JPH01190763A - Coating resin composition - Google Patents

Abstract

PURPOSE:To obtain a coating resin composition excellent in dryability, hardness, gloss, grindability, etc., by mixing a vinyl copolymer comprising adamantyl (meth)acrylate and a hydroxylated vinyl monomer with a polyisocyanate and an organic solvent. CONSTITUTION:The title composition comprises a vinyl copolymer (A) prepared by copolymerizing 2-95wt.% adamantyl (meth)acrylate (a-1) of the formula (wherein R is H or methyl), 1-50wt.% hydroxylated vinyl monomer (a-2), 0-10wt.% carboxylated vinyl monomer (a-3), 0-80wt.% copolymerizable unsaturated resin (a-4) and 4-97wt.% other vinyl monomers (a-5) copolymerizable with (a-1), (a-2), (a-3) and/or (a-4) in amounts to give a total of 100wt.%, a polyisocyanate (B) and an organic solvent (C), wherein the ratio of component (A) to component (B) (OH/NCO) falls within the range of 1/0.2-1/1.8.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new and useful resin composition for coatings,
More specifically, the vehicle contains a vinyl copolymer containing adamantyl (meth)acrylate as a specific monomer component and polyisocyanate as an essential component of the vehicle. It has excellent properties such as solubility in solvents), texture, recoatability, and hardness, and depending on the type and composition of the solvent used, it can be used to coat old coatings (existing coatings) or materials with poor solvent resistance. The present invention relates to a resin composition for paint that is suitable for automobile repair, automobile parts, motorcycles, architectural exteriors, woodwork, roofs, general metals, etc., and does not have a negative effect on the surface of the vehicle.

[Problems to be Solved by the Prior Art and the Invention] Acrylic urethane paints have excellent coating performance and have been used in passenger cars, motorcycles, passes, trucks, railway vehicles, and home appliances in the past. It is widely used in the form of painting or repair painting on metal parts and plastic parts, such as industrial machinery, buildings, plants, structures, wood products, plastic products, and steel furniture. However, due to the limitations of conventional paints and their poor drying properties, when repainting the entire surface or part of the various objects mentioned above, for example, metallic paints are used as the first coat. When applying a two-coat finish such as applying enamel paint and then applying clear paint as the second coat, the aluminum particles and enamel layer from the first coat may get mixed into the second coat (
If the desired finish is not achieved due to lifting (uneven return) or lifting, it may be necessary to dry the product for a long time, or to apply a second coat slowly over a long period of time. There is a need to.

Furthermore, even if you perform forced drying, if you try to repaint it, you will need to dry it for more than one day and night.

This type of sanding is possible because with primers, facers, sanding sealers, etc., sanding cannot be performed without taking a long time before starting the next polishing process after painting and curing. There is a strong need for the development of paints that can be produced in a short amount of time.

By the way, in order to eliminate the various drawbacks mentioned above,
Although curing accelerators such as dibutyltin dilaurate, nitrocellulose, cellulose acetate butyrate, or vinyl chloride-vinyl acetate copolymers have been added, In some cases, the pot life may be shortened, weather resistance or gloss may deteriorate, and paints that contain large amounts of nitrocellulose may yellow or crack during outdoor exposure. Moreover, paints containing a large amount of cellulose acetate butyrate have the disadvantage of poor gloss, poor surface texture, and poor water resistance.

[Failure to solve the problem]

However, in view of the considerable drawbacks in the prior art as described above, the present inventors have developed a method that cures quickly at room temperature or forced drying and does not require a long drying time.
Therefore, even if you repaint immediately, there will be no dust or lifting, and when finishing with two coats, the aluminum particles and enamel layer of the first coat will not return unevenly. It does not attack old paint films (existing paint films) or painted materials with poor solvent resistance, and it also has weather resistance, hardness, water resistance, gasoline resistance,
It has excellent chemical resistance, solubility in non-polar organic solvents, texture, and sharpness, and is used for automotive repair, architectural exteriors, woodworking, plastics, automobiles, and motorcycles. As a result of extensive research in order to obtain a paint resin composition that would enable coatings that require a high-quality finish, we combined a vinyl copolymer containing adamantyl (meth)acrylate as a specific monomer component with polyisocyanate. The present invention has been completed by discovering that the various objects mentioned above can be achieved.

That is, the present invention uses adamantyl (meth)acrylate (a-1) represented by the general formula as an essential component.
95% by weight, 1 to 50% by weight of the hydroxyl group-containing vinyl monomer (a-2), and the carboxylic group-containing vinyl monomer (a-2).
0 to 10% by weight of (a-3), 00 to 80% by weight of copolymerizable unsaturated bond-containing resin (a-4), and these (a-
1), (a-2), (a-3) and/or (a-4
) and other vinyl monomers (a-5) copolymerizable with 4-
97% by weight, selected so that the total amount is 100% by weight, and copolymerized in the presence of a radical generator.
The number average molecular weight (Mn) is 3,000 to 30,000, and the weight average molecular weight (MW)/number average molecular weight (Mn
)-1,8 to 25, a vinyl copolymer (A), a polyisocyanate (B), and an organic solvent (C), and the vinyl copolymer (A) and the polyisocyanate ( The ratio with B) is OH/NCO=110.2~1/
A coating resin with excellent drying properties, hardness, gloss, abrasiveness, solubility in non-polar organic solvents, texture, and recoatability, which is blended at an equivalence ratio of 1.8. It is intended to provide a composition.

Here, the adamantyl (meth)acrylate)
(a-1) is a substance that provides effects such as drying properties, gloss, hardness, weather resistance, solubility (especially solubility in non-polar organic solvents), texture, sharpness, compatibility, and pigment dispersibility. If it is less than 2% by weight, it is difficult to obtain the effect of use, while if it exceeds 95% by weight, the brittleness of the coating film becomes noticeable, so the content should be 2 to 95% by weight, especially 5 to 5% by weight. 75% by weight
It is preferable to fall within this range.

Next, the above-mentioned hydroxyl group-containing vinyl monomer (a-2)
A typical example is 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxyzorobyl (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-motuptyl fumarate, polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate, or Adducts of these and ε-caprolactone or “Zolaxel FM
or hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as “FA monomer” (caprolactone addition monomer manufactured by Daicel Chemical ■); (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or any α,β-ethylenically unsaturated carboxylic acids such as α,β-ethylenically unsaturated mono- or dicarboxylic acids such as citraconic acid, monoesters of these dicarboxylic acids and monohydric alcohols, or the above-mentioned α , β-unsaturated unsaturated carboxylic acid hydroxyalkyl ester sitomaleic acid citric acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "Noh imisocic acid" [Hitachi Chemical ■ products], adducts of polycarboxylic acids such as tetrachlorophthalic acid or dodecynylsuccinic acid with anhydrides, and Carzyla El (glycidyl ester of branched synthetic fatty acids manufactured by Shell, Netherlands), glycidyl coconut oil fatty acids. esters or monoglycidyl esters of monovalent carbic acid such as octylic acid glycidyl ester, or adducts with monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide, or adducts of these with ε-caprolactone; hydroxyethyl vinyl ether, etc. be.

