JPH0778197B2 - Resin composition for wood coatings - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a new and useful resin composition for wood coatings. More specifically, the present invention comprises a specific alkyd resin-modified vinyl copolymer as an essential component and comprises a cellulose derivative, an ultraviolet absorber, and further a drier and / or a polyisocyanate, among others, a drying property, The present invention relates to a resin composition for wood coatings, which is excellent in thinner resistance, sensation of flesh, and polishing properties.

"Prior Art" Conventionally, as paints for woodworking, there are lacquer-based paints that do not participate in crosslinking and acid-curing aminoalkyd-based or urethane-based paints that contribute to crosslinking.

Among them, the lacquer type is quick-drying and easy to use, but on the other hand, the coating performance, gloss or appearance is inferior to that of the urethane type, and since it does not affect crosslinking, the coating performance is also of the urethane type. It is several orders of magnitude inferior to the ones. On the other hand, acid-curing aminoalkyd-based ones are quick-drying and relatively good in abrasiveness, and in addition to being curable, they are hard and brittle,
It has the drawback of being prone to cracking in the cycle test, and the greatest drawback is the generation of harmful free formalin from paints and cured coatings. Urethane-based ones are also curable, and while they have excellent coating performance, they cannot be said to be generally quick-drying.If the environmental temperature is low in winter, the progress of the crosslinking reaction will slow down and the curing will be insufficient, Excellent coating performance cannot be obtained. Therefore, the advent of a paint system capable of compensating for the defects of both the racker system and the urethane system is desired.

Separately, a method of adding a drying oil fatty acid to an epoxy group-containing acrylic copolymer to obtain an air-curable resin is disclosed in British Patent No. 767476, and such a method is also known. In order to solve the drawback that the resin thus obtained is insufficient in gloss due to insufficient wetting of the pigment, an improved method as described in JP-A-53-51232 and 53-99231 has been proposed. There is.

However, each of the above improved methods is a method of adding a drying oil fatty acid to a glycidyl group in an acrylic resin, and then esterifying with a dicarboxylic acid anhydride such as tetrahydrophthalic anhydride. (1) Production of an acrylic copolymer, (2) modification by addition of a drying oil fatty acid to the copolymer, and (3) esterification of the fatty acid modified copolymer with dicarboxylic acid anhydride. It cannot be said to be a preferable method because it results in extension of the total reaction time consisting of steps and complication of reaction control, resulting in cost increase in production.

"Problems to be Solved by the Invention" In view of the above-mentioned circumstances, the present inventors have proposed a simple method to obtain a drying oil fatty acid-modified vinyl which has good wettability to pigments and excellent gloss. In order to obtain a copolymer, the modified copolymer is additionally used, which is a resin composition for woodworking paint which is quick-drying and has excellent luster and suppleness, and does not easily attack a base coating film or an old coating film. As a result of earnest studies to obtain the above, the present invention has been completed.

"Structure of the Invention" That is, the present invention relates to an epoxy group-containing vinyl monomer of
-25% by weight and 0-60% by weight of aromatic vinyl monomer
Of an alkyd resin having an unsaturated bond capable of copolymerization
0.1 to 10% by weight is copolymerized with 5 to 95% by weight of other vinyl monomers copolymerizable with them, and then,
100 parts by weight of the epoxy group-containing alkyd resin-modified vinyl copolymer thus obtained, an alkyd resin-modified vinyl obtained by addition reaction of a drying oil fatty acid having an iodine value of 100 to 200 in a ratio of 5 to 60 parts by weight. Copolymer (A)
60 to 100% by weight and 0 to 40 of the cellulose derivative (B)
Further, 0 to 10% by weight of the ultraviolet absorber (C) is added to the mixture consisting of 10% by weight and the dryer (D) and / or polyisocyanate ( The present invention is intended to provide a resin composition for woodwork coatings, which is also highly practical, which is particularly excellent in drying properties, thinner resistance, feeling of holding and polishing property, and which also comprises E).

Here, as a typical dry oil fatty acid having an iodine value of 100 to 200, examples of natural oils and fats such as cottonseed oil, soybean oil, rice bran oil, dehydrated castor oil, linseed oil, tall oil or Chinese tung oil are listed. Fatty acids, "Hidiene", "Hidiene H", "Hidiene S", "SK conjugated fatty acid # 20"
[These are products of Soken Chemical Industry Co., Ltd.] or
MOLYN) 200, 300 ”(product of Hercules Co., USA), such as synthetic dry oil fatty acids, which can be used alone or in admixture at any ratio, and the iodine value of such fatty acids can be adjusted. In order to do so, in some cases iodine such as coconut oil fatty acid, castor oil fatty acid, octylic acid, lauric acid, "versatetic acid" (synthetic drying oil fatty acid manufactured by Ciel of the Netherlands), stearic acid or hydroxystearic acid. Use a fatty acid having a valency of less than 100 or a saturated fatty acid in combination with a drying oil fatty acid as described above, as long as the amount is within a range that does not impair the air-drying property of the modified vinyl copolymer (A) obtained. Of course, you can also do it.

The amount of the drying oil fatty acid as described above is appropriately 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the epoxy group-containing vinyl copolymer.

If the amount used is less than 5 parts by weight, the target modified copolymer (A) will be poor in air-curability, and the coating film will not have a sufficient three-dimensional structure, resulting in poor physical properties and solvent resistance. If the amount exceeds 60 parts by weight, yellowing is likely to occur and the weather resistance is also reduced. Flexibility is impaired, resulting in a brittle coating film, which cannot be put to practical use.

