0002]

[Prior Art] Stainless Steel Material, Aluminum Material, Alumite Material, Zinc Material, Copper Bronze Material, Color Stainless Steel Material, Color Alumite Material, Glass Material, AB
S-chrome plating materials, electroless nickel plating materials, aluminum vapor deposition materials, and inorganic-filled plastics are used in many fields. However, in order to coat the surface of these materials with one coat, a coating composition using an acrylic resin having a hydroxyl group as a base resin and an isocyanate compound as a curing agent is adopted, but the adhesion is insufficient. In addition, a coating composition using an acrylic resin containing a tertiary amino group as a base resin and a compound having both an epoxy group and an alkoxysilyl group as a curing agent has been proposed as a one-coat coating with good adhesion to the above materials. Has been done.
However, this method has the drawback of being inferior in water whitening resistance, stain resistance, and chemical resistance.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks and provides a single coat coating on the surface of a material with good adhesion, and also has water whitening resistance, stain resistance, solvent resistance, chemical resistance, etc. An object is to provide an excellent coating composition.

[0004]

In order to solve the above-mentioned drawbacks, the present invention provides an acrylic resin having at least one tertiary amino group in one molecule and an acrylic resin having at least one hydroxyl group in one molecule. (1) an isocyanate compound and a compound containing at least one epoxy group in one molecule, or a compound having an epoxy group and a hydrolyzable silyl group in one molecule as a curing agent. Or (2) an isocyanate compound and a compound containing at least one epoxy group in one molecule, or a compound having an epoxy group and a hydrolyzable silyl group in one molecule, and a hydrolyzable silyl group And / or a compound having a silanol group is added, and if necessary, a hydrolysis-condensation catalyst is added to cure the compound. Or with that paint composition,

Alternatively, at least one 3 in one molecule
(1) An isocyanate compound and a compound containing at least one epoxy group in one molecule, or an epoxy group and a hydrolyzable silyl group in one molecule as a curing agent in an acrylic resin having a primary amino group and a hydroxyl group. Or (2) an isocyanate compound and a compound having at least one epoxy group in one molecule, or a compound having an epoxy group and a hydrolyzable silyl group in one molecule, A coating composition was obtained in which a compound having a decomposable silyl group and / or a silanol group was added, and a hydrolysis-condensation catalyst was further added, if necessary, to cure.

[0006]

As described above, in the coating composition of the present invention, a highly durable coating film is formed by the reaction between the hydroxyl group of the acrylic resin and the isocyanate group, so that stain resistance, solvent resistance, chemical resistance, etc. Can exhibit excellent properties, and
Due to the hydrolyzable silyl group and epoxy group contained, a coating composition having excellent adhesion to the above materials can be obtained.

[0007]

The present invention will be described below. Acrylic resin having both tertiary amino group and hydroxyl group, or 3
The acrylic resin having a primary amino group and the acrylic resin having a hydroxyl group can be obtained by copolymerizing an amino group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer and other α, β-ethylenically unsaturated monomers.

Specific examples of the amino group-containing vinyl monomer include dialkylaminoalkyl such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and diethylaminopropyl (meth) acrylate. (Meth) acrylates or N-dialkylamino such as N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide In addition to alkyl (meth) acrylamides, there are t-butylaminoethyl (meth) acrylate, t-butylaminopropyl (meth) acrylate and the like.

Specific examples of the hydroxyl group-containing vinyl monomer include C _{2 to} C ₈ hydroxyalkyl esters of (meth) acrylic acid such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, or their (meth ) and the like adducts of hydroxyalkyl esters and ε over caprolactone C ₂ -C ₈ acrylic acid, and lactones such as γ over valerolactone.

Specific examples of the α, β-ethylenically unsaturated monomer include (meth) acrylic acid ester, carboxyl group-containing vinyl monomer, acid anhydride group-containing vinyl monomer, and carboxylic acid amide group-containing vinyl monomer. Examples thereof include a monomer, a sulfonamide group-containing vinyl monomer, a (perfluoro) alkyl group-containing vinyl monomer, and an aromatic vinyl monomer.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Iso-propyl (meth) acrylate, n-butyl (meth) acrylate and Iso-butyl (meth). Acrylate, ter
(meth) acrylic acid having 1 to 18 carbon atoms such as t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate. Examples include alkyl esters of acrylic acid.