These are used to impart a function as a crosslinking point to the resulting vinyl copolymer (4), and are
5-40% weight of 50% weight! ! :% is preferable. If the amount used is less than 1% by weight, sufficient crosslinking points cannot be obtained, and if it is more than 50% by weight, the number of crosslinking points is too large, resulting in large strain stress during curing, which tends to cause a decrease in adhesion. A solvent system with weak dissolving power is not preferable because it may separate or become cloudy.

Next, representative examples of the carboxyl group-containing vinyl monomer (a-3) include the above-mentioned unsaturated mono- or dicarboxylic monomers such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Including acids, these radicals? α,β-ethylenically unsaturated cargenic acids such as monoesters of phosphoric acid and monohydric alcohol; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate; ) acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)
Acrylate, C-2-hydroxyethyl fumarate,
α,β-unsaturated unsaturated carpinic acid hydroalkyl esters as mentioned above, such as mono-2-hydroxyethyl-motsputyl fumarate or polyethylene glycol mono(meth)acrylate, inic acid, succinic acid, phthalic acid, hexahydrophthalic acid , tetrahydrophthalic acid, benzenetricarbic acid, benzenetetracarzanic acid, "no-iminocic acid" [product of Hitachi Chemical Co., Ltd.], polycarboxylic acid such as tetrachlorophthalic acid or dodecynylsuccinic acid. Examples include adducts of phosphoric acid with anhydride.

These carboxyl group-containing vinyl monomers (a-3)
often exhibit an internal catalytic action when blended with the polyisocyanate component (B) described below, which shortens the storage stability of the paint, so when using these materials, care should be taken to Considering the effects of improving adhesion and compatibility with other resins, the amount used is 0 to 10% by weight.
In particular, it is desirable to keep the content within the range of 0.2 to 5% by weight.

The copolymerizable unsaturated bond-containing resin used as component (a-4) is a resin that improves the pigment dispersibility of the resulting vinyl copolymer carrier component, increases the non-volatile content during coating, and has a non-polar organic These are used mainly to improve solubility in solvents, and examples include JIJ ester resins, vinyl copolymers, petroleum resins, rosin esters, and polyether polyols. In case,
Polyester resins (including oil-modified types) and vinyl copolymers are preferred, and in particular, when considering the physical properties of the cured coating, they should contain as many hydroxyl groups as possible in their structure in addition to unsaturated bonds. A more favorable result can be obtained.

Such polyester resin systems and vinyl copolymers include:
Japanese Patent Publication No. 45-22011, Japanese Patent Publication No. 46-20502, Japanese Patent Publication No. 44-7134, Japanese Patent Publication No. 48-7823
As disclosed in Publication No. 3 and Publication No. 50-58123, a raw material component having a copolymerizable unsaturated bond is essential, and a copolymerizable unsaturated bond is added to the resin skeleton obtained by reacting with other raw material components. Those with saturated bonds, or those published in Japanese Patent Publication No. 49-47916 or No. 50-6223
As disclosed in the above publication, first a saturated polyester having no copolymerizable unsaturated bonds is obtained, and then functional groups such as hydroxyl groups or carboxyl groups, chile, or jepoxy By using epoxy groups introduced by reacting compounds, we can create compounds with functional groups and vinyl groups that are reactive with these functional groups, such as (meth)acrylic acid chloride, which has an acid chloride group and a vinyl group. Those with an epoxy group and a vinyl group such as glycidyl (meth)acrylate, those with an alkoxysilanol group and a vinyl group such as vinylmethoxysilane and (meth)acryloxyethyltrimethoxysilane, maleic anhydride and tetrahydrocarbon Those with an acid anhydride group and a vinyl group such as phthalic anhydride, those with a carboxyl group and a vinyl group such as fumaric acid and (meth)acrylic acid, 2-hydroxyzologyl (meth)acrylate and hexamethylene diisocyanate. equimolar adducts of, isocyanate ethyl methacrylate and other vinyl monomers having an incyanate group and a vinyl group, etc., which have a hydroxyl group and a copolymerizable unsaturated group obtained by adding them to a saturated polyester; Hydroxyl group, kill? This is similar to copolymerization using vinyl monomers having functional groups such as xyl groups or epoxy groups as an essential component, and copolymerizable unsaturated bonds being introduced into the above-mentioned saturated polyester into vinyl copolymers having these functional groups. In addition, a compound having a vinyl group and a functional group that is reactive with the functional group contained in this vinyl copolymer, for example, a compound having an acid chloride group and a vinyl group such as (meth)acrylic acid chloride. , those with epoxy groups and vinyl groups such as glycidyl (meth)acrylate, those with alkoxysilanol groups and vinyl groups such as vinylmethoxysilane and (meth)acryloxyethyltrimethoxysilane, maleic anhydride and tetrahydrophthalic anhydride. Those with acid anhydride groups and vinyl groups such as fumaric acid and (meth)acrylic acid, those with carbyxyl groups and vinyl groups such as fumaric acid and (meth)acrylic acid, and those with 2-hydroxyprogyl (meth)acrylate and hexamethylene diisocyanate. Equimolar adduct.

Suitable examples include those obtained by adding a vinyl monomer having an isocyanate group and a vinyl group, such as isocyanate ethyl methacrylate, to a vinyl copolymer, and those having a hydroxyl group and a copolymerizable unsaturated bond.

Such polyester resins contain saturated fatty acids such as octylic acid, lauric acid, stearic acid or "persatic acid" (a synthetic fatty acid manufactured by Shell); oleic acid, linoleic acid, lyluic acid, eleostearic acid or ricinoleic acid Unsaturated fatty acids such as "F Serine 200 or 300" (synthetic drying oil fatty acid manufactured by Berkeyless, USA), Chinese tung oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid) Or cottonseed oil (fatty acid), soybean oil (fatty acid), oil (fatty acid), safflower oil (fatty acid), castor oil (fatty acid)
or (semi-)drying oils (fatty acids) such as rice bran oil (fatty acids); or 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. Ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1.6-hexanediol, 1.2.6- with or without species or mixtures of two or more species. One or more polyhydric alcohols such as hexanethritol, R-ntaerythritol or sorbitol and benzoic acid, pt-butylbenzoic acid, phthalic acid (anhydride), hexahydro(anhydride) heptalic acid, tetrahydro( Phthalic anhydride, tetrachlorophthalic anhydride, hexachlorophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid, Himic acid, succinic anhydride, maleic anhydride, fumaric acid , (anhydrous) with one or more cardanic acids such as itaconic acid, adigic acid, sepatic acid or oxalic acid in a conventional manner, and if necessary, "Toray Silicone 5H-6018J ()- Resilicone Product], rX-22-160AS, KR-2
12 or 213” [Shin-Etsu Chemical ■ product].