Next, the above-mentioned epoxy group-containing vinyl copolymer will be described. First, typical examples of the epoxy group-containing vinyl monomer include glycidyl (meth) acrylate and β
-Methyl glycidyl (meth) acrylate or (meth) allyl glycidyl ether, unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, fumaric acid, maleic acid or itaconic acid, or monovalent with such unsaturated dicarboxylic acids Α, β-ethylenically unsaturated carboxylic acids such as monoesters with alcohol, and “HO
A-MP "or" HOA-HS "[above, a carboxyl group-containing acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.] or a carboxyl group-containing compound, or mono-2- (meth) acryloyloxyethyl phthalate 2 −
Hydroxy group-containing vinyl monomers such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or di-2-hydroxyethyl fumarate and maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, benzenetricarboxylic acid, "Himitic acid" (a product of Hitachi Chemical Co., Ltd.), todecynyl succinic acid, succinic acid, or an adduct obtained by an equimolar addition reaction with a polycarboxylic acid (anhydride) such as tetrachlorophthalic acid. For various unsaturated carboxylic acids,
"Epiclon 200, 400, 441, 850 or 1050" [Epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.], "Epicoat 828, 1001 or 1004" (epoxy resin manufactured by Ciel), "Araldite 6071 or 6084" (Epoxy resin manufactured by Ciba-Geigy, Switzerland), 1 molecule such as "Chitsonokkusu 221" [Epoxy compound manufactured by Chitso Corporation] or "Denacol EX-611" [Epoxy compound manufactured by Nagase & Co., Ltd.] There are epoxy group-containing polymerizable compounds and the like obtained by addition-reacting various polyepoxy compounds having at least two epoxy groups in an equimolar ratio, and these are used alone or in combination of two or more. It can be used, but considering the reactivity, the number of reaction steps, the viscosity or the price of the final product, glycidyl (meth) acrylate or β-methylglycidyl (Meth) liable relatively molecular weight low types of monomers is the most use of such acrylates.

The epoxy group-containing vinyl monomer is used in an amount of 5 to 25% by weight, but since the epoxy group in the monomer is involved in the reaction with the drying oil fatty acid as described above, the amount of the monomer used is Needless to say, it should be determined mainly depending on the amount of the dry oil fatty acid used, and usually, it is used in a ratio of 1.0 to 1.25 equivalent epoxy groups per equivalent of the dry oil fatty acid carboxyl group. It is preferable from the standpoint of reaction rate and the point of preventing the adverse effect of residual carboxyl groups on the coating film.

Further, the above-mentioned alkyd resin having a copolymerizable unsaturated bond is not limited to titanium oxide, pigments having a small oil absorption such as rouge, and particularly quinacridone-based, phthalocyanine-based, azo-based organic pigments and the like. It is used for the purpose of improving the dispersibility of a pigment having a relatively large oil absorption, such as carbon black, which has a poor dispersibility.
In that sense, it can be said that the alkyd resin does not significantly contribute to the coating film performance itself.

As the alkyd resin, those modified with oil or fatty acid, or not modified with them, so-called oil-free alkyd resins are used, but in the present invention, among these alkyd resins, In particular, those having an unsaturated bond copolymerizable with each vinyl monomer are suitable in the present invention.

As the alkyd resin, octylic acid, lauric acid,
Saturated fatty acids such as stearic acid or "versatetic acid"; unsaturated fatty acids such as oleic acid, linoleic acid, linoleic acid, eleostearic acid or ricinoleic acid; "Pamoleen 200, 300", Chinese tung oil (fatty acid), linseed oil (Fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid), cottonseed oil (fatty acid), soybean oil (fatty acid), olive oil (fatty acid), safflower oil (fatty acid), castor oil (fatty acid) or rice bran oil (fatty acid) ) Such as (semi) dry oil (fatty acid) or hydrogenated coconut oil (fatty acid), coconut oil (fatty acid) or non-drying oil (fatty acid) such as palm oil (fatty acid), or one of fatty acids or Ethylene glycol, propylene glycol, glycerin, trimethylolethane, triglyceride with or without a mixture of two or more One or more polyhydric alcohols such as thyrolepropane, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanetriol, pentaerythritol or sorbitol, benzoic acid, pt-butyl. Benzoic acid, (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, tetrahydro (anhydrous) phthalic acid, phthalic acid, tetrachloro (anhydrous) phthalic acid, hexachloro (anhydrous) phthalic acid, tetrabromo (anhydrous) phthalic acid, trimellitic acid , "Hymitic acid", (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, adipic acid, sebacic acid or carboxylic acid such as citric acid. According to the law, if necessary, "Cardeura E-
Monoepoxy compounds such as glycidyl esters of fatty acids such as "10" (product of Ciel), "Epiclon 200, 40
0 ”,“ Epicoat 828, 1001 ”, or a polyisocyanate compound such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or 4,4′-methylenebis (cyclohexyl isocyanate), and each of these diisocyanates One or more polyisocyanates obtained by addition reaction with polyhydric alcohols or water, or polyisocyanates having an isocyanuric ring obtained by (co) polymerization of diisocyanates with each other. Those obtained by reacting by a conventional method by substituting a part of the compounds and carboxylic acids are suitable.

At this time, as the alkyd resin, a saturated fatty acid or a non-drying oil (fatty acid) modified type having no or less copolymerizable unsaturated bonds, or an oil-free alkyd resin type not modified with an oil or a fatty acid is used. For those, a copolymerizable unsaturated bond to be a grafting point of each other vinyl monomer is introduced into the alkyd resin using an unsaturated carboxylic acid such as maleic acid or fumaric acid. Needless to say, is necessary.

Then, the alkyd resin thus obtained is
Within the range of 0.1 to 10% by weight, preferably 0.5 to 8% by weight
However, when the amount is less than 0.1% by weight, the desired pigment dispersibility cannot be sufficiently achieved, while when the amount is more than 10% by weight and too much. Inevitably, the solvent resistance and stain resistance are inferior. In addition, when the amount is too large, the carboxyl group in the alkyd resin and the epoxy group in the epoxy group-containing vinyl monomer react with each other at the time of polymerization to cause gelation. Since it comes out, either case is not preferable.

Therefore, as the amount of the alkyd resin used, within the range as described above, the acid value, the oil length, and the amount of the copolymerizable unsaturated bond so that gelation does not occur due to the reaction between these groups. In addition, it is preferable to determine in consideration of the molecular weight of the alkyd resin and the molecular weight of the resulting modified copolymer (A).

Next, typical examples of the above-mentioned aromatic vinyl monomer include styrene, α-methylstyrene, pt-butylstyrene, vinyltoluene, etc. Among them, styrene is most preferable in terms of price. .

And as the amount of the aromatic vinyl monomer used,
When it is used in a large amount exceeding 60% by weight, the weather resistance of the resulting coating film is poor, making it unsuitable as a resin for outdoor coatings. It should be appropriately determined according to each required performance such as feeling of holding and weather resistance. The range of 10 to 50% by weight is preferable from the viewpoint of the balance of gloss, texture, leveling property and weather resistance.

Furthermore, typical examples of the epoxy group-containing vinyl monomer, aromatic vinyl monomer and other vinyl monomer copolymerizable with the alkyd resin having a copolymerizable unsaturated bond listed above include methyl ( (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, Such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate or alkoxyalkyl (meth) acrylate. each (Meth) acrylates; diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with monohydric alcohols; vinyl acetate, vinyl benzoate or "Veova" (vinyl ester manufactured by Ciel) Vinyl esters; "Viscoat
BF, BFM, 3F or 3FM "[fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, diperfluorocyclohexyl fumarate or Ni-propyl perfluorooctane sulfonamide Fluorine-containing compounds such as (per) fluoroalkyl group-containing vinyl esters such as ethyl (meth) acrylate, vinyl ethers, (meth) acrylates or unsaturated carboxylic acid esters;
Alternatively, it is an olefin such as (meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride.

Further, as typical hydroxyl group-containing vinyl monomers, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate Or hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as polyethylene glycol mono (meth) acrylate; unsaturated such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid The above-mentioned α, β-ethylenically unsaturated carboxylic acids such as monomers and dicarboxylic acids, monoesters of these dicarboxylic acids and monohydric alcohols, and the above-mentioned α, β-unsaturated carboxylic acid hydroalkyl esters. An adduct with various polycarboxylic acids (anhydrides) such as "cardeula E-10", monoglycidyl esters of monovalent carboxylic acids such as coconut oil fatty acid glycidyl ester or octyl acid glycidyl ester, or butylglycidyl ether; Monoepoxy compounds and adducts such as ethylene oxide or propylene oxide; or methylol group-containing compounds such as N-methylol acrylamide or hydroxyethyl vinyl ether can also be used, but monomers containing functional groups such as hydroxyl group-containing vinyl monomers. In that case, it is of course necessary to determine the amount used so as not to cause gelation, and the hydroxyl group in the hydroxyl group-containing vinyl monomer and the (β-methyl) glycidyl (meth) acrylate (β The amount should be determined so that gelation due to reaction with the -methyl) glycidyl group does not occur.

Next, as the above-mentioned cellulose derivative (B), any one can be used as long as it is usually used for paints. Among them, particularly representative ones are nitrocellulose, cellulose acetate, cellulose acetate propio And cellulose acetate butyrate, methyl cellulose, ethyl cellulose or benzyl cellulose.

The cellulose derivative may be used when it is necessary to further improve the drying property, the polishing property, the gasoline resistance and the adhesion property, but the amount used is 40%.
The amount is preferably not more than 30% by weight, preferably not more than 30% by weight, and it does not prevent the use of a conventional and commonly used plasticizer such as dibutyl phthalate or dioctyl phthalate, if desired.

If the amount used exceeds 40% by weight, stain resistance, water resistance, moisture resistance and the like are noticeably reduced, which is not preferable.

The above-mentioned ultraviolet absorber (C) is a component used when it is necessary to further enhance the durability of the composition of the present invention, and it may be added and mixed each time. In that case, It may be used in the range of 0 to 10% based on the total weight of the modified copolymer (A) and the cellulose derivative (B).

If the amount used exceeds 10% and is used in a large amount, the effect is great, but on the other hand, the water resistance is lowered and the cost is often disadvantageous.

