JP2002121472A - Resin composition for colored coating and method for lamination coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is useful for colored coatings, maintains excellent chipping resistance and excellent peeling resistance, even when prepared in a high solid content, has an excellent metal-orientation, and gives a good finished appearance, and to provide a method for lamination coating with the resin composition. SOLUTION: This resin composition for colored coatings, characterized by comprising a curing agent and a polyester resin that contains hydroxy groups and is obtained by reacting a polyhydric alcohol with a polybasic acid whose >=60 mol.% is an alicyclic polybasic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful resin composition for a colored paint and a method of laminating the same. More specifically, the present invention relates to a method of applying a base paint on a substrate to form a coating film. The present invention relates to a resin composition for a colored coating for a base coating used in a multilayer coating finishing method in which a top clear coating is applied on a base coating to form a cured coating, and more specifically, an alicyclic polybasic acid as a raw material. The purpose is to achieve both a reduction in paint volatiles and the prevention of peeling of the coating film, which is called chipping or peeling, using a specific polyester resin as the main component obtained by using it as a part of the product. And a laminated coating method using the same.

[0002]

2. Description of the Related Art A coating method in which a metal material is coated with an electrodeposition primer and an intermediate coating and a top coating including a base coating containing a pigment and a top clear coating (hereinafter referred to as "top clear") is laminated thereon. It accounts for the majority of automotive coating systems.

[0003] In this laminated coating,
The electrodeposited primer coating is intended mainly for the anticorrosion function of metal materials, and the intermediate coating is to act as an undercoat for smoothing the top coating and obtaining a glossy coating. And that
It has the function of making the electrodeposited primer coating and the top coating having different functions adhere to each other for a long period of time.

Further, the base coating film includes a solid color base coating film containing an inorganic and / or organic pigment or a metallic base coating film containing a metallic powder such as aluminum or bronze. The top clear coating film is intended to impart appearance such as gloss and glossiness and long-term weather resistance to the coating film.

Further, in recent years, from the viewpoint of cost reduction, a lamination coating in which the intermediate coating step is omitted, a base coating is applied in two layers on the electrodeposited primer coating film, and a top clear is applied thereon has been adopted. I have.

In such a top coat, from the viewpoint of shortening the process and saving energy, the base paint and the top clear are applied in a wet-on-wet manner and are simultaneously baked. A so-called two-coat one-bake method and a three-coat one-bake method are used.

While the two-coat one-bake method or the three-coat one-bake method has many advantages, there are many problems. As the base paint, a resin system is generally used in which an acrylic resin is used as an essential main component and an amino resin is used as an essential curing agent, and these components are combined.

However, these paints do not have sufficient orientation of aluminum, which is a commonly used luminous agent (hereinafter referred to as metal orientation), and generally have a low coating non-volatile content.

In recent years, due to increasing environmental problems, emission regulations for organic solvents have become strict. In particular, development of paints having a low solvent content in base paints that discharge a large amount of solvent has been actively studied. .

[0010] In order to reduce the solvent content in the paint and to increase the non-volatile content of the paint, a method of lowering the viscosity of the acrylic resin is partially adopted as a means of lowering the viscosity of the resin in the paint, but the metal orientation decreases. In addition, due to the decrease in the physical properties of the coating due to the lower molecular weight of the acrylic resin, peeling (chipping or peeling) of the coating at the interface between the intermediate coating film and the electrodeposition coating film caused by pebbles or the like during running becomes a problem. I have.

In order to solve the above-mentioned problem of peeling of a coating film, a system in which a polyester resin is blended with a resin component of an acrylic resin / amino resin has been proposed. However, a sufficient improvement effect on the peeling of a coating film can be obtained. Not.

As described above, in the base paint according to the conventional technology, the metal orientation as described above is good, and the coating performance such as the conventional coating such as the performance of preventing the peeling of the coating called chipping or peeling is good. Further, there has not yet been obtained a practically usable material which can satisfy all of today's required performances such as high paint non-volatile content.

[0013]

[Problems to be solved by the invention]

Therefore, the present inventors have developed a highly useful base coating material for the purpose of maintaining the conventional coating film performance while performing high coating non-volatile differentiation of the base coating material in order to reduce coating volatile components. Intensive research has been undertaken in search of a resin composition for a colored paint.

[0015] Accordingly, the problem to be solved by the present invention is to provide a colored material which retains excellent chipping resistance and peeling resistance and has excellent metal orientation and a good finished appearance even after high solidification. An object of the present invention is to provide a resin composition for a paint and a multilayer coating method using the same.

[0016]

Means for Solving the Problems The present inventors have made intensive studies on the high solid differentiation of a resin composition for a colored coating, aiming at the above-mentioned problems. As a result, a polyester resin (A) having a hydroxyl group and containing more than 60 mol% of alicyclic polybasic acid in the polybasic acid component
And a resin composition for a colored coating containing a curing agent (B) or a polyester resin (A), a curing agent (B), and a resin composition for a colored coating containing a rheology control agent (C), It is capable of high solid differentiation and has excellent coating properties such as chipping or peeling as well as excellent metal orientation in the coating film performance of a base paint formed using the same. Further, the polyester resin (A) has a weight average molecular weight of 800 -30,000, solid content hydroxyl value 50-2
00 mg KOH / g, solid content acid value 9-20 mg KOH /
g of a polyester resin is more preferable, and among these, a weight average molecular weight of 1,000 to 20,000, a solid content hydroxyl value of 80 to
150 mgKOH / g, solid content acid value 5-20 mgKOH
/ G of a polyester resin is particularly preferred, as the curing agent (B), an amino resin and / or a blocked isocyanate resin is more preferred, and a resin solid content weight ratio (A) of the polyester resin (A) and the curing agent (B) / B)
As a result, it is found that 50/50 to 90/10 is more preferable, and the present invention has been completed.