Monoepoxy compounds such as glycidyl esters of fatty acids such as "Cardura E", "Epiclon 200 or 400" or "Epicoat 828 or 100I"
Polyepoxy compounds such as J, or diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, and 4,4'-methylenebis(cyclohexyl isocyanate).

One or more types of polyisocyanates obtained by addition reaction of these diisocyanates with the above-mentioned polyhydric alcohol or water, or polyisocyanates having an isocyanuric ring obtained by (co)polymerization of diisocyanates with each other, Suitable are those obtained by substituting a part of the polyhydric alcohol or carboxylic acid and reacting in a conventional manner.

In addition, as the copolymerizable unsaturated bond-containing vinyl copolymer described above, monomers are appropriately selected from among the vinyl monomers described above or described later, and copolymerized with a desired monomer composition by a conventional method. A suitable product is one that can be obtained by

The polyester resin and vinyl copolymer may be used alone or in combination, or may be used alone or in combination of two or more. These substances are used in a range of 0 to 80% by weight.

If it exceeds 80% by weight, the viscosity of the copolymer increases, it becomes dull during the reaction, and its weather resistance deteriorates, making it undesirable.

(a-1), (a-2), (a-3) as listed above
and/or other vinyl monomers (a-5) that can be copolymerized with each component (a-4), such as (a): styrene, α-methylstyrene, pt-butylstyrene, vinyltoluene, etc. Aromatic vinyl monomer.

(b) Ester (meth)acrylate, ethyl (meth)
Acrylate, n-zorogyl (meth)acrylate, l
-Propyl (meth)acrylate, n-butyl (meth)
Acrylate, l-butyl(meth)azilylate, t-
Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dipromoglovir (meth)acrylate, tribromophenyl (meth)acrylate or alkoxyalkyl (meth)acrylates (
meth)acrylates; diesters of monohydric alcohols with unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid; vinyl acetate, vinyl benzoate or ``Peova'' (vinyl ester manufactured by Shell); Esters; “Visco-) 8F, 8FM, 17FM
, 3F or 3FMj [fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical ■], barfluorocyclohexyl (
Vinyl esters and vinyl ethers containing () and -)fluoroalkyl groups, such as meth)acrylate, diperfluorocyclohexyl fumarate or N-1-7'ropylperfluorooctanesulfonamidoethyl (meth)acrylate.

Fluorine-containing polymerizable compounds such as (meth)acrylates or unsaturated polycarboxylic acid esters; or (meth)acrylonitrile, vinyl chloride, vinylidene chloride,
There are vinyl monomers that do not have functional groups, such as olefins such as vinyl button or vinylidene button.

Others that can be used include (c): (meth)acrylamide, dimethyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-octyl (meth)acrylamide, diacetone acrylamide, dimethylaminopropylacrylamide, or amide bond-containing vinyl monomers such as alkoxylated N-methylolated (meth)acrylamides, di) di-alkyl [(meth)acryloyloxyalkyl] phosphates or (meth)acryloyloxyalkyl acid phosphates or dialkyl [( (meth)acryloyloxyalkyl] phosphites or (meth)acryloyloxyalkyl acid phosphites, and furthermore, alkylene oxide addition of the above (meth)acryloyloxyalkyl acid phosphates or acid phosphites. thing.

Glycidyl (meth)acrylate and methylglycidyl (
Ester compounds of epoxy group-containing vinyl monomers such as meth)acrylate and phosphoric acid or phosphorous acid or acidic esters thereof, phosphorus atom-containing vinyl monomers such as 3-chloro-2-acid phosphoxyzorobyl (meth)acrylate, ( e) Nidimethylamine ethyl (meth)
Acrylates or dialkylaminoalkyl (meth)acrylates such as diethylaminoethyl (meth)acrylate.

The above-mentioned amide bond-containing vinyl monomers (c), phosphorus atom-containing vinyl monomers) and dialkylaminoalkyl (meth)acrylates (e) are all used to impart internal catalytic ability to acrylic copolymers. These are used when it is desired to improve adhesion to materials, compatibility with other resins, pigment dispersibility, etc. These can be used alone or in combination, and the amount used depends on the amount used. In terms of effectiveness, phosphorus atom-containing vinyl monomers are 0.0
5 to 5% by weight, amide bond-containing vinyl monomers and dialkylaminoalkyl (meth)acrylates 0.
It may be used in a range of 0.05 to 10% by weight.

Further, other vinyl monomers used as the component (a-5) include (f) nigericidyl (meth)acrylate, (β-methyl)glycidyl (meth)acrylate, and (meth)allyl glycidyl ether as mentioned above. α, β-ethylenically unsaturated carboxylic acids or mono-2-(meth)
Various unsaturated carboxylic acids such as equimolar adducts of hydroxyl group-containing vinyl monomers such as acryloyloxymonoethyl phthalate and the polycarboxylic acid anhydrides,
J [Epoxy resin manufactured by Dainippon Ink and Chemicals Co., Ltd.], [
Epicote 828.1001 or 1o04J (epoxy resin manufactured by Shell), [Araldite 6071 or 6084J (epoxy resin manufactured by Cipa-Geigy, Switzerland), Chissonox 221 J [epoxy compound for Nisso mounting] or [Bunacol EX- 611J
Epoxy group-containing polymerizable compounds obtained by addition-reacting various polyepoxy compounds having at least two epoxy groups in one molecule in equimolar ratios, such as [Nagao industrial epoxy compounds], etc. ): Silicon monomers such as vinyl ethoxysilane, α-methacryloxyprogyltrimethoxysilane, trimethylsiloxyethyl (meth)acrylate, or rKR-215 or X-22-5002J [Shin-Etsu Chemical Co., Ltd. product].

In addition, for the purpose of further improving weather resistance, for example, rT-
It is also possible to copolymerize a polymerizable ultraviolet absorber or light stabilizer such as 37 or LA-82J (Adeka Argus Kagaku ■ product).

Various monomers as the component (a-5) include (a-1), (a-2), (
-3) and (a-4), copolymerizability, coating workability, gloss, hardness, flexibility,
The amount of each monomer component to be used and the combination thereof may be determined in the range of 4 to 97% by weight from the viewpoint of weather resistance, drying property, solvent resistance, compatibility, dilubility, solubility, pot life, etc. In particular, when aromatic vinyl monomers such as styrene and vinyltoluene are required, the amount used should be kept to 40% by weight or less, especially 35% by weight or less when weather resistance or yellowing resistance is required. is preferred.

