JP2987863B2 - Resin composition for paint - Google Patents

Description

The present invention relates to a novel and useful coating resin composition. More specifically, the present invention relates to a coating resin composition containing a vinyl copolymer modified with a rosin glycidyl ester as an essential base resin component,
When used with or without a curing agent component, it has excellent gloss, luster, crispness, solid feeling, hardness, compatibility with other resins, and solubility in solvents. A resin composition for a paint is provided.

[Conventional technology]

So far, a resin in the form of a carboxyl group-containing vinyl copolymer modified with a glycidyl ester of a branched monocarboxylic acid of a synthetic resin group represented by "Kajura E" (product of Shell, The Netherlands) has been used as a coating material. And Japanese Patent Publication Nos. Sho 45-1462, Sho 45-13233, French Patent Nos. 1,531,224 and 1,548,182, and are widely used in practice.

However, since such glycidyl esters have carboxylic acid residues themselves derived from synthetic fatty acids, the solubility in solvents, the compatibility with other resins, or the feeling of meat retention are relatively low. Although it is easy to be
On the other hand, from the place where the refractive index is low, gloss,
It cannot be denied that there is a disadvantage that it is difficult to obtain gloss, sharpness, hardness and the like.

By the way, recently, in fields used for automobiles, automobile repairs, motorcycles, plastics, woodwork, concrete panels, etc., high gloss, high gloss, high sharpness or high feeling of body feeling etc. There is an increasing demand for a coating film that gives an appearance excellent in various performances.

However, as long as the conventional technology is followed, a glycidyl ester-modified vinyl-based copolymer, especially a glycidyl-modified vinyl-based copolymer in which styrene is not used as a vinyl monomer, has a high refractive index. The reality is that it is difficult to obtain a coating film having high gloss, high gloss, high image clarity, and high texture.

[Problems to be solved by the invention]

Therefore, the present inventors have eagerly started research in order to overcome various defects in a conventional paint using a so-called synthetic fatty acid glycidyl ester-modified vinyl copolymer.

Therefore, the problem to be solved by the present invention is, at least, a problem that a curing agent is blended as long as a specific vinyl copolymer modified with glycidyl ester of rosin is used as an essential base resin component. Resin for paints or paints with excellent gloss, luster, clarity, texture, hardness, compatibility with other resins, and solubility in solvents, whether or not blended It is to provide a resin composition.

[Means for solving the problem]

To this end, the present inventors have focused on the problems to be solved by the invention as described above, that is, the present state of the art, the drastic solution of various unresolved problems in the prior art, and the state of the art in the art. Standing on the wishes,
As a result of repeated investigations, a vinyl copolymer modified with glycidyl ester of rosin, obtained by reacting glycidyl ester of rosin with a vinyl copolymer containing carboxyl group, was used as an essential base resin component. The present invention has been completed by finding that such paints have excellent various performances as described above.

That is, the present invention comprises, as an essential base resin component, a reaction product of a carboxy group-containing vinyl copolymer and a glycidyl ester of rosin.
Alternatively, the reaction product comprises the reaction product and a cellulosic compound and / or a saccharose-based compound. Further, as an essential film-forming component, the above-mentioned reaction product and a cellulosic compound and / or a saccharose-based compound are contained. An object of the present invention is to provide a highly useful coating resin composition comprising a compound and a curing agent.

Here, first, the above-mentioned carboxyl group-containing vinyl copolymer [hereinafter, also referred to as copolymer (A). ], For example, those obtained by copolymerizing a vinyl monomer mixture containing a carboxyl group-containing vinyl monomer as an essential component by a conventional method.

At that time, if only typical examples of the carboxyl group-containing vinyl monomer used as an essential component are exemplified, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid Α, β-ethylenically unsaturated carboxylic acids such as monoesters of these dicarboxylic acids and monohydric alcohols, such as unsaturated mono- or dicarboxylic acids; 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (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-hydro Α, β-unsaturated carboxylic acid hydroalkyl esters such as ciethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol mono (meth) acrylate with maleic acid, succinic acid, phthalic acid, hexahydro Adducts of polycarboxylic acids with anhydrides such as phthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "Hymic acid" (a product of Hitachi Chemical Co., Ltd.) and tetrachlorophthalic acid or dodecylsuccinic acid and so on.

Examples of other typical vinyl monomers to be copolymerized with various carboxyl group-containing vinyl monomers as described above include 2-hydroxyethyl (meth) acrylate and 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-
Α, β-ethylenically unsaturated carboxylic acids such as hydroxyethyl-monobutyl fumarate, polypropylene glycol or polyethylene glycol mono (meth) acrylate, “Placcel FM, FA monomer” (caprolactone-added monomer manufactured by Daicel Chemical Co., Ltd.) Hydroxyalkyl esters of acids or adducts thereof with ε-caprolactone; unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid; Α, β-ethylenically unsaturated carboxylic acids such as monoesters of dicarboxylic acids and monohydric alcohols, or the above α, β-unsaturated carboxylic acid hydroxyalkyl esters with maleic acid, succinic acid, phthalic acid, hexa Hydrophthalic acid, Tramic phthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid "Hymic acid" (product of Hitachi Chemical Co., Ltd.) Various types of adducts with anhydrides of polycarboxylic acids such as tetrachlorophthalic acid or dodecylsuccinic acid Unsaturated carboxylic acids and monoglycidyl esters of monovalent carboxylic acids or butyl glycidyl ethers such as "Cardura E", glycidyl esters of coconut oil fatty acids or glycidyl octylate (excluding glycidyl esters of rosin), ethylene oxide or Adducts with monoepoxy compounds such as propylene oxide or adducts thereof with ε-caprolactone; hydroxyl-containing vinyl monomers such as hydroxyethyl vinyl ether; and other copolymerizable vinyl monomers. Examples of the mers include (a): aromatic vinyl monomers such as styrene, α-methylstyrene, pt-butylstyrene, and vinyltoluene; (b): methyl (meth) acrylate and ethyl (meth).
Acrylate, n-propyl (meth) acrylate, i
-Propyl (meth) acrylate, n-butyl (meth)
Acrylate, i-butyl (meth) acrylate, t-
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, dibromopropyl (meth) acrylate, (Meth) acrylates such as tribromophenyl (meth) acrylate or alkoxyalkyl (meth) acrylate; diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with monohydric alcohols; vinyl acetate, benzoic acid Vinyl esters such as vinyl and "Veoba" (vinyl ester manufactured by Shell); "Viscoat 8F, 8FM, 17FM, 3F or 3FM"
[Fluorine-containing acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or Ni-propyl perfluorooctanesulfonamidoethyl (meth) acrylate. Per) fluoroalkyl group-containing vinyl esters, vinyl ethers,
Fluorinated polymerizable compounds such as (meth) acrylates or unsaturated polycarboxylic esters; or (meth) acrylonitrile, vinyl chloride, vinylidene chloride,
There are vinyl monomers without functional groups, such as olefins such as vinyl fluoride or vinylidene fluoride or chlorotrifluoroethylene. Other usable materials include (c): (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide, dimethylaminopropylacrylamide Amide bond-containing vinyl monomers such as alkoxylated N-methylolated (meth) acrylamides; (d): dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) acryloyloxyalkyl acid phosphates And dialkyl [(meth) acryloyloxyalkyl] phosphites or (meth) acryloyloxyalkyl acid phosphites. Further, the above (meth) acryloyloxyalkyl acid phosphates, Or an alkylene oxide adduct of an acid phosphite, an ester compound of an epoxy group-containing vinyl monomer such as glycidyl (meth) acrylate or methyl glycidyl (meth) acrylate with phosphoric acid or phosphorous acid, or an acid ester thereof, Phosphorus-containing vinyl monomers such as -2-acid phosphoxypropyl (meth) acrylate; (e) dimethylaminoethyl (meth) acrylate;
Dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate; (f): vinylethoxysilane, α-methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth) acrylate, “KR-215” and “X −22−500
2 "[products of Shin-Etsu Chemical Co., Ltd.].

