JP2822478B2 - Resin composition for paint - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel and useful coating resin composition. More specifically, a vinyl copolymer having a lactone adduct of an esterified product of an α, β-ethylenically unsaturated carboxylic acid and a natural or synthetic fatty acid glycidyl ester as a specific monomer component, a polyisocyanate, and a specific organic compound Comprising solvent and essential components of the vehicle, among others, dryness, hardness, sharpness, fleshyness, recoatability,
And solubility-particularly excellent in solubility in a non-polar organic solvent or a mixed solvent thereof with a polar solvent, and
Depending on the type and composition of the solvent used, it does not adversely affect existing coatings or old coatings or materials with poor solvent resistance, and is used for automobile repairs, automotive parts, motorcycles, building exteriors, and roofs The present invention relates to a resin composition for a high-elongation paint suitable for woodworking, general metal use and the like.

[Conventional technology]

Acrylic urethane paint itself has excellent coating performance in general, so far,
Painting or repair painting on metal parts and plastics parts such as motorcycles, buses, trucks, railway cars or home appliances, as well as industrial machinery, buildings, structures, plants, woodworking products, plastic products or steel furniture. It is often used in the form.

However, in the case of the conventional acrylic urethane paint, when the paint is re-painted entirely or partially from the place where the drying property is poor, for example, a metallic paint or an enamel paint is applied on the first coat, and then on the second coat. In the case of a so-called two-coat finish, such as when applying a clear paint, the first coat of aluminum particles or enamel layer is mixed into the second coat (so-called return unevenness occurs),
In order to obtain a desired finish due to lifting or the like, it was necessary to bake and dry once, or to slowly apply the second coat over a long period of time.

In addition, even if it is forcibly dried, if you want to repaint it, it is necessary to dry it for more than one night, and even if it is in a primer surfacer or sanding sealer, after painting and curing, There is also a keen need for the appearance of a paint that requires a long time before entering the polishing process, from the point where sanding itself cannot be performed, to the point of time when the sanding becomes possible.

By the way, in order to solve these various disadvantages, it is necessary to use a curing accelerator such as dibutyltin dilaurate, or to add a large amount of nitrocellulose, cellulose acetate butyrate or vinyl chloride-vinyl acetate copolymer. Although well-known, the use of a curing accelerator, first of all, has the disadvantage that the pot life is shortened, and the weather resistance and gloss are likely to deteriorate, and then nitrocellulose is used. In paints added in large amounts, yellowing and cracking are likely to occur during outdoor exposure, and even in paints added in a large amount of cellulose acetate butyrate, gloss, painted skin, and water resistance are likely to deteriorate There was a disadvantage.

In addition, in the field of architectural exteriors, first coat the first coat on the undercoat layer using an acrylic emulsion or the like, which has poor solvent resistance, and then repeat the second coat, When coated, there is a drawback that this first coat inevitably causes lifting, but in addition to this fact, JIS A-691
At present, a product which can completely satisfy the performance of high elongation at room temperature and −10 ° C. required at 0 has not yet been put on the market.

[Problems to be solved by the invention]

However, the present inventors, in view of the existence of various drawbacks in the prior art as described above, hardens quickly in room temperature drying or forced drying, and therefore does not require a long drying time, and immediately repaints. In the case of a two-coat finish, no uneven return of the aluminum particles and enamel layer of the first coat occurs, and depending on the solvent composition used, the old paint film and solvent resistance It does not attack weak coating materials and has excellent solubility in non-polar solvents, hardness, texture, sharpness, weather resistance, water resistance, gasoline resistance, chemical resistance, extensibility, etc. For repair, building exterior, woodworking, plastics, automobiles and motorcycles, etc. When a specific vinyl copolymer containing an lactone adduct of an esterified product of a β-ethylenically unsaturated carboxylic acid and a natural or synthetic fatty acid glycidyl ester as an essential component is combined with a polyisocyanate, and a specific non-polar organic solvent or When also using a mixed solvent having a specific ratio of this and a polar solvent, it is possible to achieve all of the above-mentioned objects, in other words, to find a useful coating resin composition that meets the above-mentioned objects brilliantly. The present invention has been completed.

[Means for solving the problem]

That is, in the present invention, α, β-ethylenically unsaturated carboxylic acid and natural or synthetic fatty acid glycidyl ester [hereinafter referred to as (synthetic) fatty acid glycidyl ester are abbreviated as essential components. And a specific vinyl copolymer (A) obtained by using the lactone adduct (a-1) of the esterified product as one of the essential monomer components, specifically, such an α, β-ethylenically unsaturated monomer The lactone adduct (a-1) of an esterified product of a carboxylic acid and a (synthetic) fatty acid glycidyl ester, the vinyl monomer (a-2) in which the alkyl group in the side chain has 3 to 18 carbon atoms, and the above ( vinyl copolymer (A) obtained by copolymerizing each of the components a-1) and (a-2) with another copolymerizable vinyl monomer (a-5) in the presence of a radical generator And a polyisocyanate (B) and a non-polar organic solvent, preferably an organic solvent (C) containing a non-polar organic solvent having an aniline point or a mixed aniline point of 7 to 70 ° C. as an essential component. Highly extensible, comprising as an ingredient It is intended to provide a postal resin composition.

More specifically, the present invention provides 5-95% by weight of the lactone adduct (a-1), 1-90% by weight of the vinyl monomer (a-2), and a hydroxyl group-containing vinyl monomer (a-3). ), 0 to 80% by weight of the copolymerizable unsaturated bond-containing resin (a-4), and (a-1), (a-2), and (a-3) above. And / or 1 to 94% by weight of another vinyl monomer (a-5) copolymerizable with each component (a-4) so that the total amount becomes 100% by weight, and the presence of a radical generator is selected. A vinyl copolymer (A) having a number average molecular weight of 3,000 to 30,000 and a weight average molecular weight / number average molecular weight ratio of 1.8 to 25 obtained by copolymerization, and a polyisocyanate. (B) and an aniline point or a mixed aniline point of 7
The vinyl copolymer (A) component, as an essential component, a nonpolar organic solvent at a temperature of ~ 70 ° C and an organic solvent (C) having a weight ratio of the polar organic solvent of 100/0 to 80/20; The equivalent ratio of OH / NCO to the polyisocyanate (B) component is 1 / 0.2 to 1
/1.8 containing, to provide a resin composition for coatings having excellent solubility in the organic solvent, drying properties, hardness, sharpening properties, solid feeling, recoatability and extensibility. Things.

Here, the lactone adduct of an esterified product of an α, β-ethylenically unsaturated carboxylic acid and a (synthetic) fatty acid glycidyl ester, which is used as the component (a-1), is itself a vinyl copolymer obtained. It acts as a crosslinking point in (A), and has effects on solubility—in particular, solubility in a nonpolar organic solvent, compatibility with the polyisocyanate (B) and the like, and pigment dispersibility and extensibility. 5% by weight
If less than the function as a sufficient cross-linking point, especially, it is difficult to achieve both effects such as solubility and extensibility in non-polar organic solvents, and if it exceeds 95% by weight,
Inevitably, the number of cross-linking points becomes excessive, the strain stress at the time of curing becomes large, and instead, the adhesive strength is reduced, and the hardness, the solvent resistance, the stain resistance and the like become conspicuous. The use amount of the component (a-1) is appropriately in the range of 5 to 95% by weight, preferably 10 to 85% by weight.

First, typical examples of such α, β-ethylenically unsaturated carboxylic acids include unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. Α, β-ethylenically unsaturated carboxylic acids such as monoesters of these dicarboxylic acids and monohydric alcohols; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl Fumarate, mono-2-hydroxyethyl-mo Α, β-unsaturated carboxylic acid hydroxyesters such as nobutyl fumarate or polyethylene glycol mono (meth) acrylate and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid,
Benzenetetracarboxylic acid, "Hymic acid" (manufactured by Hitachi Chemical Co., Ltd.), and adducts of polycarboxylic acids such as tetrachlorophthalic acid or dodecinylsuccinic acid with anhydrides.

On the other hand, as typical examples of the (synthetic) fatty acid glycidyl ester to be esterified with these α, β-ethylenically unsaturated carboxylic acids, first, a general formula A saturated fatty acid such as capric acid, lauric acid, myristic acid, palmitic acid or stearic acid which is 4 or more among the saturated fatty acids represented by the formula: Represented by lindenic acid, oleic acid, elaidic acid,
So-called linole having two double bonds, such as oleic unsaturated fatty acids having only one double bond, such as erucic acid or whale oil acid, and linoleic acid, also called "dry oil fatty acids" Acid-type unsaturated fatty acid; general formula A so-called linolenic acid type unsaturated fatty acid having three double bonds such as linolenic acid or eleostearic acid; or a so-called ricinoleic acid type or hydroxyl such as ricinoleic acid which is an oxy derivative of oleic acid. Group-containing unsaturated fatty acids; or various unsaturated fatty acids as described above, that is, various types of drying oil fatty acids as constituent units, and linseed oil, sunflower oil,
Fatty acids from a drying oil such as soybean oil or tall oil; fatty acids from a drying oil such as sesame oil, rapeseed oil, cottonseed oil or rice sugar oil; or a nondrying oil such as olive oil, coconut oil, palm kernel oil, castor oil or peanut oil Fatty acids from
Furthermore, natural fatty acids such as rosin or a hydrogenated product thereof, a hydrogenated product thereof or a disproportionated hydrogenated product thereof or a resin acid such as shellac, or “versatic acid”
(Product of Shell Co., The Netherlands), "neodecanoic acid" (product of Exxon Chemical Co., Ltd.), "isononanoic acid" (product of Hoechst, West Germany), "SA-9 or SA-13" (product of Idemitsu Petrochemical Co., Ltd.) Or various fatty acids such as secondary or tertiary acid-type synthetic branched fatty acids such as 2-ethylhexanoic acid and epichlorohydrin according to a conventional method and under appropriate conditions under dehydrochlorination or desalination. What can be obtained by making it react is mentioned.