In addition, in the case of silicone monomers such as vinyl ethoxysilane that have a hydrolyzable alkoxy group, if used in large amounts, they may form a silane, so if such monomers are used, the amount used should be It is preferable to suppress the content to 5% by weight or less, particularly 5% by weight or less.

In order to prepare the vinyl copolymer (4) component used in the present invention, the above-mentioned (a-1), (a-2), (a-3), (
It can be carried out by making full use of the known and commonly used copolymerization reaction method or graft copolymerization reaction method using each of the raw material components a-4) and (a-5). Lonitrile (AIBN).

Penzoylnog-oxide (Bpo), t-butyl perbenzonylic acid (TBPB), t-butyl hydroperoxide, di-t-butyl peroxide (DTBPO)
) or cumene hydroperoxide (CHP) may be used alone or in combination.

The organic solvent (C) used in the present invention has an aniline point or mixed aniline point of 7 to 70°C, particularly 8 to 65°C.
Non-polar organic solvents in the temperature range of °C are preferred, typical examples include toluene (mixed ani'Jy point 8.8 °C).
, xylene (mixed aniline point 10.8℃), "Tsuruni Tsuso 100J (mixed aniline point 13.5℃: Exxon Chemical Products)," Tsurupetz 150J (mixed aniline point 16℃)
: Same), "Swazol 100J (mixed aniline point 24,
6℃: Maruzen Petroleum Products), "Swazol 200J (mixed aniline point 29, 4 degrees Celsius)," Suwazol 31o (mixed aniline point 4386 degrees Celsius), "Swazol 1000"
J (mixed aniline point: 12.7°C: same), [Swazol 1500J (mixed aniline point: 16.5°C: same), [Esso Naphtha IEr, 3 J (aniline point: 58°C: Exxon Chemical Products), "Esson Naphtha/FL5 J" (aniline point: 55℃: same), "Esso Naphtha A6J (aniline point: 43℃: same),"``House'' (aniline point: 15℃: Nigel Chemical Products), "Wauth" (aniline point: 44℃: same)
, "Vegasol ARO-80J (mixed aniline point 25℃
: Mobil Oil Products), “-2 Gasol R-100J
(Mixed aniline point 14℃), [-! Gasol R-1
50J (mixed aniline point: 16°C), [PEGASOL 1725NJ (aniline point: 56°C: same), Gasol 3040J (aniline point: 56°C: same), Pegasol AN-45J (aniline point: 44°C), "Non-polar aromatic hydrocarbons and aliphatic hydrocarbons with relatively weak dissolving power such as Vegasol 1725J (aniline point 56°C), methylcyclohexane (aniline point 40°C) or ethylcyclohexane (aniline point 44°C) and naphthenic hydrocarbon-based organic solvents.These may be used alone or in combination of at least two or more.

In addition, typical examples of polar organic solvents that can be used in combination with the non-polar organic solvent in the present invention include ethyl acetate, butyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, or 3-methoxybutyl acetate. Strong solvents that do not have functional groups that react with isocyanate groups, such as ester solvents or ether ester solvents, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone. Can be mentioned.

The blending ratio of these non-polar organic solvents and polar organic solvents is determined based on the performance required for the paint, such as drying properties, coating workability, solvent resistance of the coated material, finished appearance, coating viscosity, and intended use. Although it varies depending on the degree of requirement, non-polar organic solvent/polar organic solvent = 10010~ in the final coating system
It may be selected as appropriate within the range of 40/60 (weight ratio). In this case, the vinyl copolymer solution prepared using only a non-polar organic solvent as the solvent system may be diluted with a diluting thinner and a non-polar organic solvent to form a paint, or the mixture ratio may be within the range described above. It may also be diluted with a polar organic solvent to make it into a paint. Conversely, a vinyl copolymer solution prepared only with a polar organic solvent may be diluted with a non-polar organic solvent as a dilution thinner to achieve the above-mentioned blending ratio, or a non-polar organic A vinyl copolymer solution may be prepared using a combination system of a solvent and a polar organic solvent, and diluted with a non-polar organic solvent and/or a polar organic solvent to obtain the above-mentioned blending ratio to form a coating.

Number average molecular weight (Mn) of the vinyl copolymer (4) obtained
If it is less than 3,000, the physical properties of the coating film such as weather resistance, drying property, hardness, and solvent resistance will be poor; if it exceeds 30,000, the physical properties of the coating film as described above are good, but it will be susceptible to non-polar solvents. It is not preferable because it deteriorates the solubility, texture, finished appearance, leveling property, etc.

Therefore, Mn=3,000-30,000. In particular,
It is preferably within the range of about 5,000 to 20,000. Also, 5 weight average molecular weight (Mw)/number average molecular weight (
When the ratio Mn ) is less than 1.8, weather resistance, drying properties, solvent resistance, flexibility, pigment dispersibility, etc. are poor, while when it exceeds 25, pigment dispersibility may be improved. Both are unfavorable since they tend to cause problems in painting workability, dilutability, non-volatile content during painting, pot life, etc. Therefore, the ratio Mw/Mn is 1
．． If a resin composition with a good sealing layer and pigment dispersibility is desired, a range of 8 to 25 is appropriate.

The polyisocyanate (B) used as a curing agent in the present invention includes aromatic diisocyanates such as tolylene diisocyanate or diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexane diisocyanate; isophorone diisocyanate, methylcyclohexane- alicyclic diisocyanates such as 2,4 (or 2,6)-diincyanate), 4,4'-methylenebis(cyclohexyl isocyanate) or 1,3-(isocyanatomethyl)cyclohexane; or these diincyanates and ethylene glycol; Polyether polyols (such as polyethylene glycol, polyzolobylene glycol or polycaprolactone polyols), polyhydric alcohols such as trimethylolethane or trimethylolethane, and low molecular weight polyester resins with functional groups that react with incyanate groups (oil-modified ), vinyl copolymers, adducts with water, etc., vinyl copolymers, copolymers (oligomers) of diisocyanates, or 2-hydroxypropyl (meth)acrylate and hexamethylene diisocyanate. A copolymer containing as an essential component a vinyl monomer having an isocyanate group and a copolymerizable unsaturated bond such as an equimolar adduct or incyanate ethyl methacrylate; furthermore, JP-A-61-7201
Incyanurate obtained by reacting C2 to C8 alkylene, cycloalkylene, and aralkylene diisocyanates with C4° to C4o diols in the presence of an isocyanurate catalyst as disclosed in Publication No. 3 Examples include polyisocyanates that have rings and are soluble in non-polar organic solvents, but in so-called weak solvent paint systems that use a large amount of non-polar organic solvents, JP-A-61
Use of polyisocyanates soluble in non-polar organic solvents, such as those disclosed in Japanese Patent No. 72013, provides particularly favorable results.