That is, the present invention provides: A polyester resin (A) obtained by reacting a polyhydric alcohol with a polybasic acid, wherein at least 60 mol% of the polybasic acid component is an alicyclic polybasic acid and contains a hydroxyl group, and a curing agent A resin composition for a colored paint, comprising (B),

2. A polyester resin (A) obtained by reacting a polyhydric alcohol with a polybasic acid, wherein at least 60 mol% of the polybasic acid component is an alicyclic polybasic acid and contains a hydroxyl group, a curing agent ( B), and a resin composition for a colored coating, comprising a rheology control agent (C),

3. The polyester resin (A) has a weight average molecular weight of 800 to 30,000 and a solid content hydroxyl value of 50 to 2
00 mg KOH / g, solid content acid value 5-20 mg KOH / g
g, a resin composition for a colored coating according to the above 1 or 2,

4. Polyester resin (A) has a weight average molecular weight of 1,000 to 20,000, a solid content hydroxyl value of 80 to
150 mgKOH / g, solid content acid value 5-20 mgKOH
/ G polyester resin, the resin composition for a colored coating according to the above 1 or 2,

5. The curing agent (B) is an amino resin and / or
Or a blocked isocyanate resin, the resin composition for a colored coating according to any one of the above 1 to 4,

6. The resin solid content weight ratio (A / B) of the polyester resin (A) and the curing agent (B) is 50 / 50-
90/10, wherein the resin composition for a colored coating according to any one of the above 1 to 5,

7. The content of the rheology control agent (C) is 0 to 10 with respect to the resin solid content weight (A + B).
The resin composition for a colored coating according to any one of the above 2 to 6, which is 0% by weight,

8. The resin composition for a colored paint according to any one of the above 1 to 7, wherein the polyester resin (A) is a water-soluble or water-dispersible material,

9. After applying a base paint comprising the resin composition for a colored paint according to any one of the above 1 to 8 on a base material to form a coating film, a top clear paint is applied on the base coating film. And to form a cured coating film by the method of the present invention.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific structure of the present invention and its function and effect will be described. The colored paint resin composition of the present invention has a hydroxyl group and a polybasic acid content of 6%.
It comprises a polyester resin (A) containing more than 0 mol% of an alicyclic polybasic acid and a curing agent (B).

The polyester resin (A) used here may be any resin having a hydroxyl group and containing more than 60 mol% of alicyclic polybasic acid in the polybasic acid component. , High solid differentiation is relatively easy, curability is good, cross-linking density is sufficient, coating performance such as hardness is excellent, and a coating with good appearance is obtained without occurrence of 'repelling' and decrease in gloss. From the weight average molecular weight of 800 to 30
000, solid content hydroxyl value 50-200 mgKOH / g,
A polyester resin having an acid value of 5 to 20 mg KOH / g in solid content is preferable, and a weight average molecular weight of 1000 to 200 is particularly preferable.
Polyester resins having a hydroxyl value of from 80 to 150 mgKOH / g and an acid value of from 5 to 20 mgKOH / g are particularly preferred.

The alicyclic polybasic acid component used when preparing the polyester resin (A) includes, for example, 1,1-cyclohexanedicarboxylic acid, hexahydro (anhydride) phthalic acid, 1,3-cyclohexanedicarboxylic acid, , 4-
Cyclohexanedicarboxylic acid, tetrahydro (anhydride) phthalic acid, methylhexahydro (anhydride) phthalic acid, (anhydrous) hetic acid, (anhydride) hymic acid (registered trademark of Hitachi Chemical Co., Ltd.), hydrogenated (anhydrous) Various alicyclic carboxylic acids such as melitic acid are mentioned, and further, if necessary, various alicyclic monocarboxylic acids including 4-tert-butylcyclohexanemonocarboxylic acid, hexahydrobenzoic acid, or these. Can also be used.

In preparing the polyester resin (A), an acid component and a polyhydric alcohol component which are usually used can be used as long as the characteristics of the present invention are not impaired. Among them, only typical ones are exemplified. First, as the acid component, (anhydride) phthalic acid, isophthalic acid, terephthalic acid, p-tert-butylbenzoic acid, (anhydrous) trimellit Acid, various aromatic acids such as tetrachloro (anhydride) phthalic acid; adipic acid, azelaic acid, sebacic acid, (anhydride) maleic acid,
Fumaric acid, itaconic acid and the like can also be used.

As typical examples of polyhydric alcohol components used together with these acid components, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, , 6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, cyclohexanedimethanol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol and the like. Can be

Incidentally, in preparing the polyester resin (A), an oil component can be used as a part of the component within a range where the oil length is less than 30%.

Particularly representative of these oil components are coconut oil, hydrogenated coconut oil, "Kajura E" (branched aliphatic monocarboxylic acids manufactured by Shell), octenoic acid, isononanoic acid and the like. However, if necessary, rice bran oil fatty acid, tall oil fatty acid, soybean oil, castor oil, dehydrated castor oil and the like can also be used as appropriate.

As the polyester resin (A) using each of the above-mentioned raw material components, either a linear structure or a branched structure may be used. The method for preparing the polyester resin (A) is not particularly limited, and any of a melting method and a solvent method may be used by making full use of a well-known production method by an esterification reaction between an acid component and an alcohol component. .

For example, using a polybasic acid component and a polyhydric alcohol component as raw materials so as to have a predetermined molecular weight, a hydroxyl value and an acid value, the generated water is successively removed at 150 to 250 ° C. in a nitrogen stream. The esterification reaction can be carried out while the esterification reaction is completed, and by adding a predetermined amount of solvent or water, the polyester resin (A) having a predetermined acid value and a hydroxyl value can be obtained.

The polybasic acids and polyhydric alcohols as the reaction components may be added all at once or may be added in several portions. In addition, in the case of an esterification reaction for preparing the polyester resin (A), dibutyltin oxide, antimony trioxide, zinc acetate, zinc acetate, manganese acetate, manganese acetate, cobalt acetate, if necessary, for accelerating the reaction. Known catalysts such as calcium acetate, lead acetate, tetrabutyl titanate and tetraisopropyl titanate may be used.