Among these, industrially, glycidyl octylate, glycidyl coconut oil, "Kajura E" (glycidyl ester of the above "versatic acid"; Shell products), "Neototo" (Tobu Kasei Co., Ltd.) Glycidyl neodecanoate] or “SA-9G or SA-130” [Idemitsu Petrochemical Co., Ltd.
Products], as well as "KE-828" [Arakawa Chemical Co., Ltd., a disproportionated and hydrogenated rosin, that is, a product of the company's product "KR-610" glycidyl ester. As shown in [name], it can be used as it is because it is already supplied in the form of glycidyl ester, but from the viewpoint of weather resistance, the glycidyl ester is saturated (synthetic). It is desirable to use those based on fatty acids.

On the other hand, as the glycidyl ester, (half)
Those based on drying oil fatty acids can also impart air-curing properties to the composition of the present invention in the form of a drier or further using an organic peroxide.

This means not only the so-called dryer curing using a dryer or an organic peroxide, but also the dryer curing together with the so-called isocyanate curing using the polyisocyanate (B). And a complex curing method with the above. This point is part of the usefulness of the present invention.

The α, β-ethylenically unsaturated carboxylic acid and the (synthetic) fatty acid glycidyl ester listed above are:
By subjecting both components to a ring-opening esterification reaction in advance and then a lactone addition reaction, a lactone adduct (a-1) of the desired esterified product can be obtained, or (a -3) When the component is not used, α, β
-A carboxyl group of an ethylenically unsaturated carboxylic acid,
(Synthesis) A ring-opening esterification reaction between a glycidyl group of a fatty acid glycidyl ester and a ring-opening addition reaction between a generated secondary hydroxyl group and a lactone may be performed.

At that time, for the purpose of accelerating the ring-opening esterification reaction, known and commonly used tertiary amine compounds such as triethylamine, 2-methylimidazole or diazabicycloundecene, and Lewis acids such as BF ₃ ethyl etherate. A ring opening esterification catalyst may be used.

In addition, particularly preferable examples of the lactone suitable for adding to the obtained esterified product include propiolactone (β-lactone), butyrolactone (γ-lactone), δ-valerolactone (δ-lactone), There are ε-caprolactone or macrocyclic lactone, etc., which are easily available industrially, that the hydroxyl group generated by the addition reaction is a highly reactive primary hydroxyl group,
From the viewpoint that the effect of use is remarkable, ε-
The use of caprolactone, butyrolactone or valerolactone is particularly desirable.

The amount of the lactone to be added, that is, the amount of addition, is 1 to 10 moles, preferably 1 mole of the lactone with respect to 1 equivalent of the hydroxyl group in the esterified product.
A range of about 6 mol is appropriate.

If the addition amount exceeds 10 moles and becomes too large, it becomes difficult to obtain a vinyl copolymer (A) having a high hydroxyl value, and it is difficult to obtain solubility in a non-polar organic solvent, hardness and contamination resistance. It is not preferable because various properties such as properties are deteriorated.

Thus, in the lactone addition reaction, after obtaining the above-mentioned esterified product, a predetermined amount of the lactone and various catalysts such as acetylacetone zinc salt, stannous halide or tin octylate are added, The reaction may be continued at a temperature of 100 to 130 ° C.

Next, the carbon number of the alkyl group in the side chain is 3 to 18
Typical examples of the vinyl monomer (a-2) include n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) Acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, "Acryester SL" [manufactured by Mitsubishi Rayon Co., Ltd. Mixture of lauryl methacrylate and tridecyl methacrylate),
Aliphatic or alicyclic monohydric alcohols having 3 to 18 carbon atoms such as cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, adamantyl (meth) acrylate or isobornyl (meth) acrylate ) Acrylates; or di-n-propylmalate, di-n-butylmalate, diisobutylmalate, di-2-ethylhexylmalate, dilaurylmalate, mono-n-propylmono-n-butylmalate, Mono-n-butyl
Mono-2-ethylhexyl fumarate, di-n-propyl fumarate, di-n-butyl fumarate, diisobutyl fumarate, di-2-ethylhexyl fumarate, dilauryl fumarate, mono-n-propyl mono-n -Butyl fumarate, mono-n-butyl mono-2-ethylhexyl fumarate, di-n-propyl itaconate,
Di-n-butyl itaconate, diisobutyl itaconate, di-2-ethylhexyl itaconate, dilauryl itaconate, mono-n-propyl mono-n-butyl itaconate, mono-n-butyl mono-2-ethylhexyl Examples include diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with aliphatic or alicyclic monohydric alcohols having 3 to 18 carbon atoms, such as itaconate or dicyclohexylmalate.

The vinyl monomer (a-2) is also essential for making the obtained vinyl copolymer (A) soluble in a non-polar organic solvent, as in the case of the lactone adduct of an esterified product (a-1) described above. When the amount of the component is less than 1% by weight, it is insufficient to impart solubility to a non-polar organic solvent. On the other hand, when the amount exceeds 90% by weight,
In any case, the hardness, solvent resistance, stain resistance, weather resistance, and the like are inferior, and none of them is preferable. Is suitably in the range of 5 to 80% by weight.

Further, the above-mentioned hydroxyl group-containing vinyl monomer (a-3)
Representative examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono-2-hydroxyethyl-monobutyl fumarate Or polyethylene-
Or polypropylene glycol-mono (meth) acrylate, or an adduct of these various hydroxyalkyl (meth) acrylates or hydroxyalkyl fumarate with ε-caprolactone, or “Placcel FM or FA monomer” [Daicel Chemical Co., Ltd. A), which has an α, β-ethylenically unsaturated bond and a hydroxyl group, such as hydroxyvinyl ether, in addition to hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids. .

The vinyl monomer (a-3) also functions as a crosslinking point, and may be used in combination with the lactone adduct (a-1) of the esterified product, or may not be used at all.

By the way, the lactone adduct (a-
1) First, a case where it is difficult to obtain a vinyl copolymer having a high hydroxyl value because there are many compounds having a relatively large molecular weight, or by adjusting the hydroxyl value, crosslink density, etc., or modifying the crosslink structure Or letting them do, or
In the case where initial curability, that is, so-called shrinkage is required, when such shrinkage is somewhat problematic, the lactone adduct (a-1) of the vinyl monomer (a-3) and the esterified product is used. Such a problem can be satisfactorily solved by the use of the present invention, so that there is a part of the usefulness of the present invention here.

When the use amount of the monomer (a-3) exceeds 50% by weight, the number of cross-linking points becomes too large, so that the strain stress at the time of curing becomes large, and the adhesive strength is reduced,
In addition, the solubility in a non-polar organic solvent is also reduced, and the resulting solution or non-aqueous dispersion of the vinyl copolymer becomes cloudy or eventually separates, which is not preferable. Monomer (a-3)
The use amount of 0 to 50% by weight, preferably 0 to 40% by weight, and more preferably 0 to 30% by weight is appropriate.

Furthermore, the copolymerizable unsaturated bond-containing resin (a-
4) The main purpose is to improve the pigment dispersibility of the obtained vinyl copolymer (A), to increase the non-volatile content during coating, and to improve the solubility in non-polar organic solvents. The resin (a-
Typical examples of 4) include polyester resin, vinyl copolymer resin, petroleum resin, rosin ester, and polyether polyol. In the present invention, polyester resin (including oil-modified type) is used. ) And vinyl copolymer resins are desirable.
Above all, when the physical properties of the cured coating film are taken into account, the resin (a-4)
What you have in the structure of
More favorable results are obtained in terms of solvent resistance and stain resistance.

Such polyester resins and vinyl copolymer resins include, for example, JP-B-44-7134, JP-B-45-22011, JP-A-46-20502, JP-A-48-78233 or JP-A-50-58123. As disclosed in, for example, a raw material component having a copolymerizable unsaturated bond is essential, and a resin obtained by reacting with another raw material component has the copolymerizable unsaturated bond retained in a skeleton thereof. As disclosed in JP-B-49-47916 or JP-B-50-6223, first, a saturated polyester having no copolymerizable unsaturated bond is obtained, and then a saturated polyester is present in the saturated polyester. These functional groups (reactive groups) can be combined with functional groups such as hydroxyl groups or carboxyl groups, or other functional groups such as epoxy groups introduced by further reacting the saturated polyester with a diepoxy compound. Compound having both a functional group having reactivity and a vinyl group (α, β-ethylenically unsaturated group), for example, a compound having an acid chloride group and a vinyl group such as (meth) acrylic acid chloride, glycidyl ( Those having an epoxy group and a vinyl group such as (meth) acrylate, those having an alkoxysilanol group and a vinyl group such as vinylmethoxysilane and (meth) acryloxyethyltrimethoxysilane,
Those having an acid anhydride group such as maleic anhydride and tetrahydrophthalic anhydride and a vinyl group, those having a carboxyl group and a vinyl group such as fumaric acid and (meth) acrylic acid,
2-hydroxypropyl (meth) acrylate to hexamethylene diisocyanate equimolar adduct, isocyanate ethyl methacrylate and other vinyl monomers having an isocyanate group and a vinyl group, etc. A copolymer having a bond and a vinyl monomer having a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group is copolymerized as an essential component in advance. Similar to the introduction of a copolymerizable unsaturated bond into a polyester, a compound having a vinyl group and a functional group having reactivity with a functional group contained in a vinyl copolymer resin, for example, (meth) acrylic acid Those having an acid chloride group such as chloride and a vinyl group, Those having an epoxy group and a vinyl group, such as Le (meth) acrylate, those having vinyl silane, an alkoxy silanol group and a vinyl group such as (meth) acryloxyethyl trimethoxysilane,
Those having an acid anhydride group such as maleic anhydride or tetrahydrophthalic anhydride and a vinyl group, those having a carboxyl group such as fumaric acid or (meth) acrylic acid and a vinyl group,
2-hydroxypropyl (meth) acrylate-hexamethylene diisocyanate and the like, and a hydroxyl group obtained by adding a vinyl monomer such as isocyanate ethyl methacrylate and the like having a vinyl group to an isocyanate ethyl methacrylate and a vinyl group are copolymerizable. Those having an unsaturated bond are suitable.