The vinyl copolymer of each of the above-mentioned components (4) and (B)
From the viewpoint of coating film performance, the blending ratio of the component with polyisocyanate is OH/NCO = 1/0.2 to 1/1.
．． 8 (equivalence ratio), particularly preferably within the range of 1/(0.5 to 1.5). 0.2 of NGO per equivalent of OH
If the amount is less than the equivalent, the desired physical properties of the coating film will not be obtained;
．． If the amount exceeds 8 equivalents, the physical properties of the coating film will be sufficient, but there is a risk of foaming under high humidity, and this is not preferable in terms of paint price.

The resin composition for paint of the present invention is used for automobile repair.

When applying or repairing coatings that are susceptible to polar solvents, such as those for roofs or building exteriors, reducing or eliminating the amount of polar solvents It does not cause the lifting (chidemi) that occurs when applying paints containing paints, and provides a smooth and good coating film with high commercial value.It also has excellent abrasiveness and can be sanded as a sanding sealer or Zolaimer surfacer. It saves time, and problems such as vent cracks are less likely to occur with plastic materials with poor solvent resistance, such as polycarbonate, which is easily attacked by polar solvents. In addition, for two-tone finishing or repair of automobiles or motorcycles, the repainting interval is very short, and if you use a non-polar organic solvent that is photochemically inactive and has low toxicity, it is possible to Compared to the case where highly toxic polar solvents are used, the working environment is significantly improved, pollution is reduced, and performance can be significantly improved.

In addition, in the present invention, room temperature drying or forced drying,
Paper cure (vapor cure) is cured in an amine stream.
(abbreviation for parmiatlon curing) system and VIC (vapor injection curin) system.
It can be applied under any curing conditions, such as the curing system (abbreviation for g), and generally uses paint additives known and commonly used in the industry, such as pigment dispersants, ring agents, ultraviolet absorbers, or curing accelerators. Needless to say, plasticizers and other resins such as vinyl copolymers, fibers, etc. can be used for the purpose of improving performance, as long as they are compatible and soluble in the coating resin composition of the present invention. Elemental compounds, vinylated alkyd resins, alkyd resins, silicone resins, fluororesins, or epoxy resins can be used in combination as appropriate, and pigments can be mixed to form an enamel paint, or they can be used as a clear paint without being mixed. You can also do it.

Coating can be done by a known method such as spraying or roller.

〔Example〕

Next, the present invention will be specifically explained using reference examples, working examples, and comparative examples.

In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 [Example of preparation of copolymerizable unsaturated bond-containing resin (a-4)] 513 of isophthalic acid was placed in a four-way flask equipped with a stirrer, a thermometer, a reaction product water removal device, and a nitrogen gas introduction tube.
parts, 19 parts of maleic anhydride, 106 parts of ashichonic acid,
391 parts of neoantyl glycol, 83 parts of trimethylolpropane, 30 parts of pentaerythritol, and 0.005 parts of an antifoaming agent were charged, the temperature was raised to 180°C, and the temperature was maintained for 2 hours. The temperature was raised to 220'C over time, and maintained at the same temperature under a nitrogen gas atmosphere until the acid value became 9 or less, and toluene/n-butyl acetate = 85 so that the nonvolatile content was about 60%. /15 (weight ratio), the nonvolatile content is 60%, the Gardner viscosity at 25°C (the same applies hereinafter) is U, and the acid value is 5.
An unsaturated bond-containing polyester resin having an OH value of 0 and an OH value of 72 was obtained.

Hereinafter, this will be 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 4-ntaerythritol, and The same procedure as in Reference Example 1 was carried out, except that 0.005 part of the antifoaming agent was charged and "Swazol 310" was used as the solvent. 3.6, an OH value of 54, and an oil length of 40%, a dehydrated castor oil fatty acid-modified unsaturated bond-rich polyester resin was obtained.

Hereinafter, this will be abbreviated as resin (a-4-2).

Reference Example 3 (same as above) 300 parts of toluene and 500 parts of n-butyl acetate were charged into a four-way flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and after raising the temperature to 115°C, styrene was added. 200 parts of, 300 parts of methyl methacrylate,
417 parts of n-butyl methacrylate, 58 parts of β-hydroxyethyl acrylate, 200 parts of toluene, t
- A mixture of 30 parts of butyl peroctoate and 5 parts of di-tert-butyl peroxide was added dropwise over a period of 4 hours, and after maintaining the same temperature for about 15 hours, 25 parts of maleic anhydride was added. Then, at the same temperature, the acid value is about 7.
When the non-volatile content was 50% and the viscosity was Y
An unsaturated gold-containing vinyl copolymer having an acid value of 7.5 was obtained. Hereinafter, this will be abbreviated as resin (a-4-3).

Reference Example 4 (same as above) Into a reactor similar to Reference Example 3, 300 parts of toluene and 500 parts of n-butyl acetate were charged, the temperature was raised to 115°C, and at the same temperature, 80 parts of n-butyl methacrylate, 300 parts of adamantyl acrylate, 140 parts of 2-hydroxyethyl methacrylate, 20 parts of methacrylic acid, n
- a mixture consisting of 460 parts of butyl acrylate, 233 parts of toluene, 30 parts of t-butyl peroctoate and 5 parts of 1-butyl peroctoate for 4 hours)
The solution was added dropwise to the solution, kept at the same temperature for about 15 hours, and then lowered to 90°C.

Then 0.03 parts of hydroquinone, 33 parts of glycidyl methacrylate and 0.03 parts of 2-methylimidazole were added.
．． When 1 part was added and held at this temperature of 90°C until the acid value became 1 or less, the nonvolatile content was 50%, the viscosity was U, the acid value was 0.9, and the OH value was 35. , an unsaturated gold-containing vinyl copolymer was obtained.

Hereinafter, this will be abbreviated as resin (a-4-4).

Reference Example 5 [Preparation example of vinyl copolymer (4)] 700 parts of "House" (petroleum hydrocarbon solvent) was charged into a Yotsuro flask equipped with a stirrer, a thermometer, an inert gas inlet, and a condenser. The temperature was raised to 120°C, and at the same temperature, 150 parts of styrene, 8 parts of methacrylic acid, 21 parts of methyl methacrylate, 140 parts of 2-hydroxyethyl methacrylate, 200 parts of n-butyl acrylate, 481 parts of adamantyl methacrylate, ``House'' 300
9. A mixture of 10 parts of t-butyl perbenzoate, 5 parts of di-t-butyl peroxide, and 30 parts of t-butyl peroctoate was added dropwise over a period of 4 hours. When kept at the same temperature for about 15 hours, the nonvolatile content was 50%, the viscosity was P, and the acid value was 3.0.
A desired copolymer (4) having an OH value of 30 and Mw/Mn = 2.0 was obtained. Hereinafter, this will be abbreviated as copolymer (A-1).