Further, the resin composition for coloring paints using the polyester resin (A) may be a solution type high solid type or a non-aqueous dispersion type in order to reduce the amount of organic solvent discharged in addition to the conventional organic solvent solution type. Although it can be used as a resin type or an aqueous type, the use of an aqueous base paint is the most effective means for reducing the amount of organic solvent discharged.

As the aqueous base coating used in this case, any type of base coating using a water-soluble or water-dispersible polyester resin can be used in the present invention.

Here, as a method of solubilizing or dispersing the polyester resin (A) in water, a water-soluble or water-dispersible polyester resin can be obtained by various known and commonly used methods.

Of these, only typical ones are exemplified, and acid groups such as carboxyl group and sulfonic acid group contained in the resin are neutralized with an organic base or an inorganic base. The resulting, water-soluble or water-dispersible polyester resin,

Obtained by conducting a polymerization reaction in an organic solvent,
Add various surfactants to polyester resin,
A water-dispersible polyester resin obtained by an emulsification method (post-emulsification) in which a solvent is converted from an organic solvent to water and the resin is dispersed in water,

In the post-emulsification method as described above, the above-mentioned side chains and terminals of the polyester resin are previously provided with a polyether moiety which is an anionic moiety, a cationic moiety or a nonionic moiety. By introducing a unique surface-active site when synthesizing each resin, or by introducing it after synthesis, after imparting self-emulsifying properties, it is possible to perform only post-emulsification without adding various emulsifiers. And a water-dispersible polyester resin.

The curing agent (B) used in the present invention is not particularly limited as long as it reacts with a hydroxyl group in the polyester resin (A) to form a crosslink. Benzoguanamine resin, urea resin,
Examples include amino resins such as thiourea resins, polyisocyanate compounds, polyisocyanates such as blocked isocyanate compounds and polycarboxylic anhydrides such as trimellitic anhydride, among which one-pack type is easy to handle. The use of certain amino resins or blocked isocyanate compounds is particularly preferred.

Examples of amino resins, particularly melamine resins, which are particularly typical, include alkyl etherified melamine resins. Further, if only a typical example of such an alkyl etherified melamine is given as an example, “Super-Beckamine L-117-
Butoxymethylmelamine resins such as "60" (manufactured by Dainippon Ink and Chemicals, Inc.) and "Uban 255" (manufactured by Mitsui Chemicals, Inc.); "CYMER 301" and "CYMER 30"
3, "Symel 325", "Symel 327" (manufactured by Mitsui Cytec Co., Ltd.), "Watersol S-69"
Methoxymethylmelamine resin such as "5" (manufactured by Dainippon Ink and Chemicals, Inc.); "CYMER 235" and "CYMER 1"
130 "(Mitsui Cytec Co., Ltd.)," BEETLE
BE3020 "," BEETLE BE3021 ",
"BEETLE BE3751" [Both British BI
P. Ltd.], methoxy-butoxy mixed etherified methyl melamine resin.

Similarly, resins that can be suitably used as the curing agent (B) include various resins obtained by blocking various polyisocyanate compounds with various blocking agents as described below. By heat, such as a compound containing various uretdione structures, such as a block polyisocyanate compound of the type or a compound obtained by cyclizing and dimerizing an isocyanate group,
A class of compounds in which isocyanate groups are regenerated are fried.

As the polyisocyanate compound used at this time, if only typical ones are exemplified, tolylene diisocyanate, diphenylmethane-
Various aromatic diisocyanates such as 4,4'-diisocyanate; meta-xylylene diisocyanate;
various aralkyl diisocyanates, such as α, α, α ', α'-tetramethyl-meta-xylylene diisocyanate;

Various fats such as hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 2-methyl-1,3-diisocyanatecyclohexane, 2-methyl-1,5-diisocyanatecyclohexane and isophorone diisocyanate Group or alicyclic diisocyanates;

Prepolymers having isocyanate groups obtained by subjecting various polyisocyanates as described above to addition reaction with polyhydric alcohols; cyclized trimerization of the various polyisocyanates as described above Prepolymers having an isocyanurate ring; polyisocyanates having a biuret structure obtained by reacting various polyisocyanurates with water as described above;

Homopolymers of vinyl monomers having various isocyanate groups such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate and (meth) acryloyl isocyanate; (Meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, etc., which can be copolymerized with isocyanate group-containing vinyl monomers such as And various vinyl copolymers such as an isocyanate group-containing acrylic copolymer, a vinyl ester copolymer or a fluoroolefin copolymer obtained by copolymerization with an epoxy resin.

Among such polyisocyanates, aliphatic or alicyclic diisocyanate compounds, and various prepolymers or isocyanates derived from each of these diisocyanate compounds, particularly from the viewpoint of weather resistance and the like. Use of a group-containing vinyl polymer or the like is particularly desirable.

Next, only typical blocking agents used in preparing blocked isocyanates from the above-mentioned polyisocyanates will be exemplified, such as methanol, ethanol, benzyl alcohol and lactate. Various carbinol group-containing compounds; various phenolic hydroxyl group-containing compounds such as phenol, salicylic acid ester and cresol; various amides such as ε-caprolactam, 2-pyrrolidone and acetanilide; various acetones such as acetone oxime and methyl ethyl ketoxime Oximes: Various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, and acetylacetone.

Commercially available resins that can be suitably used as the curing agent (B) include, for example, “Barnock DB-9”
80K "," Barnock B7-887-60 "," Barnock B3-867 "(above, block isocyanate resin manufactured by Dainippon Ink and Chemicals, Inc.)," Coronate 2507 "(block isocyanate resin manufactured by Nippon Polyurethane Co., Ltd.) And "Takenate B-815N" (a blocked isocyanate resin manufactured by Takeda Pharmaceutical Co., Ltd.).