For the purpose of further improving the weather resistance and the like among the various properties of the coating, for example, for example, `` NORBLOC 7966 '' disclosed in U.S. Pat.No. 4,523,311 [US Noramco "NORAMC
O) products, or various benzotriazole-based acrylic monomers; or "ADK STAB T-37"
Various polymerizable unsaturated ultraviolet absorbers, such as [Asahi Denka Co., Ltd. products], and various polymerizable lights, such as "ADEKA STAB LA-82" (hindered amine-based acrylic monomers manufactured by Dojo Co.) Stabilizers and the like can be copolymerized.

Further, for the purpose of further improving the pigment dispersibility of the modified vinyl copolymer obtained as the copolymer (A), various kinds of so-called prepolymers having so-called copolymerizable unsaturated bonds are used. Can be used in the range of about 0.1 to 20% by weight.

In this case, the amount of the glycidyl ester of rosin used is not reduced even if a large amount of the copolymerizable unsaturated bond-containing resin is used in excess of 20% by weight. Is not preferred.

If only particularly typical examples of such copolymerizable unsaturated bond-containing resins are given, examples thereof include polyester resin, acrylic copolymer, petroleum resin, rosin ester, and polyether polyol. However, it is particularly preferable to use a polyester resin (including an oil-modified type) or an acrylic copolymer. In particular, in consideration of the properties of the cured coating film, in addition to the unsaturated bond,
As far as possible, those having hydroxyl groups in the structure give the most desirable results.

Examples of such polyester resins and acrylic copolymers are JP-B Nos. 45-22011 and 46-20502,
JP-A-44-7134, JP-A-48-78233 and JP-A-50-581.
A material having a copolymerizable unsaturated bond in the resin skeleton obtained by reacting it with other raw material components as essential, as known in JP 23 Publication Or JP-B-49-47916, 50-6
First, as in Patent No. 223, a saturated polyester having no copolymerizable unsaturated bond is obtained, and then a functional group such as a hydroxyl group or a carboxyl group present in the saturated polyester, or further reacted with a diepoxy compound. Compounds having a functional group reactive with these functional groups and a vinyl group by utilizing the epoxy group introduced by the method described above, for example, those having an acid chloride group and a vinyl group such as (meth) acrylic acid chloride, Those having an epoxy group and a vinyl group such as glycidyl (meth) acrylate, those having an alkoxysilanol group and a vinyl group such as vinylmethoxysilane and (meth) acryloxyethyltrimethoxysilane, maleic anhydride, tetrahydrophthalic anhydride, etc. Having acid anhydride groups and vinyl groups, fumaric acid, (meth) acrylic acid A polyester having a carboxyl group and a vinyl group such as an acid, a molar addition product of 2-hydroxypropyl (meth) acrylate to hexamethylene diisocyanate, a vinyl monomer such as an isocyanate group having a vinyl group such as ethyl methacrylate and a saturated polyester Such as those having a hydroxyl group and a copolymerizable unsaturated bond obtained by being added to, or a hydroxyl group, a carboxyl group, a vinyl monomer having a functional group such as an epoxy group is previously copolymerized as an essential component, these Functional groups having reactivity with the functional groups contained in the acrylic copolymer, as well as the introduction of copolymerizable unsaturated bonds into the saturated polyester described above in the acrylic copolymer having the functional group of And a compound having a vinyl group, such as (meth) acrylic acid chloride. Having an epoxy group such as glycidyl (meth) acrylate and a vinyl group; alkoxysilanol groups such as vinylmethoxysilane and (meth) acryloxyethyltrimethoxysilane; and a vinyl group. 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 ( A hydroxyl group and a copolymerizable unsaturated bond obtained by adding a vinyl monomer such as a meth) acrylate-hexamethylene diisocyanate equimolar adduct or an isocyanate ethyl methacrylate or the like having an isocyanate group and a vinyl group to an acrylic copolymer. And something with is there.

Such polyester resins include saturated fatty acids such as octylic acid, lauric acid, stearic acid or "versatic acid" (synthetic fatty acids from Shell); oleic acid,
Unsaturated fatty acids such as linoleic acid, linoleic acid, eleostearic acid or ricinoleic acid; "Pamoline 200 or 300" (synthetic drying oil fatty acid manufactured by Hercules, USA), chinagiri oil (fatty acid), linseed oil (fatty acid), Dehydrated castor oil (fatty acids), 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 bran oil (fatty acids) Using one or a mixture of two or more drying oils (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,
Trimethimerol propane, neopentyl glycol,
1,6-hexanediol, 1,2,6-hexanetritol,
One or more polyhydric alcohols such as pentaerythritol or sorbitol, and benzoic acid, pt-
Butyl benzoic acid, (phthalic anhydride), hexahydro (phthalic anhydride) phthalic acid, tetrahydro (phthalic anhydride) phthalic acid, tetrachloro (phthalic anhydride) phthalic acid, hexachloro (phthalic anhydride) phthalic acid, tetrabromo (phthalic anhydride) phthalic acid, trimellitic acid,
"Himic acid", one or more carboxylic acids such as (anhydride) succinic acid, (anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid, adipic acid, sebacic acid or oxalic acid, in a conventional manner If necessary, a reaction such as "Toray Silicone SH-6018" (product of Toray Silicone Co., Ltd.) or "X-22-160AS, KR-212 or 213" (product of Shin-Etsu Chemical Co., Ltd.) Silicone resin, monoepoxy compound such as glycidyl ester of fatty acid such as "Kajura E", "Epiclon 200 or 400"
Polyepoxy compounds such as "Epicoat 828 or 1001", or diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-methylenebis (cyclohexyl isocyanate), these diisocyanates and the above-mentioned polyhydric alcohols One or more polyisocyanates having an isocyanuric ring obtained by (co) polymerization of diisocyanates or polyisocyanates obtained by addition reaction with water, and a part of the polyhydric alcohol or carboxylic acid And those obtained by reacting in a conventional manner are suitable.