Such polyester resins include saturated fatty acids such as octylic acid, lauric acid, stearic acid or "versatic acid"; oleic acid, linoleic acid, linoleic acid,
Unsaturated fatty acids such as eleostearic acid or ricinoleic acid; "Pamoline 200 or 300" (a synthetic dry oil fatty acid manufactured by Hercules Inc. of the United States), Chinese nagiri oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), (Semi) drying oils (fatty acids) such as tall oil (fatty acids) or cottonseed oil (fatty acids) soybean oil (fatty acids), olive oil (fatty acids), safflower oil (fatty acids), castor oil (fatty acids) or rice sugar oil (fatty acids); Ethylene with or without using one or a mixture of two or more oils selected from oils or fatty acids, such as non-drying oils (fatty acids) such as hydrogenated coconut oil fatty acids, coconut oil fatty acids or palm oil fatty acids. Glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6 Hexanediol, 1,2,6-hexanetriol Torr, and one or more polyhydric alcohols such as pentaerythritol or sorbitol, benzoic acid, p-tert-butylbenzoic acid,
(Anhydride) phthalic acid, hexahydro (anhydride) phthalic acid, tetrahydro (anhydride) phthalic acid, tetrachloro (anhydride) phthalic acid, hexachloro (anhydride) phthalic acid, tetrabromo (anhydride) phthalic acid, trimellitic acid, "Hymic acid"
[Products of Hitachi Chemical Co., Ltd.], one or more carboxylic acids such as (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydride) itaconic acid, adipic acid, sebacic acid or oxalic acid And “Toresilon SH-6018” (manufactured by Toray Silicone Co., Ltd.), “X-22-160AS, KR-212 or 21” as necessary.
3 "(a product of Shin-Etsu Chemical Co., Ltd.), a reactive silicone resin, a monoepoxy compound such as a glycidyl ester of a (synthetic) fatty acid such as the above-mentioned" Kajura E ",
Polyepoxy compounds such as "Epiclon 200 or 400" and "Epicoat 828 or 1001", or diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-methylenebis (cyclohexyl isocyanate), and diisocyanates thereof (Co) of polyisocyanates or diisocyanates obtained by the addition reaction of
It is appropriate to use one or more polyisocyanates having an isocyanuric ring obtained by polymerization, which are obtained by reacting the polyhydric alcohol or carboxylic acid by a conventional method by partially substituting the polyhydric alcohol or carboxylic acid.

Further, as the above-mentioned copolymerizable unsaturated bond-containing vinyl copolymer, a monomer is appropriately selected from vinyl monomers described above or as described later, and copolymerized by a usual method with a desired monomer composition. What is obtained by performing the above is appropriate.

The polyester resin and the vinyl copolymer resin may be used alone or in combination, or one or more of them may be used in combination. These compounds are used in the range of 0 to 80% by weight. When the amount exceeds 80% by weight, the viscosity of the resulting solution or non-aqueous dispersion of the vinyl copolymer (A) increases, It is not preferable because it is liable to be gelled or the weather resistance or the like tends to decrease.

Furthermore, the component of the vinyl monomer (a-5) used in the present invention is other vinyl copolymerizable with the components of (a-1) to (a-4) listed above. Monomer, and typical examples of the vinyl monomer (a-5) include aromatic vinyl monomers such as styrene, α-methylstyrene, p-tert-butylstyrene, and vinyltoluene; A) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate, and alkoxyalkyl (meth) methoxyethyl (meth) acrylate or ethoxyethyl (meth) acrylate (Meth) acrylates such as acrylates; supra Such vinyl monomer (a-2)
Diesters of unsaturated dicarboxylic acids and monohydric alcohols, excluding vinyl acetate; vinyl esters such as vinyl acetate, vinyl benzoate or "Vova" (vinyl ester manufactured by Ciel); "Viscoat 8F, 8FM, 17FM, 3F or 3FM "[fluorinated acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, di-
(Per) fluoroalkyl group-containing vinyl esters, vinyl ethers, (meth) acrylates or unsaturated polycarboxylic acid esters such as perfluorocyclohexyl fumarate or N-isopropyl perfluorooctanesulfonamidoethyl (meth) acrylate A fluorine-containing polymerizable compound; or (meth)
Non-functional vinyl monomers such as olefins such as acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride. Other usable materials include (meth) acrylamide, dimethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide, dimethylaminopropylacrylamide and alkoxylated N-
Vinyl monomers containing an amide bond such as methylolated (meth) acrylamides; dialkyl [(meth) acryloyloxyalkyl] phosphates, (meth) acryloyloxyalkyl acid phosphates, dialkyl [(meth) acryloyloxyalkyl] phosphites Or (meth) acryloyloxyalkyl acid phosphites, and the like. Further, the above (meth) acryloyloxyalkyl acid phosphates, or alkylene oxide adducts of acid phosphites, glycidyl (meth) aurylate and methyl glycidyl An ester compound of an epoxy group-containing vinyl monomer such as (meth) acrylate and phosphoric acid or phosphorous acid or an acid ester thereof, or 3-chloro-
Phosphorus-containing vinyl monomers such as 2-acidphosphoxypropyl (meth) acrylate; dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate; (meth) acrylic acid; Unsaturated mono- or dicarboxylic acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, and α, β-ethylenically unsaturated carboxylic acids which are monoesters of these dicarboxylic acids and monohydric alcohols Or hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids as described above, and maleic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid "Himic acid", the adduct comprising various carboxyl group-containing vinyl monomers and anhydrides of such polycarboxylic acids tetrachlorophthalic acid or dodecinyl succinic acid.

Here, the various carboxyl group-containing vinyl monomers as described above often exhibit an internal catalytic action when the polyisocyanate (B) component described below is blended, and often impair the storage stability of the paint. Therefore, when these monomers are used, the use of the carboxyl group-containing vinyl monomers should be considered in consideration of effects such as improvement in adhesion and compatibility with other resins. It is desirable to keep the amount within a range of 0 to 10% by weight, preferably 0.2 to 5% by weight.

Further, as described above, amide bond-containing vinyl monomers, phosphorus atom-containing vinyl monomers, dialkylaminoalkyl (meth) acrylates, and the like are all vinyl copolymers similarly to the above-mentioned carboxyl group-containing vinyl monomers. To give the internal catalytic ability to the coalescence,
Adhesion to the material, compatibility with other resins, or used to improve the pigment dispersibility, etc., these various vinyl monomers may be used alone or in combination of two or more, and, From the viewpoint of the effect of each use, the amount of each of these various vinyl monomers is preferably 0.05 to 5% by weight in the case of phosphorus atom-containing vinyl monomers, and then the amide bond-containing vinyl monomers and dialkyl. In the case of aminoalkyl (meth) acrylates, a range of 0.05 to 10% by weight is appropriate.

Further, as the vinyl monomer (a-5), glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate or (meth) allyl glycidyl ether, or α, β-ethylenically unsaturated carboxylic acids or Various unsaturated carboxylic acids such as mono-2- (meth) acryloyloxymonoethyl phthalate, such as an equimolar adduct of a hydroxyl group-containing vinyl monomer with the above-mentioned polycarboxylic acid anhydride, can be added to “Epiclone 200,400,44”.
1,850 or 1050 "(epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.)," Epicoat 828,1001 or 100
4 "(epoxy resin manufactured by Ciel)," Araldite 6
071 or 6084 "(epoxy resin manufactured by Ciba Geigy, Switzerland)," Chissonox 221 "(Chisso Corporation)
Addition reaction of various polyepoxy compounds having at least two epoxy groups in one molecule, such as an epoxy compound manufactured by Epson Corporation or "Denacol EX-611" (an epoxy compound manufactured by Nagase Sangyo Co., Ltd.) at an equimolar ratio. Epoxy group-containing polymerizable compound obtained by or vinyl ethoxysilane, α-methacryloxypropyl trimethoxysilane,
Trimethylsiloxyethyl (meth) acrylate or "KR
-215 or X-22-5002] [Shin-Etsu Chemical Co., Ltd. product]
And other silicon-based monomers.