Reference Example 6 (same as above) In a reactor similar to Reference Example 5, 34 parts of the unsaturated bond-containing polyester resin (a-4-1) obtained in Reference Example 1, 400 parts of xylene, and 400 parts of isobutyl acetate were added. part and t
- 5 parts of butyl peroctoate, 140 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid,
150 parts of methyl methacrylate5 100 parts of t-butyl methacrylate, 20 parts of styrene, 330 parts of ethyl methacrylate, 200 parts of isobutyl acrylate
and 150 parts of a monomer mixture consisting of 50 parts of adamantyl acrylate and 50 parts of adamantyl acrylate were charged, heated to 90°C, kept at the same temperature for 30 minutes, and heated to 90°C.
The temperature was raised to 115°C in minutes.

Then, at a temperature of 115 DEG C., the remaining 830 parts of the monomer mixture and 186 parts of toluene were combined with 20 parts of -butyl peroctoate, 5 parts of azobisisobutyronitrile and 10 parts of t-butyl perbenzoate. A mixture of
After holding for 0 hours, the nonvolatile content was 50%, the viscosity was V, the acid value was 4.0, the OH value was 35, and Mw/Mn =
A desired copolymer pellet of 4.9 was obtained. Hereinafter, this will be abbreviated as copolymer (A-2).

Reference Example 7 (same as above) In a reactor similar to Reference Example 5, the resin obtained in Reference Example 1 (
a-4-1), 333 parts of the resin obtained in Reference Example 2 (a
-4-2), 5 parts of t-butyl-octoate, 2 parts of fumaric acid, and 367 parts of "Nous", and as vinyl monomers, 8 parts of methacrylic acid, 8 parts of styrene, 100 parts, 190 parts of n-butyl methacrylate, 10 parts of inbutyl methacrylate
0 parts and 100 parts of adamantyl methacrylate, and as the remaining solvent, 300 parts of "Swazol 310", and as a polymerization initiator (radical generator), 15 parts of t-butyl perbenzoate, The non-volatile content was 50%, the viscosity was U, and the acid value is 4.8, OH value is 28, and Mw
A target copolymer (A) having /Mn = 9.0 was obtained.

Hereinafter, this will be abbreviated as copolymer (A-3).

Reference Example 8 (same as above) 700 parts of toluene was charged into the reactor, and the vinyl monomers were 100 parts of 2-hydroxyethyl methacrylate, 50 parts of 2-hydroxyethyl acrylate, 20 parts of methacrylic acid, and methyl. Reference except that 230 parts of methacrylate, 200 parts of n-butyl methacrylate, 200 parts of inbutyl methacrylate, and 200 parts of adamantyl acrylate were used, and 300 parts of toluene was used as the remaining solvent. In the same manner as in Example 5, a desired copolymer having a nonvolatile content of 50%, a viscosity of T, an acid value of 6.5, an OH value of 34, and Mw/Mn = 2°3 was obtained. . Hereinafter, this will be abbreviated as copolymer (A-4).

(,41) Reference Example 9 (same as above) In a reactor similar to Reference Example 5, the resin obtained in Reference Example 2 (
As the vinyl monomers, 1,083 parts of a-4-2), 8 parts of t-butyl nog-octoate, and 267 parts of "Walx" were charged. 9 of methacrylate
0 parts and 50 parts of adamantyl acrylate, and the remaining solvent is 200 parts of
Furthermore, as polymerization initiators, 15 parts of t-butyl benzoate, 5 parts of di-t-butyl peroxide and 100 parts of n-butyl acetate were used. The non-volatile content was 50 parts in the same manner as in Reference Example 6 except that 20 parts were used.
%, the viscosity is X, the acid value is 2.0, the OH value is 50, and MY / Mn = 15 (4
) was obtained. Hereinafter, this will be abbreviated as copolymer (A-5).

Reference Example 10 (same as above) In a reactor similar to Reference Example 5, the resin obtained in Reference Example 1 (
a-41), 475 parts of xylene, and 100 parts of n-butyl acetate.
parts, 9 parts of acrylic acid, 170 parts of methyl methacrylate
Reference Example 6 except that 100 parts of cyclohexyl methacrylate, 86 parts of n-butyl acrylate and 200 parts of adamantyl methacrylate were used, and 300 parts of xylene was used as the solvent for the remainder. Similarly, the nonvolatile content is 50% and the viscosity is Y.
So, the acid value is 4.5, the OH value is 75, and Mw /
A desired copolymer (4) with Mn = 3.0 was obtained.

Hereinafter, this will be abbreviated as copolymer (A-6).

Reference Example 11 (same as above) The resin obtained in Reference Example 2 (
a-4-2), 300 parts of toluene, and 200 parts of "Naphtha No. 3".As vinyl monomers, 50 parts of ethyl methacrylate, 287 parts of n-butyl methacrylate (containing monomer), 287 parts of n-butyl methacrylate,
- 100 parts of ethylhexyl methacrylate, 100 parts of adamantyl acrylate and 200 parts of adamantyl methacrylate, and the remaining solvent is 300 parts of toluene, and the polymerization initiator is t-butyl・Mother - 15 of benzoate
5 parts of di-t-butyl peroxide and 25 parts of t-butyl peroctoate. , the acid value is 0.9, the OH value is 40, and Mw
A desired copolymer (5) having /Mn=3.4 was obtained. below,
This is abbreviated as copolymer (A-7).

Reference Example 12 (same as above) In a reactor similar to Reference Example 5, the resin obtained in Reference Example 1 (
34 parts of a-4-1), the resin obtained in Reference Example 2 (a-
4-2) and 586 parts of "House", the vinyl monomers were 10 parts of rT-37J [UV-absorbing monomer manufactured by Adeka Argus Chemical ■], r LA-82J ( 10 parts of methacrylic acid (same as above), 8 parts of methacrylic acid, 22 parts of 2-hydroxyethyl acrylate
part, 210 parts of n-butyl acrylate, 110 parts of adamantyl methacrylate, and 510 parts of adamantyl acrylate, and as the remaining solvent, 300 parts of "Swazol 310" were used.
Furthermore, as a polymerization initiator, 15 parts of t-butylnoyachenzoate, 10 parts of di-t-butyl peroxide, 10 parts of t-butyl peroc)ate, and 35 parts of t-butyl peroctoate are used. The same procedure as Reference Example 6 was carried out except that the non-volatile content was 50%,
The viscosity is S, the acid value is 4.6, the OH value is 20, and M
A desired copolymer having w/Mn=6.2 was obtained. Hereinafter, a copolymer (A-8) was obtained from this.

Reference Example 13 (same as above) Into a reactor similar to Reference Example 5, 500 parts of toluene and 200 parts of "Naphtha No. 3" were charged, the temperature was raised to 100°C, and at the same temperature 150 parts of styrene and methacrylic acid were added. Part 8 of
200 parts of 2-ethylhexyl acrylate, 140 parts of 2-hydroxyethyl methacrylate, 100 parts of n-butyl methacrylate, 402 parts of adamantyl acrylate, 300 parts of "Esson Naphtha No. 3", 10 parts of t-butyl peroctoate. A mixture of 5 parts of di-t-butyl peroxide and 30 parts of t-butyl peroctoate was added dropwise over 4 hours, and after the dropwise addition was completed, the same temperature was maintained for about 15 hours. Non-volatile content is 5
0%, a viscosity of T, an acid value of 3.0, an OH value of 30, and a desired copolymer powder having Mw/Mn = 2.1 was obtained. Hereinafter, this will be abbreviated as copolymer (A-9).

Reference Example 14 [Preparation example of polyisocyanate (B) by the method disclosed in JP-A No. 61-72013] A glass product with a capacity of 51, equipped with a stirrer, a thermometer, an air-cooled tube, and a nitrogen gas introduction tube. In a four-eye flask K, under a nitrogen gas atmosphere, 3,5% of "Desmosil H" (hexamethylene diisocyanate, manufactured by Bayer AG, West Germany) was added.
00 parts and [Roxanol] (manufactured by Henkel, West Germany, 12-hydroxystearyl alcohol; purity =
716.3 parts (approximately 80%) were prepared.

Next, this flask was attached to an oil bath and heated for 65 minutes while stirring.
When the temperature was raised to ℃, the contents of the flask became a homogeneous liquid.

Subsequently, the temperature was maintained at the same temperature for 2 hours, and then the temperature was lowered to 55°C.

After that, N, N,
3.4 parts of a 20% butyl cellosolve solution of N-trimethyl-N-2-hydroxypropylammonium paratertiary buterpenezoate was added in portions, followed by holding at 60°C for 3 hours to carry out the reaction. The isocyanurate reaction was completed by adding 3.4 parts of a 7% xylene solution of monochloroacetic acid to deactivate (deactivate) the isocyanurate catalyst.

Next, after cooling the reaction mixture to room temperature, the 1.00%
0 part was subjected to molecular distillation, and the distillation residue was 549% of the desired polyisocyanate having an incyanurate ring.
．． 4 parts (conversion rate = 55.0%) and 450.0 parts (recovery rate =
45.0%).

Thereafter, this incyanurate ring-containing polyisocyanate was diluted to a concentration of 75% with a non-polar solvent, "NO-US", to obtain a transparent solution of the target product. Hereinafter, this will be abbreviated as polyisocyanate (B-1), which has a nonvolatile content of 75.1%, a Gardner color number of 1 or less, a viscosity of E-F, and an isocyanate group content. was 11.2%, Mn was 953, and the dilution rate with respect to the diluting solvent "NO-US" was 1,000% or more.

Examples 1 to 9 and Comparative Examples 1 to 4 Each copolymer obtained in Reference Examples 5 to 13 (A-1
) to (A-9) were used in accordance with the formulations shown in Table 1 to form a paint by a conventional method.

Next, among the various paints obtained in this way, a mixed solvent of "House"/xylene/"Esso Naphtha No. 3 J = 50/40/10 (weight ratio) was used for the example products, and a mixed solvent of "House"/xylene/"Esso Naphtha No. 3 J = 50/40/10 (weight ratio)" was used for the comparative example products. Xylene/n-butyl acetate-50
Using a mixed solvent of 150 (weight ratio) as a thinner, these various paints were diluted to 12 to 13 seconds with Foudkazzo #4.

Thereafter, each of the paints diluted in this way was spray-coated onto a Gende #144 treated dull steel plate, forcedly dried at 60° C. for 40 minutes, and then left at room temperature for 7 days to harden.

The cured coating films thus obtained were evaluated for various physical properties as shown below.

In addition, among these physical property evaluations, test items (1) to (4) and (force) to be conducted for these evaluations are as follows: After being force-dried at 60° C. for 40 minutes, it was left to stand at room temperature for 7 days to harden.

The results of physical property evaluation are summarized in Table 2.

(Test items) (1) Gloss: 600 gloss (2) Hardness: Hardness caused by scratches caused by a pencil.

(3) Adhesion: Secondary adhesion (gopan adhesion) after exposure to blister GEX at 50° C. and 98% RH for 240 hours.

(4) Gasoline resistance Visually judge the condition of the painted surface after immersing it in Futatsuki regular gasoline for 2 hours at room temperature.

(5) Lifting property: The following three cases are possible, and the test was conducted for each of them.

Case of ■: A painted plate with a structure of coating film ■/paint film @/coating film θ/steel plate, and this coating film ■ is the same as each of the paints obtained in Examples 1 to 9 and Comparative Examples 1 to 4. This is a new repair coating film by , the coating film @ is a lacquer type Zolaimer surfacer, and the coating film θ is a crosslinked type so-called old coating film (existing coating film), which is a urethane-based, It is obtained using a crosslinked resin such as a thermosetting acrylic resin or a thermosetting polyester resin.

In such a case, after forming a coating film @ on the coating film θ, force drying at 60°C for 40 minutes, leave it for a day and night, and then polish it with #400 waterproof coating. However, when a paint film (■) is formed on the degreased material, lifting occurs in the part of the paint film (@).

In this test, "New One Coat" was used as this coating film.
The one obtained using [Isamu Paint ■ Product] was used.

Case of ■: A painted plate with a structure of coating film ■/paint film @/coating film θ/steel plate, and this coating film ■ is the same as each of the paints obtained in Examples 1 to 9 and Comparative Examples 1 to 4. The above coating film @ is a cross-linked Deraimercer-7 Acer, and the above coating film θ is a lacquer type so-called old coating film (existing coating film), and the above coating film @ is a so-called old coating film (existing coating film) of a lacquer type, and is an NC lacquer. , modified acrylic lacquer, straight acrylic lacquer or high solid lacquer.

In such cases, after forming a coating film @ on the coating film θ, force drying at 60°C for 40 minutes, leaving it overnight, and polishing with #400 waterproof paper.
When coating film (■) is applied on a degreased surface, lifting occurs in the area of this coating film (θ).

In this test, “Hipura Surf 2C” was used as the coating film@.
The one obtained using Isamu Paint ■Product] was used.