In addition, if only typical examples of the copolymerizable unsaturated bond-containing acrylic copolymer are given as examples, from among the above-mentioned vinyl monomers, a suitable monomer may be selected. Those obtained by copolymerization with a desired monomer composition by a conventional method are suitable.

The polyester resin and the acrylic copolymer,
Each of them may be used alone or in combination.
More than one type may be used in combination.

In this case, the weight average molecular weight / number average molecular weight ratio ( _w / _n ) of the obtained copolymer (A), that is, the modified vinyl copolymer is about 3 to 40, and When the number average molecular weight ( _n ) is in the range of about 3,000 to 50,000, the most desirable result is obtained in terms of pigment dispersibility.

The amide bond-containing vinyl monomers (c), the phosphorus atom-containing vinyl monomers (d), and the dialkylaminoalkyl (meth) acrylates (e) all impart internal catalytic activity to the acrylic copolymer. Or, it is used when it is desired to improve the adhesion to the material and the compatibility with other resins and the pigment dispersibility.These can be used alone or in combination. From the viewpoint of the effect of use, the phosphorus atom-containing vinyl monomer is 0.05%.
-5% by weight, amide bond-containing vinyl monomer and dialkylaminoalkyl (meth) acrylate are 0.05%
It may be used in the range of up to 10% by weight.

By the way, the amount of the above-mentioned carboxyl group-containing vinyl monomer to be used is suitably an amount within the range of 1 to 40% by weight in the objective modified vinyl copolymer.

If the amount used is less than 1% by weight, the amount of glycidyl ester of rosin used for denaturation is inevitably reduced, and the desired effect is completely lost.
Can no longer be obtained, while if it exceeds 40% by weight,
If the equivalent amount of the glycidyl ester of rosin used for the modification is less than the equivalent amount of the carboxyl group-containing vinyl monomer, the solution of the modified vinyl copolymer itself obtained is inevitable. The viscosity tends to be high, and the dilutability is also reduced, which is undesirable because the so-called coating appearance, such as gloss, gloss, sharpness and solid feeling, is reduced.

When the equivalent number of the carboxyl group-containing vinyl monomer is equal to the equivalent number of the rosin glycidyl ester, the solution viscosity of the resulting modified vinyl copolymer itself is: Conversely, it tends to be low and the dilutability is a place to be improved.
Although the appearance of the coating film represented by gloss, sharpness, and feeling of solidity is improved, the Erichsen value and impact resistance value are reduced, and the brittleness appears. Also, it is not preferable.

Therefore, as described above, the amount of the carboxyl group-containing vinyl monomer used is 1 to 40% by weight,
Preferably, the range of 5 to 30% by weight is appropriate.

Next, if only glycidyl esters of rosin described above are exemplified, gum rosin, tall oil rosin, wood rosin, disproportionated rosin, hydrogenated rosin (water-added rosin), or disproportionated. And a hydrogenated rosin, that is, a glycidyl ester obtained by using a rosin such as "KR-610" (manufactured by Arakawa Chemical Industries, Ltd.).

Specifically, for example, from various rosins as described above, first, a so-called rosin soap is prepared by a reaction with calcium hydroxide, sodium hydroxide, or the like, and then reacted with epichlorohydrin to form a glycidyl ester. None, and then a method of using the product through a purification process such as washing with water may be used.

Examples of the disproportionated and hydrogenated rosin glycidyl ester include, for example, the above-mentioned “KR-610”
Can also be obtained as glycidyl ester "KE-828".

Of course, it can be prepared according to a method other than those described above, and it goes without saying that resin acids other than rosin (eg, shellac) can be used similarly to rosin.

The glycidyl ester of the rosin itself may be added to the resulting copolymer (A) as a modified vinylic copolymer in gloss, luster, sharpness, fleshy feeling, solvent solubility, compatibility with other resins, etc. Is used for the purpose of imparting, the amount of the glycidyl ester used,
When the number of equivalents of the glycidyl group in the glycidyl ester is less than 0.2 equivalent relative to 1 equivalent of the carboxyl group in the above-mentioned carboxyl group-containing vinyl copolymer, the above-described imparting effect is inevitably achieved. On the other hand, if the glycidyl group exceeds 1 equivalent, the glycidyl group is likely to remain in a free form, which is not preferable in any case.

Therefore, the amount of the glycidyl ester used is appropriately in the range of 0.2 to 1 equivalent, preferably 0.3 to 1 equivalent, relative to 1 equivalent of the carboxyl group in the copolymer (A).

Thus, the modified vinyl copolymer as the copolymer (A) is prepared by using a known and common copolymerization reaction method or a graft copolymerization reaction using various raw material components as described above. In this case, for example, azobisisobutyronitrile, benzoyl peroxide, t-butylperoxybenzoate,
Various known radical-generating polymerization catalysts such as t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide are used. Such a radical-generating polymerization catalyst may be used alone or in combination of two or more. Of course, it is possible.

Further, if only a typical example of the solvent used in the process is exemplified, toluene, xylene,
"Solvesso 100" (product of Exxon, USA),
Aromatic hydrocarbons such as "Swazol 1000" (product of Maruzen Petrochemical Co., Ltd.); n-hexane, heptane, octane,
Fatty acids or alicyclic hydrocarbons such as mineral spirits, methylcyclohexane, ethylcyclohexane, "LAWS" (product of Shell); ethyl acetate, butyl acetate,
Isobutyl acetate, cellosolve acetate, 3-methoxybutyl acetate, "EEP" (ester solvents such as products of Eastman Kodak Company, USA; or acetone, methyl ethyl ketone, methyl isobutyl ketone,
In a system that does not use a polyisocyanate compound (c-2) as a curing agent (C) component, such as ketone solvents such as cyclohexanone, etc., soypropyl alcohol, n-butanol, and isobutanol may be used. Alcohol solvents such as ethyl cellosolve and butyl cellosolve.