Examples of the vinyl monomer containing a carboxyl group include dialkyl esters of unsaturated dibasic acids such as (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, as well as dimethyl maleate and dimethyl fumarate. is there. Examples of the acid anhydride group-containing vinyl monomer include maleic anhydride and itaconic anhydride.

Examples of vinyl monomers containing a carboxylic acid amide group include (meth) acrylamide and N-alkoxy (meth) acrylamide. Examples of the sulfonamide group-containing vinyl monomer include p-styrene sulfonamide. Examples of the (per-) fluoroalkyl group-containing vinyl monomer include per-fluorocyclohexyl (meth) acrylate. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene and p-chlorostyrene.

Next, examples of the compound containing at least one epoxy group in one molecule include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin containing triglycidyl isocyanate or hydantoin epoxy, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, propylene Aliphatic epoxy resins such as glycol diglycidyl ether and pentaerythritol polyglycidyl ether, reaction products of aliphatic or aromatic carboxylic acids with epichlorohydrin, spiro ring-containing epoxy resins,
Examples thereof include a reaction product of an orthoarylphenol novolac compound and epichlorohydrin (glycidyl ether type epoxy resin), a reaction product of a diallyl bisphenol compound and epichlorohydrin, and one or a mixture of two or more of them is used.

As a compound having both an epoxy group and a hydrolyzable silyl group in one molecule, a vinyl copolymer having both reactive groups and a silane coupling agent having an epoxy group are typical. The vinyl copolymer having both reactive groups is a vinyl monomer having an epoxy group, a vinyl monomer having a hydrolyzable silyl group, and optionally an amino group-containing vinyl monomer, which can be copolymerized It is obtained by copolymerizing any of vinyl monomers.

As the vinyl monomer having an epoxy group, (β-methyl) glycidyl (meth) acrylate,
Allyl glycidyl ether and the like. Examples of the vinyl monomer having a hydrolyzable silyl group include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. . As the silane coupling agent having an epoxy group, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropylmethyldiethoxysilane and the like.

Further, the compounds having a hydrolyzable silyl group include alkoxysilanes, alkenyloxysilanes, acyloxysilanes, halosilanes, partial hydrolyzed condensates of alkoxysilanes, and alkenyloxysilanes. There are partial hydrolysis-condensation products and the like.

Examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane and diphenyldiethoxysilane. As alkenylsilanes,
Examples include tetraisopropenyloxysilane and phenyltriisopropenyloxysilane. Examples of the acyloxysilanes include tetraacetoxysilane and γ-mercaptopropyltriacetoxysilane. Halosilanes include tetrachlorosilane and phenyltrichlorosilane.

As the isocyanate compound, for example, m
-Or p-xylylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, m- or p-phenylene diisocyanate, aromatic diisocyanate compounds such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4 '-Methylenebis (cyclohexyl isocyanate), methylcyclohexane 2,4 (2,6) diisocyanate, 1,
In addition to aliphatic (alicyclic) diisocyanates such as 3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, etc., an adduct of the diisocyanate compound and a polyol (ethylene glycol, trimethylolpropane, etc.), the diisocyanate compound And a burette type isocyanate compound. Among these,
It is desirable to use an aliphatic or alicyclic isocyanate compound because a coating film with little deterioration and excellent weather resistance can be obtained.

The present invention will be described in more detail with reference to examples. "Parts" in Examples and Comparative Examples are based on weight.
The viscosity means a value measured by Ford cup # 4 (20 ° C).

Production Example 1 (Preparation Example of Acrylic Resin Having Tertiary Amino Group, Acrylic Resin Having Hydroxyl Group) 42 parts of toluene and 42 parts of toluene were placed in a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet. , Isobutyl acetate 2
After charging 8 parts and raising the temperature to 80 ° C. in a nitrogen atmosphere, 51 parts of methyl methacrylate, 36 parts of n-butyl acrylate, 13 parts of dimethylaminoethyl methacrylate were added.
Part, 1 part of azobisisobutyronitrile (hereinafter referred to as AIBN), 1 part of tert-butylperoxyoctate and 20 parts of toluene under stirring 3
Dropped over time. After completion of the dropping, the mixture was aged at the same temperature for 2 hours, and then a mixture of 1 part of AIBN and 10 parts of toluene was added dropwise. After that, the temperature was kept at the same temperature for 4 hours, the nonvolatile content was 50%, and the number average molecular weight was 15,000.
To obtain an acrylic resin solution having a tertiary amino group.