Case of ■: A painted board with a structure of coating film ■-■/painting film ■-■/painting film @/slate board, and both of these coating films ■-■ and ■-■ are the same as Examples 1 to 9 and These are top coats using the respective paints obtained in Comparative Examples 1 to 4, and first,
It is obtained by applying the first coat, leaving it at 30°C for about 6 hours, and then applying the same paint as a second coat, and the above coating film has the following composition: Mastic paint layer.

[MS-10OJ Into powdered calcium carbonate] 1
Part 44 “Demol EP J [Dispersant manufactured by Kao ■]
3 parts ethylene glycol 3 parts 2 parts
8% ammonia water 1 part water
24 In such cases, on top of the above coating.

The targets are those in which a coating film ■-■ is formed, and then a coating film ■-■.
■ Lifting occurs.

(6) Effect of paint and solvent used on material: Visually judge the degree of occurrence of solvent cracks.

(Weather resistance: Gloss retention rate (%) after one year of outdoor exposure in Miyazaki.

(8) Repairability: Each paint obtained in Examples 1 to 9 and Comparative Examples 1 to 4 was applied to an ABS resin plate until the dry film thickness was 1.
The gradient was applied separately to 0 to 60 microns by spray coating, forced drying at 60°C for 40 minutes, and left at room temperature for 30 to 40 minutes. The paint was spray-coated separately to a dry film thickness of 40 microns, forced drying was performed at 60° C. for 40 minutes, and the condition of the painted surface after drying was visually determined.

(9) Metal return Shimura: “Acridic 47-
567J (Acrylic polyol manufactured by Dainippon Ink and Chemicals; non-volatile content = 50%, OH value = 30) "Alpece) 170ONLJ
A mixture of 10% and 10% traps is used. ]
was spray-coated onto a tin plate and left at room temperature for 40 minutes. Next, a portion of the thus obtained coated plate was coated with each of the paints obtained in Examples 1 to 9 and Comparative Examples 1 to 4 (however, ``A type of clear paint that lacks the use of Thai hardness CR-93J'') with the specified thinner, respectively.
After diluting to a spray viscosity, the resulting paint was poured separately and cured, and the flow state of the aluminum particles was visually determined.

OC drying property: Evaluated by the dryness to the touch when painted on a glass plate.

0υ Solid content during painting: This is the solid content when diluted with a specified thinner in a Ford cup #4 for 11 to 12 seconds.The higher this value, the better the texture. This means good dilutability to solvents.

"Swasol 310" of α2 vinyl copolymer (4)
Tolerance: Vinyl Copolymer II! Displayed as dilution rate (%).

(131 Pigment Dispersibility 2) The above three pigments were used in the prescribed PWC, and the primary color enamel paste was milled separately in a sand mill for 60 minutes, and according to Table 1, Examples 1 to 9 and Comparative Example 1 were prepared. ~4
and each white enamel paint obtained in TlO2/
Cargen black = 98/2 (weight ratio), TlO2/quinacridone red or phthalocyanine blue = 951
5 (weight ratio), and further add a predetermined amount of "Burnock DN-980" and "Silicone Oil KF".
-69J (leveling agent from Shin-Etsu Chemical Co., Ltd.) was mixed, diluted with a mixed solvent of xylene/n-butyl acetate = 50150 (weight ratio) to a spray viscosity, sprayed each separately, and after drying to the touch, The same paint is applied to each part separately and cured, and the color difference between the sprayed part and the flow-coated part is compared and determined.

*1) "Acrydic A-801-PJ: Acrylic liol manufactured by Inu Nippon Ink Chemical Industry ■; Non-volatile content = 5
0%, OH number = 50, solvent = toluene/n-butyl acetate.

Junior High 2) [Acrydic 52-614J: Non-volatile content = 5
0%, OH number = 17.5, solvent = xylene/n-butyl acetate.

3) [Acrydic A-808J: Same as above.

However, OH value = 20° *4) [Tie Bake CR-93J: Rutile type titanium oxide manufactured by Ishihara Sangyo ■.

Umbrella 5) Tinuvin 328 J Ultraviolet absorber manufactured by Cipa-Geigy, Switzerland.

6) Tinuvin 770 J: A light stabilizer manufactured by the same company.

Umbrella 7) Thinner ■ 2 "House"/xylene/"Essonaphtha No. 3 J = 50/40/10 (weight ratio) mixed solvent.

*8) Thinner ■: xylene/n-butyl acetate; 501
50 (by weight) mixed solvent.

Book 9) “Burnock DN-950J: Hexamethylene diisocyanate-trimethylolzolo-benzene addition polyisocyanate manufactured by Dainippon Ink & Chemicals ■; Non-volatile content =
75%, isocyanate group content = 12.5%.

*10) "Burnock DN-980J: Hexamethylene diisocyanate-based isocyanurate type polyisocyanate manufactured by the same company; non-volatile content = 75%, incyanate group content = 15%.

〔Effect of the invention〕

As is clear from the results in Table 2, the resin composition for paints of the present invention has excellent drying properties, solubility, repaintability, and has little effect on materials with low solvent resistance. Moreover, it can be used in a wide range of applications as mentioned above, as it has excellent hardness, texture and hardness of the coating film.

Agent: Patent Attorney Katsutoshi Takahashi Procedural amendment April β, 1986

Claims (1)

[Claims] 1. (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [However, R in the formula represents a hydrogen atom or a methyl group. ] Adamantyl (meth)acrylate (a-1
)2 to 95% by weight Hydroxyl group-containing vinyl monomer (a-2) 1 to 50% by weight Carboxyl group-containing vinyl monomer (a-3) 0 to 10% by weight Copolymerizable unsaturated bond-containing resin (a-4) 0 to 80% by weight
and the above (a-1), (a-2), (a-3)
and/or 4 to 97% by weight of other vinyl monomer (a-5) copolymerizable with each component (a-4) so that the total amount is 100% by weight, and in the presence of a radical generator. The number average molecular weight (@Mn@
) is 3,000 to 30,000, and weight average molecular weight (@Mw@) / number average molecular weight (@Mn@) = 1.8 to 2
5, (B) a polyisocyanate, and (C) an organic solvent as essential components, and the ratio of the vinyl copolymer (A) to the polyisocyanate (B). A resin composition for paint, characterized in that OH/NCO is in the range of 1/0.2 to 1/1.8 (equivalent ratio). 2. The organic solvent (C) described above is a non-polar organic solvent having an aniline point or mixed aniline point of 7 to 70°C, and a polar organic solvent, and the non-polar organic solvent/polar organic solvent = non-polar organic solvent/polar organic solvent
The resin composition for paint according to claim 1, wherein the resin composition is within the range of 100/0 to 40/60 (weight ratio).