In preparing the copolymer (A), various methods can be practically used to cause the glycidyl ester of rosin to undergo an addition reaction with the carboxyl group-containing vinyl copolymer. if Tomere to mention something only, as one, after obtained by combining the carboxyl group-containing vinyl copolymer, BF ₃ - presence of etherate and 2-methylimidazole such conventionally known ring-opening esterification catalyst A method of reacting a rosin glycidyl ester in the presence or absence of a rosin is known in the art.A carboxyl group-containing vinyl monomer and a rosin glycidyl ester are reacted with a known and commonly used polymerization inhibitor and ring-opening. After reacting in the presence of an esterification catalyst to obtain an additional monomer, the carboxyl group-containing vinyl There is also a method of polymerizing with other vinyl monomers copolymerizable with the monomer other than the nomer, and as the three, a vinyl monomer mixture containing a carboxyl group-containing vinyl monomer as an essential component, There is also a method in which a glycidyl ester of rosin is allowed to coexist in the same reaction system and a copolymerization reaction and a ring-opening esterification reaction are allowed to proceed at the same time to obtain a desired modified vinyl copolymer. Each method should be appropriately selected and used.

On the other hand, if only typical examples of the above-mentioned cellulosic compounds are exemplified, nitrocellulose,
Cellulose acetate butyrate or cellulose acetate propionate, or the like, and if only typical examples of the saccharose-based compounds described above are given, examples thereof include saccharose acetate butyrate and saccharose acetate isobutyrate. .

If the amount of the cellulose compound and / or saccharose compound (B) used is less than 2% by weight based on the total amount of the modified vinyl copolymer (A), the compound must be used. When the effect of (B) cannot be exhibited, on the other hand, when it exceeds 50% by weight,
In any case, the gloss, the sharpness, the flexibility, the adhesion and the like are liable to be reduced, so that any case is not preferable.

Therefore, the amount of the compound (B) used is 2
An appropriate amount is within a range of 5050% by weight, preferably 5-40% by weight.

Further, as the above-mentioned curing agent (C) component, a polyepoxy compound capable of reacting with a carboxyl group present in the above-mentioned modified vinyl copolymer (A) and a hydroxyl group introduced as required, respectively (C-1) or an amino resin (c-3), or a polyisocyanate compound (c-2).

Among them, first, the polyepoxy compound (c-1)
As only typical examples, diglycidyl ethers of polyhydric alcohols or phenols; diglycidyl esters of polycarboxylic acids;
Or compounds having at least two epoxy groups in one molecule, such as tri (methyl) glycidyl isocyanurate; or copolymers of (methyl) glycidyl (meth) acrylate.

The amount of the polyepoxy compound (c-1) used is less than 0.5 equivalent of the epoxy group relative to 1 equivalent of the carboxyl group in the modified vinyl copolymer (A) having a carboxyl group as an essential component. In such a case,
In any case, it becomes easy to obtain a resin composition for a target paint having desired coating film performance, and on the other hand, the compound (c) is used in an amount exceeding 1.5 equivalents relative to 1 equivalent of a carboxyl group.
When the amount of -1) is used, weather resistance,
None of them is preferable because the solvent resistance, hardness, stain resistance, and the like are easily reduced.

Therefore, the amount of the compound (c-1) to be used is appropriately 0.5 to 1.5 equivalents, preferably 0.8 to 1.1 equivalents, per 1 equivalent of the carboxyl group in the copolymer (A). .

In this case, various known and commonly used curing accelerators such as triphenylphosphine, BF ₃ -etherate or various imidazoles can also be used as appropriate for promoting the curing. Of course may be any conventional amount.

Then, if desired, the copolymer (A) having a hydroxyl group and a carboxyl group introduced as essential functional groups is, of course, a polyisocyanate compound (c-2) as a component of the curing agent (C). Resin (c-3) can also be used as the curing agent (C) component.

If only typical examples of the polyisocyanate compound (c-2) are exemplified, aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexane diisocyanate; isophorone Alicyclic diisocyanates such as diisocyanate, methylcyclohexane-2,4 (or 2,6) -diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), and 1,3- (isocyanatomethyl) cyclohexane; or these diisocyanates ethylene glycol,
Polyether polyols (such as polyethylene glycol, polypropylene glycol or polycaprolactone polyol), polyhydric alcohols such as trimethylolethane or trimethylolpropane, and low molecular weight polyester resins having a functional group that reacts with isocyanate groups (including oil-modified types) ) Or an adduct with an acrylic copolymer or water; or a burette, a copolymer (oligomer) of diisocyanates; or a molar adduct such as 2-hydroxypropyl (meth) acrylate to hexamethylene diisocyanate; copolymer was vinyl monomer as essential components with an isocyanate group and a copolymerizable unsaturated bond such as ethyl methacrylate; as disclosed in JP-61-72013, JP-made C ₂ -C ₈ al Len -, cycloalkylene - Yes and or aralkylene diisocyanates, and a C ₁₀ -C ₄₀ becomes diols, in the presence of isocyanurate catalysts, having an isocyanurate ring obtained by reacting, in a non-polar organic solvent And soluble polyisocyanates.

Further, the above-mentioned polyisocyanate compound (c-
2) is, of course, oximes, keto-enol compounds,
A so-called blocked polyisocyanate compound in a form blocked by various known and commonly used blocking agents such as phenols or methanol can also be used as one kind of the curing agent (C).

A modified vinyl copolymer (A) having a hydroxyl group as an essential component,
The mixing ratio with the polyisocyanate compound (c-2) is OH / NCO = 1 / 0.2 to 1 / 1.8 from the viewpoint of coating film performance.
(Equivalent ratio), preferably in the range of 1 / 0.5 to 1 / 1.5 (same as above).

When the NCO is less than 0.2 equivalent to 1 equivalent of OH for each equivalent ratio, it becomes difficult to obtain the desired coating film physical properties. On the other hand, when the NCO exceeds 1.8 equivalent, Although, although the coating film properties are sufficient, there is a risk of foaming under high humidity,
It is not preferable in terms of paint price.

In this case, various known and commonly used curing accelerators such as tertiary amines, acid phosphates or dibutyltin dilaurate or dibutyltin dioctoate,
That is, a curing accelerator commonly used in urethane-based coatings is appropriately used in a range of a conventional dose.

Further, if desired, the copolymer (A) having a hydroxyl group and a carboxyl group introduced as essential functional groups may, of course, be an amino resin (c) as the curing agent (C) component.
As mentioned above, -3) can also be used. However, if only typical examples of the amino resin (c-3) are given, various amino resins such as melamine, urea, and benzoguanamine can be used. One of the amino compounds
More species or two or, formaldehyde feed material, for example, lower the condensation product obtained by reacting such with formalin or paraformaldehyde (C ₁ ~C ₄₎ etherified obtained by reacting an alcohol and the like.