A similar reactor was charged with 42 parts of toluene and 28 parts of isobutyl acetate and charged in a nitrogen atmosphere at 80 parts.
After the temperature was raised to ℃, 53 parts of methyl methacrylate, n-
A mixture of 30 parts of butyl acrylate, 17 parts of 2-hydroxyethyl acrylate, 1 part of AIBN, 1 part of tert-butyl peroxyoctoate, and 20 parts of toluene was added dropwise under stirring for 3 hours. After dripping, aging at the same temperature for 2 hours, and then adding AIBN 1
And 10 parts of toluene were added dropwise. Thereafter, the temperature was kept at the same temperature for 4 hours to obtain an acrylic resin having a hydroxyl group with a nonvolatile content of 50% and a number average molecular weight of 15,000. Furthermore, the acrylic resin having an amino group and the acrylic resin having a hydroxyl group are in a weight ratio of 1: 1.
To obtain acrylic resin #A.

Production Example 2 (Preparation Example of Acrylic Resin Having Tertiary Amino Group and Hydroxyl Group) A reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube was charged with 42 parts of toluene and isobutyl acetate. 28
Parts, and heated to 80 ° C. in a nitrogen atmosphere, then 45 parts of methyl methacrylate, n-butyl acrylate 2 parts
5 parts, 13 parts of dimethylaminoethyl methacrylate,
17 parts of 2-hydroxyethyl acrylate, AIBN
1 part of tert-butyl peroxyoctoate
And a mixture of 20 parts of toluene were added dropwise with stirring for 3 hours. After completion of the dropping, the mixture was aged at the same temperature for 2 hours, and then a mixture of 1 part of AIBN and 10 parts of toluene was added dropwise. The acrylic resin solution #B having a tertiary amino group and a hydroxyl group, which has a nonvolatile content of 50% and a number average molecular weight of 15,000, is then kept at the same temperature for 4 hours.
Got

Production Example 3 (Example of Preparation of Acrylic Resin Having Tertiary Amino Group) 42 parts of toluene and 28 parts of isobutyl acetate were placed in a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube. After charging and heating to 80 ° C. in a nitrogen atmosphere, 51 parts of methyl methacrylate and 36 parts of n-butyl acrylate were used.
Part, 13 parts of dimethylaminoethyl methacrylate, A
A mixture of 1 part of IBN, 1 part of tert-butyl peroxyoctoate and 20 parts of toluene was stirred under stirring 3
Dropped over time. After the dropping was completed, the temperature was kept at the same temperature for 2 hours, and then a mixture of 1 part of AIBN and 10 parts of toluene was added dropwise. Thereafter, the mixture was aged at the same temperature for 4 hours to obtain an acrylic resin solution #C having a tertiary amino group having a nonvolatile content of 50% and a number average molecular weight of 15,000.

Example 1 (Colored paint) EX-212 (Nagase Chemical Industries Co., Ltd.) was added to a mixture of 60 parts of acrylic resin #A obtained in Production Example 1, 2 parts of carbon black, 16 parts of toluene and 22 parts of isobutyl acetate. Made, 1,
6-hexanediol diglycidyl ether) to 3.5
Department and Duranate 24A-100 (Asahi Kasei Corporation)
Made, hexamethylene diisocyanate burette type)
After adding 8 parts of the above, the viscosity was adjusted to 12 seconds with a paint mixed solvent consisting of toluene, ethyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate to obtain a paint composition # A-1.

Coating composition # A-1 was spray-coated on the following material degreased with toluene, forcedly dried at 80 ° C. for 40 minutes, and then left at room temperature for 3 days to give a test piece. (A) SUS430 (b) ABS-chromium plating (c) ABS-electroless nickel plating

Example 2 (Clear paint) 60 parts of acrylic resin #A obtained in Production Example 1, toluene 16
Part, a mixture of 24 parts of isobutyl acetate, 5 parts of A-187 (manufactured by Nippon Unicar Co., Ltd., γ-glycidoxypropyltrimethoxysilane) and silicate 40 (manufactured by Tama Chemical Co., Ltd., tetraethoxysilane). (Partially hydrolyzed condensate) of 7 parts and 8 parts of Duranate 24A-100 are added, and a viscosity of 12 is obtained with a paint mixture solvent consisting of toluene, ethyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate. Adjust to seconds,
A coating composition # A-2 was obtained.

Coating composition # A-2 was spray-coated on the following material degreased with toluene, and after forced drying at 80 ° C. for 40 minutes, it was left at room temperature for 3 days to obtain a test piece. (A) SUS430 (b) ABS-chromium plating (c) ABS-electroless nickel plating

Example 3 (Clear coating) To a mixture of 60 parts of acrylic resin #A, 16 parts of toluene and 24 parts of isobutyl acetate, 5 parts of A-187 and 8 parts of Duranate 24A-100 were added, followed by toluene, The viscosity was adjusted to 12 seconds with a mixed solvent consisting of ethyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate to obtain coating composition # A-3. Coating composition # A-3 was spray-coated on the following material degreased with toluene, forcedly dried at 80 ° C. for 40 minutes, and then left at room temperature for 3 days to give a test piece. (A) SUS430 (b) ABS-chrome plating (c) ABS-electroless nickel plating

Example 4 (Coloring paint) 5 parts of A-187 and silicate 40 were added to a mixture of 60 parts of acrylic resin #B obtained in Production Example 2, 2 parts of carbon black, 16 parts of toluene and 22 parts of isobutyl acetate. 7.5
Parts, 8 parts of Duranate 24A-100 were added,
The viscosity was adjusted to 12 seconds with a paint mixed solvent consisting of toluene, ethyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate, and paint composition #B
-1 was obtained. Coating composition # B-1 was spray-coated on the following material degreased with toluene, forcedly dried at 80 ° C. for 40 minutes, and then left at room temperature for 3 days to obtain a test piece. (A) SUS430 (b) ABS-chromium plating (c) ABS-electroless nickel plating

Example 5 (Clear paint) A mixture of 60 parts of acrylic resin #B, 16 parts of toluene, and 24 parts of isobutyl acetate was added to 5 parts of A-187, 7.5 parts of silicate 40, and 8 parts of duranate 24A-100. After adding 1 part, the viscosity was adjusted to 12 seconds with a paint mixed solvent composed of toluene, ethyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate to obtain a paint composition # B-2. Paint composition # B-2 is spray-painted on the following materials degreased with toluene at 80 ° C 40
After forced drying for a minute, the test piece was left at room temperature for 3 days. (A) SUS430 (b) ABS-chromium plating (c) ABS-electroless nickel plating

Example 6 (Clear paint) To a mixture of 60 parts of acrylic resin #B, 16 parts of toluene and 24 parts of isobutyl acetate, 5 parts of A-187 and 8 parts of Duranate 24A-100 were added, followed by toluene, The viscosity was adjusted to 12 seconds with a mixed solvent consisting of ethyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate to obtain coating composition # B-3. Coating composition # B-3 was spray-coated on the following material degreased with toluene, forcedly dried at 80 ° C. for 40 minutes, and then left at room temperature for 3 days to give a test piece. (A) SUS430 (b) ABS-chrome plating (c) ABS-electroless nickel plating

Comparative Example 1 (Clear paint) An acrylic-urethane type paint (Origiplate Z manufactured by Origin Denki Co., Ltd.) was spray-coated on the following material degreased with toluene, and after forced drying at 80 ° C. for 40 minutes, 3 at room temperature
The test piece was left for one day. (A) SUS430 (b) ABS-chromium plating (c) ABS-electroless nickel plating

Comparative Example 2 (Clear coating) 60 parts of acrylic resin #C obtained in Production Example 3 and 16 parts of toluene
Part, a composition of 24 parts isobutyl acetate, A-18
After adding 5 parts of 7 and 7.5 parts of silicate 40, the viscosity was adjusted to 12 seconds with a mixed solvent consisting of toluene, ethyl acetate, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate, and coating composition #C -1 was obtained. Coating composition #C on the following materials degreased with toluene
-1 by spray coating and after forced drying at 80 ° C for 40 minutes,
The test piece was left at room temperature for 3 days. (A) SUS430 (b) ABS-chrome plating (c) ABS-electroless nickel plating

Comparative Example 3 (Clear coating) 5 parts of A-187 was added to a mixture of 60 parts of acrylic resin #C, 16 parts of toluene, and 24 parts of isobutyl acetate, and then toluene, ethyl acetate, methyl isobutyl ketone, The viscosity was adjusted to 12 seconds with a mixed solvent composed of ethylene glycol monoethyl ether acetate to obtain coating composition # C-2. Coating composition # C-2 was spray-coated on the following material degreased with toluene, forcedly dried at 80 ° C. for 40 minutes, and then left at room temperature for 3 days to give a test piece. (A) SUS430 (b) ABS-chrome plating (c) ABS-electroless nickel plating

The evaluation results are shown in Table 1. The test conditions for performance evaluation are as follows. (A) Adhesion: A 1 mm cross-cut cellophane tape peeling test was performed. (B) Warm water resistance: After dipping in hot water of 40 ° C. for 240 hours and taking out, the appearance of the coating film was observed, and further left at room temperature for 30 minutes to perform an adhesion test. (C) Solvent resistance; 45 ° C for WAX removal solution (ST-7)
After soaking for 10 minutes at room temperature, it was left at room temperature for 24 hours to perform a pencil hardness test.

(D) Chemical resistance Alkali resistance: About 0.2 ml of a 1% sodium hydroxide aqueous solution was dropped on the coating film, and the mixture was allowed to stand at a temperature of 22 ° C. for 4 hours.
The appearance was observed. Acid resistance: About 0.2 ml of a 3% sulfuric acid aqueous solution was dropped on the coating film, and the appearance was observed after standing at a temperature of 22 ° C. for 4 hours. (E) Weather resistance: The appearance after 1000 hours of SWOM was observed.

[0038]

[Table 1]

[0039]

As is clear from the results shown in Table 1, the coating composition of the present invention has good adhesion to the surface of the material as described above, and has water-whitening resistance, stain resistance and solvent resistance. Of course, it is possible to form a coating film with excellent chemical resistance, as well as aluminum material, alumite material, zinc material, copper bronze material, color stainless material, color alumite material, glass material, ABS-chrome plating. The same effect as described above can be obtained for a material such as a material, an electroless nickel plating material, an aluminum vapor deposition material, and an inorganic-filled plastic whose surface is partially or entirely inorganic or metal.

Claims (4)

[Claims] 1. A resin composition comprising an acrylic resin having at least one tertiary amino group in one molecule and an acrylic resin having at least one hydroxyl group in one molecule,
As a curing agent, an isocyanate compound and a compound containing at least one epoxy group in one molecule, or a compound having both an epoxy group and a hydrolyzable silyl group in one molecule are added and further hydrolyzed as necessary. A coating composition characterized by adding a condensation catalyst and curing. 2. A resin composition comprising an acrylic resin having at least one tertiary amino group in one molecule and an acrylic resin having at least one hydroxyl group in one molecule,
As a curing agent, an isocyanate compound, a compound containing at least one epoxy group in one molecule, or a compound having an epoxy group and a hydrolyzable silyl group in one molecule, a hydrolyzable silyl group and / or silanol A coating composition comprising the addition of a compound having a group and, if necessary, a hydrolysis-condensation catalyst for curing. 3. An acrylic resin having at least one tertiary amino group and hydroxyl group in one molecule, as a curing agent,
An isocyanate compound and a compound containing at least one epoxy group in one molecule, or a compound having both an epoxy group and a hydrolyzable silyl group in one molecule are added, and if necessary, a catalyst for hydrolysis-condensation A coating composition characterized by being added with and cured. 4. An acrylic resin having at least one tertiary amino group and hydroxyl group in one molecule, which is used as a curing agent.
An isocyanate compound and a compound containing at least one epoxy group in one molecule, or a compound having both an epoxy group and a hydrolyzable silyl group in one molecule, and a compound having a hydrolyzable silyl group and / or silanol group And a hydrolysis-condensation catalyst, if necessary, for curing.