The ratio (A / B) of the polyester resin (A) to the curing agent (B) in the resin solid content is not particularly limited, but the ratio of 50/50 to 90/10 is preferably in the range of 50/50 to 90/10. It is more preferable that a base coating film excellent in various performances and curability is obtained, and especially, 60/40 to 85/15
The following range is particularly preferable.

Examples of the rheology control agent (C) include Disparon 6900 [Kusumoto Kasei Co., Ltd.]
Urea-based rheology control agent such as BYK410 (manufactured by Big Chemie, USA), Dispalon 4200 [manufactured by Kusumoto Kasei Co., Ltd.]
And various commercially available rheology control agents such as polyethylene wax and cellulose acetate butyrate (manufactured by Eastman Chemical Products Co., USA).

Further, a urea-based RC agent obtained by reacting a di- or polyisocyanate such as hexamethylene diisocyanate or diphenylmethane diisocyanate with various amino compounds such as alkylamine or phenylethylamine in a resin or a solvent;

Water-soluble cellulose ether, hydroxyethyl cellulose, nitrocellulose, methylcellulose, carboxycellulose, polyvinyl alcohol,
Vinylpyrrolidone (co) polymer, (meth) acrylic acid (co) polymer, (meth) acrylamide (co) polymer,
Styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer,

Inorganic RC agents such as bentonite, montmorillonite, silica powder, calcium carbonate,

Alternatively, internally crosslinked fine particles obtained by emulsion polymerization, aqueous suspension polymerization or non-aqueous dispersion polymerization may be used.

As a method for preparing such internally crosslinked fine particles, for example, the following methods are available. That is, at least two or more (α, β-ethylenic) in one molecule
Monomers having unsaturated bonds, ie, polyfunctional monomers, and monomers having one (α, β-ethylenic) unsaturated bond in one molecule, ie, monofunctional monomers Body and
A method such as polymerization using an organic and / or inorganic radical polymerization initiator at a temperature of 20 ° C. or more and less than 200 ° C. in an aqueous emulsion, an aqueous suspension or a non-aqueous dispersion state, or inside a particle. There is a method in which a compound having a reactive functional group is used in combination and reacted to crosslink.

Here, only typical representative examples of the polyfunctional monomers used in the above are ethylene glycol di (meth) acrylate and oligoethylene glycol having a total carbon number of 10 to 28. Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, 1,3-butylene glycol di (meth)
Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol di (meth) acrylate propylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate Poly (meth) acrylates of various polyhydric alcohols such as acrylate and pentaerythritol tetra (meth) acrylate;

Esters of various allyl alcohols such as diallyl succinate, diallyl phthalate and triallyl isocyanurate; butadiene, pentadiene,
Various dienes such as isoprene and chloroprene; or divinylbenzene or dicyclopentenyl (meth) acrylate, but especially divinylbenzene, dicyclopentenyl (meth) acrylate, triallyl isocyanurate or polyhydric alcohol. The use of poly (meth) acrylates and the like is desirable.

The total content of the polyfunctional monomer in the internally crosslinked fine particles used in the above-mentioned internal crosslinking technique may be 0 in view of the aluminum orientation, dispersion stability, etc. of the paint after application. 0.01 to 90% by weight is preferred.

The monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
1 carbon atom such as n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate To 22 alkyl alcohols and various alkyl esters of (meth) acrylic acid;

Various aralkyl (meth) acrylates such as benzyl (meth) acrylate and phenethyl (meth) acrylate; various cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobonyl (meth) acrylate; methoxy Various alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate and methoxybutyl (meth) acrylate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
Various hydroxyalkyl (meth) acrylates such as -hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate;

2-hydroxyethyl vinyl ether, 4
Various hydroxyl group-containing vinyl ethers such as -hydroxybutyl vinyl ether; various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether;
A class of various polyoxyalkylene glycols obtained from various polyether polyols represented by polyethylene glycol and the like and various unsaturated carboxylic acids represented by (meth) acrylic acid and the like. Monoesters;

Various adducts of various epoxy group-containing unsaturated monomers represented by glycidyl (meth) acrylate and the like, and various acids represented by acetic acid and the like; Various unsaturated carboxylic acids represented by, for example, (meth) acrylic acid, and α-olefins represented by, for example, “Kajura E” (trade name of Shell Co., Netherlands). Adducts with various monoepoxy compounds other than epoxides;

The above various hydroxyl group-containing vinyl monomers and γ
-Butyrolactone, δ-valerolactone, γ-valerolactone, γ-caprolactone, ε-caprolactone, γ
-Various hydroxyl group-containing vinyl monomers having a (poly) lactone chain, such as adducts with various lactones represented by nonanoic lactone, δ-dodecanolactone, and the like;

2-trimethylsiloxyethyl (meth) acrylate, 2-trimethylsiloxyethyl vinyl ether, 2- (1-ethoxy) ethoxyethyl (meth) acrylate, 2- [2- (meth) acryloyloxy]
Various blocked hydroxyl-containing vinyls such as ethoxy terahydrohydrofuran, 3- [2- (meth) acryloyloxy] ethyl oxazolidine, and 2,2-dimethyl-3- [2- (meth) acryloyloxy] ethyl oxazolidine System monomers;

Various unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid or fumaric acid; monomethyl itaconate, mono-n-butyl itaconate Various monoesters (half esters), such as, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate;

Monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate; anhydrides of various unsaturated polycarboxylic acids such as maleic anhydride and itaconic anhydride; acrylic acid anhydride or anhydride Anhydrides of various unsaturated monocarboxylic acids, such as methacrylic acid; or various unsaturated carboxylic acids, such as acrylic acid or methacrylic acid, and various unsaturated carboxylic acids, such as acetic acid, propionic acid, and benzoic acid. Vinyl monomers having a carboxylic acid anhydride group, such as a mixed acid anhydride with an acid;

Trimethylsilyl (meth) acrylate,
Dimethyl-t-butylsilyl (meth) acrylate, 1
-Ethoxyethyl (meth) acrylate, 2- (meth)
Vinyl monomers containing a blocked carboxyl group, such as acryloyloxytetrahydrofuran;