Typical examples of the ultraviolet absorber (C) are benzophenone, 2,4-dihydrobenzophenone, 2,2 ', 4,
4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxybenzophenone, 2-hydroxy -4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-5
Sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-
Methoxy-2'-carboxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl-acryloxyisopropoxybenzophenone; 2- (2'-hydroxy-5'-methyl-phenyl) -benzo Triazole, 2- (2-hydroxy-3,5-di-t-amyl-phenyl) -2H-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl-phenyl) benzo Triazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-
Butyl-phenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-isoamyl-phenyl) benzotriazole, (2-hydroxy-5-t-butylphenyl) benzotriazole ;
Phenyl salicylate, 4-t-butyl-phenyl salicylate, p-octyl-phenyl salicylate; ethyl-2-cyano-3,3'-diphenyl-acrylate,
2-Ethylhexyl-2-cyano-3,3'-diphenyl-acrylate; hydroxy-5-methoxy-acetophenone, 2-hydroxy-naphthophenone; 2-ethoxyethyl-p-methoxycinnamate; nickel-bisoctylphenyl sulfaide 4-benzoyloxy-2,
2,6,6-tetramethylpiperidine, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate or "Tinuvin 292" (product of Ciba Geigy), etc., which are used alone However, two or more kinds may be used in combination.

To further increase effectiveness, or "Sumilyzer BH
"T" [Sumitomo Chemical Co., Ltd. product], "Shinotux BCS"
[Products of Shiraishi Calcium Co., Ltd.], “Irganocus 1010
Or use well-known conventional antioxidants such as "1076" (product of Ciba-Geigy), "Noclyzer TNP" [product of Ouchi Shinko Co., Ltd.] or "antioxidant KB" (product of Bayer, West Germany). Or, a conventional anti-skinning agent such as methyl ethyl ketoxime can be used in combination.

Next, the above-mentioned dryer (D) may be any as long as it is usually used for paints, but among them, a typical one is cobalt,
Vanadium, manganese, cerium, lead, iron, calcium, zinc, zirconium, cerium, naphthenates such as nickel or tin, octylates or resinates, etc., but as the amount used, from the usual dose, It may be appropriately determined according to the type of the dryer, the combination of each component, the required performance, and the like.

In that case, a small amount of organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide or t-butyl perpenzoate may be used together to enhance the effect of using the dryer.

Further, known and commonly used additives for coating materials such as pigment dispersants or leveling agents can also be used in combination.

Further, typical examples of the above-mentioned polyisocyanate (E) include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate or diphenylmethane diisocyanate; fats such as tetramethylene diisocyanate, hexamethylene diisocyanate or trimethylhexamethylene diisocyanate. Group diisocyanates; or isophorone diisocyanate, methylcyclohexane-2,4- (or 2,6
-) Diisocyanates such as alicyclic diisocyanates such as diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate) or 1,3-di (isocyanatomethyl) cyclohexane, or each of these diisocyanates and the above polyhydric alcohols, Additives with low molecular weight polyester resins (including oil-modified types) having functional groups that react with isocyanate groups, acrylic copolymers (including those containing styrene as a comonomer component), or water. , And further, a biuret form or the above-mentioned diisocyanates (co)
Examples include polymers (including oligomers).

By the way, in using the polyisocyanate, yellowing by ultraviolet rays, or the use of aromatic diisocyanates or their derivatives that cause cracking is not suitable for outdoor use, and requires only weather resistance. Not suitable for indoor paints. Therefore, in such a case, for outdoor use, an aliphatic diisocyanate or an alicyclic diisocyanate having good weather resistance, or various derivatives thereof may be used.

The amount of polyisocyanate used is OH / NCO = 1 /
An equivalent ratio of 0.1 to 1 / 1.2 is suitable.

In obtaining the composition of the present invention, first, the epoxy group-containing vinyl copolymer is usually prepared by solution polymerization, and then this copolymer is added with the above-mentioned dry oil and fat acid, Although the intended alkyd resin-modified vinyl copolymer (A) is to be obtained, in the copolymerization reaction which should be called the first step reaction, the polymer conversion ratio of the epoxy group-containing vinyl copolymer is Normally,
If 95% or more is secured, it is advantageous because the drying oil fatty acid can be added and the addition reaction, which should be called the second step reaction, can proceed without waiting for the completion of the copolymerization reaction. .

Further, the reaction temperature is not subject to any particular limitation, and a temperature suitable for the polymerization of each component compound as described above at the time of the copolymerization reaction, that is, a temperature within the range of 50 to 140 ° C. which is usually adopted, may be used. On the other hand, during the addition reaction, a temperature suitable for addition of each reaction component as described above, that is, a temperature in the range of 110 to 180 ° C., may be used, and particularly during the addition reaction, a high temperature may be set to promote this reaction. This is also advantageous because it can.

Furthermore, in order to accelerate the addition reaction, an epoxy group ring-opening catalyst may be used, and in this case, any known and commonly used catalyst can be used. Among them, particularly representative ones are triethylamine, diethylenetriamine or imidazole. Such as tertiary amines, BF ₃ complexes or acids such as phosphoric acid or sulfuric acid.

Further, as the polymerization initiator used in carrying out the polymerization, any known and commonly used one can be used. Among them, particularly representative ones are exemplified by azobisisobutyronitrile and benzoyl peroxide. , T-butyl perbenzoate, t-butyl peroctate, di-
Examples include t-butyl peroxide.

Known solvents can be used, and among them, representative ones include aromatic solvents such as toluene or xylene, ester solvents such as ethyl acetate, butyl acetate or cellosolve acetate, alcohol solvents such as methanol or butanol. Or a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone, and an aliphatic or alicyclic solvent such as hexane, heptane, cyclohexane, methylcyclohexane, petroleum naphtha or mineral spirits can also be used.

The type, combination, and amount of the solvent used can be appropriately determined in consideration of the amount of the drying oil fatty acid used and the amount of the vinyl moiety in the epoxy group-containing vinyl copolymer.

"Effect of the invention" The alkyd resin-modified vinyl copolymer thus obtained is obtained by grafting an alkyd resin, which is in the form of a so-called drying oil fatty acid-modified vinyl copolymer. Its good wettability to pigments provides excellent luster, and, due to such a characteristic structure, air curing is also possible by incorporating a dryer.

Further, in the present invention, during the preparation of the epoxy group-containing vinyl copolymer, that is, the alkyd resin is not only radical polymerization during radical polymerization, but the carboxyl group in the alkyd resin within the specific amount is the epoxy group. As a result of the progress of the addition reaction with the epoxy group in the vinyl monomer contained, the resulting modified copolymer (A) also has a wide molecular weight distribution, and therefore has excellent pigment dispersibility and a long-lasting feeling. It is always advantageous to obtain a product having excellent adhesion between the base material and the base material.

The composition of the present invention meets various needs in the art as described above. That is, the resin composition for woodworking paints of the present invention may be said to be a third type of woodworking paint, which is a crosslinking reaction by oxidative polymerization based on a drying oil fatty acid residue contained in the modified copolymer (A). Alternatively, a cross-linking reaction between a hydroxyl group slightly present in the modified copolymer (A) and a polyisocyanate (E) blended therewith, and further, three types of cross-linking reactions of these two are a cross-linking reaction. It can be said that one modified vinyl copolymer (A) is a unique composition that can be adopted as desired and that a coating film with excellent performance can be obtained through such a crosslinking reaction. Further, it goes without saying that it can be used as an enamel paint using known pigments or as a clear paint without using it.

Since the drying oil fatty acid is introduced into the modified vinyl copolymer (A) as an essential component of the composition of the present invention, the composition of the present invention is used as a whole for acrylic polyols used in urethane systems. It has the advantage of being able to use a large amount of a weak solvent because it is more likely to be dissolved in a solvent that has a weaker dissolving power (weak solvent) than a solvent, thus making it difficult to attack the base coating and old coating. Can be obtained.

Furthermore, the modified copolymer (A), which is an essential component of the composition of the present invention, has a hydroxyl group by the unique method of adding a dry oil fatty acid to the epoxy group-containing vinyl copolymer, and in addition, In the present invention, in addition to the epoxy group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer can be used in combination, if necessary, so that it is possible to further contain a hydroxyl group by such means, and as a result, a polyisocyanate is obtained. By blending (E), it is possible to adopt a method of urethane cross-linking and curing, and also a method of curing by oxidative polymerization cross-linking and curing by a dryer (D) and two cross-linking reactions of this urethane cross-linking and curing. There are advantages.

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

Reference Example 1 [Preparation Example of Modified Vinyl Copolymer (A)] In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet, 800 parts of xylene and “Betuzol P-470- 70 "[a long oil alkyd resin manufactured by Dainippon Ink and Chemicals, Inc.] and 71 parts of di-t-butyl peroxide (hereinafter abbreviated as DTBPO) were charged to prepare 1
When the temperature is raised to 25 ℃ and reaches the same temperature, styrene (St)
400 parts, 300 parts of methyl methacrylate (MMA), 55 parts of acrylonitrile (AN), 125 parts of glycidyl methacrylate (GMA), 70 parts of ethyl acrylate (EA), 10 parts of azobisisobutyronitrile (AIBN) , A mixture of 7 parts of t-butyl peroctate (TBPO) and 4 parts of t-butyl perbenzoate (TBPB) was added dropwise over 5 hours, and the mixture was kept at the same temperature for 5 hours after the completion of the addition of non-volatile components ( NV) is 53.9% and 50 parts of linseed oil fatty acid, 150 parts of soybean oil fatty acid and 2-methylimidazole (2MI
Z) and 0.2 parts of Z) to carry out the addition reaction between the glycidyl group and the carboxyl group at the same temperature.
A solution of a fatty acid-modified vinyl copolymer having a viscosity of 0.3% and a viscosity (Gardner; the same below) of Z ₆ and an acid value of 2.6 was obtained.
To this, 400 parts of xylene was added to adjust the NV to 50%.

The resin solution thus obtained has an NV of 50.1% and a viscosity of Y-
In Z, the number of colors (Gardner; the same applies below) is 5 to 6, and the number average molecular weight (hereinafter abbreviated as ▲ ▼) by gel permeation chromatography (GPC) is 8,30.
It was a clear solution of 0. Hereinafter, this is abbreviated as modified copolymer (A-1).

Reference Example 2 (same as above) In a flask similar to Reference Example 1, "Betuzol 1343" was added.
(Domestic oil alkyd resin manufactured by the same company)
Charge 1,300 parts and 3 parts of DTBPO and heat up to 120 ℃,
At the same temperature, 300 parts St, 300 parts MMA, 200 parts GMA, 100 parts n-butyl acrylate (BA), 15 parts AIBN, 1 part TBPO.
A mixture consisting of 0 part and 2 parts of TBPB was added dropwise over 5 hours and kept at the same temperature for 12 hours to continue the polymerization.
At this stage, NV was 42.0%, and a white wax-like vinyl copolymer which was not dissolved in the terpene was obtained at this stage.

