JP2548906B2 - High solid content coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful high solid content coating composition. More specifically, the present invention relates to a hydroxyl group-containing polymer, a specific curing resin, and a non-aqueous dispersion. Type fine particles polymers as an essential base resin component, that is, as a coating film forming component, and further contains a specific amount of solvents as an essential component. The present invention relates to a coating composition having improved workability and the like and having extremely high practicality.

One of the recent trends in the coating industry is the trend toward low-pollution coating systems.

Traditionally, the direction of this type of low-pollution coating system has been to reduce the amount of solvents that are volatizing and diffusing at the time of coating, which is also a cause of environmental pollution. Is it the development of a split coating composition,
Alternatively, it is being promoted in the form of using water-based paints that can replace solvent-based paints.

However, there are still many drawbacks to such a method, for example, in the case of a high-solid type coating composition, since the solvent layer in the system is significantly smaller than that of the conventional coating composition, it is applied to the substrate during spraying. Since the content of the deposited film-forming component (coating-forming component) becomes extremely high, the conventional coating composition controls the smoothness (leveling) of the film surface, which is controlled by the evaporation rate of the diluted thinner. The expression or maintenance is deteriorated, and in addition, especially in the case of a baking type coating system, the film-forming component applied to the substrate during baking causes a decrease in viscosity and is apt to cause "sag". Existed.

Explaining these drawbacks in detail, as a method for obtaining a high-solid type coating composition, it is possible to reduce the molecular weight of the film-forming polymers, or to employ non-aqueous dispersion type polymerization. Although a method has been proposed, in the case of the former method, it is easy to cause "drip" at the time of baking, which is caused by the low molecular weight of the film-forming polymers, and moreover, "repellency" is likely to occur simultaneously. However, particularly when using vinyl-based polymers, there is a drawback that a functional group capable of reacting with a curing agent cannot be efficiently introduced, and on the other hand, when using condensation-based polymers, introduction of a functional group is required. Although it is easy, it has a drawback that it is inferior in weather resistance to vinyl polymers.

In the latter method, that is, in the case of using non-aqueous dispersion type polymers, since these polymers are dispersed in a solvent while having the shape of particles, the close packing of such particles is exceeded. It has the drawback that it is impossible to differentiate it into a highly solid form, and in addition, it lacks long-term storage stability due to the sedimentation of these polymer particles, and even when it is a cured coating film, it has acid resistance. In addition, the coating film performance such as gasoline resistance is inferior.

Furthermore, in the case of using water-based paint, since the dispersion medium is water with poor volatility, it is difficult to spray, or it is difficult for water to evaporate even when it is applied to the substrate, and the humidity of the atmosphere However, when forming a multi-layer film, it also causes defects such as "armpits" in the coating film.

For the above reasons, there are many points that still have to be solved in low-pollution type paints, and it is the current situation that it has not reached the widely practical range.

However, in view of the existence of various drawbacks in the conventional techniques as described above, the present inventors have found that various types of high-solids-type coating compositions containing low-molecular weight polymers as a main component are used. In order to improve the drawbacks, as a result of intensive and repeated studies, hydroxyl-containing polymers and a specific curing resin,
The combination with non-aqueous dispersion type fine particle polymers (hereinafter, also referred to as fine particle polymers) is particularly effective in preventing "repellency" and "dripping", respectively, during coating on substrates. In addition to finding that there is, in particular, that it is possible to give a coating film excellent in curability and weather resistance,
Here, the present invention has been completed.

That is, the present invention basically comprises, as essential components, 90 to 30 parts by weight of a hydroxyl group-containing polymer (A), an aminoplast or a blocked or unblocked polyisocyanate (B), respectively. 10 to 70 parts by weight and 0.1 to 100 parts by weight per 100 parts by weight of both components (A) and (B), respectively, to (1) polybutadiene-based unsaturated bond-containing polymers. ,
A graft copolymer obtained by polymerizing a core monomer or a core monomer and (meth) acrylic acid, and an addition reaction of an unsaturated bond-containing epoxy compound to a carboxyl group in the graft copolymer. Terminally unsaturated bond-containing graft copolymer obtained at most; (2) Alkyl etherified melamine resin etherified with alkyl alcohol having 4 to 12 carbon atoms; (3) Alkyd resin; (4) Hydroxyl group-containing saturated fatty acid The carboxyl group at the terminal position of the self-condensed polyester of, the terminal unsaturated bond-containing graft copolymer obtained by addition-reacting the unsaturated bond-containing epoxy compound is further polymerized with a core monomer, or a core monomer and ( Graft copolymer obtained by polymerizing (meth) acrylic acid; (5) Carbon number of 4 or more It is obtained by addition reaction of an unsaturated bond-containing epoxy compound to the carboxyl group in the copolymer obtained by polymerizing vinyl-based monomers whose main component is (meth) acrylic acid ester of alkyl alcohol Terminal unsaturated bond-containing graft copolymer, and graft copolymer obtained by further polymerizing the terminal unsaturated bond-containing graft copolymer with a core monomer; and (6) Alkyl having 4 or more carbon atoms Hydrolyzable silyl group-containing copolymer obtained by polymerizing a vinyl-based monomer containing an alcohol (meth) acrylic acid ester as a main component and a hydrolyzable silyl group-containing monomer, and the hydrolyzable silyl group-containing copolymer The copolymer was obtained by polymerizing a monomer having a functional group capable of reacting with the hydrolyzable silyl group and a core monomer. A segment soluble in an aliphatic or alicyclic hydrocarbon solvent, which is obtained by using at least one dispersion stabilizer selected from the group consisting of unsaturated bond-containing graft copolymers, and an insoluble segment. And a non-aqueous dispersion type fine particle polymer (C) having both
The solvent (D) is contained as an essential component in an amount of 55% by weight or more, and particularly, coating workability and coating film performance are remarkably improved. It is an attempt to provide a high high solids coating composition.

Here, the above-mentioned hydroxyl group-containing polymers (A) are (condensed) polymers having at least 1, preferably at least 2 hydroxyl groups per molecule, and the objective composition of the present invention. A high-solid content coating composition is referred to as having a molecular weight within a necessary and sufficient range for differentiating the high-solid content of the coating composition, and thus any of those that meet these conditions can be applied. Preferably, specific resins that meet the following conditions are suitable.

Vinyl resins having a number average molecular weight (▲ ▼) of 500 to 8,000 and a hydroxyl value (OHV) of 40 to 250, ▲ ▼ of 200 to 3,000 and OHV of 40 to 6
At least one resin selected from the group consisting of alkyd resin, oil-free alkyd resin and urethane resin in the range of 00, and a mixture of the above resins and resins.

Among these, in order to prepare the resins, a hydroxyl group-containing monomer and another monomer having a copolymerizability therewith may be copolymerized by a conventional method. Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 3-hydroxybutyl (meth) acrylate. , 4-hydroxybutyl (meth) acrylate, 3-
Hydroxyalkyl esters of (meth) acrylic acid such as chloro-2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate; monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride, and ethylene glycol Unsaturated-alkyl-containing hydroxyalkyl ester monocarboxylic acids such as adducts with glycols; or unsaturated-bond-containing polyhydroxyalkyl esters such as dihydroxyalkyl esters of polyvalent carboxylic acids such as maleic acid and fumaric acid; hydroxy There are hydroxyalkyl vinyl ethers such as ethyl vinyl ether.

On the other hand, typical examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2- (meth) acrylate.
(Meth) acrylic acid esters such as ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and benzyl (meth) acrylate; unsaturated dicarboxylic acids and monohydric alcohols such as dimethyl maleate, diethyl fumarate and dibutyl itaconate With diesters; vinyl acetate, vinyl benzoate, "Veova"
Vinyl esters such as (Ciel, Netherlands);
"Viscoat 8F, 8FM, 3F or 3FM" (fluorine-containing (meth) acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.) or perfluorocyclohexyl (meth) acrylate,
Di-perfluorocyclohexyl fumarate or N
-Iso-propyl perfluorooctane sulfonamide ethyl (meth) acrylate-containing vinylidene esters containing perfluoroalkyl groups; vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl halides such as vinylidene fluoride; ethylene, Α-olefins such as propylene; styrene, α-methylstyrene, p
Aromatic vinyl monomers such as -tert-butylstyrene, o-methylstyrene, p-methylstyrene; (meth)
Acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid-containing carboxyl group-containing monomers (unsaturated mono- or dicarboxylic acids); maleic anhydride, itaconic anhydride-containing acid anhydride group-containing monomers; (Meth) acrylamide, N, N-dimethyl (meth)
Acrylamide, N-alkoxymethylated (meth) acrylamide, diacetone (meth) acrylamide, N-
Carboxylamide group-containing monomers such as methylol (meth) acrylamide; p-styrenesulfonamide, N
-Sulfonamide group-containing monomers such as methyl-p-styrenesulfonamide and N, N-dimethyl-p-styrenesulfonamide; N, N-dialkylaminoalkyl such as N, N-dimethylaminoethyl (meth) acrylate (Meth) acrylates; such as adducts of the above-mentioned acid anhydride group-containing monomers with a compound having an active hydrogen group capable of reacting with an acid anhydride group such as N, N-dimethylaminopropylamine and a compound having a tertiary amino group. Monomers containing primary amino groups; Monomers containing cyano groups such as (meth) acrylonitrile; Hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as hydroxyalkyl esters of (meth) acrylic acid, and phosphoric acid or Monomers having a phosphate ester bond, which is a condensation product with a phosphate ester; or 2- Acrylamide-2-methyl - sulfonic acid group-containing monomers or organic amine salts such as propane sulfonic acid and the like.

Of the various monomers described above, the amount of the hydroxyl group-containing monomers used varies depending on the molecular weight of the vinyl resin to be obtained, but it is desirable that the amount of hydroxyl group-containing monomers generally occupy 10 to 50% by weight of all the monomers. The remaining 90 to 50% by weight is taken into consideration from other desired factors such as the physical properties of the finally obtained cured coating film and the pigment dispersibility among the other copolymerizable monomers as described above. You can choose freely.

In addition, among the other copolymerizable monomers as described above, a carboxyl which also serves as a latent catalyst for a crosslinking reaction between the vinyl resin and the aminoplast or (block) polyisocyanate as the curing resin is included. Since there are acidic group-containing monomers such as group-containing monomers and sulfonic acid group-containing monomers, it is desirable to use these specific monomers.

Then, in order to prepare such a hydroxyl group-containing vinyl resin, a known conventional method such as a solution polymerization method, a solution pressure polymerization method, a bulk polymerization method, an emulsion polymerization method or a suspension polymerization method can be directly applied. The solution radical polymerization method is the simplest.

Typical solvents used at that time are hydrocarbons such as toluene, xylene, cyclohexane, n-hexane and octane; methanol, ethanol, iso-propanol, n-butanol, iso-butanol, sec- Alcohols such as butanol, ethylene glycol monomethyl ether; esters such as methyl acetate, ethyl acetate, n-butyl acetate, amyl acetate; ketones such as acetone, methyl ethyl ketone, methyl-iso-butyl ketone, methyl amyl ketone, cyclohexanone; or There are amide-based compounds such as dimethylformamide and dimethylacetamide, and it goes without saying that any mixture thereof can also be used.

Polymerization may be carried out by a conventional method using the solvent and various radical polymerization initiators such as azo type or peroxide type. Further, if necessary, lauryl mercaptan as a molecular weight regulator may be used. , Various chain transfer agents such as octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer can also be used. In particular, when a hydroxyl group-containing chain transfer agent such as 2-mercaptoethanol is used, it is possible to efficiently introduce such a hydroxyl group into a fraction having an average molecular weight of the obtained resin or less, but the weather resistance Due to its inferiority, it should be directed to limited applications.

Further, as a method for preparing such a hydroxyl group-containing vinyl resin, there is an ionic polymerization method in addition to the solution radical polymerization method described above, and a resin obtained by this ionic polymerization method is also used in the present invention without any trouble. be able to.

According to such an ionic polymerization method, polymerization is performed using an ionic polymerization initiator in a form in which functional groups are previously blocked, and then the blocking agent at the terminal of the obtained resin is eliminated, so that the molecular weight distribution is extremely narrow. Moreover, it is possible to obtain a resin having one or more functional groups in one molecule without fail, and such an ionic polymerization method is disclosed in JP-A-58-1
As described in detail in Japanese Patent No. 3608, the same can be applied as it is.

The glass transition point of the hydroxyl group-containing vinyl resin thus obtained is suitably within the range of -20 to + 50 ° C.

Next, all of the above-mentioned alkyd resin, oil-free alkyd resin and / or urethane resin are characteristic in that the raw material components and ▲ ▼ and OHV are limited, and so-called synthetic conditions such as esterification method are Well-known and conventional means can be applied as they are.

Here, the urethane resin refers to a resin having one or more urethane bonds in one molecule, such as an isocyanate-modified acrylic resin, an isocyanate-modified alkyd resin, or an isocyanate-modified polyester resin. It is preferable to use an isocyanate-modified alkyd resin and / or polyester resin from the standpoint of relatively low risk of gelation.

First, as a method for preparing urethane resin,
It is preferable to extend the molecular chain by reacting an alkyd oligomer or polyester oligomer having at least one hydroxyl group with an organic diisocyanate compound.

Typical examples of organic diisocyanate compounds that can be used include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate; or tolylene diisocyanate, 4,4 ′. -Aromatic diisocyanates such as diphenylmethane diisocyanate, etc. may be mentioned, and it is needless to say that they may be used in combination, but from the viewpoint of the weather resistance of the coating film, it is preferable to use aliphatic diisocyanates. .

In addition, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 min-diphenyl are typical polybasic acid components used in synthesizing the polyester component of the resins. Enyldicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid Acid, adipic acid,
Reactivity of azelaic acid, pimelic acid, suberic acid, sebacic acid or dimeric fatty acid (dimer acid), or tremellitic acid, trimesic acid, pyromellitic acid or cyclopentanetetracarboxylic acid, or their alkyl esters or anhydrides Examples of the derivative include hexahydrophthalic acid, methylhexahydrophthalic acid, hexahydroterephthalic acid, and one or more kinds of various reactive derivatives thereof in an amount of 50 mol% or more in all polybasic acid components. When used as described above, the composition of the present invention is excellent in terms of curability and weather resistance of the coating film, as well as solubility and low viscosity, with less "repellence" in the cured coating film. Will be done.

As described above, these polybasic acid components should be appropriately selected in consideration of the physical properties of the coating film and the economical efficiency.

On the other hand, typical alcohol components used in synthesizing the polyester component of the resins include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, Alkylene glycols such as 1,5-pentanediol, 1,6-hexanediol and neobenthyl glycol; 1,4-cyclohexanedimethanol, bis-
There are aromatic or alicyclic glycols such as hydroxyethyl terephthalate, hydrogenated bisphenol A, or alkylene oxide of hydrogenated bisphenol A. Monoepoxy compounds can also be used as the alcohol component, and glycerin can also be used. , Trimethylolethane, trimethylolpropane, pentaerythritol,
Polyester compounds such as dipentaerythritol, mannitol, or adducts of the various glycol components listed above with ε-caprolactone can also be used, but there is little "repellency" in the cured coating film, and this coating film From the viewpoint of weather resistance, the use of neopentyl glycol in an amount of 30 mol% or more of all alcohol components gives good results.

Therefore, these alcohol components should be appropriately selected according to the required performance of the cured coating film finally obtained.

Further, as typical ones of fatty acids used in obtaining the alkyd resin, octylic acid, palmitic acid, stearic acid, versatic acid, oleic acid, linoleic acid, linoleic acid, coconut oil fatty acid, hydrogenated Palm oil fatty acid, tall oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, rice bran oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, safflower oil fatty acid, etc., long-chain saturated or unsaturated monobasic with C ₈ or more. Examples of the acid include acids, which should be appropriately selected in consideration of the solubility in solvents, the weather resistance of the coating film and the economical efficiency.

In this way, the polyester component used for preparing the alkyd resin, oil-free alkyd resin and / or urethane resin is obtained. In addition to the above, the total polybasic acid component and the total polybasic acid component, respectively, as the polyester forming component are obtained. 40 to the total amount of alcohol components
It is also possible to use a polyester component obtained by addition with ε-caprolactone in the range of 90 mol%. In such a case, the occurrence of "repellency" in the cured coating film is small and the cured coating film The composition of the present invention having excellent flexibility is provided.

Thus, the hydroxyl group-containing resins (A) used in the present invention can be obtained, and the alkyd resin, oil-free alkyd resin and / or urethane resin can be used alone or as a mixture of two or more thereof. It is needless to say that such a vinyl resin and an alkyd resin, an oil-free alkyd resin and / or a urethane resin can be used as a mixture, and for example, in the case of obtaining the composition of the present invention having good weather resistance, In the case of using a large amount of vinyl resin and obtaining the composition of the present invention having good flexibility, by using a large amount of alkyd resin, oil-free alkyd resin and / or urethane resin, The coating film performance can be adjusted arbitrarily.

Then, the aminoplast or (block) described above
The polyisocyanate (B) functions as a curing agent (curing resin) for the composition of the present invention, of which aminoplasts include amino acids such as melamine, urea, acetoguanamine, benzoguanamine, steroganamin or spiroguanamine. A condensation product obtained by reacting a group-containing compound with an aldehyde compound such as formaldehyde, paraformaldehyde, acetaldehyde, or glyoxal, or a condensation product obtained by reacting each condensation product with a monohydric alcohol. Typical examples are modified products obtained by
Any known and commonly used paint can be applied as it is.

Preference is given to those which are partially or completely etherified with C ₁ -C ₄ monohydric alkyl alcohols, specifically methyl etherified melamine, n-butyl etherified melamine or iso-butyl ether. Among them, methyl etherified melamine is preferable from the viewpoint of high solid type differentiation (high solidification).

Next, as the block polyisocyanate, a polyisocyanate obtained by blocking a so-called yellowing-free polyisocyanate with a known and commonly used blocking agent is used, and "Bernock D-550" and "Dainippon Ink and Chemicals (Inc. ) Product], “Takenate B 815-N” [Takeda Pharmaceutical Co., Ltd. product], or “ADDITO”
L) VXL-80 ”(a product of Hoechst Synthetic Co., Ltd.) is a typical one.

Further, typical examples of the polyisocyanate include various organic diisocyanate compounds as described above and an adduct of a polyhydric alcohol or a low molecular weight polyester or water, or a polymer of the organic diisocyanate compounds, and Isocyanate, biuret, etc., and particularly representative ones among them are "Bernock D-750, 800, DN-950, 970 or 15-45.
5 "(same company product)," Desmodule N, L, HL or IL "(West Germany Bayer company product)," Takenate D-102, 202, 110N or 123N "(same company product),
"Coronate L, HL, EH or 203" [Product of Nippon Polyurethane Industry Co., Ltd.] or "Deuranate 24-90CX"
[Asahi Kasei Co., Ltd. product] etc.

And the aminoplast or (block) polyisocyanate (B) and the hydroxyl group-containing polymer (A)
Means 90 to 30 parts by weight of the component (A) relative to the component (B).
It may be used in a proportion of 10 to 70 parts by weight.

Further, the above-mentioned fine particle polymers (C) are added in order to impart pseudoplastic viscosity behavior to the mixture of the components (A) and (B) described in detail above.

The mixture of both components (A) and (B) exhibits substantially Newtonian flow characteristics,
From the point where there is no yield value or the value is small, for example, when the coating work is performed with the substrate vertical, or when the temperature rises during baking, "sag" occurs. Both the compounds belonging to the component (A) and the compounds belonging to the component (B) have relatively low molecular weights, so that "repellency" is likely to occur during coating and baking. There are drawbacks.

However, as in the present invention, such (A),
By adding and blending the fine particle polymers (C) to the mixture of (B) both components, the apparent viscosity during standing is increased, but when high shearing force is applied to such a system, That is, during spraying, the viscosity becomes sufficiently low, so that the spraying work becomes easy, and the structural viscosity is developed within a short time of several seconds to several minutes after the base material is applied. Results,
Film defects such as "repellency" and "dripping" do not occur.

By the way, the fine particle polymers (C) refer to polymers that can be stably dispersed in the mixture of the above-mentioned component (A) and component (B) while maintaining the particle shape. is there.

Here, "the particles can be stably dispersed in the shape of the particles" means that in the medium in which the polymer in question exists, the difference in polarity or the difference in affinity between the medium and the polymers. Therefore, if the shape of the particles is retained, the polymers and the medium can be easily dissolved, that is, if the affinity between them is strong, a particulate structure is formed in the medium. It may be in a form that has some kind of scientific coupling.

Specific examples of the fine particle polymers (C) include organic compounds represented by various non-aqueous dispersion type fine particle polymers as shown below. The use of non-aqueous dispersion type fine particle polymers is desirable.

Of course, the non-aqueous dispersion type fine particle polymer is not the only one, and is not limited to the non-aqueous dispersion type fine particle polymer, and may be used in combination with, for example, an inorganic type typified by fine powdery silica, or an organic type. It does not hinder the combined use with a low molecular weight polyolefin polymer, which is also a problem.

Such non-aqueous dispersion type fine particles polymers are, as is known,
In a solvent such as an aliphatic or alicyclic hydrocarbon system, in the presence of a dispersion stabilizer having both a segment soluble in these solvents and a segment insoluble or swellable in these solvents In addition, the above-mentioned method was carried out by polymerizing monomers (hereinafter abbreviated as nuclear monomers) in which the monomer is soluble in the solvent but the polymer is insoluble in the solvent by a conventional method. It refers to polymers having a particle shape which can be stably dispersed in the solvent, which is obtained by chemically or physically binding to such a dispersion stabilizer.

The method for preparing such non-aqueous dispersion type fine particles polymers will be specifically described as follows.

That is, as the solvent used first, non-polar,
And a polymer having a relatively small dissolving power and a polymer produced from the above-mentioned nuclear monomers (hereinafter abbreviated as a nuclear polymer) is not dissolved, but any one capable of dissolving or swelling the dispersion stabilizer is used. Although typical examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, and octane; petroleum benzine, ligroin, mineral spirits, petroleum naphtha, and kerosene, which have a boiling point of 30 to 300 ° C. A range of hydrocarbon mixtures; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclosan, or mixtures thereof.

In some cases, in addition to these aliphatic hydrocarbons, hydrocarbon mixtures and / or alicyclic hydrocarbons, up to about 70% by weight of all solvents, aromatic hydrocarbon-based, ester-based, You may use what included the polar compound of alcohol type, ketone type, ether type, etc.

As the amount of the solvent used, the solid content of the resulting non-aqueous dispersion type polymers is 30 to 70% by weight, preferably 40 to 60% by weight.
An appropriate range is such that

Next, typical examples of the dispersion stabilizer include i
Unsaturated bond-containing polymers represented by various polydiene-based polymers such as polybutadiene and polyisoprene are obtained by polymerizing one or more of various nuclear monomers as described below. Or a graft copolymer obtained by copolymerizing the above-mentioned unsaturated bond-containing polymers with a core monomer and (meth) acrylic acid as described below, and the latter graft copolymer. An unsaturated bond-containing graft copolymer obtained by addition reaction of an unsaturated bond-containing epoxy compound such as glycidyl (meth) acrylate with a carboxyl group in the polymer; ii alkyd resin; iii C _{4 to} C ₁₂ alkyl alcohol Etherified alkyl etherified melamine resin condensates which are soluble in various solvents as described above; iv 12-hi A terminal unsaturated bond-containing polyester obtained by addition-reacting the above unsaturated bond-containing epoxy compound to a carboxyl group at the terminal position of a self-condensed polyester of a hydroxyl group-containing saturated fatty acid such as droxystearic acid, and then described below. Graft copolymer obtained by polymerizing such a nuclear monomer, or the above-mentioned unsaturated polyester containing terminal unsaturated bond is copolymerized with the following nuclear monomer and (meth) acrylic acid, and then the carboxyl group And an unsaturated bond-containing graft copolymer obtained by subjecting the above unsaturated bond-containing epoxy compound to an addition reaction; or vn-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylates, such as C ₄ stearyl (meth) acrylate The alkyl alcohol (meth) acrylic acid esters above mainly, optionally obtained allowed also copolymerized with other vinyl monomers (co) polymer such or, according the
Carboxyl contained in a copolymer obtained by copolymerizing (meth) acrylic acid ester of C ₄ or more alkyl alcohol as a main component with (meth) acrylic acid and optionally other vinyl monomer Unsaturated bond-containing copolymers obtained by the addition reaction of the above unsaturated bond-containing epoxy compound to a group, and one or more kinds of nuclear monomers in the unsaturated bond-containing copolymers. The graft copolymer obtained by copolymerization, or the carboxyl group in the copolymer obtained by copolymerizing the unsaturated bond-containing copolymers with the following nuclear monomers and (meth) acrylic acid On the other hand, there is an unsaturated bond-containing graft copolymer obtained by subjecting the above unsaturated bond-containing epoxy compound to an addition reaction.

Among these, each of the above dispersion stabilizers of the ii and iii groups and the above dispersion stabilizer of the v group were esterified with an alkyl alcohol of C ₄ or more,
Use of (co) copolymers containing an alkyl ester of (meth) acrylic acid as a main component, or unsaturated bond-containing copolymers derived from the (co) polymers as a dispersion stabilizer In some cases, none of these dispersion stabilizers have the solvent-insoluble segment as described above, but these classes of dispersion stabilizers are subsequently used to provide non-aqueous dispersion polymers. At the initial stage of the polymerization of the nuclear monomers during the preparation, the above-mentioned solvent-insoluble segment is formed to obtain the desired non-aqueous dispersion type polymers.

Here, as the nuclear monomers, various monomers such as those used in obtaining the hydroxyl group-containing polymers (A) can be directly applied,
Hydroxyalkyl esters of (meth) acrylic acid,
Unsaturated bond-containing hydroxyalkyl esters monocarboxylic acids, unsaturated bond-containing polyhydroxyalkyl esters, to the like C ₁ -C ₃ consisting of alcohol (meth) acrylic acid alkyl esters or cyano group-containing monomers, while Typical examples of the other monomer copolymerizable with the core monomers include (meth) acrylic acid alkyl esters of C ₄ or more alcohols as described above;
Dialkyl esters of unsaturated dicarboxylic acids; perfluoroalkyl group-containing vinyl esters; α-olefins; aromatic vinyl monomers; vinyl halides (vinylidene) s; acid anhydride group-containing monomers; carboxylic acid amide group-containing monomers Examples thereof include sulfonic acid amide group-containing monomers, tertiary amino group-containing monomers, phosphoric acid ester bond-containing monomers, or sulfonic acid group-containing monomers or their organic amine salts.

In addition to the dispersion stabilizers exemplified above, the dispersion stabilizer having a hydrolyzable silyl group and the bond between the solvent-soluble segment and the insoluble segment described above are hydrolyzed. It is known that a dispersion stabilizer and the like, which is carried out by a reaction between a degradable silyl group and a group capable of reacting with the silyl group, can give stable non-aqueous dispersion type polymers. The present inventors have confirmed that these classes of non-aqueous dispersion type polymers are extremely useful as the fine particle polymers (C) used in the present invention.

The dispersion stabilizer having such a hydrolyzable silyl group can be prepared by the following method.

That is, for example, as shown in v above, the main component is an alkyl ester of (meth) acrylic acid esterified with an alkyl alcohol having a carbon number of ₄ or more, and these are used together with a hydrolyzable silyl group-containing monomer such as γ- (Meta)
Acryloyloxypropyltrimethoxysilane, γ-
(Meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltris (β-methoxyethoxy) A method of copolymerizing one or more kinds of silane or acryltrimethoxysilane and further another copolymerizable monomer, or a hydrolyzable silyl group-containing copolymer obtained by such a method ( (A trunk polymer), a monomer having various functional groups capable of reacting with various hydrolyzable silyl groups as described above, for example, a hydroxyl group and / or a carboxyl group, and one or two of the above-mentioned core monomers. Graft copolymerize with at least one species The method etc. can be applied.

Among these methods, in the case of the former method, a group capable of reacting with the silyl group in the hydrolyzable silyl group-containing monomer as described above (carboxyl group, hydroxyl group, etc.)
Therefore, it is necessary to use monomers having N as a nucleus monomer, and by doing so, the nucleus monomers having a group capable of reacting with a silyl group contribute to the bonding of the grafting point.

By the way, when the obtained non-aqueous dispersion type polymers are not dissolved in the above-mentioned mixture of the respective components (A) and (B), the fine particle polymers (C However, in the case where it can be dissolved, it is necessary to form a structure capable of maintaining the particles of the non-aqueous dispersion type polymer (for example, formation of an insoluble portion). However, for that purpose, it is necessary to intramolecularly cross-link the core portion to be a non-aqueous dispersion type polymer.

As a method for performing such intramolecular cross-linking, a method of using a pair of monomers having two kinds of functional groups capable of reacting with each other in combination with core monomers, or a polyfunctional vinyl-based monomer, that is, at least 2 in one molecule Examples include a method in which a vinyl-based monomer having a single unsaturated bond is used in combination with nuclear monomers.

Among these intramolecular crosslinking methods, a representative example of a pair of monomers having two kinds of functional groups capable of reacting with each other, which is used for carrying out the former method, is an example of an epoxy group and a carboxyl group. An example of an acid anhydride group and a hydroxyl group of (β-methyl) glycidyl (meth) acrylate and (meth) acrylic acid is maleic anhydride and β-hydroxyethyl (meth) acrylate of an isocyanate group and a hydroxyl group. Examples include β-isocyanate ethyl (meth) acrylate and β-hydroxyethyl (meth) acrylate, examples of isocyanate groups and amino groups include β-isocyanate ethyl (meth) acrylate and allylamine, hydroxyl groups and methylol groups. Or, for example, with an alkyl etherified methylol group, β-hydroxyethyl (meth)
Examples of hydrolyzable silyl groups and hydroxyl groups of acrylate and n-butyl ether of N-methylol (meth) acrylamide include γ- (meth) acryloyloxypropyltrimethoxysilane and β-hydroxyethyl (meth) acrylate. Examples of the hydrolyzable silyl group and the carboxyl group include a combination of γ- (meth) acryloyloxypropyltrimethoxysilane and (meth) acrylic acid, and examples of the hydrolyzable silyl groups include γ- (meth) acryloyloxypropyltrimethoxysilane may be used alone, or two types may be appropriately selected from the above-mentioned various hydrolyzable silyl group-containing monomers.

These two types of monomers forming a pair are reacted as a part of the core monomers at the same time as the non-aqueous dispersion polymerization, or are made to react by raising the temperature at the end of the non-aqueous dispersion polymerization.
Further, in order to promote such a reaction, intramolecular crosslinking may be carried out by allowing a known and commonly used catalyst to coexist and react.

On the other hand, in the case of the latter intramolecular cross-linking method in which the polyfunctional vinyl-based monomer is used in combination with the core monomer, the polyfunctional vinyl-based monomer as shown below is used as the core monomer in the same manner as the former method. By polymerizing as a part, a non-aqueous dispersion type polymer can have a cross-linking structure. Typical examples of such polyfunctional vinyl-based monomers are ethylene glycol di (meth) acrylate or trimethylol. Examples include propane tri (meth) acrylate.

The fine particle polymers (C) used in the present invention
As the above, it is particularly preferable to use non-aqueous dispersion type polymers in which the same kind of functional group capable of reacting with the component (B), that is, a hydroxyl group is introduced into both the dispersion stabilizer and the nuclear monomer.

This is when the composition of the present invention becomes a cured coating film,
Both the dispersion stabilizer portion and the core portion of the non-aqueous dispersion type polymer are obtained by reacting with the curing agent (curing resin) to obtain a uniform and highly transparent coating film. is there.

As described above, in order to prepare such a non-aqueous polymer dispersion, it is sufficient to polymerize the dispersion stabilizer and the core monomers in the presence of the solvents as described above. For example, the radical polymerization initiator as described above and, if necessary, the above chain transfer agent can be used.

The amount of the fine particle polymers (C) as described above is 100, which is the total amount of the components (A) and (B).
A suitable range is 0.1 to 100 parts by weight with respect to parts by weight.

Further, as the above-mentioned solvents (D), (A)
The solvent used in the preparation of the component or the component (C) can be applied as it is in the form of a single or a combined use, and the type and composition in the case of the combined use can be determined depending on the type of the coating method and the baking conditions. Of course, it must be decided.

In addition, when using polyisocyanate as the said (B) component, it is needless to say that the solvent (D) should select the thing which does not react with this polyisocyanate.

The thus obtained high solid content coating composition of the present invention further contains, if necessary, pigments, various resins and well-known conventional flow regulators, color separation inhibitors, antioxidants or ultraviolet absorbers. , Silane coupling agents and curing catalysts can be added.

Among them, titanium oxide is a typical pigment,
Inorganic pigments such as carbon black, or organic pigments such as quinacridone, azo and phthalocyanine pigments,
Further, various metal powders such as aluminum powder, copper powder, and zinc powder can be cited. Typical examples of resins include nitrocellulose, fibrin resin such as cellulose acetate butyrate, ketone resin, petroleum resin, etc. However, typical silane coupling agents are γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. There is.

Typical examples of the curing catalyst include dibutyltin diacetate, dibutyltin dilaurate, triethylamine and diethanolamine when the (block) polyisocyanate is used as the component (B). When aminoplast is used as the component (B), para-toluenesulfonic acid, or "Betcamine P-198" (produced by Dainippon Ink and Chemicals, Inc.), "Neikyure 155,2500X, X 49-1"
10,5225 or 3525 "(product of King USA). The amount of the catalysts used may be appropriately selected depending on the baking temperature and the baking time.

The coating composition of the present invention is applied by a conventional method such as spray coating, brush coating, and roll coater coating, and when polyisocyanate is used as the component (B), it is baked at room temperature to about 100 ° C. If a component other than the above polyisocyanate is used as the component (B), it may be added at 10 to 40 at a temperature range of 60 to 180 ° C.
A cured coating film can be obtained by baking for minutes.

Thus, the high solid content coating resin composition of the present invention can be applied especially for general baking of home electric appliances and the like, or for automobiles, more specifically, as an enamel paint for automobiles, as a metallic base paint. , Or can be used as a clear paint, respectively.

Next, the present invention will be described in detail with reference to Reference Examples, Examples and Comparative Examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 [Preparation example of hydroxyl group-containing polymers (A)] 160 parts of xylene and 160 parts of n-butyl acetate were charged into a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser. In a nitrogen atmosphere, the temperature is raised to 125 ° C., 120 parts of styrene, 180 parts of n-butyl acrylate, n-
120 parts of butyl methacrylate, 108 parts of β-hydroxypropyl acrylate, 66 parts of β-hydroxypropyl methacrylate and 6 parts of acrylic acid, 80 parts of n-butanol, 48 parts of tert-butyl peroxyoctate.
Part, 3 parts of di-tert-butyl peroxide and 12 parts of azobisisobutyronitrile were added dropwise over 8 hours, and after the addition was completed, the mixture was kept at the same temperature for 15 hours to give a nonvolatile content ( NV) is 60%, Gardner color (G.
C.) was 1 or less, the Gardner viscosity at 25 ° C. (same below) was E, ▲ ▼ was 3,000, and a solution of a hydroxyl group-containing vinyl polymer (A) having a glass transition point of 0 ° C. was obtained. Hereinafter, this is abbreviated as polymers (A-1), but the OHV of the solid component of this polymer was 109.

Reference Example 2 (Same as above) In a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reaction product water distiller, 215 parts of adipic acid and 63.8 mol% of all polybasic acid components, hexahydrophthalic anhydride. Of 40
Charge 0 parts, 44.6 parts of trimethylolpropane, 50 parts of ethylene glycol and 390.2 parts of neopentyl glycol corresponding to 76.7 mol% of all alcohol components, and gradually increase to 230 ° C over 5 hours under a nitrogen atmosphere. Warm up and keep at the same temperature until the acid value becomes 10, OHV is 111,
Moreover, an oil-free alkyd resin having a ▲ ▼ of 1,010 was obtained.

Then, the resin is cooled to 100 ° C or below,
50 parts was added to obtain a solution of oil-free Alky resin having an NV of 80%. Hereinafter, this is abbreviated as polymers (A-2).

Reference Example 3 (Same as above) 83.2 parts of adipic acid, 82 mol% of all polybasic acid components, 400 parts of hexahydrophthalic anhydride, 61.1 parts of trimethylolpropane and 90 mol% of all alcohol components, neo An oil-free alkyd resin was obtained by reacting until the acid value reached 10 as in Reference Example 2, except that 423 parts of pentyl glycol was charged.

The resin is then cooled to 100 ° C or below and
Add 50 parts and 0.1 part of dibutyltin dilaurate to 65
100 parts of hexamethylene diisocyanate was gradually added dropwise over 2 hours while raising the temperature to ℃ and keeping the same temperature, paying attention to the heat generation, and at the same temperature for 2 hours after the addition was completed.
The temperature was further raised to 80 ° C. and kept for 1 hour to obtain a solution of a partially urethanized oil-free alkyd resin having an NV of 80%. Hereinafter, this is abbreviated as a polymer (A-3). The OHV of the solid component of this is 118, and ▲ ▼ is
It was 1,070.

Reference Example 4 (Same as above) 157.4 parts of adipic acid, 64.4 mol% of all polybasic acid components, 300 parts of hexahydrophthalic anhydride, 203.8 parts of trimethylolpropane, 59 mol% of all alcohol components Neo An 80% solution of the alkyd resin was obtained by reacting until the acid value reached 10 in the same manner as in Reference Example 2 except that 230 parts of pentyl glycol and 200 parts of coconut oil fatty acid were charged. Hereinafter, this is abbreviated as polymers (A-4), but the OHV of the solid component of this is 125,
And ▲ ▼ was 1,140.

Reference Example 5 (same as above) A reactor similar to that of Reference Example 1 was charged with 134 parts (1 mol) of trimethylolpropane, 684 parts (6 mol) of ε-caprolactone and 0.04 part of tetrabutyl titanate, and 180 ° C. The temperature was raised to 10 ° C. and kept at the same temperature for 10 hours to obtain a lactone-added polyester resin. Hereinafter, this is abbreviated as a polymer (A-5), but this has a NV of 100%,
Gardner viscosity is X, OHV is 206, and ▲ ▼
Was 820.

Reference Example 6 (same as above) Instead of xylene and n-butyl acetate, "LAWS"
(Netherlands Ciel product) NV was 60%, GC was the same as in Reference Example 1 except that 320 parts were used.
Was obtained, and a solution of a hydroxyl group-containing vinyl polymer (A) having a Cardner viscosity of F was obtained. Hereinafter, this will be abbreviated as polymers (A-6), but the OHV of the solid content of this polymer was 109, and ▲ ▼ was 3,100.

Reference Example 7 [Preparation Example of Fine Particle Polymers (C)] In the same reactor as in Reference Example 1, "ISOPAR E" (aliphatic hydrocarbon mixture manufactured by Exxon Co., USA; bp = 115 to 142) was used.
C.] and 67.5 parts of n-butanol are charged and heated to 110.degree. C. under a nitrogen atmosphere, and then 465 parts of 2-ethylhexyl acrylate, 10 parts of .beta.-hydroxypropyl acrylate and .gamma.-methacryloyl at the same temperature. 25 parts of oxypropyltrimethoxysilane, 5 parts of tert-butylperoxyoctoate, 2.5 parts of tert-butylperoxybenzoate and 100 parts of "Isopar E"
It is a polymer solution in which the mixture consisting of 1 part and 4 parts is added dropwise over 4 hours, and the temperature is kept at the same temperature for 10 hours after completion of the addition, NV is 60%, GC is 1 or less, and Cardner viscosity is A _1. A dispersion stabilizer was obtained. Hereinafter, this is abbreviated as a dispersion stabilizer (1).

Separately, 166.7 parts of this dispersion stabilizer (1) and 400 parts of "Isopar E" were charged in the same reactor as in Reference Example 1, heated to 90 ° C under a nitrogen atmosphere, and kept at the same temperature. , 360 parts of methyl methacrylate, 360 parts of ethyl acrylate, 153 parts of β-hydroxyethyl acrylate
Part, 9 parts of glycidyl methacrylate, 18 parts of acrylic acid
Part, 3 parts of tetrabutyl titanate, 1 part of 2-methylimidazole, 200 parts of "Isopar E" and tert-
A mixture consisting of 13.5 parts of butyl peroxy octoate was added dropwise over 4 hours, and after completion of the reaction, the mixture was reacted at the same temperature for 10 hours to obtain a white dispersion liquid of the target fine particle polymers having an NV of 60%. It was Hereinafter, this is abbreviated as polymers (C-1), but the gurner viscosity of this product was A ₃ .

Reference Example 8 (same as above) 166.7 parts of the dispersion stabilizer (1) obtained in Reference Example 7 and 400 of "Isopar E" were placed in the same reactor as in Reference Example 1.
Parts, and heated to 90 ° C under a nitrogen atmosphere, then while maintaining the same temperature, 360 parts of methyl methacrylate, 360 parts of ethyl acrylate, 162 parts of β-hydroxyethyl acrylate, 3 parts of tetrabutyl titanate. ,
A mixture consisting of 200 parts of "Isopar E" and 13.5 parts of tert-butylperoxyoctoate was added dropwise over 4 hours, and after completion of the reaction, the reaction was carried out at the same temperature for 10 hours.
A white dispersion liquid of the target fine particle polymers having a content of 60% was obtained. Hereinafter, this is abbreviated as a polymer (C-2), but its Gardner viscosity was A ₄ .

Examples 1 to 14 As the component (A), the hydroxyl group-containing polymers (A-1) to (A-6) of Reference Examples 1 to 6 are used, and as the component (B), "Sumimar M-100C" [Sumitomo Chemical Industries, Ltd. Hexamethoxymethyl melamine; NV = 100%] and "Vernotk D-55"
0 ”[Yellow-free type manufactured by Dainippon Ink and Chemicals, Inc.
Blocked polyisocyanate resin; NV = 55%], and using the fine particle polymers (C-1) and (C-2) of Reference Examples 7 and 8 as the component (C), if necessary, The pigment and / or the curing catalyst were mixed and made into a coating material in the mixing ratio as shown in Table 1, and as the component (D), only in the case of Example 9, "Isopar E" / ethyl acetate / cellosolve acetate / n- Butanol = 60/10/10
/ 20 (weight ratio) mixed solvent, in the case of each of the other examples, "Solovesso 100" [aromatic hydrocarbon mixture manufactured by Exxon Corporation] / n-butanol / cellosolve acetate = 60/20 / A spray solution was prepared by adjusting the spray viscosity with a diluted thinner of 20 (weight ratio) as a mixed solvent.

Next, each coating solution is applied to a 0.8 mm thick mild steel plate so that the dry film thickness is about 35 μm, and set for 30 minutes, after which "Sumimar M-100C" is used as the component (B). It was baked at 140 ° C. for 30 minutes, and when “Bernock D-550” was used, it was baked at 160 ° C. for 20 minutes.

With respect to each cured coating film thus obtained, the performance evaluation was performed by observing the finished state of the coated surface such as "repellency".

 The results are summarized in the same table.

Comparative Examples 1 to 8 A coating material was formed, coated and set in the same manner as in Examples 1, 8, 9, 10, 11, 12, 13 and 14 except that the addition of the component (C) was completely omitted. Table 1 shows the results of baking and obtaining each cured coating film, and then performing the performance evaluation of the cured coating film.

As is clear from the results shown in Table 1, the high solid content coating composition of the present invention has the advantage that the coating operation can be carried out while maintaining the high solid content, and moreover, it can be obtained using the composition of the present invention. It is known that the cured coating film obtained also has the advantage that it has a beautiful appearance without "repelling".

 ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-56-161473 (JP, A) JP-A-56-50968 (JP, A) JP-A-52-139141 (JP, A) JP-A-55- 45798 (JP, A) JP 51-126287 (JP, A) JP 56-16516 (JP, A) JP 58-132016 (JP, A)

Claims (9)

(57) [Claims] 1. 90 to 30 parts by weight of a hydroxyl group-containing polymer (A), 10 to 70 parts by weight of an aminoplast or a blocked or unblocked polyisocyanate (B), and (A) and With respect to 100 parts by weight of the total of both components (B), 0.1 to 100 parts by weight of (1) polybutadiene-based unsaturated bond-containing polymers,
A graft copolymer obtained by polymerizing a core monomer or a core monomer and (meth) acrylic acid, and an addition reaction of an unsaturated bond-containing epoxy compound to a carboxyl group in the graft copolymer. Terminally unsaturated bond-containing graft copolymer obtained at most; (2) Alkyl etherified melamine resin etherified with alkyl alcohol having 4 to 12 carbon atoms; (3) Alkyd resin; (4) Hydroxyl group-containing saturated fatty acid The carboxyl group at the terminal position of the self-condensed polyester of, the terminal unsaturated bond-containing graft copolymer obtained by addition-reacting the unsaturated bond-containing epoxy compound is further polymerized with a core monomer, or a core monomer and ( Graft copolymer obtained by polymerizing (meth) acrylic acid; (5) Carbon number of 4 or more A terminal obtained by adding an unsaturated bond-containing epoxy compound to the carboxyl group in the copolymer obtained by polymerizing a vinyl-based monomer containing (meth) acrylic acid ester of alkyl alcohol as a main component. An unsaturated bond-containing graft copolymer, and a graft copolymer obtained by further polymerizing a nuclear monomer on the terminal unsaturated bond-containing graft copolymer; and (6) an alkyl alcohol having 4 or more carbon atoms. Hydrolyzable silyl group-containing copolymer obtained by polymerizing a vinyl-based monomer containing (meth) acrylic acid ester as a main component and a hydrolyzable silyl group-containing monomer, and the hydrolyzable silyl group-containing copolymer By polymerizing a monomer having a functional group capable of reacting with the hydrolyzable silyl group and a core monomer in the polymer, A segment soluble in an aliphatic or alicyclic hydrocarbon solvent, which is obtained by using at least one dispersion stabilizer selected from the group consisting of unsaturated bond-containing graft copolymers, and an insoluble segment And a non-aqueous dispersion type fine particle polymer (C) having both
A high solid content coating composition comprising 55% by weight or more of the solvent (D) as an essential component. 2. The hydroxyl group-containing polymer (A) is 50
The composition according to claim 1, which is a vinyl resin having a number average molecular weight of 0 to 8,000 and a hydroxyl value of 40 to 250. 3. The hydroxyl group-containing polymer (A) is 20
Claim 1 having at least one selected from the group consisting of alkyd resins, oil-free alkyd resins and urethane resins having a number average molecular weight of 0 to 3,000 and 40 to 600. The composition according to. 4. The hydroxyl group-containing polymer (A) is one or more polybasic acid components of hexahydrophthalic acid, methylhexahydrophthalic acid, hexahydroterephthalic acid or their reactive derivatives. Is an alkyd resin, oil-free alkyd resin and / or urethane resin containing at least 50 mol% of all acid components,
The composition according to claim 1. 5. The hydroxyl group-containing polymer (A) is 50
It has a number average molecular weight of 0 to 8,000 and a value of 250
At least one resin selected from the group consisting of alkyd resins, oil-free alkyd resins and urethane resins having a number average molecular weight of 200 to 3,000 and 40 to 600 and having a hydroxyl value of A composition according to claim 1 which is a mixture with. 6. The above aminoplast has a carbon number of 1 to
The composition according to claim 1, which is an aminoaldehyde resin etherified with an alcohol of 4. 7. The non-aqueous dispersion type fine particle polymer (C) as described above.
As an aliphatic or alicyclic hydrocarbon solvent-soluble segment and an insoluble segment, in each of the above-mentioned, respectively, aminoplast, or a blocked or unblocked polyisocyanate (B The composition according to claim 1, which has a hydroxyl group capable of reacting with (1). 8. The non-aqueous dispersion type fine particle polymer (C) as described above.
Is formed by a reaction between a hydrolyzable silyl group and a functional group capable of reacting with the silyl group, as a bond between an insoluble segment and a segment soluble in an aliphatic or alicyclic hydrocarbon solvent. The composition of claim 1 having a bond that is 9. The non-aqueous dispersion type fine particle polymers (C) as described above.
The composition according to claim 1, wherein is a segment insoluble in an aliphatic or alicyclic hydrocarbon-based solvent and has an intramolecular crosslinked structure in the segment.