The amount of the curing agent (C) component, which is the amino resin (c-3), relative to the copolymer (A) component,
The weight% ratio of the former (A) component / the latter (C) component is 30 / 70-9.
A range of 0/10 is appropriate.

When the amount of the amino resin (A) used is less than 10% by weight, it is difficult to obtain desired performance. On the other hand, when the amount is more than 70% by weight, the resin becomes too brittle. Absent.

Further, in such a combination system, the above-mentioned polyepoxy compound (c-1) can be used in a range of 0 to 30% by weight in order to further improve corrosion resistance and adhesion.

In addition, acid phosphates or p-
Various known and commonly used curing accelerators such as toluenesulfonic acid are appropriately used in the usual dose range.

The resin composition for a paint of the present invention thus obtained is used in a system using a curing agent component, or not used at all.
In other words, in a system using only the base resin component and also using a curing agent component, depending on the type of the curing agent (C), for example, for automobile repair, motorcycle, plastics, It can be used for various purposes such as for woodwork, for concrete panels, for roofs, for automobiles, for building exteriors, for heavy-duty corrosion prevention, for cans and home appliances.

Further, in the resin composition for coating of the present invention, including curing by drying at room temperature, forced drying, heat drying, etc., and further, such as paint system such as BepoCure system and VIC system for curing in amine stream. Any curing means or curing conditions can be applied according to the type of the curing agent (C) used. Further, the composition of the present invention includes a pigment dispersant, a leveling agent, an ultraviolet absorber, and a light stabilizer. Alternatively, it is needless to say that a coating additive such as a curing accelerator (curing catalyst), which is generally known in the art, can be added and blended. If soluble, for the purpose of further improving the performance, plasticizers, other acrylic copolymers or vinyl copolymers, cellulose compounds, alkyd resins, acrylated alkyd resins, Recone resin, or the like as appropriate fluorine resin or epoxy resin, can either be used in combination, as enamel paint mixing pigments or,
It can be used as a clear coating without mixing.

Further, as the 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, comparative examples, applied examples, and comparative applied examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 (Preparation agent for copolymerizable unsaturated bond-containing resin) 513 of isophthalic acid 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, 19 parts of maleic anhydride, 106 parts of adipic acid, 391 parts of neopentyl glycol, 83 parts of trimethylolpropane, 30 parts of pentaerythritol and 0.
After charging 005 parts, the temperature was raised to 180 ° C. and maintained at the same temperature for 2 hours. Then, the temperature was raised to 220 ° C. over 3 hours and maintained at the same temperature under a nitrogen gas atmosphere until the acid value became 9 or less. And then
Dilute with toluene / butyl acetate = 65/35 (weight ratio) so that the non-volatile content becomes about 60%.
The Gardner viscosity at C is S, and the acid value is S.
A solution of an unsaturated bond-containing polyester resin having a 5.0 and an OH value of 72 was obtained. Hereinafter, this is abbreviated as resin (a-1).

Reference Example 2 (same as above) 382 parts of dehydrated castor oil fatty acid and 5 of maleic anhydride
Parts, 349 parts of phthalic anhydride, 1 of neopentyl glycol
34 parts, 98 parts of trimethylolpropane, 100 parts of pentaerythritol and 0.005 part of defoamer were charged, except that the solvent was changed to "Swazol 310" (Maruzen Petrochemical Co., Ltd.). As in Reference Example 1, the nonvolatile content was 60%, the viscosity was U, the acid value was 3.6, and the OH
A solution of an unsaturated bond-containing polyester resin modified with dehydrated castor oil having a value of 54 and an oil length of 40% was obtained. Hereinafter, this is abbreviated as resin (a-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 t-butyl methacrylate, and 417 of n-butyl methacrylate.
Of 2-hydroxyethyl acrylate, 200 parts of "Solvesso 100", 30 parts of t-butylperoxyoctoate and 5 parts of di-t-butyl peroxide were added dropwise over 4 hours. After maintaining at the same temperature for about 15 hours, 25 parts of maleic anhydride was added, and the same temperature was maintained until the acid value became about 7, and the non-volatile content was 50%.
A solution of an unsaturated bond-containing vinyl copolymer resin having a viscosity of Y, an acid value of 7.5 and an OH value of 7 was obtained. Hereinafter, this is abbreviated as resin (a-3).

Reference Example 4 (Preparation Example of Glycidyl Ester of Rosin) A four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet, and a condenser was charged with 510 parts of Chinese gum rosin and heated to 90 ° C.

At this temperature, 606 parts of a 10% aqueous solution of sodium hydroxide were gradually added to form a rosin soap.

After measuring the acid value of the mixture and confirming that the conversion to the sodium salt was completely completed, 138 parts of epichlorohydrin was gradually added, and a desalination reaction was carried out.
The crude glycidyl ester was obtained.

Then, 600 parts of toluene was added thereto, and the glycidyl ester was extracted and transferred into the toluene, washed with clean water several times, and washed with sodium chloride and a small amount of residual rosin soap. After the removal, toluene and a small amount of residual water were removed from the system by distillation under reduced pressure to obtain a target glycidyl ester of gum rosin.

Reference Example 5 (same as above) In the same manner as in Reference Example 4, except that 519 parts of disproportionated rosin were used instead of Chinese gum rosin,
The desired glycidyl ester of disproportionated rosin was obtained.

Reference Example 6 (same as above) A glycidyl ester of a target hydrogenated rosin was prepared in the same manner as in Reference Example 4, except that 501 parts of a hydrogenated rosin (hydrogenated rosin) was used instead of the Chinese gum rosin. Obtained.

Example 1 Toluene was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and an inert gas inlet.
400 parts and 267 parts of butyl acetate, and 300 parts of the glycidyl ester of the Chinese gum rosin obtained in Reference Example 4 were charged and heated to 120 ° C. At this temperature, 198 parts of styrene and It consists of 200 parts, 150 parts of n-butyl acrylate, 87 parts of 2-hydroxyethyl methacrylate and 65 parts of methallylic acid, 30 parts of t-butyl peroxyoctoate and 30 parts of t-butyl peroxybenzoate. The mixture was added dropwise over 3 hours, and after completion of the addition, the temperature was raised to 120 ° C., the temperature was maintained for about 15 hours to continue the polymerization reaction, and the nonvolatile content was 60% and the viscosity was Y. A solution of the copolymer (A) mainly having a hydroxyl group, having an acid value of 4.5 and a hydroxyl value of 48 was obtained. Hereinafter, this is abbreviated as copolymer (A-1).