Diesters of various unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid with monohydric alcohols; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, vinyl benzoate , Various carboxylic acid vinyl esters such as "Veova" (vinyl esters manufactured by Shell, Netherlands);
Various alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; various cyano group-containing monomers such as (meth) acrylonitrile and crotononitrile;

2-dimethylaminoethyl (meth) acrylate, N- [2- (meth) acryloyloxy] ethylmorpholine, vinylpyridine, N-vinylcarbazole, N- (2-dimethylamino) ethyl (meth) acrylamide, N -(2-diethylamino) ethyl (meth)
Amino group-containing vinyl monomers such as acrylamide, N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide, 2-dimethylaminoethyl vinyl ether and 2-diethylaminoethyl vinyl ether Kind;

Methyl (meth) acrylamide glycolate methyl ether, methyl (meth) acrylamide glycolate, N-isopropyl (meth) acrylamide,
N-methyl (meth) acrylamide, N-vinylformamide, N, N-dimethyl (meth) acrylamide,
N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, N-vinylpyrrolidone, ethyl (acrylamide) glycolate or ethyl (acrylamide) glycolate methyl ether, etc.

N-methylol (meth) acrylamide,
Or N-methoxymethyl (meth) acrylamide,
N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, Ni-butoxymethyl (meth) acrylamide, N-phenoxymethyl (meth) acrylamide and N -N-hexyloxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, Nn-butoxyethyl (meth) acrylamide, Ni-butoxyethyl (meth) acrylamide Various amide group-containing vinyl monomers represented by N-alkoxyalkyl (meth) acrylamides and the like;

Vinyl having an epoxy group such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether, and allyl glycidyl ether System monomers;

Various 5-membered cyclocarbonates such as 2,3-carbonatepropyl (meth) acrylate, 2-methyl-2,3-carbonatepropyl (meth) acrylate and 3,4-carbonatebutyl (meth) acrylate Group-containing vinyl monomers; 5- [N- (meth) acryloylcarbamoyloxymethyl] -5-ethyl-1,3-dioxan-2-one, 5- [N- ｛2
-(Meth) acryloyloxy {ethylcarbamoyloxymethyl] -5-ethyl-1,3-dioxane-2-
Various 6-membered cyclocarbonate group-containing vinyl monomers such as on;

Vinyl monomers having a carbamate group such as methyl N- (meth) acryloylcarbamate and ethyl N- [2- (meth) acryloyloxy] ethylcarbamate;

"VISCOAT 8F, 8FM, 3F, 3F
M "[fluorinated (meth) acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], purple fluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or N-iso-propyl perfluorooctanesulfonamidoethyl Various (per) fluoroalkyl group-containing unsaturated bond-containing monomers such as (meth) acrylates; various such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene Various chlorinated olefins such as vinyl chloride and vinylidene chloride;

Ethylene, propylene, isobutylene, 1
Various α-olefins such as butene and 1-hexene; various aromatic vinyl monomers such as styrene, α-methylstyrene, p-tert-butylstyrene, O-methylstyrene and p-methylstyrene Kind;

Various sulfonic acid amide group-containing monomers such as p-styrenesulfonamide and N-methyl-p-styrenesulfonamide; 2-hydroxyethyl (meth)
Phosphate ester bond-containing monomer obtained by a condensation reaction of various hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acid, such as acrylate and 2-hydroxypropyl (meth) acrylate, with phosphoric acid or its esters. Sulfonic acid group-containing monomers or organic amine salts thereof, such as styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methyl-propane sulfonic acid;

Vinyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylethylvinylether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxy Various hydrolyzable silyl group-containing vinyl monomers such as propylmethyldimethoxysilane and 3- (meth) acryloyloxypropylmethyldichlorosilane;

Various alkyl vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and n-hexyl vinyl ether; various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and methyl cyclohexyl vinyl ether;

Various carbonyl group-containing monomers such as acrolein and methyl vinyl ketone;

"Blemmer PME" [Nippon Oil & Fats Co., Ltd.
And methacrylic acid methoxy-methoxycarbonyl-methyl ester and acrylate acetylamino-methoxycarbonyl-methyl ester.

Next, as typical examples of the reaction of the reactive functional groups used in combination as the internal crosslinking technique, the reaction of a carboxyl group with an epoxy group and the reaction of a hydroxyl group with an acid anhydride will be described. Examples of the reaction include a reaction, a reaction between an epoxy group and an amino group, a reaction between a hydroxyl group and an alkyl ether group represented by melamine and the like, and a self-condensation between alkyl ether groups.

The internal crosslinking by the reaction between the carboxyl group and the epoxy group is achieved, for example, by copolymerizing the carboxyl group-containing compound and the epoxy group-containing compound.

As the carboxyl group-containing compounds used here, only typical ones are exemplified, and the above-mentioned various unsaturated carboxylic acids and polycarboxyl compounds having at least two carboxyl groups in one molecule can be used. and so on.

Next, as the epoxy group-containing compound,
Examples of the above-mentioned vinyl monomers having various epoxy groups and compounds having at least two epoxy groups in one molecule such as ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and glycerin triglycidyl ether. .

The internal crosslinking by the reaction between a hydroxyl group and an acid anhydride can be achieved, for example, by copolymerizing a vinyl monomer having a hydroxyl group and a vinyl monomer having a carboxylic acid anhydride group.

The internal crosslinking by the reaction between an epoxy group and an amino group can be obtained, for example, by reacting the above-mentioned epoxy group-containing compound with an amino group-containing vinyl monomer.

The internal crosslinking by the reaction between the hydroxyl group and the alkyl ether group is achieved by, for example, copolymerizing a hydroxyl group-containing monomer with an alkyl ether group-containing compound. Crosslinking is achieved, for example, by self-condensing alkyl ether group-containing compounds with each other.

As the alkyl ether group-containing compounds used here, only typical ones are exemplified, and alkyl ether group-containing resins such as melamine resin, acetoguanamine resin and benzoguanamine resin;
Examples include alkoxyalkyl (meth) acrylamides.