Furthermore, for the purpose of further improving the weather resistance, for example, a polymerizable ultraviolet absorber or light stabilizer such as "T-37 or LA-82" (manufactured by Adeka Argus Chemical Co., Ltd.) may be copolymerized. it can.

The vinyl monomer (a-5) is as described above (a-
1) to (a-4), such as balance and copolymerizability with various components, solubility, dilutability, compatibility, coating workability, and gloss, hardness, flexibility, weatherability, From the viewpoints of solvent resistance, stain resistance, pot life, and the like, the combination of each raw material component and the amount of use thereof may be determined within a range of 1 to 94% by weight.

Especially when aromatic vinyl monomers such as styrene and vinyltoluene are required to have weather resistance or yellowing resistance, their usage should be reduced to 40% by weight or less, especially 35% by weight or less. It is desirable to put.

In addition, in the case of a silicon-based monomer such as vinylethoxysilane having a hydrolyzable alkoxy group, gelling may occur if used in an excessively large amount. It is preferable to keep the content to 10% by weight or less, especially 5% by weight or less.

Using the various raw material components listed above, that is, the lactone adduct of the esterified product (a-1), the vinyl monomer (a-2) and the vinyl monomer (a-5)
And the vinyl monomer (a-
In order to prepare the vinyl copolymer (A) using the resin 3) and / or the resin (a-4), the vinyl copolymer (A) can be prepared by using a known and common copolymerization reaction method or a graft copolymerization reaction method. And the resulting vinyl copolymer (A)
May be either a uniform solvent system or a non-aqueous dispersion system.

At that time, azobisisobutyronitrile, benzoyl peroxide, tert-butylperoxybenzoate,
One or more known and commonly used radical generators such as tert-butyl hydroperoxide, di-tert-butyl peroxide or cumene hydroperoxide can be used in conventional amounts.

As the organic solvent (C) used in the present invention, a non-polar organic solvent having an aniline point or a mixed allinine point in the range of 7 to 70 ° C., preferably 8 to 65 ° C. is preferable. , "Solvetso 100" (mixed aniline point 13.5
° C: Exxon Chemical Products), “Solvetso 150” (mixed aniline point 16 ° C: same), “Swazol 100” (mixed aniline point 24.6 ° C; product of Maruzen Petrochemical Co., Ltd.), “Swazol 200” (mixed aniline point 29.4) ° C: the same), “Swazol 310” (mixed aniline point 43.6 ° C: the same), “Swazol 1000” (mixed aniline point 12.7 ° C: the same), “Swazol 1500” (the mixed aniline point 16.5 ° C: the same), “Essonafusa No. .3 ”(aniline point 58 ° C: Exxon Chemical)
"Essonaphtha No.5" (aniline point 55 ° C: same) "Essonaphtha No.6" (aniline point 43 ° C: same), "HAWS (house)" (aniline point 15 ° C: Ciel Chemical), "LAWS
(Loose) ”(aniline point 44 ° C: same),“ Pegasol AR ”
O-80 "(mixed aniline point 25 ° C; Mobil Petroleum Products),
"Pegasol R-100" (mixed aniline point 14 ° C: same),
"Pegasol R-150" (mixed aniline point 16 ° C: same),
“Pegasol 1725N” (aniline point 56 ° C: same), “Pegasol 3040” (aniline point 56 ° C: same), “Pegasol AN-45” (aniline point 44 ° C: same) or “Pegasol 1725” (aniline point 56 ° C) : A mixture of various hydrocarbons such as the above); or methylcyclohexane (aniline point
Non-polar, relatively weak dissolving power such as various single compounds such as 40 ° C), ethylcyclohexane (aniline point 44 ° C), toluene (mixed aniline point 8.8 ° C) or xylene (mixed aniline point 10.8 ° C). Examples thereof include aromatic hydrocarbons, aliphatic hydrocarbons, naphthenic hydrocarbons or alicyclic hydrocarbons, and mixtures of these various hydrocarbons.

These may be used alone or in combination of two or more.

In the present invention, the non-polar organic solvent and the polar organic solvent can be used in combination. Representative examples of such a polar organic solvent include ethyl acetate, butyl acetate, isobutyl acetate, cellosolve acetate, and propylene glycol methyl. Does not have a functional group that reacts with isocyanate groups such as ester solvents or ether ester solvents such as ether acetate and 3-methoxybutyl acetate, or ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Use of things is desirable.

The mixing ratio of the non-polar organic solvent and the polar organic solvent,
Depending on the degree of performance required for paint such as drying properties, coating workability, strength of solvent resistance of the material to be coated, finished appearance, coating viscosity or application, etc., non-polar organic solvents / polarity in the final paint system Organic solvent = 100/0-80/20
(Weight ratio) within the range. As the solvent system in this case, a solution or a non-aqueous dispersion of a vinyl copolymer prepared only with a non-polar organic solvent, as a dilution thinner, may be further diluted with a non-polar organic solvent to form a coating. Then, the mixture may be diluted with a polar organic solvent to form a coating so as to fall within the above-mentioned mixing ratio. Or,
Conversely, using a non-polar organic solvent as a diluting thinner so as to have the above-mentioned mixing ratio in a solution or a non-aqueous dispersion of a vinyl copolymer prepared only with a polar organic solvent, it may be diluted, and may be made into a paint. A solution of a vinyl copolymer or a non-aqueous dispersion prepared in a combined system of a non-polar organic solvent and a polar organic solvent is mixed with a non-polar organic solvent and / or a polar organic solvent such that the mixing ratio described above is achieved. It may be diluted or made into a paint.

When the number average molecular weight (▲) of the vinyl copolymer (A) thus obtained is less than 3,000, the coating properties such as weather resistance, drying property, hardness, or solvent resistance are poor, and when it exceeds 30,000, it is as described above. Although the coating film properties as described above are good, the solubility in a non-polar solvent, the feeling of holding the body, the finished appearance, the leveling property, etc. are unfavorably deteriorated. Therefore ▲
▼ = 3,000 to 30,000, preferably about 5,000 to 20,000. On the other hand, the weight average molecular weight (▲
If the ratio of ▼) / number average molecular weight (▲ ▼) is less than 1.8, the weather resistance, drying property, solvent resistance, flexibility or pigment dispersibility will be poor, and if it exceeds 25, the pigment dispersibility will be good. However, it is not preferable because problems such as coating workability, dilutability, non-volatile content during coating, and pot life are likely to occur. Therefore, the range of ▼ / ▲ is 1.8 to 25, and the range of 3 to 20 is appropriate if it is desired to further improve the pigment dispersibility.

In the present invention, the polyisocyanate (B) used as a curing agent includes: aromatic diisocyanates such as tolylene diisocyanate or diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexane diisocyanate; or isophorone diisocyanate; Methylcyclohexane-2,4 (or 2,
6) -Diisocyanates, alicyclic diisocyanates such as 4,4'-methylenebis (cyclohexylisocyanate) or 1,3- (isocyanatomethyl) cyclohexane; or these diisocyanates and ethylene glycol, polyether polyols (polyethylene glycol, polypropylene glycol) Or polycaprolactone polyol), polyhydric alcohols such as trimethylolethane or trimethylolpropane,
Low molecular weight polyester resins (including oil-modified types) having a functional group that reacts with isocyanate groups, acrylic copolymers, adducts with water, etc., or burettes; copolymers (oligomers) of diisocyanates A copolymer containing a vinyl monomer having both isocyanate groups such as 2-hydroxypropyl (meth) acrylate and hexamethylene diisocyanate or a copolymerizable unsaturated bond as an essential component; "Duranate TPA [Asahi Chemical Industry Co., Ltd. nonpolar solvent-soluble polyisocyanate]; or C ₂ -C ₈ comprising alkylene, such as disclosed in JP-a-61-72013, JP-cycloalkylene and / or aralkylene diisocyanates and the C ₁₀ -C ₄₀ becomes diol Non-polar organic solvent-soluble polyisocyanate having an isocyanurate rate ring obtained by reacting in the presence of an isocyanurate-forming catalyst; and as commercially available products, "Burnock DN-990,991 or 99
2 "[Non-polar solvent-soluble polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.] or" Duranate TPA "
And the like, but a large amount of the nonpolar organic solvent is used,
In a so-called weak solvent type coating system, more preferable results can be obtained by using a polyisocyanate soluble in a non-polar organic solvent as disclosed in JP-A-61-72013.

As described above, the mixing ratio of the vinyl copolymer (A) and the polyisocyanate (B) is OH / NCO = 1 / 0.2 to 1 / 1.8 (equivalent ratio) from the viewpoint of coating film performance. Medium, 1 /
A range of 0.5 to 1 / 1.5 is appropriate.

When NCO is less than 0.2 equivalent to 1 equivalent of OH, it is difficult to obtain a composition having desired coating film performance. On the other hand, when NCO exceeds 1.8 equivalent, sufficient coating Although performance can be expected, foaming may occur under high humidity, and this is not desirable in terms of paint price.

The thus obtained coating resin composition of the present invention is widely used for automobile repair, bridges, maintenance of plants, etc., for roofs, for building exteriors or for automobile bumpers. Therefore, for example, when applying the composition of the present invention to a material on which a coating film that is easily attacked by a polar solvent is already formed, or when repairing such a material with the composition of the present invention,
As in the case of the composition of the present invention, the amount of the polar solvent used is reduced, and in the case of a paint composition in a form in which none is further eliminated,
No lifting phenomenon occurs when a coating composition containing only a polar solvent is applied, thus providing a smooth, high commercial value, good coating film and a primer. For surfacer use, it does not attack old coatings and has excellent sharpness.Also, for solvent-resistant plastics materials such as polycarbonate which are easily attacked by suitable solvents, solvent cracking Troubles such as occurrence of occurrence are less likely to occur.