Example 2 A mixture of 72 parts of fumaric acid, 300 parts of toluene and 267 parts of butyl acetate was charged with 150 parts of styrene, 228 parts of methyl methacrylate, and 50 parts of n-butyl acrylate.
And 500 parts of the glycidyl ester of the disproportionated rosin obtained in Reference Example 5, 20 parts of t-butyl peroxyoctoate and 20 parts of t-butyl peroxybenzoate.
20 parts and the mixture was dropped, and after the completion of the drop, 333 parts of xylene was added to dilute the mixture so that the nonvolatile content was 50% and the viscosity was Z. A solution of the copolymer (A) having an acid value of 3.5 and a hydroxyl value of 18 and having no highly reactive primary hydroxyl group was obtained. Hereinafter, this is abbreviated as copolymer (A-2).

Example 3 A mixture of 350 parts of xylene and 300 parts of butyl acetate was charged with 250 parts of styrene and 107 parts of isobutyl methacrylate.
Parts, 50 parts of di-n-butyl fumarate, 100 parts of 2-ethylhexyl acrylate, 103 parts of 2-hydroxyethyl methacrylate, 109 parts of 1,4-butylene glycol monoacrylate, mono-2-methacryloyloxyethyl phthalate 71 parts, 20 parts of "T-37" (polymerizable ultraviolet absorber), 100 parts of cyclohexyl methacrylate,
And 90 parts of the glycidyl ester of hydrogenated rosin obtained in Reference Example 6 and 35 parts of t-butyl peroxyoctoate.
, A mixture of 10 parts of di-t-butyl peroxide and 15 parts of t-butyl peroxide was dropped, and after the dropping was completed, 350 parts of toluene was used as a diluting solvent.
Parts, the non-volatile content is 50%, the viscosity is XY, and the acid value is 2.0.
Thus, a solution of a copolymer (A) having a hydroxyl value of 50 and having mainly a hydroxyl group was obtained. Hereinafter, this is abbreviated as copolymer (A-3).

Example 4 To a place charged with 400 parts of "LAWS" and 267 parts of "Swazol 310" and 300 parts of "KE-828" (a disproportionated, hydrogenated glycidyl ester of rosin), n
140 parts of -butyl methacrylate, 400 parts of t-butyl methacrylate, 50 parts of "Acryester SL" (higher alcohol methacrylate manufactured by Mitsubishi Rayon Co., Ltd.), 2
8 parts of acid phosphoxyethyl methacrylate, 2
40 parts of hydroxyethyl acrylate and 62 parts of methacrylic acid and 40 parts of t-butyl peroxyoctoate.
Except for changing such that dropping a mixture of 20 parts parts and t- butyl peroxybenzoate, the same procedure as in Example 1, a nonvolatile content of 60% and a viscosity at Z _1, acid value 3.1 Thus, a solution of the copolymer (A) having a hydroxyl value of 36 and having mainly a hydroxyl group was obtained. Hereinafter, this is abbreviated as copolymer (A-4).

Example 5 400 parts of xylene and 267 of methyl isobutyl ketone
Parts, and 22 parts of fumaric acid, 100 parts of the glycidyl ester of hydrogenated rosin obtained in Reference Example 6 and 50 parts of "KE-828" were charged to 350 parts of styrene and n-butyl methacrylate. 68 parts of t-butyl methacrylate 157
Parts, 160 parts of di-n-butyl fumarate, 4 parts of acrylic acid
3 parts and 50 parts of mono-2-methacryloyloxyethyl phthalate and t-butyl peroxyoctoate
The procedure was as in Example 1, except that the mixture of 40 parts and 20 parts of t-butyl peroxybenzoate was added dropwise, with a non-volatile content of 60%, a viscosity of W and an acid number of 24. And a solution of a copolymer (A) mainly having a carboxyl group and having a hydroxyl value of 8 was obtained. Less than,
This is abbreviated as copolymer (A-5).

Example 6 84 parts of the resin (a-1) obtained in Reference Example 1 and "KE
-828 ", 400 parts of xylene and 233 parts of butyl acetate were charged to 200 parts of styrene, 80 parts of methyl methacrylate, 100 parts of ethyl acrylate,
-210 parts of ethylhexyl methacrylate, 109 parts of 2-hydroxyethyl methacrylate, 41 parts of methacrylic acid
Part and a mixture of 10 parts of “LA-82” (polymerizable light stabilizer), except that the mixture was changed to drop-wise, and the non-volatile content was 60% and the viscosity was as in Example 1. In Z,
A solution of the copolymer (A) mainly having a hydroxyl group, having an acid value of 3.8, a hydroxyl value of 48, and _w / _n of 4.5 was obtained. Hereinafter, this is abbreviated as copolymer (A-6).

Example 7 180 parts of xylene, 0.12 parts of hydroquinone, "KE-8
28 parts "and 0.1 part of 2-methylimidazole were charged and the temperature was raised to 120 ° C. At this temperature, a mixture consisting of 40 parts of acrylic acid and 76 parts of methacrylic acid was added dropwise over 1 hour. After the completion, the temperature was maintained at the same temperature until the acid value became 4 or less to obtain a rosin glycidyl ester-added monomer.

Next, the same reaction vessel was charged with 310 parts of xylene, 333 parts of toluene, 253 parts of butyl acetate, and 34 parts of the resin (a-2) obtained in Reference Example 2. 386 parts of methyl methacrylate, 86 parts of t-butyl methacrylate, 145 parts of cyclohexyl methacrylate, 5 parts of dimethylaminoethyl methacrylate, and 448 parts of the previously synthesized additional monomer, and t-butyl peroxy. A mixture of 40 parts of octoate and 20 parts of t-butylperoxybenzoate was added dropwise, and the non-volatile content was reduced in the same manner as in Example 1 except that the reaction temperature was changed to 90 ° C. A solution of copolymer (A) having mainly hydroxyl groups, having a viscosity of 50%, a viscosity of V, an acid value of 3.5, a hydroxyl value of 22, and a _w / _n of 3.8, was obtained. Hereinafter, this is abbreviated as copolymer (A-7).

Example 8 To a place where 300 parts of xylene, 200 parts of toluene, 400 parts of butyl acetate, 100 parts of "KE-828", and 200 parts of the resin (a-3) obtained in Reference Example 3 were charged. 100 parts of styrene, 63 parts of n-butyl methacrylate, 150 parts of t-butyl methacrylate, “Placcel FM-1” (ε
-Caprolactone-added monomer), 50 parts of 2-hydroxyethyl acrylate, 226 parts of 1,4 butylene glycol monoacrylate, 21 parts of methacrylic acid,
A mixture consisting of 5 parts of "T-37", 5 times of "LA-82" and 80 parts of cyclohexyl methacrylate, 40 parts of t-butyl peroxyoctoate and 15 parts of t-butyl peroxybenzoate was prepared. A non-volatile content of 50% was obtained in the same manner as in Example 1 except that it was changed to dropping.
%, The viscosity was Z, the acid value was 3.6, the hydroxyl value was 75, and the _w / _n was 6.2, and a solution of the copolymer (A) mainly having a hydroxyl group was obtained. Hereinafter, this is referred to as a copolymer (A-
Abbreviated as 8).

Comparative Example 1 The amount of 2-hydroxyethyl methacrylate was changed to 32 parts, the amount of methacrylic acid was changed to 100 parts, and instead of the glycidyl ester of Chinese gum rosin, the same amount of "Cardura E-10" was used. And a control substance having a non-volatile content of 60%, a viscosity of Z, an acid value of 4.6, and a hydroxyl value of 48, mainly having a hydroxyl group, in the same manner as in Example 1 except that each was changed. A copolymer solution was obtained. Hereinafter, this is abbreviated as copolymer (A'-1).

Comparative Example 2 The amount of n-butyl acrylate was changed to 8 parts, the amount of fumaric acid was changed to 114 parts, and the same amount of "Cardura E-10" was used instead of the glycidyl ester of disproportionated rosin. was changed to, in the same manner as in example 2, a nonvolatile content of 50% a viscosity of Z-Z _1, an acid value of 3.4 and a hydroxyl value is 18, highly reactive primary hydroxyl group No control copolymer solution was obtained. Hereinafter, this is abbreviated as copolymer (A'-2).

Comparative Example 3 The amount of “acrylester SL” was 34 parts, the amount of 2-hydroxyethyl acrylate was 15 parts, the amount of methacrylic acid was 103 parts, and instead of “KE-828”,
The same amount of “SA-9G” (glycidyl ester of synthetic fatty acid manufactured by Idemitsu Petrochemical Co., Ltd.) was used, except that the amount was changed to 60% in the same manner as in Example 4 except that each was changed.
In, a viscosity of Z ₁ -Z _2, an acid value of 3.4 and a hydroxyl value of 3
Thus, a control copolymer solution having a hydroxyl group of 6 was obtained. Hereinafter, this is abbreviated as copolymer (A'-3).

Comparative Example 4 The amount of methyl methacrylate was changed to 365 parts, the amount of methacrylic acid was changed to 79 parts, and the same amount of “SA-9G” was used instead of “KE-828”, respectively. Except that the nonvolatile content was 50%
A control copolymer solution having a viscosity of U, an acid value of 3.6, a hydroxyl value of 22, and a _w / _n of 3.7, mainly having hydroxyl groups was obtained. Hereinafter, this is abbreviated as copolymer (A'-4).

Application Examples 1 to 13 and Comparative Application Examples 1 to 5 Each of the vinyl copolymers obtained in Examples 1 to 8 and Comparative Examples 1 to 4 was used as a base resin component,
In addition, various coating materials were obtained by coating in a conventional manner at the composition ratios shown in Table 1.

Each of the paints is represented by i) a polyisocyanate type paint,
ii) Lacquer type paint and iii) Heat-curable type paint were classified into three types, and performance evaluation was performed for each type in terms of solids content at the time of coating, dryness, and various coating film properties.

The results are shown in Table 2 for the polyisocyanate type paint, in Table 3 for the lacquer type paint, and in Table 4 for the heat-curable paint.

The coating was performed by air spray, and the coating viscosity at that time was 15 seconds using Ford Cup No. 4. For polyisocyanate type coating, xylene / butyl acetate = 60/40 On the other hand, in the case of lacquer type and heat effect type paint, xylene / butyl acetate / n-butanol = 50/30/20
(Same as above).

The drying and curing conditions were such that the polyisocyanate type was dried at room temperature for 2 weeks at room temperature, and the thermosetting type was baking at 150 ° C. for 30 minutes.

Footnotes in Table 1 "Taipaek CR-93": Rutile-type titanium oxide manufactured by Ishihara Sangyo Co., Ltd. "Cemisorb 74": UV absorber manufactured by Chemipro Kasei Co., Ltd. "Sanol LS-765": Sankyo Co., Ltd. -Made light stabilizer "CAB-551-0.01" ... cellulose acetate manufactured by Eastman Kodak Company, USA
Butyrate "Bernock DN-950" ... Hexamethylene diisocyanate prepolymer (Nonvolatile content = 75%, NCO = 12.5%) manufactured by Dainippon Ink and Chemicals, Inc. "Bernock DN-990" ... Isocyanuric ring manufactured by Dojosha Contained polyisocyanate compound (non-volatile content = 75%, NCO = 13.5%) "Super Beckamine L-117-60": Melamine resin manufactured by the same company (non-volatile content = 60%) "Epiclon 1050-70X": manufactured by the same company Epoxy resin (non-volatile content = 70%) "Denacol EX-612" ... Epoxy resin of Nagase Kasei Co., Ltd. Evaluation of various properties was performed in the following manner.

First, the gloss is represented by a 60 ° specular reflection surface (%), then the hardness means the pencil hardness, and the thinner resistance is represented by the number of rubbing by a lacquer thinner.

The stain resistance was determined by applying a felt pen in each color of red, blue and black to the coating film, and then allowing the coating to stand at room temperature for 2 hours, then mixing petroleum benzene / ethanol = 50/50 (weight ratio). When wiping with a solvent, the presence or absence of the trace and the degree of the trace were visually judged.

Further, each of the drying properties is expressed by the time (in minutes) required for “touch” after touching with a finger after painting to eliminate the fingerprint, and “blocking resistance” is defined as “drying resistance”. Four pieces of gauze were superimposed on the membrane, and a weight of 100 g was placed on the gauze. After holding for 1 minute, the presence or absence of gauze traces and the degree of the gauze traces were visually determined.

Here, the criteria for the determination of the stain resistance and the blocking resistance are as follows.

◎… No trace at all ○… Slight trace remains △… Thin but considerable trace ×× Dark and considerable trace ××… Clear traces and cannot be easily wiped further In addition, the finished appearance has three cases, respectively, as shown below.First, as the case, each paint is separately applied to a lacquer type primer surfacer coated iron plate, and the forced drying conditions described above are applied. It is an evaluation of the coating film cured in, and then, as a case, a coating of a urethane type primer surfacer coated iron plate, each coating is applied separately, and dried under the above-mentioned room temperature drying conditions. It ’s an evaluation,
As a case of, the polyester-based intermediate paint coated iron plate, each paint is applied separately, and the evaluation of the coating film cured under the above-mentioned baking conditions, based on the following criteria, leveling, The gloss, the finished skin, the sucking property, and the like were comprehensively determined visually.