The total content of the compound having a reactive functional group used in the above-mentioned internal cross-linking method in the internally cross-linked fine particles may be determined from the viewpoints of aluminum orientation, dispersion stability and the like of the coating material after application. 0.1 to 70% by weight is preferred.

On the other hand, potassium persulfate,
Various inorganic compounds such as ammonium persulfate or hydrogen peroxide; or acetyl peroxide, propionyl peroxide, isobutyryl peroxide,
Benzoyl peroxide, tert-butyl peroxyoctoate, tert-butyl hydroperoxide, tert-butylcumyl peroxide, tert
Various organic compounds such as hobutyl peroxybenzoate, di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide or azobisisobutyronitrile are particularly typical.

Thus, the internally crosslinked fine particles in the aqueous emulsion or suspension obtained after various types of polymerization can be obtained by the method such as evaporation or azeotropic distillation of water, sedimentation or aggregation of polymer (particles), etc. It can be separated in the form of a solid by physical or chemical means, or when applying such physical or chemical means, resins and resins different from the various polymers in each paint In the presence of an organic solvent and / or the like, the medium of the intended internally crosslinked fine particles can be directly replaced by water with the resin and / or the organic solvent.

The content of the rheology control agent (C) is 0.01% with respect to the resin solid content weight (A + B).
-100% by weight is more preferable, and can provide excellent metal orientation and high coating nonvolatile content.

In the resin composition for a colored paint of the present invention, a solvent is usually used together with the polyester resin (A) and the curing agent (B) or the rheology control agent (C). Examples of the solvents used here include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane; ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monoethyl ether acetate; acetone, methyl ethyl ketone; Ketone solvents such as methyl isobutyl ketone, methyl amyl ketone and cyclohexanone; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, se
alcoholic solvents such as c-butanol, tert-butanol, ethylene glycol monoalkyl ether;
Alternatively, a mixture thereof and the like can be mentioned.

Further, as a solvent for the aqueous base, in addition to water, an organic solvent soluble in water such as an alcohol solvent can be used in combination.

In order to accelerate the curing of the colored paint resin composition of the present invention, curing catalysts can be used. However, if only typical examples of such curing catalysts are given, Acid catalysts such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, or an amine-blocked product thereof, a half-esterified product of tetrachlorophthalic anhydride and a monohydric alcohol, and an organic acid such as trichloroacetic acid; tetraisopropyl Various metal-containing compounds such as titanate, dibutyltin laurate, dibutyltin acetate, dibutyltin dioctate, and cobalt naphthenate; various phosphorus-based acidic compounds such as monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid, and dialkylphosphoric acid. is there.

The amount of the curing catalyst used is not particularly limited, but the polyester resin (A) and the curing agent (B)
Is more preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content.

In addition, it goes without saying that pigments are used in the resin composition for colored coatings of the present invention when used as a base coating. For example, aluminum powder, carbon black, titanium oxide, magnesium oxide, zinc oxide, metal oxides such as iron oxide, silicates, strontium chromate, zinc chromate, inorganic pigments such as barium sulfate, phthalocyanine blue, phthalocyanine green, Organic pigments such as perylene, quinacridone and benzisidazolone can be mentioned, and these can be used alone or in any combination.

The thus obtained resin composition for a colored coating of the present invention contains, if necessary, other resins and the like.
Various known and commonly used additives such as a color separation inhibitor, a leveling agent, an ultraviolet absorber, an antioxidant, an antifoaming agent, and a plasticizer can be added.

Using the colored paint resin composition of the present invention,
In order to form a target coating film having a high practical effect, for example, the surface of a substrate to be coated is subjected to a surface treatment or, if necessary, a primer layer (for example, an electrodeposition coating layer) is applied in advance. Next, the intermediate coating is applied and crosslinked by a usual method under desired conditions so that the dry film thickness becomes 10 to 50 μm.

Thereafter, as a top coat, a base paint comprising the composition for a colored paint of the present invention was dried to a film thickness of 20%.
After applying to a thickness of about 80 μm, a top clear paint is applied thereon, followed by baking under desired conditions, that is, a two-coat, one-bake (2C1B) coating and curing. is there.

Further, three coats and one bake (3 coats) in which the intermediate coat and the top coat are applied by so-called wet-on-wet.
It is also possible to use a method of coating and curing under conditions such as C1B).

In a system using a thinner having a low volatilization rate as represented by an aqueous base paint, it is possible to forcibly dry (preheat) at a predetermined temperature during the flash time.

In general, the above crosslinking conditions are suitably performed at 110 to 170 ° C. for about 15 to 40 minutes, particularly preferably at 120 to 160 ° C. for 20 to 30 minutes.

The top clear that can be used in the present invention is not particularly limited as long as it is a baking coating, but is preferably an acrylic resin, an alkyd resin, a polyester resin, a fluorine resin, or a silicone resin. And a synthetic resin-based baking coating containing a resin component such as a base resin or a urethane resin.

The curing agent component used at that time includes:
Known and commonly used curing agents having reactivity with hydroxyl groups, such as amino resins, isocyanate resins, and polycarboxylic anhydrides, can be used.

In recent years, acid rain-resistant paints have been developed. In place of the melamine curing system, a reaction system of a carboxyl group and an epoxy group, a reaction system of a carboxyl group and a cyclocarbonate group, or an acid anhydride group and a hydroxyl group It is also possible to use a clear coating containing a novel curable resin such as a reaction system with the above.

Further, from the viewpoint of increasing resource saving and environmental problems, it is of course possible to use a high solid clear paint or a powder clear paint having a reduced organic solvent content.

The above-mentioned base paint and top clear paint are applied by various known and commonly used coating methods such as air spray coating, electrostatic spray coating, and rotary atomizing electrostatic coating. Can be adopted.