Next, 100 parts of cottonseed oil fatty acid and 300 parts of dehydrated castor oil fatty acid were added to this copolymer and reacted at 150 ° C. until the acid value became about 1, NV was 50.8% and viscosity was ZZ ₁
Thus, a transparent resin solution having an acid value of 1.1, a color number of 1 to 2 and an n of 7,200 was obtained. Hereinafter, this is abbreviated as a modified copolymer (A-2).

Reference Example 3 (same as above) In a flask similar to Reference Example 1, 1,200 parts of xylene,
Charge 29 parts of "Betuzol P-470-70" and 4 parts of DTBPO, heat up to 125 ℃ and reach the same temperature. Then 200 parts of St,
230 parts of MMA, 125 parts of GMA, 100 parts of BA, 225 parts of n-butyl methacrylate (BMA), 100 parts of 2-hydroxyethyl methacrylate (2-HEMA), 5 parts of AIBN, 3 parts of TBPO and A mixture consisting of 5 parts of TBPB was added dropwise over 5 hours, and the polymerization was continued at the same temperature until the NV reached 44%. 100 parts of linseed oil fatty acid and 1 part of safflower oil fatty acid were added.
When 00 parts and 0.02 part of BF ₃ etherate were added and reacted to an acid value of about 1, NV was 50.5%, viscosity was Z ₄ , color number was 2, acid value was 1.8 and hydroxyl value was 35 and n is 14,00
A transparent resin solution of 0 was obtained. Hereinafter, this is abbreviated as modified copolymer (A-3).

Reference Example 4 (Same as above) In a flask similar to Reference Example 1, 1,075 parts of xylene,
125 parts of "Betuzol J-571" (long oil alkyd resin manufactured by the same company) and 4 parts of DTBPO were charged and heated to 125 ° C. When the temperature reached the same temperature, 400 parts of St, 200 parts of BMA Department, GMA
50 parts, 2-HEMA 100 parts, AN 50 parts, BA 100 parts, TBPO
18 parts of TBPB and 4 parts of TBPB were added dropwise over 4 hours,
After continuing the polymerization for 12 hours, the temperature was raised to 150 ° C., 100 parts of dehydrated castor oil fatty acid was added and the addition reaction was continued until the acid value was close to 1, NV was 49.3%, viscosity was Z ₁ , acid value was Is 1.2,
A transparent resin solution having a hydroxyl value of 30, a color number of 5 to 6, and a triangle of 11,000 was obtained. Hereinafter, this is abbreviated as modified copolymer (A-4).

Reference Example 5 (same as above) A flask similar to that of Reference Example 1 was used, except that a water separator was used instead of the reflux condenser, and 545 parts of isophthalic acid, 248 parts of adipic acid, and 36 of neopentyl glycol.
2 parts, 276 parts of trimethylolpropane and 18 parts of fumaric acid were charged and reacted in a N ₂ stream at 180 ° C. for 3 hours, then heated to 220 ° C. over 2 hours to continue the reaction,
At the same temperature, when the solid content acid value reaches about 6, the temperature is lowered, and then NV is diluted to 60% with a mixed solvent of xylene / butyl acetate = 50/50 (weight ratio), and the viscosity is HI, Acid value is 3.
An oil-free alkyd resin solution containing a polymerizable unsaturated bond having a hydroxyl value of 8, a color number of 2, and a color number of 2 was obtained.

Then, 34 parts of this resin solution, 1,200 parts of xylene, and 5 parts of DTBPO were charged into a flask similar to that of Reference Example 1 and heated to 125 ° C., and at the same temperature, St300 parts, MMA30
Parts, t-butyl methacrylate (t-BMA) 100 parts, GMA1
25 parts, BMA285 parts, 2-HEMA40 parts, BA100 parts, AIBN8 parts, TB
A mixture of 3 parts PO and 5 parts TBPB was added dropwise over 5 hours, and the polymerization was continued at the same temperature until the NV reached 44%. 100 parts of linseed oil fatty acid and 100 parts of safflower oil fatty acid were added. And 0.04 parts of BF ₃ etherate to add acid value 1
After reacting to the vicinity, NV is 50.1%, viscosity is YZ, acid value is 1.9, color number is 2, hydroxyl value is 25, and ▲ ▼ is 1.
2,000 clear resin solutions were obtained.

Hereinafter, this is abbreviated as modified copolymer (A-5).

Reference Example 6 (Same as above) NV was 50.6%, viscosity was Y, color number was 2 and acid value was the same as in Reference Example 2 except that the same amount of t-BMA was used instead of St. Was obtained, and a transparent resin solution having a ▲ ▼ of 7,100 was obtained. Hereinafter, the modified copolymer (A
It is abbreviated as -6).

Reference Example 7 (Same as above) Instead of 200 parts St, 100 parts t-BMA, 50 parts Ni
-Propyl perfluorooctane sulfonamide ethyl acrylate and 50 parts of "biscoat 8F" [Octafluorobutyl methacrylate manufactured by Osaka Organic Chemical Co., Ltd.]
Same as Reference Example 3, except that the NV was changed to 49.8%, the viscosity was Z ₃ , the color number was 2, the acid value was 1.7, the hydroxyl value was 35, and ▲ ▼ was 14,000. A resin solution was obtained. Hereinafter, this is abbreviated as modified copolymer (A-7).