In addition, even if the resin composition for coating of the present invention is used for finishing or repairing 2 tons of automobiles and motorcycles, the repainting interval is very short, and photochemical non-chemicals can be used as an organic solvent. The use of an active and low-toxic one significantly improves the working environment and lowers the pollution compared to the case where a highly toxic polar solvent is used. It becomes possible.

Further, in the resin composition for a coating of the present invention, curing by ordinary temperature drying or forced drying, or curing in an amine stream, or a vapor curing system or a VIC system, etc., can be applied by any curing means or curing conditions. In addition, the compositions of the present invention can be used with paints commonly known in the art, such as pigment dispersants, leveling agents, UV absorbers, light stabilizers or curing accelerators (curing catalysts). Needless to say, additives can be added and compounded. Further, if the additives are compatible with and soluble in the composition of the present invention, for the purpose of further improving the performance, a plasticizer or other acrylic resin is used. A copolymer or vinyl copolymer, a cellulose compound, an alkyd resin, an acrylated alkyd resin, a silicone resin, a fluororesin or an epoxy resin may be appropriately used in combination. It may, as enamel paint mixing pigment or can be used as a clear coating without mixing.

Further, as a coating method, a known method such as spray coating or roller coating can be applied.

〔Example〕

Next, the present invention will 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 Example 1 [Preparation Example of Copolymerizable Unsaturated Bond-Containing Resin (a-4)] Isophthalic acid 513 was placed in a four-necked flask equipped with a stirrer, a thermometer, a device for removing reaction water, and a nitrogen gas inlet tube.
Parts, maleic anhydride 19 parts, adipic acid 106 parts, neopentyl glycol 391 parts, trimethylolpropane 83 parts,
After charging 30 parts of pentaerythritol and 0.005 part of an antifoaming agent, the temperature was raised to 180 ° C. and maintained at the same temperature for 2 hours.
The temperature was raised to 220 ° C. over time and maintained at the same temperature under an atmosphere of nitrogen gas until the acid value became 9 or less, and then toluene / butyl acetate = 65/35 so that the nonvolatile content became about 60%.
(Weight ratio), the nonvolatile content is 60%, the Gardner viscosity at 25 ° C. (the same applies hereinafter) is S, the acid value is 5.0,
A solution of an unsaturated bond-containing polyester resin having an OH value of 72 was obtained. Hereinafter, this is abbreviated as resin (a-4-1).

Reference Example 2 (same as above) 382 parts of dehydrated castor oil fatty acid, 5 parts of maleic anhydride, 349 parts of phthalic anhydride, 134 parts of neopentyl glycol, 98 parts of trimethylolpropane, 100 parts of pentaerythritol and 0.005 part of an antifoaming agent were charged. Swazole 3 as solvent
As in Reference Example 1, except that the composition was changed to use 10, the nonvolatile content was 60%, the viscosity was U, the acid value was 3.6, and
A solution of a dehydrated castor oil-modified unsaturated bond-containing polyester resin having an H value of 54 and an oil length of 40% was obtained. Less than,
This is abbreviated as resin (a-4-2).

Reference Example 3 (same as above) A four-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube was charged with 800 parts of “Solvesso 100”.
The temperature was raised to 115 ° C., and at the same temperature, 200 parts of styrene, 300 parts of tert-butyl methacrylate, and 4 parts of n-butyl methacrylate
A mixture consisting of 17 parts, 58 parts of 2-hydroxyethyl acrylate, 200 parts of "Solvesso 100", 30 parts of tert-butyl peroctoate (TBPO) and 5 parts of di-tert-butyl peroxide (DTBPO) The solution was added dropwise over 4 hours, kept at the same temperature for about 15 hours, and then treated with maleic anhydride.
Charge 25 parts and maintain at the same temperature until the acid value is about 7, 50% non-volatile content, Y viscosity, 7.5 acid value, and OH
A solution of an unsaturated bond-containing vinyl copolymer resin having a valence of 7 was obtained. Hereinafter, this is abbreviated as resin (a-4-3).

Reference Example (same as above) In the same reaction vessel as Reference Example 3, “Swazole 310” was added.
And 500 parts of xylene were charged and heated to 115 ° C. At the same temperature, 460 parts of n-butyl methacrylate, 300 parts of isobornyl acrylate, 140 parts of 2-hydroxyethyl methacrylate, and 20 parts of methacrylic acid were added. Parts, 80 parts of n-butyl acrylate, 233 parts of toluene, 30 parts of TBPO
Part and tert-butyl peroxybenzoate (TBPB)
Was added dropwise over 4 hours, and the mixture was kept at the same temperature for about 15 hours and then cooled to 90 ° C.

Next, 0.03 part of hydroquinone (HQ), 33 parts of glycidyl methacrylate and 0.1 part of 2-methylimidazole were added thereto, and the mixture was maintained at 90 ° C until the acid value became 1 or less. Viscosity U, acid value 0.9
Thus, a solution of an unsaturated bond-containing acrylic copolymer having an OH value of 35 was obtained. Hereinafter, this is abbreviated as resin (a-4-4).

Reference Example 5 [Preparation Example of Polyisocyanate (B)] In this example, an isocyanurate ring-containing polyisocyanate was prepared according to the method disclosed in JP-A-61-72013. In a glass four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, an air cooling tube and a thermometer, 3,500 parts of hexamethylene diisocyanate (using "Desmodule H" manufactured by Bayer) in a nitrogen gas stream. And 716.3 parts of 12-hydroxystearyl alcohol (using "Roxanol" having a purity of about 80%, manufactured by Henkel) were charged.

Next, an oil bath was attached to the flask, and the temperature was raised to 65 ° C. while stirring, so that the contents of the flask became a homogeneous liquid. Subsequently, after maintaining at the same temperature for 2 hours, the temperature was lowered to a temperature of 55 ° C.

N, N, N-trimethyl- as an isocyanuration catalyst
N'-2'-hydroxypropyl ammonium p-tert
-20% butyl cellosolve solution of butyl benzoate 3.4
The reaction was continued for 3 hours at a temperature of 60 ° C., and then a 7% xylene solution of monochloroacetic acid was added in 3.
The isocyanurate-forming catalyst was deactivated by adding 4 parts, and the isocyanurate-forming reaction was terminated.

After the reaction mixture was cooled to room temperature, 1,000 parts thereof were subjected to molecular distillation, and 549.4 parts of polyisocyanate having an isocyanurate ring (conversion rate: 50%) as distillation residue and 450.0 parts of hexamethylene diisocyanate as distillate (45.0% recovery rate) ) Got.

The obtained polyisocyanate having an isocyanurate ring was diluted to a concentration of 75% with "HAWS" which is a non-polar solvent to obtain 732.2 parts of a transparent polyisocyanate solution (B).

The polyisocyanate solution (B) thus obtained is
Non-volatile content 75.1%, Gardner color number 1 or less, viscosity EF,
The isocyanate content was 11.2%, the molecular weight was 953, and the dilution ratio with respect to the diluent "HAWS" was 1,000% or more.

Reference Example 6 [Preparation example of lactonized product (a-1)] In a four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet, and a condenser, “versatic acid” glycidyl ester (“Cardura E-10”) was added. Use)
Charge 508 parts and raise the temperature to 125 ° C. At the same temperature, gradually add 116 parts of fumaric acid while paying attention to heat generation, and keep the same temperature until the acid value becomes 5 or less even after the addition is completed. Has an acid value of 3.
One esterified product was obtained.

Then, after the temperature was lowered to 120 ° C., 114 parts of ε-caprolactone and 0.11 part of zinc acetylacetone were added thereto, and the mixture was kept at 120 ° C. for 15 hours to continue the reaction. Was 2.8 and the desired product had an OH value of 152. Hereinafter, this is referred to as a lactonized product (a-1-1).
Abbreviated.

Reference Example 7 (same as above) In place of "Cajura E-10", the same amount of "SA-9"
G "(glycidyl ester of Idemitsu synthetic fatty acid" SA-9 ") and the amount of ε-caprolactone was changed to 228 parts in the same manner as in Reference Example 6, except that the acid value was changed. The target product having a 3.2 and an OH value of 135 was obtained.
Hereinafter, this is abbreviated as lactonized product (a-1-2).

Reference Example 8 (same as above) In the same reaction vessel as Reference Example 6, 340 parts of “SA-13G”
(Glycidyl ester of Idemitsu synthetic fatty acid “SA-13”) and 2.6 parts of methyl etherified hydroquinone were charged and heated to 100 ° C. At the same temperature, 264 parts of mono-2-hydroxyethyl acrylate phthalate were treated with attention to heat generation While gradually adding 0.04 parts of BF ₃ .ethyl etherate and maintaining until the acid value becomes 5 or less, and then 172 parts of γ-butyrolactone and 0.15 parts of zinc acetylacetone salt Was added, and the mixture was kept at the same temperature to obtain a target product having an acid value of 3.8 and an OH value of 76. Hereinafter, this is referred to as a lactonized product (a-1-
Abbreviated as 3).