The thus-obtained colored coating composition and laminated coating method of the present invention are mainly applied to iron products, stainless steel, aluminum, brass, polystyrene, polyethylene, polypropylene, acrylic resin, polycarbonate resin, ABS resin and the like. Things.

Thus, the base paint obtained by using the resin composition for a colored paint of the present invention has a high solid content itself, and is about 5 to 40% by weight as compared with the case where a conventional resin for a base paint is used. A high-solids base paint with a low degree of coating volatile content is obtained, and the base coat obtained using this base paint is followed by a top clear coating. This is a place where the performance of preventing the peeling of the coating film, which is referred to as, is remarkably excellent.

The resin composition for a colored coating of the present invention can be generally used as a base coating, but is particularly highly practical as a base coating for automobiles.

[0117]

EXAMPLES The present invention will now be described more specifically with reference examples, examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Examples 1 to 6 (Preparation of Polyester Resin) A 3-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser equipped with a dehydration trap, and a nitrogen gas inlet tube was prepared.
The raw materials shown in Table 1 and 0.5 part of dibutyltin oxide were charged and heated to 220 ° C. Further, a dehydration-condensation reaction was performed at this temperature, and the reaction was continued until the hydroxyl value of the solid content reached the target value. After completion of the reaction, the reaction mixture was cooled and xylene was added to obtain a polyester resin solution having a nonvolatile content of 65%. The properties are shown in Table 1.

[0119]

[Table 1]

The abbreviations in Table 1 mean the following compounds. HHPA: Hexahydrophthalic anhydride THPA: Tetrahydrophthalic anhydride NPG: Neopentyl glycol TMP: Trimethylolpropane 1,6-HD: 1,6-hexanediol

Reference Example 7 (Preparation of water-dilutable polyester resin) A 3-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser equipped with a dehydration trap, and a nitrogen gas inlet tube was prepared.
82 parts of phthalic acid, 394 parts of HHPA, 81 parts of adipic acid, 222 parts of NPG, 148 parts of TMP, 1,6
-73 parts of HD and 0.5 parts of dibutyltin oxide were charged, and the temperature was raised to 220 ° C. Further, a dehydration condensation reaction is performed at this temperature, and the hydroxyl value of the solid content is 100 mg KOH.
/ G. Thereafter, the temperature was cooled to 100 ° C., diluted with 230 parts of butyl cellosolve, and neutralized with 51 parts of triethylamine to obtain a water-dilutable polyester resin (A-5) having a nonvolatile content of 80%. .

Reference Example 8 (Preparation Example of Internally Crosslinked Fine Particles) Pure water was charged into a reaction vessel under a nitrogen atmosphere, and the temperature was raised to 80 ° C. Next, according to the raw material composition shown in Table 2, 1/10 of the mixture (a) and 1/5 of the mixture (b) were used.
30 minutes later, 9 / of the mixture (a)
10 and 3/5 of the mixture (b) were added dropwise over 3 hours.

After completion of the dropwise addition, 1/5 of the mixture (b) was added, and the mixture was maintained at 80 ° C. for 1 hour while stirring to terminate the reaction. The emulsion was filtered through a 200-mesh filter cloth. , An internally crosslinked fine particle emulsion having an NV of 20% and a particle diameter of 0.1 μm (Ce-
1) was obtained.

Further, this emulsion was spray-dried to obtain a microgel powder having a nonvolatile content of 98%. Hereinafter, this is abbreviated as internally crosslinked fine particles (C-1).

[0125]

[Table 2]

<< Footnotes in Table 2 >>
Parts by weight.

"Hytenol N-08": polyoxyethylene dodecyl phenyl ether sulfate ammonium salt manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

Reference Example 9 (Preparation of urea-based RC agent) In a flask equipped with a thermometer, a reflux condenser, a stirrer, a nitrogen inlet tube and a dropping funnel, 1446 parts of polyester resin (A-1), 32 parts of xylene, By charging 36.1 parts of 1-phenylethylamine and then adding 23.9 parts of hexamethylene diisocyanate with stirring at room temperature, a urea-based RC agent-containing resin (C-2) having a nonvolatile content of 65% was obtained. Obtained.

Examples 1 to 18 Preparation of base paint

The components were blended according to the blending composition ratios shown in Table 3 and were diluted with Ford Cup NO.
By adjusting the viscosity according to No. 4 to 13 seconds, a base paint was obtained.

Preparation of Diluent Solvent Xylene 15 parts Solvesso 100 15 parts Toluene 40 parts n-butyl acetate 10 parts Ethyl acetate 20 parts

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

[Table 5]

[0135]

[Table 6]

[0136]

[Table 7]

[0137]

[Table 8]

"A-322" ... "Acridic A-
322 ", Dainippon Ink and Chemicals, Inc.
Acrylic resin (solution type); nonvolatile content = 50%

"L-117-60" is an abbreviation for "Super-Beckamine L-117-60", n-butylated melamine resin manufactured by the same company; nonvolatile content = 60%

"DB-980K" ... "Barnock DB"
-980K ", a block isocyanate manufactured by the same company; nonvolatile content = 75%

“FS Maroon PSK” is an abbreviation for “First Gen Super Maroon PSK”.
Perylene pigments manufactured by the same company

"7160N" ... "Alpaste 716"
0N ", an aluminum paste manufactured by Toyo Aluminum Industry Co., Ltd .; non-volatile content = 65%

Examples 17 and 18 (Preparation of aqueous base coat paint) The aqueous base coat paint was obtained by mixing according to the composition ratios shown in Table 4.

[0144]

[Table 9]

"S-695" ... Water-soluble melamine resin "Watersol" manufactured by Dainippon Ink and Chemicals, Inc.
S-695 "Non-volatile content 65%

"WXM-760b": aqueous aluminum paste "Alpaste WXM-760b" manufactured by Toyo Aluminum Kogyo Co., Ltd., nonvolatile content 58%

"TT-935" thickener "Primal TT-935" manufactured by Rohm & Haas Japan 30% non-volatile content

(Preparation of Top Clear Coating) Ford Cup No. 1 was prepared by mixing a composition prepared by the following composition with a diluting solvent obtained by mixing xylene / 1-butanol at a weight ratio of 8/2. The resulting clear coat paint was prepared by adjusting the viscosity at 4 in the range of 22 to 24 seconds.