Reference Example 8 (Preparation Example of Modified Vinyl Copolymer for Control) This example is a modified vinyl copolymer for control in which the use of an alkyd resin having a copolymerizable unsaturated bond is completely absent. For preparing a combined product, a flask similar to that of Reference Example 1 was charged with 818 parts of xylene and 2 parts of DTBPO, and the temperature was raised to 125 ° C.

After reaching the same temperature, the NV was changed by repeating the same operation as in Reference Example 1 except that the amount of EA used was changed to 120 parts.
At 54.1%, 50 parts of linseed oil fatty acid, 150 parts of soybean oil fatty acid and 0.2 part of 2-MIZ were added, and the addition reaction was continued until the acid value became around 2.5.

Next, 400 parts of xylene was added to adjust the NV to 50%, and the NV was 49.8%, the viscosity was Y, the color number was 5 to 6, the acid value was 2.2, and ▲ ▼ was 8,000. A different resin solution was obtained. Hereinafter, this is abbreviated as a modified copolymer (A-8).

Reference Example 9 (Same as above) Except that the use of "Betuzol 1343" was completely absent, the amount of terpen used was 1,400 parts, and a white wax-like vinyl copolymer having an NV of 41.8% was obtained. When the same procedure as in Reference Example 2 was performed, NV was 50.1%, viscosity was YZ, acid value was 1.0, the number of colors was 1-2, and ▲ ▼ was
7,000 clear resin solutions were obtained. Hereinafter, this is abbreviated as modified copolymer (A-9).

Reference Example 10 (same as above) Instead of 3.4 parts of the polymerizable unsaturated bond-containing oil-free alkyd resin solution, 20 parts of BMA and 14 parts of xylene were used, and the initial charging amount to the flask was 1,200 parts to 1,214 parts.
Parts, and except that the amount of BMA to be dropped was changed from 285 parts to 305 parts, NV was 49.9%, viscosity was XY ² , acid value was 1.8 and color number was the same as in Reference Example 5. 1, the hydroxyl value is 25,
Moreover, a transparent resin solution having a ▲ ▼ of 12,000 was obtained. Hereinafter, this is abbreviated as modified copolymer (A-10).

Reference Example 11 (same as above) Instead of 200 parts of St, the same amount of t-BMA was used, and instead of 29 parts of "betucosol P-470-70", 20 parts of BMA and 9 parts of xylene were used, respectively. In the same manner as in Reference Example 3, except that the vinyl monomer and the solvent were used not as an initial charge but as a drop, the NV was 50.0% and the viscosity was Z ₂ ,
The number of colors is 1, the acid value is 1.9, the hydroxyl value is 35, and ▲ ▼
A transparent resin solution having a viscosity of 14,000 was obtained. Hereinafter, this is abbreviated as modified copolymer (A-11).

The modified copolymers (A) obtained in Examples 1 to 20 and Comparative Examples 1 and 2 and Reference Examples 1 to 7
-1) to (A-7) and "Taipec CR-93" [Rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.] as shown in Tables 1 and 2, 6% cobalt naphthenate A white enamel paint was also prepared by using a dryer containing 24% lead naphthenate = 50/50 (weight ratio), a cellulose derivative, an ultraviolet absorber and / or a polyisocyanate. However, Comparative Examples 1 and 2 are examples in which commercially available acrylic urethane-based paints for woodworking were used.

The cellulose derivatives are 1/4 second nitrocellulose (1/4 ″ NC) and “CAB-551-0.2”.
[Cellulose acetate butyrate (CAB) manufactured by Eastman Kodak Co., USA] is used, and as a UV absorber, "Tinuvin 292" / "Tinuvin 900" = 50/5
A mixture of 0 (weight ratio) (both “Tinubin” is a product of Ciba Geigy in West Germany) was used as the polyisocyanate “Vernotsk DN-950” [Hexamethylene diisocyanate-based polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.]. Isocyanate] and “Coronate EH” (hexamethylene diisocyanate polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) were used, but in Examples 2 and 22, 2 parts of butylbenzyl phthalate plasticizer was also used. All of the cellulose derivatives were used as a 40% methyl ethyl ketone solution.

Then, the white enamel is made into a paint by adding 100 parts of the modified copolymer (A) which is the main ingredient of the varnish for paint and a predetermined amount of "Taipaque CR-93", and further adding 30 parts of xylene and 200 parts of glass beads. Was added and kneaded in a sand mill for 90 minutes to obtain a PWC of 35%. As a thinner for this dilution, xylene / i-butyl acetate = 90.
A mixed solvent of / 10 (weight ratio) was used.

Next, the coating was carried out by the spray coating method, but as the base material for the evaluation of Tables 1 to 3, a teak material whose substrate was adjusted with a glass plate and an acrylic urethane sanding sealer was used. A tin plate is used in Table 4, and a teak material is used in Table 5. As the curing condition, forced drying at 50 ° C for 40 minutes is adopted, and each coating film performance test is conducted after such forced drying.
It was done after leaving it for a day. (First to third and fifth)
Table) Among the test items, the "adhesion" test was performed after cutting the edges, that is, after inserting the crosscut and then peeling the cellophane tape.

The "weather resistance" test was conducted at 1,500 hours of exposure on a Sunshine Weatherometer, and at 2 in Miyazaki City.
The gloss retention rate (%) is shown when exposed outdoors for one year.