Reference Example 9 (same as above) Instead of “SA-13G”, 522 parts of coconut oil fatty acid glycidyl ester and, instead of mono-2-hydroxyethyl acrylate phthalate, 14 parts of acrylic acid
In the same manner as in Reference Example 8, except that the acid value was changed to 3.3 parts and to use 912 parts of ε-caprolactone instead of γ-butyrolactone.
Thus, the desired product having a hydroxyl value of 74 was obtained. This is abbreviated as lactonized product (a-1-4).

Reference Example 10 (same as above) Instead of "Kajura E-10", 340 parts of "SA-1
3G "and, instead of fumaric acid, 172 parts of mono-n
Reference Example 6 except that -butylmalate was used and the amount of ε-caprolactone was changed to 684 parts.
In the same manner as in the above, a target product having an acid value of 3.3 and an OH value of 50 was obtained. Hereinafter, this is referred to as a lactonized product (a-1-
Abbreviated as 5).

Reference Example 11 (same as above) In a reaction vessel similar to Reference Example 6, 34
After charging 6 parts, the temperature was raised to 50 ° C., and at the same temperature, 808 parts of a 10% aqueous sodium hydroxide solution was gradually added, and the acid value of the reaction system was measured to complete the conversion to the sodium salt. After confirming that, 183 parts of epichlorohydrin was gradually added thereto to cause a desalination reaction.

Then, 500 parts of toluene was added to the reaction mixture to extract the desired product ("neodecanoic acid" glycidyl ester), which was then washed several times with clean water. After removing the “sodium salt”, toluene and a trace amount of water were distilled off from the system by distillation under reduced pressure to obtain a desired glycidyl ester of “neodecanoic acid”.

Thereafter, 460 parts of this glycidyl ester and 0.2 parts of HQ were charged into the same reaction vessel as in Reference Example 6 and heated at 100 ° C.
To 130 parts of itaconic acid while paying attention to heat generation.
Add gradually over 0 minutes, further add 0.05 parts of BF ₃ -ethyl etherate, keep at the same temperature until the acid value is 5 or less, ester with an acid value of 3.6 and an OH value of 190 Compound was obtained. Next, 800 parts of γ-valerolactone and 0.2 parts of acetylacetonate zinc salt were added thereto, and the reaction was continued at 100 ° C., whereby the target product having an acid value of 3.3 and an OH value of 84 was obtained. . This is abbreviated as lactonized product (a-1-6).

Reference Example 12 [Preparation Example of Vinyl Copolymer (A)] In a reaction vessel similar to that of Reference Example 6, 686 parts of xylene,
34 parts of the resin (a-4-1) obtained in Reference Example 1 were charged, and 150 parts of the lactonized product (a-1), 100 parts of styrene, 200 parts of n-butyl methacrylate, and tert-
175 parts of butyl methacrylate, 100 parts of isobutyl acrylate, 100 parts of “Placcel FM-1”, 203 parts of 2-hydroethyl methacrylate and 100 parts of a monomer mixture 830 parts of 2 parts of methacrylic acid, and TB
After charging 2 parts of PO, raising the temperature to 120 ° C. and maintaining at this temperature for 1 hour, the remaining monomer mixture (730 parts), 300 parts of toluene, 10 parts of TBPB, 5 parts of DTBPO and 5 parts of TBPO
The mixture consisting of 30 parts was dropped over 4 hours and kept at the same temperature for about 15 hours after the completion of the dropping. The nonvolatile content was 50%, the viscosity was U, the acid value was 2.5, and the OH value was 68. And ▲ ▼ / ▲
A solution of the target copolymer with ▼ = 4.0 was obtained. Hereinafter, this is abbreviated as copolymer (A-1).

Reference Example 13 (same as above) Instead of the resin (a-4-1), 167 parts of the resin (a-
4-2) as a lactonized compound, (a-1-
Instead of 1), 250 parts of (a-1-2), and further, as vinyl monomers, 100 parts of styrene, 100 parts of n-butyl methacrylate, 290 parts of tert-butyl methacrylate, and 290 parts of 2-ethylhexyl methacrylate 50 copies,
A composition comprising 58 parts of stearyl methacrylate, 60 parts of 2-hydroxyethyl methacrylate and 2 parts of actylic acid was further used as a non-polar solvent.
A non-volatile content of 50 parts was obtained in the same manner as in Reference Example 12 except that three parts of “Swazol 310” were changed to use, respectively.
%, The viscosity is Y, the acid value is 3.0, the OH value is 35, and
A solution of the target copolymer with ▲ ▼ / ▲ ▼ = 4.9 was obtained. Hereinafter, this is abbreviated as copolymer (A-2).

Reference Example 14 (same as above) In the same reaction vessel as in Reference Example 12, the resin (a-4-3) was added.
After charging 1,400 parts and raising the temperature to 120 ° C., 100 parts of the lactonized compound (a-1-3), 70 parts of isobornyl methacrylate, 100 parts of tert-butyl methacrylate, “Placcel FM-1” 27 parts of acrylic acid, 3 parts of acrylic acid, TBPO
The same procedure as in Reference Example 12 was carried out except that the mixture consisting of 10 parts, 20 parts of TBPB and 300 parts of “HAWS” was dropped over 3 hours, and the nonvolatile content was 50% and the viscosity was Z. so,
Acid value is 6.4, OH value is 12, and ▲ ▼ / ▲ ▼
= 4.2 was obtained. Hereinafter, this is abbreviated as copolymer (A-3).

Reference Example 15 (same as above) In place of resin (a-4-1), resin (a-4-3)
In place of the lactonized compound (a-1-1),
The lactonized product (a-1-4) of 00 parts was used as the other monomers, as 62 parts of isobornyl acrylate, 200 parts of methyl methacrylate, 200 parts of tert-butyl methacrylate, 50 parts of lauryl methacrylate, 26 parts of hydroxyethyl acrylate, 50 parts of dodecyl methacrylate, 2 parts of methacrylic acid and 10 parts of "T-37"
Parts, and as a nonpolar solvent, 800 parts of "Solvesso 100" is used, and 5 parts of
A non-volatile content was 50%, a viscosity was W, an acid value was 3.0, and O
A solution of the target copolymer having an H value of 15 and ▲ /／ = 9.0 was obtained. Hereinafter, this is referred to as a copolymer (A-4)
Abbreviated.

Reference Example 16 (same as above) Instead of the resin (a-4-1), “Super Veccosol J-537” [a safflower oil-modified isophthalic acid-based alkyd resin manufactured by Dainippon Ink and Chemicals, Ltd .; oil length = 65
%, Solvent = mineral spirit, non-volatile content = 60%]
0 parts, 200 parts of (a-1-5) instead of (a-1-1) as a lactonized product, 105 parts of styrene and 2 parts of tert-butyl methacrylate as vinyl monomers.
07 parts, 100 parts of “acrylester SL” and 80 parts of 2-hydroxyethyl acrylate were used. As a nonpolar solvent, 800 parts of “LAWS” was used, and 5 parts of DTBPO. And in the same manner as in Reference Example 12, except that 5 parts of AIBN were further used.
Non-volatile content is 50%, viscosity is V, acid value is 2.9, OH value is 25,
In addition, a solution of the target copolymer in which ▼ /／ = 9.8 was obtained. Hereinafter, this is abbreviated as copolymer (A-5).

Reference Example 17 (same as above) The amount of “Super Veccosol J-537” was added to 834 parts,
The amount of “LAWS” was changed to 666 parts, and 160 parts of (a-1-6) were used instead of (a-1-5) as the lactonized compound, and isovol was used as the vinyl monomer. In the same manner as in Reference Example 16, except that 100 parts of nil methacrylate, 100 parts of isobutyl methacrylate, and 100 parts of tert-butyl methacrylate were changed to use a composition consisting of 50 parts of 2-ethylhexyl methacrylate, Min 50%, viscosity X, acid number 3.3
Thus, a solution of the target copolymer having an OH value of 22 and ▼ / ▲ = 14 was obtained. Hereinafter, this is referred to as a copolymer (A-
Abbreviated as 6).

Reference Example 18 (same as above) In a reaction vessel similar to Reference Example 12, 700 parts of xylene,
150 parts of "Kajura E-10", 0.1 part of hydroquinone monomethyl ether, 0.1 part of zinc salt of acetylacetone
Parts, 132 parts of ε-caprolactone and 5 parts of methacrylic acid.
After charging 0 parts, the temperature was raised to 120 ° C. and maintained until the acid value became 4 or less. At this temperature, 100 parts of isobutyl methacrylate, 300 parts of tert-butyl methacrylate, 122 parts of 2-ethylhexyl acrylate, A mixture consisting of 78 parts of 2-hydroxyethyl methacrylate, 20 parts of TBPO, 10 parts of TBPB and 300 parts of xylene was added dropwise over 3 hours and kept at the same temperature for about 18 hours to obtain 50% non-volatile. Viscosity is V, acid value is 4.6, OH value is 50, and ▲ ▼ / ▲
A solution of the target copolymer with ▼ = 2.4 was obtained. Hereinafter, this is abbreviated as copolymer (A-7).