◎: All performances such as leveling, gloss, finished skin, and sucking property are excellent.…: Some of these performances are slightly inferior.

Δ: Most of these properties are considerably inferior in terms of level. ×: All of these properties are inferior. Also, as described above, the solid content at the time of coating is determined by using a predetermined thinner. It is indicated with the solid content (non-volatile content) of each paint when diluted to 15 seconds with Ford Cup No.4, and the higher this value, the better the feeling of meat retention. And good solubility in a solvent (dilutability with a solvent).

In addition, natural exposure is expressed as the gloss retention (%) after one year of exposure in the suburbs of Miyazaki City.

Application Examples 14 to 16 and Comparative Example 6 In addition to the above-mentioned various properties, one of the pigments was used to confirm the effect of modifying the modified vinyl copolymer (A) with the resin containing a copolymer unsaturated bond. The dispersibility was evaluated under the following test conditions. The procedure of the evaluation test is as follows, and the results of the evaluation test are as shown in Table 6.

First, evaluation tests include i) evaluation of the cohesiveness of the enamel base, and ii) gloss of the cured coating film.

i) Evaluation of coagulability of enamel base As pigments, "Mitsubishi Carbon MA-100"
[Carbon black manufactured by Mitsubishi Kasei Kogyo Co., Ltd.], “Fast Gen Super Red YE” [Shinkasha Red manufactured by Dainippon Ink & Chemicals, Inc.], “Fast Gen Blue BN” (manufactured by Dojo Corporation) In the case of carbon black, using four types of cyanine blue) and "Fast Gen Green S" (Cyanine Green manufactured by the same company) and according to the composition ratio of the meat mixture shown in Table 5 5% PWC, 10 for regional, Shinkasha Red, Cyanine Blue and Cyanine Green
%, The respective pigment systems were blended, and each of these primary color systems was kneaded with a sand mill and made into a paint to obtain various enamel bases.

Next, for each enamel base, the presence or absence of aggregation and the degree of aggregation were visually determined.

 In addition, those determination criteria are as follows.

…: No aggregation ×: aggregation ii) Evaluation of gloss of cured coating film To each enamel base obtained as described above, an amount of a curing agent component as shown in Table 5 was added,
Further, using a thinner of xylene / butyl acetate = 50/50 (weight ratio), dilute with Ford Cup No. 4 so that the time becomes 15 seconds, and then spray paint each paint obtained on the tin plate, After that, at 60 ° C
After forced drying for 40 minutes, various cured coating films were obtained.

Next, the 60 ° specular reflectance (%) of each cured coating film was measured. The results are summarized in the sixth
As shown in the table.

The higher the value, the better the pigment dispersibility.

[Effect of the Invention] As is clear from Tables 2, 3 and 4, the coating resin composition of the present invention has high gloss, high definition, high flesh, and high gloss. Moreover, it is known that the dilutability with a solvent is good, and that the hardness is also good, that the weather resistance is excellent, and that the thinner resistance is also excellent.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification code FI C09D 175/00 C09D 175/00 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 81/00-81/02 C09D 163/00-163/10 C09D 151/00-153/02 C08L 63/00-63/10

Claims (11)

(57) [Claims] 1. A carboxyl group-containing vinyl copolymer,
A resin composition for a paint, comprising a reaction product of rosin with a glycidyl ester as an essential base resin component. 2. A carboxyl group-containing vinyl copolymer,
A reaction product (A) of rosin with a glycidyl ester,
A resin composition for a coating, comprising a cellulose compound and / or a saccharose compound (B) as an essential base resin component. 3. A carboxyl group-containing vinyl copolymer,
A reaction product (A) of rosin with a glycidyl ester,
A resin composition for a coating, comprising a curing agent (C) as an essential film-forming component. 4. A carboxyl group-containing vinyl copolymer,
A reaction product (A) of rosin with a glycidyl ester,
A resin composition for a coating, comprising a cellulose compound and / or a saccharose compound (B) and a curing agent (C) as essential film-forming components. 5. The carboxyl group-containing vinyl copolymer and the reaction product (A) with rosin glycidyl ester are obtained by adding the carboxy group-containing vinyl copolymer to the rosin glycidyl ester. The glycidyl ester in the latter glycidyl ester is obtained by a ring-opening esterification reaction at a ratio of 0.1 to 1.0 equivalent relative to 1 equivalent of the carboxyl group in the copolymer, and is added to the glycidyl ester. 5. The coating resin composition according to any one of items 1 to 4. 6. The content ratio of the reaction product of the above-mentioned carboxyl group-containing vinyl copolymer with glycidyl ester of rosin and the above-mentioned cellulose compound and / or saccharose compound is such that the former reaction product 50 ~
The coating resin composition according to claim 2 or 4, wherein the amount is 98% by weight and 2 to 50% by weight of the latter compound. 7. A polyepoxy compound (c-c) having two or more epoxy groups in one molecule, wherein said curing agent (C) is
The resin composition for a paint according to claim 3 or 4, which is at least one compound selected from the group consisting of 1), a polyisocyanate compound (c-2), and an amino resin (c-3). 8. A reaction product (A) of the above-mentioned carboxyl group-containing vinyl copolymer and glycidyl ester of rosin, and a polyepoxy compound (c) having two or more epoxy groups in one molecule. -1)
The epoxy group in the latter compound (c-1) is 0.5 to 1.5 with respect to 1 equivalent of the carboxyl group in the former reaction product (A).
8. The coating resin composition according to claim 3, which is within an equivalent range. 9. A reaction product (A) of the above-mentioned carboxyl group-containing vinyl copolymer with glycidyl ester of rosin, and the above-mentioned polyisocyanate compound (c-
4. The use ratio with 2), wherein the isocyanate group in the latter compound (c-2) is in the range of 0.2 to 1.8 equivalents to 1 equivalent of the hydroxyl group in the former reaction product (A). ,Four
Or the resin composition for coating according to 7. 10. The use ratio of the reaction product (A) of the above-mentioned carboxyl group-containing vinyl copolymer with glycidyl ester of rosin and the amino resin (c-3) is the former reaction product. The coating resin composition according to claim 3, 4 or 7, wherein the content is 30 to 90% by weight of (A) and 10 to 70% by weight of the latter resin (c-3). 11. A reaction product (A) of the above-mentioned carboxyl group-containing vinyl copolymer and glycidyl ester of rosin, and a polyepoxy compound (c) having two or more epoxy groups in one molecule. -1) and the above-mentioned amino resin (c-3), and the reaction product (A)
30 to 90% by weight, and 30% by weight or less of the compound (c-1)
And 10 to 70% by weight of the resin (c-3). Claim
8. The coating resin composition according to 3, 4, or 7.