The "drying" test was to dry on the glass plate after touch-drying (unit: min), put 4 layers of gauze on the surface of the coating, and then put 100 g of weight on it for 1 minute. Gauze traces were made by visual inspection, and the dryness evaluation criteria were as follows.

⊙ No gauze traces at all ○ …… Slight gauze traces are present △ …… Gauze traces are significantly present × …… Remarkably gauze traces are shown in Table 1 for Examples 1 to 20. Tables 1 and 2 also show Comparative Examples 1 and 2.

The water whitening resistance and the feeling of meat retention were evaluated according to the following evaluation criteria.

A: Excellent B: Good B: Inferior X: Remarkably inferior Incidentally, Comparative Examples 3, 4, 5 and 6 are examples in which commercially available acrylic urethane-based paints for woodworking were used.

As for the water whitening resistance, the degree of gloss and whitening of the coating film after visually immersing in 40 ° C. water for 5 days was visually evaluated. Crack resistance is −
One cycle of holding at 20 ° C. for 2 hours and then at 80 ° C. for 2 hours is shown as the number of cycles until cracking occurs in the coating film.

Examples 21 to 30 and Comparative Examples 3 to 6 Each of the Examples and Comparative Examples in this series was evaluated as a clear coating, and the coating was performed by a spray coating method. Curing conditions were forced drying at 50 ° C. for 40 minutes.

Each Example and Comparative Example of this series is for conducting comparative examination on pigment dispersibility, and first,
All enamel bases have the prescribed PW as shown below.
Modified copolymers (A-1) to (A-11) so that C becomes
100 parts by weight of each of the pigments were weighed, 30 parts of xylene and 200 parts of glass beads were added separately and kneaded in a sand mill for 2 hours to prepare. Various paints were prepared by adding a mixture of 4%, 6% cobalt naphthenate / 24% lead naphthenate = 50/50 (weight ratio) to the solid content of the modified copolymer used therein. .

White …… “Taipec CR-93”, PWC: 35% Black …… “Royal Spectra Mark II” (Carbon black made by Columbia Carbon Co., USA), PWC: 30
% Red …… “Farstogen Super Red BN” [Quinacridone pigment manufactured by Dainippon Ink and Chemicals, Inc.], PWC:
10% green …… “Farstogen Green S” (Cyanine Green manufactured by Doujinsha Co., Ltd.), PWC: 10% Next, we examined the pigment dispersibility of each paint. The evaluation criteria for the presence or absence of pigment aggregation are as follows.

◎ …… No abnormality × …… Thixotropic property or cohesive property and poor dispersibility Next, color difference between spray / flow coating of four color mixture system (△ E)
Is the ratio of white / black / red / green = 100/5/5/5 (weight ratio),
Mix each of the above enamel varnishes, and then add a mixture of 6% cobalt naphthenate / 24% lead naphthenate = 50/50 (weight ratio) to prepare a four-color mixed paint separately on a tin plate. It is carried out by measuring the color difference (ΔE) of a coated plate which has been spray-coated, then touch-dried and then flow-coated. The smaller this value, the smaller the color difference, and thus the better the pigment dispersibility. Can be said.

The above results are summarized in Table 3 below.
Neither thixotropy nor pigment aggregation was observed in each of the examples and comparative examples when "Taipaque CR-93" was used as titanium oxide, and therefore, it is not shown in the table.

Examples 38 to 43 and Comparative Examples 11 to 13 Each of the Examples and Comparative Examples in this series was evaluated for a sanding sealer, and the coating was performed by a spray coating method. Curing conditions were forced drying at 50 ° C. for 40 minutes.

The abrasiveness is 30 ° C after forced drying at 50 ° C for 40 minutes.
After 40 minutes, hand polish with # 400 sandpaper 20 times to visually evaluate the sharpness of the coating on the paper and the state of scuffing of the scraps on the paper. displayed.

⊙: Excellent polishability, no paper scuffing ○: …… Smoothness, normal paper with some scuffing △ ……… Poor grindability, paper scuffing is also possible × The results of Example 38 and Comparative Examples 11 to 13 are shown in Table 4 together.

As is clear from the above results, the coating films obtained in the respective examples have a balance of gloss, drying property, thinner resistance, flesh feeling and polishing property as compared with those of the comparative examples. You can see that it is good.

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Claims (1)

[Claims] 1. An alkyd resin having an unsaturated bond capable of copolymerization with 5 to 25% by weight of an epoxy group-containing vinyl monomer, 0 to 60% by weight of an aromatic vinyl monomer and 0.1 to 1% of an alkyd resin having a copolymerizable unsaturated bond.
0% by weight and 5 to 95% by weight of other vinyl monomers copolymerizable with these are copolymerized, and then 100 parts by weight of the epoxy group-containing alkyd resin-modified vinyl copolymer (A) thus obtained is added. On the other hand, 60 of an alkyd resin-modified vinyl copolymer (A) obtained by addition reaction of a dry oil fatty acid having an iodine value of 100 to 200 at a ratio of 5 to 60 parts by weight.
To 100 parts by weight and 0 to 40 parts by weight of the cellulose derivative (B), and 0 to 10% by weight of the ultraviolet absorber (C) based on the weight of the mixture. Alternatively, a resin composition for wood coating composition, characterized by further containing a drier (D) and / or a polyisocyanate (E).