Reference Example 19 (same as above) 400 parts of xylene was charged into a reaction vessel similar to that of Reference Example 12, heated to 120 ° C, and 200 parts of methyl methacrylate was added.
156 parts of rt-butyl methacrylate, 16 parts of 2-hydroxyethyl methacrylate, 128 parts of methacrylic acid, TBP
A mixture consisting of 20 parts of O, 10 parts of TBPB and 100 parts of xylene was added dropwise over 4 hours, and the mixture was kept at the same temperature for about 15 hours to confirm that the nonvolatile content was 50%. added 0.1 parts of 500 parts of BF ₃ · ethyl etherate of castor oil fatty acid glycidyl ester was heated to 125 ° C., until the acid value became 5 or less, and held at this temperature, with treatment became 5 or less , 509 parts of ε-caprolactone and 0.1 part of acetylacetonate zinc salt were added, and the temperature was raised to 130 ° C. and maintained at the same temperature until unreacted ε-caprolactone disappeared. Is 50%,
Viscosity is O, acid value is 3.4, OH value is 33, and ▲ ▼ /
A solution of the target copolymer in which ▲ = 2.5 was obtained. Less than,
This is abbreviated as copolymer (A-8).

Reference Example 20 (same as above) The amount of “Super Veccosol J-537” was changed to 84 parts,
As the lactonized compound, 377 was used instead of (a-1-5).
(A-1-1), 100 parts of styrene and 100 parts of methyl methacrylate
Parts, 200 parts of tert-butyl methacrylate, 71 parts of isopropyl acrylate, 100 parts of "Acryester SL"
Parts and 2 parts of methacrylic acid, and as a solvent, 700 parts of “LAWS” and 2 parts
The same procedure as in Reference Example 16 was carried out, except that the non-volatile content was changed to 50%,
Viscosity is W, acid value is 3.0, OH value is 32, and ▲ ▼ /
A solution of the target copolymer with 溶液 = 3.6 was obtained. Less than,
This is abbreviated as copolymer (A-9).

Reference Example 21 (same as above) In the same reaction vessel as Reference Example 12, “Swazol 310” was added.
Of the lactone (a-
1-1) 400 parts, styrene 200 parts, isobutyl methacrylate 100 parts, tert-butyl methacrylate 200 parts
Parts, 100 parts of "Acrylic ester SL", 20 parts of TBPO, D
A mixture consisting of 5 parts of TBPO and 300 parts of “Swazol 310” was added dropwise at the same temperature over 4 hours, and then kept at the same temperature for about 15 hours to obtain a nonvolatile content of 50%, a viscosity of U, and an acid. Value
A solution of the target copolymer having an OH value of 1.5, an OH value of 30, and ▼ /／ = 2.8 was obtained. Hereinafter, this is referred to as a copolymer (A
−10).

Reference Example 22 (same as above) As a lactonized product, 200 parts of (a-1-3) and 544
Part of (a-1-4), the solvent used is "LAWS" such as a vinyl monomer having a composition consisting of 200 parts of tert-butyl methacrylate and 56 parts of isopropyl methacrylate. ) And 600 parts of “Swazol 310” in combination, and as radical generators (polymerization initiators), TBPO and DTBP
In the same manner as in Reference Example 21, except that the amount of O was changed to 5 parts each, the nonvolatile content was 50%, the viscosity was Q, the acid value was 1.0, the OH value was 28, and ▲ ▼ /▲▼=2.6 to obtain a solution of the target copolymer. Hereinafter, this is abbreviated as copolymer (A-11).

Reference Example 23 (same as above) The amount of “Super Veccosol J-537” was added to 134 parts,
As a lactonized product, 393 parts of (a-1-3) was used, and 100 parts of n-butyl methacrylate was used.
100 parts of isobutyl methacrylate, 227 parts of tert-butyl methacrylate and 100 parts of “acrylester SL”
In the same manner as in Reference Example 16, except that the amount of “LAWS” was changed to 946 parts, and the nonvolatile content was 50% and the viscosity was X. , Acid value is 1.2, OH value is 18, and ▲ ▼ / ▲
A solution of the target copolymer with ▼ = 3.9 was obtained. Hereinafter, this is abbreviated as copolymer (A-12).

Reference Example 24 (Preparation Example of Control Vinyl Copolymer) Instead of the lactonized product (a-1-1), 53 parts of 2-hydroxyethyl methacrylate and 97 parts of methyl acrylate were used, and n-butyl methacrylate was added. Except that the same amount of ethyl methacrylate was used instead of tert-butyl methacrylate, and the same amount of ethyl acrylate was used instead of isobutyl acrylate. As in Reference Example 12, the nonvolatile content was 50%
, The viscosity is Y, the acid value is 2.2, the OH value is 68, and ▲
Lactone (a-1) where ▼ / ▲ ▼ = 3.9
A solution of the vinyl copolymer free was obtained. Hereinafter, this is abbreviated as copolymer (A'-1).

Reference Example 25 (same as above) Instead of the lactonized compound (a-1-2), 78 parts of 2-
Hydroxyethyl methacrylate and 172 parts of methyl acrylate, and the same amount of ethyl methacrylate instead of n-butyl methacrylate, and the same amount of methyl methacrylate instead of tert-butyl methacrylate, furthermore, 2-ethylhexyl methacrylate And instead of stearyl methacrylate, the same amount of ethyl acrylate as the total amount of both,
Except having been changed to use, in the same manner as in Reference Example 13,
Non-volatile content is 50%, viscosity is Z, acid value is 2.8, OH value is 35,
In addition, a solution of a vinyl copolymer containing no lactonized product (a-1-2) was obtained in which ▲ /／ = 4.7.
This was slightly hazy. Hereinafter, this is abbreviated as copolymer (A'-2).

Reference Example 26 (same as above) 23 parts of 2-hydroxyethyl methacrylate and 177 parts of methyl acrylate were used instead of the lactonized product (a-1-5), and the same amount of methyl methacrylate was used instead of tert-butyl methacrylate. In addition, "Acryester
The reaction was carried out in the same manner as in Reference Example 16, except that the same amount of ethyl acrylate was used instead of `` SL '', respectively, and the mixture was separated as cloudy, and a transparent copolymer solution was not obtained. Was. This example also lacks the use of the esterified product (a-1-5) at all.

Reference Example 27 (same as above) Instead of the lactonized compound (a-1-1),
141 parts of 2-hydroxyethyl acrylate and 259 parts of methyl acrylate were also replaced with a combination of isobutyl methacrylate and tert-butyl methacrylate, except that the same amount of methyl methacrylate was used as the total amount of both. When the reaction was carried out in the same manner as in Reference Example 21, no clear copolymer solution was obtained, and the mixture was separated as cloudy. In this example, the lactonized product (a-
Needless to say, the use of 1-1) is completely absent.

Examples 1 to 13 and Comparative Examples 1, 2, 5 and 6 For the various vinyl copolymers obtained in Reference Examples 12 to 25, paints were separately formed with the composition as shown in Table 1. Was. Each of the paints was prepared by kneading with a sand mill for 60 minutes.

For each of the paints thus obtained, Example 1
In the case of ~ 13, "LAWS" / Xylene / "Essonafusa"
No.3 ”= 50/30/20 (weight ratio) mixed solvent,
In the case of Comparative Examples 1, 2, 5, and 6, the specific nonpolar organic solvent specified in the present invention, on the other hand, a mixed solvent of xylene / n-butyl acetate = 50/50 (weight ratio), The organic solvent other than the definition in the present invention,
Used as dilution thinner, 18-20 for Ford Cup No. 4
Second, then spray-coat, forcibly dry at 60 ° C for 40 minutes, and then leave at room temperature for 7 days to obtain a cured coating. A comparative study of physical properties was conducted over various items as described below.

The test items (1) to (4) and (7) were separately coated on a dull steel plate treated with Bonde # 144, and (15) on a urethane plate for a bumper so that the dry coating film became 40 μm. Thereafter, as described above, the drying was performed on the coated plate obtained by forcibly drying and drying at room temperature.

 The results are summarized in Table 2.

(1) Gloss: 60mm gloss (2) Hardness: Hardness with scratch by pencil (3) Adhesion: 2 in a blister box of 50 ° C x 98% RH
Secondary adhesion after exposure for 40 hours (sticking to the eyes) (4) Gasoline resistance: Visual determination of coating surface after immersion in Nisseki regular gasoline at room temperature for 2 hours (5) Lifting property: Normal The following three cases were conceivable, and all of them were performed.

First, the first case [hereinafter abbreviated to the case (5-1)]. ] Has a structure of coating film (a) / coating film (b) / coating film (c) / steel plate, wherein (a) designates a new repair coating film, This corresponds to a coating film obtained from the paint obtained in the comparative example. (B) designates a lacquer type primer surfacer. In the case of (5-1), the coating film portion causes lifting, (C) refers to an old coating film of a cross-linking agent such as a urethane type, a thermosetting acrylic type or a thermosetting polyester type.

Then, in the case of (5-1), (c)
After coating (b) on the surface, forcibly dry at 60 ° C for 40 minutes, and after one day, apply (a) on the degreased one after polishing with # 400 water-resistant paper. Lifting will occur.

In this case, the lacquer-type primer surfacer serving as the coating film (b) is “New One Coat”
[Product of Isamu Paint Co., Ltd.] was used.

Next, a second case [hereinafter abbreviated as (5-2) case]. ] Is the same as the case of the above (5-1), ie, coating film (a) / coating film (b) / coating film (c) /
(A) is a new repair coating film, and a coating film obtained by applying the coating material obtained in each of Examples and Comparative Examples corresponds to this (a). However, only that (b) is a crosslinked primer surfacer and (c) is an old lacquer type coating such as NC lacquer, modified acrylic lacquer, straight acrylic lacquer or high solid lacquer (5)
This is basically different from the case of -1).

Then, in the case of (5-2), (c)
After coating (b) on the surface, forcibly drying at 60 ° C for 40 minutes, and after one day, polishing (a) on the degreased one after polishing with # 400 water-resistant paper, Lifting will occur.