127 parts of Acridic A-345 [acrylic resin manufactured by Dainippon Ink and Chemicals, Inc.] Super Beckamine L-117-60 50 parts [melamine resin manufactured by Dainippon Ink and Chemicals, Inc.] Tinuvin 900 3 parts (UV absorber manufactured by Ciba-Geigy) Tinuvin 765 1 part (Radical scavenger manufactured by Ciba-Geigy) KP-321 0.05 parts [Leveling agent manufactured by Shin-Etsu Chemical Co., Ltd.]

<Guide for Evaluation Judgment>

The base paints of Examples 1 to 18 and Comparative Examples 1 to 8 were coated on a coated plate obtained by coating an electrodeposition primer for automobiles and an intermediate coating surfacer on a mild steel plate which had been subjected to a phosphorylation treatment. After spray coating, the dried film is coated to 17 microns (μm).
We set for 3 minutes. Next, the above-mentioned top clear paint was applied so that the dry coating film became 30 μm.

After leaving at room temperature for 10 minutes,
It was placed in an electric hot air drier at 140 ° C. for 25 minutes to cure.

In Examples 17 and 18 in which the aqueous base coat was applied, the base paint was applied at 80 ° C. for 10 minutes.
After forced drying for 10 minutes and cooling to room temperature, a clear coat paint is applied thereon. The coating is left at room temperature for 10 minutes, and then placed in an electric hot air drier at 140 ° C.
Allowed for 0 minutes to cure.

The performance of each of the thus obtained coating films was compared and examined. The results are collectively shown in Tables 5 (1) to (6).

[Outline of Evaluation of Coating Film Performance]

Finished appearance (glossiness, etc.) ... Evaluated by a mapping lightness meter manufactured by Suga Test Instruments Co., Ltd. These are indices indicating the sharpness of the coating film. , Which means good clarity.

Finish appearance (metal orientation, etc.) is indicated by an IV value measured by a metallic feeling measuring device “ALCOPELMR-100” (manufactured by Kansai Paint Co., Ltd.). It means that the finished appearance of the coating film is good.

Finish appearance (metal orientation, etc.): Visual evaluation of coating unevenness of cured coating film ◎: No unevenness, good glossiness: no unevenness,: unevenness but glossy finish ×: glossy finish

Chipping resistance: Using a stepping stone tester “JA-400” (manufactured by Suga Test Instruments Co., Ltd.), the use conditions were that 50 g of No. 7 crushed stone was used. At a pressure of 4 kg / cm 2, the peeled coating film was visually evaluated. ：: good, Δ: bad, ×: extremely poor

[0160]

[Table 10]

[0161]

[Table 11]

[0162]

[Table 12]

[0163]

[Table 13]

[0164]

[Table 14]

[0165]

[Table 15]

[0166]

[Table 16]

As described above, the resin composition for a colored coating and the method of laminating coating according to the present invention have a high non-volatile content at the time of coating, and have a high metal orientation and a high chipping resistance. It's easy to find out that it's excellent and extremely practical.

[0168]

According to the present invention, the resin composition for a colored coating and the method of laminating a coating composition form a coating film having a high solid content and excellent in various properties such as gloss, curability and chipping resistance. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B05D 7/24 302 B05D 7/24 302V C09D 161/20 C09D 161/20 175/04 175/04 F term ( Reference) 4D075 AE03 CB06 EA06 EA43 EB35 EC37 4J038 BA052 BA082 BA092 BA212 CA022 CB002 CB072 CC002 CC022 CE002 CE022 CE052 CG002 CG032 CG122 CG142 CG172 CH012 CH052 CH062 CH122 CH172 CK012 DG0312 DG0312 HA286 HA446 HA556 JB18 KA03 KA07 KA08 MA02 MA08 MA09 MA10 MA14 NA11 NA12 NA24 PA14

Claims (9)

[Claims] 1. A polyester resin (A) obtained by reacting a polyhydric alcohol with a polybasic acid, wherein at least 60 mol% of the polybasic acid component is an alicyclic polybasic acid and contains a hydroxyl group. ) And a curing agent (B). 2. A polyester resin (A) obtained by reacting a polyhydric alcohol with a polybasic acid, wherein at least 60 mol% of the polybasic acid component is an alicyclic polybasic acid and contains a hydroxyl group. ), A curing agent (B), and a rheology control agent (C). 3. The polyester resin (A) has a weight average molecular weight of 800 to 30,000 and a solid content hydroxyl value of 50 to 200.
The resin composition for a colored coating according to claim 1 or 2, which is a polyester resin having a mgKOH / g and an acid value of 5 to 20 mgKOH / g in a solid content. 4. The polyester resin (A) has a weight average molecular weight of 1,000 to 20,000 and a solid content hydroxyl value of 80 to 15.
0 mgKOH / g, solid content acid value 5-20 mgKOH / g
The resin composition for a colored coating according to claim 1, wherein the resin composition is a polyester resin. 5. The resin composition for a colored coating according to claim 1, wherein the curing agent (B) is an amino resin and / or a blocked isocyanate resin. 6. A polyester resin (A) and a curing agent (B)
Resin solid content weight ratio (A / B) of 50 / 50-90 /
The resin composition for a colored coating according to any one of claims 1 to 5, which is 10. 7. The colored paint according to claim 2, wherein the content of the rheology control agent (C) is 0 to 100% by weight based on the weight of the resin solid content (A + B). Resin composition. 8. The resin composition for a colored coating material according to claim 1, wherein the polyester resin (A) is a water-soluble or water-dispersible material. 9. A base paint comprising the resin composition for a colored paint according to any one of claims 1 to 8, which is applied to a base material to form a coating film. And a top clear paint to form a cured coating film.