In this case, "Hyplasaf 2C" (a product of Isamu Paint Co., Ltd.) was used as the cross-linked primer surfacer to be the coating film (b).

Further, the third case [hereinafter, this is abbreviated as the case (5-3)]. ] Is the coating film (a) -1 / coating film (a)
−2 / coating film (b) / slate plate, where (a) -1 first paints the first coat,
C. for about 6 hours, the second coat was used as a top coat, and the same, that is, a paint obtained in each of Examples and Comparative Examples was applied. (A) -2: Top coat ( The first coat) is used, and the paint obtained in each of the examples and the comparative examples is used. In the case of (5-3), the coating film portion causes lifting. (B) refers to the "mastic paint" layer obtained by the following formulation. That is, "NS-100" (calcium carbonate manufactured by Nitto Powder Co., Ltd.) 144
Part "Taipec R-550" (rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) 1.5 parts "Demol EP" (dispersant manufactured by Kao Corporation) 3 parts "Neugen EA-120" [Daiichi Kogyo Pharmaceutical Co., Ltd. 1.5 parts Ethylene glycol 3 parts "SN Deformer 154" [Anti-foaming agent manufactured by San Nopco Co., Ltd.] 1.5 parts 28% ammonia water 1 part Water 24 parts 2% "High Metros 90 SH-15000" [Shin-Etsu Thickener manufactured by Chemical Industry Co., Ltd.] Aqueous solution 18.6 parts "Boncoat 3650" [Acrylic emulsion manufactured by Dainippon Ink and Chemicals, Inc.] 104.6 parts "Celltop HP-103" 1.1 parts (6) Influence of solvent used: Judgment of the degree of solvent cracking is visually determined. (7) Weather resistance: Indicated by gloss retention after one year of outdoor exposure in the suburbs of Miyazaki City. (8) Repairability: No. 1 on ABS resin plate Apply the various paints shown in the table Separately, so that the dry film thickness is 10-60 μm,
Gently apply by spray coating and perform forced drying at 60 ° C. for 40 minutes, then leave at room temperature for 30 to 40 minutes, and then further apply the same paint on the coating so that the dry film thickness becomes 40 μm. Spray painting, forced drying at 60 ° C for 40 minutes, and then visually determine the coated surface after drying. (9) Metal return unevenness: “Acridic 47-56
7] [Acrylic polyol manufactured by Dainippon Ink and Chemicals, Ltd .; nonvolatile content = 50%, OH value = 30] / "Bernock DN
-950 ”metallic base [Aluminium paste is“ Alpaste ”manufactured by Toyo Aluminum Co., Ltd.
1700NL "blended so that PWC is 10%]
Is spray-painted on a tin plate, left at room temperature for 40 minutes, and then mixed with various paints shown in Table 1 [however,
This was based on the formulation of a clear paint without the use of "Taipec CR-93" (product of the same company). The paint was diluted according to the formula [1] and diluted to the spray viscosity with a predetermined thinner. The paint was then applied to a part of the coated plate and cured, and the flow state of the aluminum particles was visually determined. (10) Drying : Each paint obtained in each Example and Comparative Example, that is, the paint shown in Table 1 was spray-coated on a glass plate so that the dry film thickness became 40 μm.
(11) Solid content at the time of painting: The solid content when diluted to a viscosity of 18 to 20 seconds with Ford Cup No. 4 using the specified thinner using the specified thinner. However, the higher the value, the better the texture and the better the dilutability in a solvent.

(12) Tolerance of the vinyl copolymer (A) or (A ') to various solvents: the vinyl copolymers (A-1) to (A-12) obtained in Reference Examples 12 to 23, and Reference Examples 23 and (13) Pigment dispersibility: Three types as described below, expressed as dilution ratio (%) per 1 g of each of the control vinyl copolymers (A'-1) and (A'-2) obtained in 24. The primary color enamel base obtained by kneading the pigment of the following PWC with a sand mill using a sand mill for 60 minutes and a white enamel as shown in Table 1 were mixed with Ti
O ₂ / carbon black = 98/2 (weight ratio), TiO ₂ / quinacridone red or phthalocyanine blue = 95/5 (weight ratio), and a predetermined amount of “Varnock DN-99
0 "(a polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.) and" Silicone Oil KF-69 "(a product of Shin-Etsu Chemical Co., Ltd.), and then xylene / acetic acid-n
-Dilute to the spray viscosity with a mixed solvent of butyl = 50/50 (weight ratio), spray-coat, dry to the touch, apply the same paint to a part of it, cure it, and then pour it with the spray-painted part The determination was made by comparing the color difference with the painted portion.

Carbon black: "Mitsubishi Carbon Black MA-100"
[Mitsubishi Kasei Kogyo Co., Ltd. PWC = 3% Kinacridone Red ... "Fast Gen Super Red YE" [Dainippon Ink and Chemicals Co., Ltd.] PWC = 10
% Phthalocyanine Blue: "Fast Gen Blue NK"
(Same company product) PWC = 10% (14) Elongation: Measured at two points at room temperature and -10 ° C using Tensilon (a tensile tester manufactured by Toyo Baldwin Co., Ltd.) (15) Low temperature flexibility: Each test plate cooled to -30 ° C
Perform a bending test with a mandrel of φ-10 mm,
The presence or absence of crack generation was evaluated.

The case where there was no crack was determined to be “No abnormality”, and the case where a crack was present was determined and displayed as “Fail”.

Note * 1) "Acridic A-801-P": Acrylic polyol manufactured by Dainippon Ink and Chemicals, Ltd., nonvolatile content 50
%, OH value 50, solvent toluene / butyl acetate * 2) "Acridic A-808": Acrylic polyol manufactured by Dainippon Ink and Chemicals, Ltd., nonvolatile content 50
%, OH value 20, solvent xylene / n-butyl acetate * 3) "Taipek CR-93": titanium oxide manufactured by Ishihara Sangyo Co., Ltd. * 4) "Tinuvin 328": ultraviolet absorber manufactured by Ciba Geigy * 5) "Tinuvin 770": light stabilizer manufactured by Ciba Geigy * 6) Thinner: "LAWS" / xylene / "Essonafusa No.3" = 50/30/20 (weight ratio) mixed solvent * 7) Thinner : Xylene / n-butyl acetate = 50/5
0 (weight ratio) mixed solvent * 8) "Varnock DN-950": hexamethylene diisocyanate-trimethylolpropane-added polyisocyanate manufactured by Dainippon Ink and Chemicals, Ltd .;
75%, NCO content 12.5% * 9) "Varnock DN-980": hexamethylene diisocyanate isocyanurate type polyisocyanate manufactured by Dainippon Ink and Chemicals, Ltd .; non-volatile content 75%, NC
O content: 15% [Effect of the Invention] As is clear from the results in Table 2, the resin composition for a coating material of the present invention is excellent in drying property, solubility, hardness, recoating property, and feeling of holding. It is a very excellent resin composition for coatings that has little effect on materials having poor solvent resistance, and can be used for a wide range of applications as described above.

Claims (3)

(57) [Claims] 1. A vinyl copolymer (A) containing a lactone adduct (a-1) of an esterified product of an α, β-ethylenically unsaturated carboxylic acid and a natural or synthetic fatty acid glycidyl ester as an essential monomer component. A highly extensible coating resin composition comprising, as essential components, a polyisocyanate (B) and a non-polar organic solvent. 2. A lactone adduct (a-1) of an esterified product of an α, β-ethylenically unsaturated carboxylic acid and a natural or synthetic fatty acid glycidyl ester, and a side chain alkyl group having 3 to 18 carbon atoms. A vinyl monomer (a-2) and another vinyl monomer (a-5) copolymerizable with the components (a-1) and (a-2) described above are mixed with each other in the presence of a radical generator. A vinyl copolymer (A) obtained by copolymerization, a polyisocyanate (B), and an organic solvent (C) containing a nonpolar organic solvent having an aniline point or a mixed aniline point of 7 to 70 ° C. as an essential component. Is a highly extensible resin composition for paints, comprising as an essential component. 3. A lactone adduct (a-1) of an esterified product of an α, β-ethylenically unsaturated carboxylic acid and a natural or synthetic fatty acid glycidyl ester in an amount of 5 to 95% by weight, and the number of carbon atoms in the side chain alkyl group. Is a vinyl monomer (a-
2) 1 to 90% by weight of a hydroxyl group-containing vinyl monomer (a-
3) 0 to 50% by weight of a copolymerizable unsaturated bond-containing resin (a
-4) from 0 to 80% by weight, and (a-1),
1 to 94% by weight of the other vinyl monomer (a-5) copolymerizable with the components (a-2), (a-3) and / or (a-4) is 100% by weight as a whole. The number average molecular weight obtained by copolymerization in the presence of a radical generator is 3,000 to 30,000, and the ratio of weight average molecular weight / number average molecular weight is in the range of 1.8 to 25. Vinyl copolymer (A) and polyisocyanate (B)
And a nonpolar organic solvent having an aniline point or a mixed aniline point of 7 to 70 ° C. and a polar organic solvent in a weight ratio of 100/0 to 8
An organic solvent (C) of 0/20 as an essential component, the equivalent ratio of OH / NCO of the vinyl copolymer (A) component and the polyisocyanate (B) component is from 1 / 0.2 to 1 / 1.8. A highly extensible resin composition for a paint, comprising: