JPH09316275A - Non-aqueous dispersion resin composition and resin composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having high stability and useful as a coating material having excellent vividness, gloss, etc., and high weather resistance, etc., by modifying a polymer insoluble in an organic solvent and a polymer soluble in an organic solvent with a fatty acid. SOLUTION: This resin composition contains (A) a non-aqueous dispersion resin produced by polymerizing (B) a vinyl monomer in (C) an organic solvent capable of dissolving the vinyl monomer and incapable of dissolving the polymer composed of the monomer in the presence of (D) a polymer soluble in the component C. A polymer modified with a fatty acid is used as the vinyl polymer insoluble in the component C and/or the polymer soluble in the component C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful resin composition of a non-aqueous dispersion type resin, and a novel and useful coating composition containing the resin as an essential film-forming component. The present invention relates to a resin composition.
More specifically, the present invention relates to a non-aqueous dispersion type resin composition in which dispersed particles and / or a dispersion stabilizer are modified with a fatty acid, and a coating resin composition using the same, and the coating film is In addition, the pigment dispersibility is good, and in particular, the image clarity, the gloss and the feeling of longevity are excellent, and the weather resistance is also good.

In particular, it is useful as a top coat for anticorrosion paints, paints for metals and building exteriors, and unlike conventional organic solvents, it has little effect on old paint films (existing paint films) and , A non-aqueous dispersion type resin composition having a coating film performance comparable to that of a system using conventional organic solvents, and a coating comprising the non-aqueous dispersion type resin The present invention relates to a resin composition.

[0003]

2. Description of the Related Art Non-aqueous dispersion type resins are used as binders for interior and exterior of buildings, metals, automobiles and the like, but it is one of the difficult techniques to form dispersed particles stably in a solvent. there were. Conventionally,
The coating film of a general acrylic non-aqueous dispersion type resin lacked sharpness and had a slightly low gloss.

[0004]

As described above, in the conventional technique, the stability is good even in the design in which the amount ratio of the dispersion stabilizer is small, and the resulting coating film has clearness and gloss. The actual situation is that no good non-aqueous dispersion type resin has been developed.

[0005] Therefore, the problem to be solved by the present invention is to solve the problem, in particular, to realize improvement of stability of a non-aqueous dispersion resin, and to obtain a fresh resin obtained by using the obtained resin. It has excellent image clarity and luster, has little effect on the old coating film, and the coating film performance is very similar to that of the conventional solvent type. It is to provide a resin composition for paints.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive investigations focusing on the problems to be solved by the invention as described above, the polymer (A) insoluble in the organic solvent and the polymer (B) soluble in the organic solvent have the essential components thereof. By modifying with fatty acid as
The present invention has now been completed upon finding that the stability of the non-aqueous dispersion type resin can be improved.

That is, according to the present invention, in an organic solvent in which vinyl monomers are dissolved but a polymer comprising the vinyl monomer is not dissolved, a polymer which can be dissolved in this organic solvent is used. In a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl monomer in the presence thereof as an essential film-forming component, a vinyl polymer (A) which is insoluble in the above-mentioned organic solvent and/
Alternatively, the present invention intends to provide and claims a non-aqueous dispersion type resin composition comprising a polymer (B) soluble in an organic solvent, which has been modified with a fatty acid. There

Further, according to the present invention, there is provided a polymer which is soluble in the organic solvent in an organic solvent in which the vinyl monomer is soluble but the polymer comprising the vinyl monomer is insoluble. In the presence of a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component, the above-mentioned non-aqueous dispersion type resin is further blended with a dryer. The present invention seeks to provide and claims a resin composition for a non-aqueous dispersion coating, which comprises a heat treatment.

Further, the present invention provides a polymer which can be dissolved in an organic solvent in an organic solvent in which vinyl monomers are dissolved but a polymer made of the vinyl monomer is not dissolved. In the presence of a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component, a metal alkoxide, a metal acylate or a metal chelate is also added. It is said that it is intended to provide a resin composition for a non-aqueous dispersion coating, which comprises compounding, and claims for the resin composition for the non-aqueous dispersion coating,

The present invention further relates to a polymer which can be dissolved in an organic solvent in an organic solvent in which a vinyl-based monomer is dissolved but a polymer comprising the vinyl-based monomer is not dissolved. In the presence of, in a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component,
It is intended to provide a resin composition for a non-aqueous dispersion coating, which is also made by blending a polyisocyanate, and claims for the resin composition for the non-aqueous dispersion coating. ,

Further, according to the present invention, in an organic solvent in which vinyl-based monomers are soluble but a polymer comprising the vinyl-based monomer is insoluble, a heavy solvent which can be dissolved in the organic solvent is used. In the presence of coalescence, in a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film forming component, further comprising an amino resin, It is intended to provide a resin composition for a water dispersion coating, and claims the resin composition for a non-aqueous dispersion coating.

Among them, particularly, the vinyl polymer (A) which is insoluble in an organic solvent is 0 to about 60% by weight of the fatty acid adduct of the epoxy group-containing vinyl monomer, and other copolymerizable non-polymerizable monomers. About 40 monomers with saturated double bonds
The present invention is intended to provide and claims a non-aqueous dispersion type resin composition in a specific form and a resin composition for a non-aqueous dispersion coating, which comprises 100 to 100% by weight. Then

On the other hand, in particular, the vinyl polymer (B) soluble in an organic solvent comprises 0 to about 60% by weight of a fatty acid adduct of an epoxy group-containing vinyl monomer, and other copolymerizable unsaturated double bonds. About 40 to 100% by weight of the monomer having a bond
It is intended to provide a non-aqueous dispersion type resin composition in a specific shape, which is composed of and, and is claimed.

In particular, in the vinyl polymer (A) which is insoluble in an organic solvent, as the other monomer having a copolymerizable unsaturated double bond, its side chain has a carbon number of 1
Or a non-aqueous dispersion type resin composition in a specific form, which is obtained by using (meth) acrylic acid ester and / or vinyl acetate having an alkyl group of 2 as an essential monomer They are trying to provide a resin composition for a dispersion coating, and are claiming it.

Further, in the vinyl polymer (B) which is soluble in an organic solvent, as a monomer having another copolymerizable unsaturated double bond, the side chain thereof has 3 or more carbon atoms. A specific form of non-methacrylic acid ester having a (meth) acrylic acid ester having an alkyl group and / or styrene having an alkyl group in a side chain in an amount of at least about 30% by weight based on the total amount of monomers. It is intended to provide a water dispersion type resin composition and a resin composition for a non-water dispersion coating composition, and it is claimed.

Furthermore, a vinyl polymer (A) which is insoluble in an organic solvent and a polymer (B) which is soluble in an organic solvent.
The composition ratio of the former polymer (A) / the latter polymer (B)
By weight, the solid content is about 10 / about 90 to about 90 / about 1.
The specific form of the non-aqueous dispersion type resin composition and the resin composition for the non-aqueous dispersion paint, which is 0, are intended to be provided and claimed.

Alternatively, for each resin composition,
Furthermore, it consists of blending a dryer and metal alkoxides, metal acylates, metal chelates or polyisocyanates or amino resins,
We are trying to provide and claim a specific non-aqueous dispersion coating composition.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Here, a vinyl polymer (A) that does not dissolve in the above-mentioned organic solvent and a polymer (B) that dissolves in the above-mentioned organic solvent, which form a non-aqueous dispersion type resin, are used. As a method of modifying with a fatty acid, a method of grafting a fatty acid onto an epoxy group-containing vinyl monomer is the most convenient and common method.

As the fatty acids used in the present invention, only the representative ones mentioned above are exemplified, and examples thereof include cottonseed oil, soybean oil, rice bran oil, dehydrated castor oil, linseed oil, tall oil or Chinese tung oil. Such as dry oil fatty acid of various natural fats and oils, "Hidiene", "Hidiene H", "Hidiene S", "SK conjugated fatty acid # 20"
[The above are products of Soken Chemical Industry Co., Ltd.] or “Pamoleen (P
AMOLYN) 200 or 300 "(product of Hercules, USA) and various synthetic dry oil fatty acids.

Alternatively, coconut oil fatty acid, castor oil fatty acid,
Octylic acid, lauric acid, "versatidic acid" (trade name of synthetic non-drying oil fatty acid, manufactured by Shell in the Netherlands),
There are various fatty acids such as stearic acid or hydroxystearic acid having an iodine value of less than 100, and various saturated fatty acids. These semi-drying oils, non-drying oils or saturated fatty acids are the drying oils described above. Of course, it can be used as a mixture with a fatty acid.

As the epoxy group-containing vinyl monomers, only typical ones are exemplified, and glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) allyl glycidyl ether and the like are further included. Is (meth) acrylic acid,
Various unsaturated monomers or dicarboxylic acids such as fumaric acid, maleic acid or itaconic acid, or various α, β-ethylenic monomers such as monoesters of such unsaturated dicarboxylic acids with monohydric alcohols. Saturated carboxylic acids,

"HOA-MP" or "HOA-H"
S ”[above, a product name of a carboxyl group-containing acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], or a mono-2- (meth) acryloyloxyethyl phthalate or 2-hydroxyethyl. A hydroxyl group-containing vinyl monomer such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate or di-2-hydroxyethyl fumarate;

Maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, benzenetricarboxylic acid, "hymic acid" [a product of Hitachi Chemical Co., Ltd .; "hymic acid" is a registered trademark of the same company. ], Various unsaturated carboxylic acids such as an adduct obtained by an equimolar addition reaction with a polycarboxylic acid (anhydride) such as dodecynylsuccinic acid or tetrachlorophthalic acid,

"Epiclon 200, 400, 441,
850 or 1050 "[trade name of epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.]," Epicoat
828, 1001 or 1004 "(made by Shell,
Product name of epoxy resin), "Araldite 6071 or 6084" (product name of epoxy resin manufactured by Ciba-Geigy in Switzerland), "Chissonox 221"
At least two epoxy groups in one molecule such as [trade name of epoxy compound manufactured by Chisso Corporation] or “Denacol EX-810” [trade name of epoxy compound manufactured by Nagase & Co., Ltd.] Having various polyepoxy compounds,

It is a matter of course that the epoxy group-containing polymerizable compound in a form obtained by the addition reaction in an equimolar ratio may be used alone or in combination of two or more kinds. Considering reactivity, number of reaction steps, viscosity or price of final product, etc., monomers of relatively low molecular weight type such as glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate are preferred. Is that it is easy to use.

In the vinyl polymer (A) which is insoluble in the organic solvent, other copolymerizable unsaturated double bond to be used other than 0 to 60% by weight of the fatty acid adduct of the epoxy group-containing vinyl monomer is used. 40 to 10 of monomers
0% by weight, a (meth) acrylic acid ester having an alkyl group having 1 or 2 carbon atoms in its side chain, that is, methyl (meth) acrylate, ethyl (meth)
It is essential to use acrylates and / or vinyl acetate.

The monomers having a copolymerizable unsaturated double bond that can be shared with them are, respectively,

(A) Styrene;

(B) propyl (meth) acrylate,
i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate,
tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, "Acryester SL".
[Manufactured by Mitsubishi Rayon (Co.), C ₁₂ - trade name / C ₁₃ methacrylate mixture, stearyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate or adamantyl (meth) acrylate , Benzyl (meth) acrylate or cyclohexyl (meth) acrylate;

Dibromopropyl (meth) acrylate,
Various alkoxyalkyl (meth) acrylates such as tribromophenyl (meth) acrylate or methoxyethyl (meth) acrylate; dimethyl maleate, diethyl maleate, diethyl fumarate, dibutyl fumarate or dibutyl itaconate, malein Diesters of various dicarboxylic acids represented by acids, fumaric acid or itaconic acid with monohydric alcohols;

(C) 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 or mono -2-hydroxyethyl-
Starting with monobutyl fumarate,

Furthermore, polyethylene glycol or polypropylene glycol mono (meth) acrylate, or an adduct of these with ε-caprolactone,
"Plaxel FM or FA monomer" [trade name of caprolactone addition monomer manufactured by Daicel Chemical Industries]
Such as various hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids; (meth) acrylic acid,
Including various unsaturated mono- or dicarboxylic acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, and further monoesters of these dicarboxylic acids and monohydric alcohols, etc. , Various α, β-ethylenically unsaturated carboxylic acids,

Addition products of the α, β-ethylenically unsaturated carboxylic acids and ε-caprolactone or various α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters as described above, succinic acid and maleic acid. Acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid,
Benzenetricarboxylic acid, benzenetetracarboxylic acid,
"Hymic acid" [a product of Hitachi Chemical Co., Ltd.], an adduct of various polycarboxylic acids such as tetrachlorophthalic acid or dodecynyl succinic acid with an anhydride,

Monoglycidyl of various monovalent carboxylic acids such as "CARDURA E" (trade name of glycidyl ester of branched synthetic fatty acid manufactured by Shell Co., Netherlands), coconut oil fatty acid glycidyl ester or octyl acid glycidyl ester. Esters, or adducts with various monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide; or various hydroxyl group-containing vinyl monomers such as hydroxyethyl vinyl ethers,

(D) Various unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, and monoesters of these dicarboxylic acids and monohydric alcohols, etc. Such as various α, β-ethylenically unsaturated carboxylic acids; or various α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters as described above, and various polycarboxylic acids anhydrides as described above. Various carboxyl group-containing vinyl monomers such as adducts with substances;

(E) Various vinyl esters such as vinyl benzoate or "Veoba" (various product names of vinyl esters of branched aliphatic monocarboxylic acids manufactured by Shell Co.); "biscoat 3F, 3FM, 8F, 8 FM or 17 FM ”[trade name of fluorine-containing acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or N-i-propyl perfluorooctane sulfone. Various fluorine-containing polymerizations such as various (per) fluoroalkyl group-containing vinyl esters such as amidoethyl (meth) acrylate, -vinyl ethers,-(meth) acrylates or -unsaturated polycarboxylic acid esters Compounds; or (meth) acrylonitrile Shiki, various nitrogen-containing vinyl monomers and vinyl chloride, vinylidene chloride, as represented by such vinyl fluoride or vinylidene fluoride, various halogenated olefins functional group free;

(F) (meth) acrylamide, dimethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide or alkoxylated N-methylol Various amide bond-containing vinyl monomers such as (meth) acrylamides;

(To) Dialkyl [(meth) acryloyloxyalkyl] phosphates, (meth) acryloyloxyalkyl acid phosphates, dialkyl [(meth) acryloyloxyalkyl] phosphite or (meth) acryloyloxyalkyl acid phosphite Furthermore, various epoxy groups such as alkylene oxide adducts of the above (meth) acryloyloxyalkyl acid phosphates or acid phosphites, glycidyl (meth) acrylate and methylglycidyl (meth) acrylate. Ester compounds of vinyl-containing monomers and phosphoric acid or phosphorous acid or acidic esters thereof, or 3-chloro-2-acid phosphoroxypropyl (meth) acrylate Various vinyl monomers containing phosphorus atoms, such as:

(H) various dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate, and
Each of the amide bond-containing vinyl-based monomers, the phosphorus atom-containing vinyl-based monomers or the dialkylaminoalkyl (meth) acrylates is a vinyl-based, especially, in the acrylic-based copolymers, Each of them is used to impart an internal catalytic function, or to improve adhesion to a material or substrate, compatibility with another resin or pigment dispersibility,

These may be used alone or in combination of two or more kinds. The amount of each of these monomers used is about 0.05 in the case of phosphorus atom-containing vinyl monomers, from the viewpoint of use effect. To about 5% by weight is suitable, and in the case of amide bond-containing vinyl-based monomers or dialkylaminoalkyl (meth) acrylates, etc., about 0.05 to about 10% by weight. Is appropriate.

(I) Various silicon type monomers such as vinylethoxysilane, α-methacryloxypropyltrimethoxysilane or trimethylsiloxyethyl (meth) acrylate,

(E) For the purpose of further improving weather resistance, for example, US Pat.
"NO as disclosed in the specification of No. 528,311.
RBLOC 7966 "[NORAMC (NORAMC
O) products, such as benzotriazole-based acrylic monomers; or various polymerizable UV absorbers such as "ADEKA STAB T-37 or LA-82" [Asahi Denka Co., Ltd. products] It can be said that light stabilizers are copolymerized;

(L) Furthermore, JP-A-63-1280
Nos. "AA-6, AS-6, AN-6" as disclosed in Japanese Patent Application Laid-Open No.
Alternatively, various high-molecular-weight monomers (macromonomers or macromers) having a functional group end capable of copolymerization, such as AB-6 "(both manufactured by Toagosei Kagaku Kogyo Co., Ltd.) are also used. You can say that;

(W) Further, the resins having copolymerizable unsaturated bond are further improved in the pigment dispersibility of the obtained vinyl copolymer, or the nonvolatile content at the time of coating is increased. It can be said that the main purpose is to increase the solubility or to improve the solubility in non-polar organic solvents.

Specific examples of such resins include polyester resins, vinyl-based copolymers, petroleum resins, rosin esters and polyether polyols. Among them, polyester resins (including oil-modified types) or acrylic copolymers are suitable and particularly preferable.

However, since most polyester resins which are not oil-modified, that is, so-called oil-free alkyd resins, have poor solubility in solvents,
The amount of such oil-free alkyd resins used should be kept at a level such that the target copolymer can be obtained without turbidity.

Such polyester resins (including oil-modified types) or vinyl-based copolymers (among others, acrylic-based copolymers) are disclosed in Japanese Examined Patent Publication No. 45-2201.
No. 1, gazette 46-20502, gazette 44-713.
4, JP-A-48-78233 or 50
As disclosed in, for example, Japanese Patent Laid-Open No. 58123-58, a raw material component having a copolymerizable unsaturated bond is essential, and this copolymerizable unsaturated bond is contained in a resin skeleton obtained by reacting with other raw material components. The one with a sham shape,

Alternatively, as disclosed in JP-B-49-47916 or JP-A-50-6223, first, a saturated polyester having no copolymerizable unsaturated bond is first obtained, and then the saturated polyester is obtained. Utilizing a functional group such as a hydroxyl group or a carboxyl group present in the inside, or further, utilizing an epoxy group introduced by reacting a diepoxy compound,
Compounds having both a functional group having reactivity with these functional groups and a vinyl group, for example, compounds having both an acid chloride group and a vinyl group such as (meth) acrylic acid chloride;

Such as glycidyl (meth) acrylate,
Various compounds having both an epoxy group and a vinyl group;
Various compounds having both an alkoxysilanol group and a vinyl group such as vinylmethoxysilane or (meth) acryloxyethyltrimethoxysilane; an acid anhydride group and a vinyl group such as maleic anhydride or tetrahydrophthalic anhydride Various compounds having a combination thereof; Various compounds having a carboxyl group and a vinyl group, such as fumaric acid or (meth) acrylic acid;

Alternatively, vinyl-based monomers having both an isocyanate group and a vinyl group, such as 2-hydroxypropyl (meth) acrylate-hexamethylene diisocyanate equimolar adducts or isocyanatoethyl methacrylate, are obtained by addition to a saturated polyester. Various compounds having both a hydroxyl group and a copolymerizable unsaturated bond;

Vinyl monomers having various functional groups such as a hydroxyl group, a carboxyl group or an epoxy group are previously copolymerized as an essential component, and the acrylic copolymer having these functional groups is copolymerized. A compound having both a functional group having reactivity with the functional group contained in the acrylic copolymer and a vinyl group, for example, (meth) acrylic acid Compounds having both an acid chloride group and a vinyl group such as chloride; various compounds having both an epoxy group and a vinyl group such as glycidyl (meth) acrylate; vinylmethoxysilane or (meth) acryloxyethyl Various compounds having both an alkoxysilanol group and a vinyl group, such as trimethoxysilane;

Various compounds having an acid anhydride group and a vinyl group, such as maleic anhydride or tetrahydrophthalic anhydride; Various compounds having a carboxyl group and a vinyl group, such as fumaric acid or (meth) acrylic acid Or a vinyl-based monomer having both an isocyanate group and a vinyl group, such as 2-hydroxypropyl (meth) acrylate-hexamethylenediisocyanate molar adduct or isocyanate ethylmethacrylate. Examples thereof include various compounds having both a hydroxyl group and a copolymerizable unsaturated bond, which are obtained by the addition reaction of the combination.

Such polyester resins include various saturated fatty acids such as octylic acid, lauric acid, stearic acid or "versatiic acid" (trade name of synthetic fatty acid manufactured by Shell Co.); oleic acid. , Unsaturated fatty acids such as linoleic acid, linoleic acid, eleostearic acid or ricinoleic acid; various synthetic oil fatty acids such as "Pamoline 200 or 300";

Chinese laurel oil (fatty acid), flaxseed 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 various (semi) drying oils (fatty acids) such as rice bran oil (fatty acids); or various non-drying oils (fatty acids) such as hydrogenated coconut oil fatty acids, coconut oil fatty acids or palm oil fatty acids With or without at least one compound selected from the group consisting of various oils or fatty acids such as

Various polyvalent compounds such as ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanetriol, pentaerythritol or sorbitol. One or more alcohols,

Benzoic acid, p-tert-butylbenzoic acid, (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, tetrahydro (anhydrous) phthalic acid, tetrachloro (anhydrous) phthalic acid, hexachloro (anhydrous) phthalic acid, tetrabromo Various carboxylic acids such as (anhydrous) phthalic acid, trimellitic acid, "hymic acid", (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, adipic acid, sebacic acid or oxalic acid. It can be obtained by reacting one or more of the acids with a conventional method.

In that case, if necessary, "CURJURA E" (fatty acid glycidyl, manufactured by Shell Co. of the Netherlands, is used for each purpose such as improvement of adhesion, chemical resistance, weather resistance and the like. Ester brand name)
Various monoepoxy compounds represented by various fatty acid glycidyl esters, such as

"Epiclon 200 or 400"
[Product name of polyepoxy resin manufactured by Dainippon Ink and Chemicals, Inc.] or “Epicoat 828 or 100
1 "(trade name of polyepoxy resin manufactured by Shell Co.) such as various polyepoxy resins;

Various diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-methylenebis (cyclohexyl isocyanate);
Various polyisocyanates in the form of being obtained by an addition reaction of each of these diisocyanates with various polyhydric alcohols such as those listed above and water;

Or an isocyanuric ring-containing polyisocyanate in the form of being obtained by (co) polymerization of diisocyanates or one or more of various reactive silicone compounds such as those mentioned above. Various polyhydric alcohols, various compounds in the form obtained by substituting a part of carboxylic acids and the like and reacting by a conventional method.

In the vinyl polymer (B) which is insoluble in an organic solvent, it should be used in addition to 0 to about 60% by weight of the fatty acid adduct of the epoxy group-containing vinyl monomer.
About 4 other monomers having a copolymerizable unsaturated double bond
In 0 to 100% by weight, (meth) acrylic acid ester having an alkyl group having 3 or more carbon atoms in its side chain and styrene having an alkyl group in its side chain are contained in at least about 30% by weight of the total amount of monomers. It is essential to use with an amount in the range up to%.

As the (meth) acrylic acid ester, only typical ones are exemplified. Propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl. (Meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate,
"Acryester SL" [made by Mitsubishi Rayon Co.,
C ₁₂ - / C ₁₃ trade name of methacrylate mixture, stearyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, to is isobornyl (meth) acrylate or adamantyl (meth) acrylate, and the, side Specific examples of styrenes having an alkyl group in the chain include vinyltoluene, p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, and p-tert-butylstyrene.

Each of the various (meth) acrylic acid esters and / or styrenes having an alkyl group in the side chain as described above is at least one specific styrene having a weak solubility as described below. The function of dissolving in solvents
It is used for the purpose of imparting it to the obtained copolymers.

The monomer having a copolymerizable unsaturated double bond that can be shared with them is as described above in (a).
Methyl (meta) to various monomers such as (to) and (o) as long as the solubility and stability are not impaired.
Acrylate, ethyl (meth) acrylate or vinyl acetate can also be used.

The composition ratio of the vinyl polymer (A) which is insoluble in the organic solvent and the polymer (B) which is soluble in the organic solvent is the former polymer (A) / the latter polymer. The ratio by weight of the solid content of (B) is about 10 / about 90 to about 90.
Although it is essential to satisfy / about 10, it is preferable that it is 50/50 to 85/15.

If the proportion of the vinyl polymer (A) which does not dissolve in the organic solvent exceeds about 90% by weight and becomes too large, the stability of the non-aqueous dispersion is inevitably impaired. However, as an advantage of the present invention, as a general feature of the non-aqueous dispersion type resin, it has a low viscosity, and in addition, in order to achieve the characteristic effect of high thixotropic property. Also, in the design concept of increasing the proportion of the vinyl-based polymer (A) which is not soluble in an organic solvent as much as possible, it is higher than the conventional one, that is, about 80 to about 90% by weight, which is a very high proportion. There are things that can be designed even in places.

Further, a polymer (B) soluble in an organic solvent
If the ratio of too much, the stability of the non-aqueous dispersion is good, but is a general feature of the non-aqueous dispersion type resin, low viscosity, and impair the performance of high thixotropic properties. Therefore, the proportion of the polymer (B) soluble in the organic solvent is preferably about 90% by weight or less, and more preferably 50% by weight or less.

The non-aqueous dispersion type resin used in the present invention is, for example, a vinyl polymer (A) which is insoluble in an organic solvent in a resin solution of the polymer (B) which is soluble in an organic solvent. The polymer (B) and the non-aqueous dispersion type resin which can be dissolved in an organic solvent, respectively, can be obtained by polymerizing the above-mentioned copolymerization method or grafting reaction method (grafting reaction method). Copolymerization reaction method)

At that time, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), t
ert-butyl perbenzoate (TBPB), ter
t-Butyl hydroperoxide (TBHPO), di-
tert-butyl peroxide (DTBPO), cumene hydroperoxide (CHP) or o, o-ter
Various known and commonly used radical generators (radical generating polymerization catalysts or radical polymerization initiators) such as to-o (1,2,2,6,6-pentamethyl-4-piperidinyl) monoperoxycarbonate. Can be performed alone or in combination of two or more.

At that time, if desired, for the purpose of obtaining a non-aqueous dispersion resin having a so-called special function such as a water / oil repellency function or a weather resistance function, For example, it is possible to copolymerize the various substances listed below, or to carry out the copolymerization reaction after adding and mixing the various substances listed below.

That is, "Defencer" series or "Megafuck 170" series [all are products of Dainippon Ink and Chemicals, Inc.], "Aron GF-1"
50 or GF-300] [Toa Gosei Chemical Industry Co., Ltd.
Product] or “FA Series, FM Series or F
S series ”(product of Mitsubishi Petrochemical Co., Ltd.), various fluorine-based copolymer type surfactants, fluorine-based block copolymers;

"Fluoronate K-700" series [Product of Dainippon Ink and Chemicals, Inc.], "Lumiflon"
Series [Asahi Glass Co., Ltd. product] or "Kainer AD
S or SL ", various fluororesins, or various reactive silicone resins described above; or benzophenone-based, benzotriazole-based, cyanoacrylate-based, oxalic anilide-based, or salicylate esters, Various non-polymerizable ultraviolet absorbers except for the polymerizable ultraviolet absorbers and the polymerizable light stabilizers belonging to the (f) group of

"Tinuvin 144, 292, 700 or 765" (all manufactured by Ciba Geigy) or "Adeka Stab LA-52 or LA-87"
[All are products from Asahi Denka Co., Ltd.]
So-called high weather resistance raw materials such as various non-polymerizable light stabilizers other than the polymerizable light stabilizers belonging to the above (f) group, represented by amine compounds, Prior to the polymerization, the vinyl-based monomers are added and mixed, and then various vinyl-based monomers from the group (a) to the group (wo) as described above are copolymerized, thereby It is also possible to include various substances of the above in the particles.

Further, the vinyl-based monomer (A), which is used in preparing the vinyl-based polymer (B) and the non-aqueous dispersion resin, dissolves the vinyl-based monomer, but is made of the monomer. As a typical example of an organic solvent that does not dissolve

"Marcazole R or E", "Swazol 310" [all are products of Maruzen Sekiyu KK],
"LAWS, HAWS, Shersol 70 or 7
1 "(product of Shell Co.)," Diana Solvent N "
o. 0 or No. 1 "[Product of Idemitsu Kosan Co., Ltd.],
"IP Solvent 1016, 1020 or 162
0 "(same as above)," Shellzol D-40 "(product of Shell Co.)," A solvent, K solvent, AF solvent "[Nippon Oil Co., Ltd. product]," Exxon naphtha No.
3, No. 5 or No. 6 "," Exole D-
30, D-40, D-60 or D-70 "," Isopar C, E, G or H "[all are products of Exxon Chemical Co., Ltd.],

Further, there are various solvents such as n-hexane or n-heptane having an aliphatic hydrocarbon as a main component, and these hydrocarbon solvents may be used alone or, Of course, two or more kinds may be used in combination.

Further, in order to adjust the viscosity, volatility, dispersion and agglomeration, dripping property or electrostatic coating property of the composition, toluene, xylene, "Solvesso 100" are used.
Various aromatic hydrocarbon solvents such as [Exxon Chemical Co., Ltd.], or alcohol solvents; acetic acid esters; propylene glycol ether solvents; propylene glycol ether ester solvents; or ethoxyethyl pro So-called polar solvents such as pionate can also be used in combination within a range not departing from the spirit of the present invention or within a range not impairing the effects of the present invention.

Furthermore, when a trace amount of unreacted monomers is present, the unreacted monomers are removed by a suitable means such as distillation under reduced pressure, whereby the coating material is removed. It can be said that so-called odor reduction, which is one of the environmental problems related to the above, can be reduced.

In particular, when the main components of the dispersed particles are vinyl acetate and / or (meth) acrylic acid esters, the copolymerizability is poor, and therefore,
To bring the addition rate of monomers to about 90% by weight or more, especially 95% by weight or more, within a predetermined time
It is extremely difficult.

Therefore, after confirming once that the monomer addition rate has reached about 90% by weight or more, the remaining amount is about 10% by weight. Strictly speaking, it is about 3% by weight or more and less than about 10% by weight. By measuring the unreacted monomers of the above using gas chromatography (GC), it is possible to use a vacuum distillation method or to remove nitrogen or carbon dioxide etc. until the amount becomes less than about 3% by weight in the solvent. Such unreacted monomers can be removed from the system by a suitable method such as blowing a large amount of so-called inert gas into the system. It means that the odor caused by is significantly reduced.

Next, the above-mentioned dryers used as curing accelerators include all known and commonly used so-called metal driers such as cobalt-based, lead-based, zirconium-based or calcium-based. And these are used alone or 2
A combination of two or more kinds may be used, and about 0.0 to the resin solid content
It can be used in the range of 1 to about 10% by weight.

If the amount used is less than about 0.01% by weight, the effect of accelerating the curing will not be sufficiently achieved, while if it exceeds about 10% by weight and is used in too much amount. However, since there is a tendency that storage stability and colorability are inevitably deteriorated in any case, it is not preferable in any case. Therefore, the amount of the dryer used is usually about 0.01 to about A range of 10% by weight, preferably a range of 0.1 to 5% by weight is suitable.

Further, used as the above-mentioned curing agent,
As the metal alkoxides, the metal acylates or the metal chelates, various known and commonly used compounds are particularly representative, but among others, aluminum-based, zirconium-based or titanium-based compounds are industrially It is preferable because it is easily available.

Of the preferable examples, only typical ones will be exemplified.
[Hope Pharmaceuticals Co., Ltd. products], "Citacoat" [Nippon Soda Co., Ltd. products], "Planeact" [Ajinomoto Co., Inc. products], "Organics TA series, TC series, ZA series, ZB series, ZC series or AL series ”[Matsumoto Pharmaceutical Co., Ltd. products],

"AIPD, AMD, ASBD or A
LCH series ”or“ Aluminum chelate A, D or M ”[Kawaken Fine Chemicals Co., Ltd. product] or“ Tencalate TP series ”[Tenka Polymer Co., Ltd. product] etc. , And the ones that are widely used.

These may be used alone or in combination of two or more, and can be used within the range of about 0.001 to about 20% by weight based on the resin solid content.

At that time, in order to improve the storage stability, alcohols, acetylacetone, acetoacetic acid esters or lactic acid esters are used within the range not departing from the object of the present invention or the range not impairing the effects of the present invention. It is possible to add various known and commonly used stabilizers such as the above-mentioned compounds.

The metal alkoxides as listed above,
When the amount of the metal acylate or metal chelate used is less than about 0.001% by weight, the effect of promoting the curing is hard to be sufficiently exerted, while it exceeds about 20% by weight too much. When used in a large amount, storage stability, colorability and solubility tend to be inevitably deteriorated, which is not preferable in any case. Therefore, the amount used of these is usually In the range of about 0.001 to about 20% by weight, and preferably in the range of 0.05 to 10% by weight.

Further, as the polyisocyanate compound used as the above-mentioned curing agent, any known and commonly used compounds can be used. However, the solvents of the above-mentioned system, that is, a specific hydrocarbon-based compound is used. In the case of using such a compound that the solubility in solvents is not sufficient, the problem of separation occurs when it is mixed in the resin composition for a coating material to be obtained. This means that it is desirable to use a compound having sufficient solubility in hydrocarbon solvents, which itself has poor solubility.

If only typical examples of such polyisocyanate compounds are given as examples, JP-A-61-22013, JP-A-4-130124,
Compounds such as those disclosed in JP-A-130171, -132720 or 132782, and if only representative examples of the products on the market are exemplified, "Bernock DN-990, DN-99"
1, DN-991S, DN-992 or BO-35
7 "[Product of Dainippon Ink and Chemicals, Inc.]," Desmodur Z-4370 "[Sumitomo Bayer Urethane Co., Ltd.]
Product] or “Duranate THA-100” [Asahi Kasei Kogyo KK].

As described above, the amount of the polyisocyanate compound used is in the range of about 0.2 to about 1.5 equivalents of isocyanate groups with respect to 1 equivalent of hydroxyl groups in the resin composition. It is appropriate that the equivalent ratio of OH / NCO is 1 / about 0.2 to about 1.5.

When the ratio of isocyanate group used to 1 equivalent of hydroxyl group is less than about 0.2 equivalent, it is difficult to achieve the effect of use. On the other hand, when the used ratio exceeds about 1.5. If it is used in an excessively large amount, it is inevitable that it will cause problems such as foaming when the surface to be coated having a high water content is applied and the cost of the coating.
Therefore, it is usually appropriate to have an equivalent ratio within the range of 1 / about 0.2 to about 1.5, and preferably 1 / 0.5 to
An equivalent ratio of 1.2 is appropriate.

Further, to exemplify only particularly representative amino resins described above used as curing agents, alkylated melamine resins, alkyl urea resins, alkyl urea / melamine resins or Alkyl benzoguanamine resins and the like, among which, from the viewpoint of weather resistance and the like, the use of alkylated melamine resins having a mineral spirit tolerance of at least about 300% or more, preferably 500% or more is desirable.

All of these can be obtained by a conventional method, and for example, "Super Beckamine L
-161, L-117-60 or L-118-6
0 ”[all of which are products of Dainippon Ink and Chemicals, Inc.] and the like are particularly representative.

The ratio of the amino resins used is as follows:
The solid content weight ratio of non-aqueous dispersion resin / amino resin is in the range of about 50 to about 90 / about 10 to about 50, and it is particularly suitable in terms of coating film physical properties and dispersion stability. .

The amount of the amino resin used is about 10% by weight.
If it is less than 50% by weight, the physical properties of the coating tend to be difficult to appear. On the other hand, if it is used in an excessively large amount of more than about 50% by weight, the coating tends to become brittle and the acid resistance is inevitable. In any case, it is not preferable because the sex and the like will be deteriorated.

For the purpose of improving the performance, plasticizers and other materials may be used as long as they are compatible with the solvent used in the resin composition for coating composition according to the present invention. Resins of, for example, acrylic copolymers, fibrin compounds, acrylated alkyd resins, alkyd resins,
Silicon resins, fluororesins, epoxy resins, or the like can be appropriately used in combination, but at that time, within a range not departing from the object of the present invention or a range not impairing the effects of the present invention, Needless to say, it is important to use these above-mentioned materials.

Further, the non-aqueous dispersion resin for paints and the resin composition for paints according to the present invention are mixed with pigments for kneading, or by mixing with dispersed pigments, processed pigments, etc. It can be used as a so-called enamel paint, or can be used as a so-called clear paint without using pigments.

For the coating at that time, various known means such as spray, brush or roller can be applied.

Further, in the present invention, room temperature drying, forced drying and heat drying (baking), or urethane type ones, such as curing in an amine stream, that is, so-called vapor cure. It can be said that it can be applied to any curing means or curing conditions such as a system, a VIC system, etc., and pigment dispersants, leveling agents, ultraviolet absorbers, light stabilizers or curing accelerators. It goes without saying that various coating additives, which are commonly known and used in the art, can be used in conventional amounts, such as the above-mentioned classes.

The non-aqueous dispersion resin composition and the coating resin composition according to the present invention thus obtained are, in comparison with conventional non-aqueous dispersion compositions,
Since the pigment dispersibility is good, the image clarity,
It has excellent luster and longevity, good weather resistance, and
They are particularly useful as top coats for anticorrosion paints, paints for metals and building exteriors, and unlike conventional organic solvents, have little effect on old paint films (existing paint films). In addition, it is extremely practical in that it has various coating film performances that are superior to those of conventional systems using organic solvents.

[0102]

EXAMPLES Next, the present invention will be described more specifically with reference examples, examples and comparative examples. However, the present invention is by no means limited to only these illustrative examples. Absent. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 (Preparation example of non-aqueous dispersion resin solution)

[Preparation Example of Dispersion Stabilizer (S-1)]

In a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, 1,000 parts of "LAWS" (trade name of mineral spirits manufactured by Shell Co .; abbreviated as LAWS hereinafter). Was charged and the temperature was raised to 120 ° C.

There, 200 parts of styrene, 175 parts of i-butyl methacrylate, 300 parts of n-butyl methacrylate and 1 part of glycidyl methacrylate.
A mixture of 25 parts and 10 parts of benzoyl peroxide and 10 parts of tert-butyl perbenzoate, respectively, as a polymerization initiator was added dropwise over 4 hours. After the dropping, keep the same temperature for 4 hours,

By adding 200 parts of dehydrated castor oil fatty acid and 0.2 part of 2-methylimidazole and reacting until the acid value became 1.0, the nonvolatile content was 50.0.
%, The Gardner viscosity is U, the acid value is 1.0, the Gardner color number is 1, and the hydroxyl value of the solid content is 48. Thus, a solution (S-1) of the target dispersion stabilizer resin is obtained. It was

[Preparation Example of Objective NAD (N-1)]

Separately, a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 400 parts of the dispersion stabilizer (S-1) obtained above and 300 parts of LAWS. The temperature was raised to 100 ° C.

There, 400 of methyl methacrylate was added.
Parts, 237 parts of ethyl acrylate, 63 parts of glycidyl methacrylate, 100 parts of dehydrated castor oil fatty acid
Parts, 0.1 parts of 2-methylimidazole and LAWS
500 parts of benzoyl peroxide and 10 parts of benzoyl peroxide were added dropwise over 4 hours.

After completion of the dropping, the reaction is continued until the acid value becomes 1.0, so that the nonvolatile content is 50.0%, the Gardner viscosity is QR, the acid value is 1.0, and the solid value is solid. A milky white non-aqueous dispersion resin solution (N-1) having a hydroxyl value of 33.6 was obtained.

Reference Example 2 (same as above)

[Preparation Example of Dispersion Stabilizer (S-2)]

A 4-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 1,000 parts of LAWS, and the temperature was raised to 120 ° C. There, 200 parts of styrene, 175 parts of i-butyl methacrylate, n
-137 parts of butyl methacrylate and 188 parts of glycidyl methacrylate, as a polymerization initiator,
10 parts of benzoyl peroxide and t, respectively
A mixture with 10 parts of ert-butyl perbenzoate was added dropwise over 4 hours.

After the dropping, the temperature was kept at the same temperature for 4 hours, and then 300 parts of dehydrated castor oil fatty acid and 2-
Add 0.3 parts of methyl imidazole, acid value 1.0
The non-volatile content is 50.
0%, Gardner viscosity W-X, acid value 1.0,
A target dispersion stabilizer resin solution (S-2) having a Gardner color number of 1 and a solid hydroxyl value of 72 was obtained.

[Preparation Example of Objective NAD (N-2)]

Separately, a 4-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 600 parts of the dispersion stabilizer (S-2) obtained above and 300 parts of LAWS, The temperature was raised to 100 ° C.

A mixture of 200 parts of vinyl acetate, 250 parts of methyl methacrylate and 250 parts of ethyl acrylate, 400 parts of LAWS and 10 parts of benzoyl peroxide was added thereto over 4 hours. Dropped.

After the dropping, the reaction is continued until the acid value becomes 1.0, so that the nonvolatile content is 50.0%, the Gardner viscosity is O, the acid value is 1.0, and the solid content hydroxyl group is A milky white non-aqueous dispersion resin solution (N-2) having a value of 21.6 was obtained.

Reference Example 3

[Preparation Example of Dispersion Stabilizer (S-3)]

A 4-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 1,000 parts of LAWS and heated to 120 ° C. There, 200 parts of styrene, 300 parts of i-butyl methacrylate and 500 parts of n-butyl methacrylate, and 1 part of benzoyl peroxide as a polymerization initiator, respectively.
A mixture of 0 parts and 10 parts of tert-butyl perbenzoate was added dropwise over 4 hours.

After the dropping, the temperature is kept at the same temperature for 8 hours, so that the nonvolatile content is 50.0%, the Gardner viscosity is OP, the acid value is 0.3, and the Gardner color number is A target dispersion stabilizer resin solution (S-3) having a hydroxyl value of solid content of 0 or less and 0 or less was obtained.

[Preparation Example of Objective NAD (N-3)]

Separately, a 4-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 400 parts of the dispersion stabilizer (S-3) obtained above and 300 parts of LAWS. The temperature was raised to 100 ° C. 200 parts of methyl methacrylate, 275 parts of ethyl acrylate and 125 parts of glycidyl methacrylate, 100 parts of linseed oil fatty acid and 1 part of soybean oil fatty acid.
00 parts, 0.2 parts of 2-methylimidazole, LA
A mixture of 500 parts of WS and 10 parts of benzoyl peroxide was added dropwise over 4 hours.

After the dropping, the reaction is continued until the acid value becomes 1.0, so that the nonvolatile content is 50.0%, the Gardner viscosity is U, the acid value is 1.0, and the solid content hydroxyl group is A milky white non-aqueous dispersion resin solution (N-3) having a value of 38.4 was obtained.

Reference Example 4

[Preparation Example of Dispersion Stabilizer (S-4)]

A 4-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 1,000 parts of LAWS and heated to 120 ° C. There, 200 parts of styrene, 175 parts of i-butyl methacrylate, n
-250 parts of butyl methacrylate, 50 parts of 2-hydroxyethyl methacrylate and 125 parts of glycidyl methacrylate, and 10 parts of benzoyl peroxide and ter, respectively, as polymerization initiators.
4 parts of a mixture with 10 parts of t-butyl perbenzoate.
Dropped over time.

After the dropping, the temperature was kept at the same temperature for 4 hours, and then 200 parts of dehydrated castor oil fatty acid and 2-
Add 0.2 parts of methyl imidazole and acid value 1.0
The non-volatile content is 50.
0%, Gardner viscosity YZ, acid value 1.0,
The Gardner color number is 1, and the solid content hydroxyl value is 69.
A desired dispersion stabilizer resin solution (S-4) was obtained.

[Preparation Example of Objective NAD (N-4)]

Separately, a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 400 parts of the dispersion stabilizer (S-4) obtained above and 300 parts of LAWS. The temperature was raised to 100 ° C. There, 350 parts of methyl methacrylate, 237 parts of ethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate.
A mixture of 0 parts and 63 parts of glycidyl methacrylate, 100 parts of dehydrated castor oil fatty acid, 0.1 part of 2-methylimidazole, 500 parts of LAWS and 10 parts of benzoyl peroxide in 4 hours. It was dripped over.

After the dropping, the reaction is continued until the acid value becomes 1.0, the non-volatile content is 50.0%, the Gardner viscosity is W-X, the acid value is 1.0, and the solid value is solid. A milky white non-aqueous dispersion resin solution (N-4) having a hydroxyl group value of 59.5 was obtained.

Reference Example 5

[Preparation Example of Dispersion Stabilizer (S-5)]

In a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, 600 parts of LAWS and n-
400 parts of butanol was charged and the temperature was raised to 110 ° C. There, 200 parts of styrene, 175 parts of i-butyl methacrylate, 250 parts of n-butyl methacrylate, 50 parts of 2-hydroxyethyl methacrylate and 125 parts of glycidyl methacrylate, and as a polymerization initiator, A mixture with 10 parts of benzoyl peroxide and 10 parts of tert-butyl perbenzoate, respectively, was added dropwise over 4 hours.

After completion of the dropping, the mixture was kept at the same temperature for 4 hours, and then 200 parts of coconut oil fatty acid and 0.2 part of 2-methylimidazole were added to give an acid value of 1.0. The non-volatile content is 50.0%
And a Gardner viscosity of YZ, an acid value of 1.0, a Gardner color number of 1 and a solid hydroxyl value of 69.6, the solution of the target dispersion stabilizer resin (S-5 ) Got.

[Preparation Example of Objective NAD (N-5)]

Separately, 400 parts of the dispersion stabilizer (S-5) obtained above and 300 parts of "ISOPAR E" were placed in a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube. Was charged and the temperature was raised to 100 ° C.

Then, 350 of methyl methacrylate was added.
Parts, 237 parts of ethyl acrylate, 50 parts of 2-hydroxyethyl acrylate and 63 parts of glycidyl methacrylate, 100 parts of coconut oil fatty acid, and 2-
A mixture of 0.1 part of methylimidazole, 300 parts of "Isopar E", 200 parts of n-butanol, and 10 parts of benzoyl peroxide was added dropwise over 4 hours.

After completion of the dropping, the reaction is continued until the acid value becomes 1.0, so that the nonvolatile content is 50.0%, the Gardner viscosity is WX, the acid value is 1.0, and the solid value is solid. A milky white non-aqueous dispersion resin solution (N-5) having a hydroxyl group value of 59.5 was obtained.

Reference Example 6 [Preparation Example of Objective NAD (N-6)]

A four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 400 parts of the dispersion stabilizer (S-3) obtained in Reference Example 3 and 300 parts of LAWS. The temperature was raised to 100 ° C.

A mixture of 200 parts of vinyl acetate, 300 parts of methyl methacrylate and 300 parts of ethyl acrylate, 500 parts of LAWS and 10 parts of benzoyl peroxide was added thereto over 4 hours. Dropped.

After completion of the dropping, the reaction is continued until the acid value becomes 1.0, so that the nonvolatile content is 50.0%, the Gardner viscosity is M, the acid value is 1.0, and the solid content hydroxyl group is A milky white non-aqueous dispersion resin solution (N-6) having a value of 0 was obtained.

Reference Example 7 (same as above)

[Preparation Example of Dispersion Stabilizer (S-7)]

A 4-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 600 parts of LAWS and 400 parts of xylene and heated to 120 ° C.

There, 200 parts of styrene, 239 parts of i-butyl methacrylate, 400 parts of n-butyl methacrylate and 161 parts of 2-hydroxyethyl methacrylate were added, respectively, as a polymerization initiator.
A mixture with 20 parts of benzoyl peroxide and 10 parts of tert-butyl perbenzoate was added dropwise over 4 hours.

After the completion of dropping, the temperature is kept at the same temperature for 8 hours so that the nonvolatile content is 50.0%, the Gardner viscosity is YZ, the acid value is 0.3, and the Gardner color number is 1 or less, and the solid content hydroxyl value is 69.5,
A target dispersion stabilizer resin solution (S-7) was obtained.

[Preparation Example of Objective NAD (N-7)]

Separately, 400 parts of the dispersion stabilizer (S-7) obtained above and 300 parts of LAWS were placed in a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube. The temperature was raised to 100 ° C.

There, 300 of methyl methacrylate was added.
Parts, 394 parts of ethyl acrylate and 106 parts of 2-hydroxyethyl acrylate, and 300 of LAWS.
Part, 200 parts of xylene and 20 parts of benzoyl peroxide were added dropwise over 4 hours.

After completion of the dropping, the reaction is continued until the acid value becomes 1.0, so that the nonvolatile content is 50.0%, the Gardner viscosity is UV, the acid value is 1.0, and the solid content is solid. A milky white non-aqueous dispersion resin solution (N-7) having a hydroxyl group value of 59.7 was obtained.

Reference Example 8 (same as above)

[Preparation Example of Dispersion Stabilizer (S-8)]

Separately, a 4-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 600 parts of LAWS and 400 parts of n-butanol and heated to 110 ° C.
The temperature was raised to.

There, 200 parts of styrene, 239 parts of i-butyl methacrylate, 400 parts of n-butyl methacrylate and 161 parts of 2-hydroxyethyl methacrylate were added, respectively, as a polymerization initiator.
A mixture with 20 parts of benzoyl peroxide and 10 parts of tert-butyl perbenzoate was added dropwise over 4 hours.

After the dropping, the temperature is kept at the same temperature for 8 hours to obtain a nonvolatile content of 50.0%, a Gardner viscosity of XY, an acid value of 0.3, and a Gardner color number. 1 or less, and the solid content hydroxyl value is 69.5,
A target dispersion stabilizer resin solution (S-8) was obtained.

[Preparation Example of Objective NAD (N-8)]

Separately, in a four-necked flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, 400 parts of the dispersion stabilizer (S-8) obtained above and "Isopar E" were added.
And 300 parts of were charged and the temperature was raised to 100 ° C.

There, 300 of methyl methacrylate was added.
Parts, 394 parts of ethyl acrylate and 106 parts of 2-hydroxyethyl acrylate, "Isopar E"
Of 300 parts of n-butanol and 200 parts of n-butanol and 20 parts of benzoyl peroxide were added dropwise over 4 hours.

After completion of the dropping, the reaction is continued until the acid value reaches 1.0, whereby the nonvolatile content is 50.0%, the Gardner viscosity is UV, the acid value is 1.0, and the solid content is solid. A milky white non-aqueous dispersion resin solution (N-8) having a hydroxyl value of 59.7 was obtained.

[0164]

[Table 1]

<< Footnotes in Table 1 >> All numerical values in the table are parts by weight.

[0166]

[Table 2]

[0167]

[Table 3]

<< Footnotes in Table 1 >> All numerical values in the table are parts by weight.

"NAD" ......... abbreviation for "non-aqueous dispersion"

[0170]

[Table 4]

[0171]

[Table 5]

[0172]

[Table 6]

[0173]

[Table 7]

[0174]

[Table 8]

[0175]

[Table 9]

[0176]

[Table 10]

[0177]

[Table 11]

[0178]

[Table 12]

[0179]

[Table 13]

[0180]

[Table 14]

[0181]

[Table 15]

Examples 1 to 6 and Comparative Examples 1 to 3 Each of the non-aqueous dispersion resins and titanium oxide obtained in each of the reference examples was adjusted so that the PWC was 40% and the Various kinds of white enamel were prepared by blending them according to the blending ratio as shown in Table 2 and then dispersing with a sand mill.

Thereafter, the white enamel was further blended with a drier or a chelating agent, if necessary, to give a white enamel base agent.

Further, if necessary, a curing agent was blended, diluted with LAWS to have a spray viscosity, then coated on a mild steel plate, and dried or baked under predetermined conditions.

Each coating film thus obtained was subjected to an evaluation judgment test of coating film performance. The results are summarized in Table 2.

[0186]

[Table 16]

<< Footnotes in Table 2 >> All numerical values in the table are parts by weight.

"Taipaque CR-93" ......... Trade name of titanium oxide manufactured by Ishihara Sangyo Co., Ltd.

[0189]

[Table 17]

<< Footnotes in Table 2 >> All numerical values in the table are parts by weight.

“DN-990” ………………………………………… Product name of polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Inc.

Abbreviation for “L-117-60” ……………………………… “Super Beckamine L-117-60” (trade name of melamine resin manufactured by the same company)

[0193]

[Table 18]

<< Footnote in Table 2 >> "μm" ......... Meaning of micrometer

"6% cobalt naphthenate" means that the content of metallic cobalt (that is, the content of active ingredient) is 6%.

"12% zirconium octenoate" means that the metal zirconium content (that is, the active ingredient content) is 12%.

"Skinner TM" is a trade name of an anti-skinning agent manufactured by Toagosei Co., Ltd.

"Aluminum chelate A" is a trade name of aluminum chelate manufactured by Kawaken Fine Chemicals Co., Ltd., and is used in the form of a 40% acetylacetone solution.

[0199]

[Table 19]

[0200]

[Table 20]

[0201]

[Table 21]

[0202]

[Table 22]

[0203]

[Table 23]

[0204]

[Table 24]

As described above, since the resin composition for coating material obtained by using the non-aqueous dispersion resin composition according to the present invention has particularly good pigment dispersibility,
In particular, it gives a coating film which is excellent in sharpness, gloss and fleshness, and also has good weather resistance. Therefore, it is particularly useful for top coats of anticorrosion paints, for metals and for building exteriors. It is useful as a paint, and is extremely highly practical in terms of other various coating film performances, as compared with those using conventional organic solvents.

[0206]

As described above, the non-aqueous dispersion resin composition according to the present invention has little influence on the old coating film (existing coating film) and has good pigment dispersibility. In particular, it has excellent image clarity, luster and feeling of flesh, and has good weather resistance.
Respectively, a non-aqueous dispersion resin composition, a resin composition for coating obtained by using the non-aqueous dispersion resin composition, both, particularly, a top coat of anticorrosion coating,
It is very useful as a coating for metals and building exteriors, and it is extremely practical in terms of other coating film performance as well as that of conventional organic solvents. It is a thing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 131/04 PFU C09D 131/04 PFU 133/10 PGF 133/10 PGF 157/02 PDC 157/02 PDC

Claims (10)

[Claims] 1. An organic solvent in which vinyl-based monomers are soluble but a polymer comprising the vinyl-based monomer is insoluble, in the presence of a polymer soluble in the organic solvent, In a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component, a vinyl-based polymer (A) which is insoluble in the above organic solvent and / or the above The non-aqueous dispersion type resin composition, wherein the polymer (B) soluble in the organic solvent described above is modified with a fatty acid. 2. An organic solvent in which vinyl monomers are soluble but a polymer comprising the vinyl monomer is insoluble, in the presence of a polymer soluble in the organic solvent, In a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component, the above-mentioned non-aqueous dispersion type resin is further characterized by being blended with a drier. And a resin composition for a non-aqueous dispersion paint. 3. An organic solvent in which vinyl monomers are soluble but a polymer comprising the vinyl monomer is insoluble, in the presence of a polymer soluble in the organic solvent, In a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component, it is possible to further compound a metal alkoxide, a metal acylate or a metal chelate. A resin composition for a non-aqueous dispersion coating, which is characterized. 4. An organic solvent in which vinyl-based monomers are soluble but a polymer comprising the vinyl-based monomer is insoluble, in the presence of a polymer soluble in the organic solvent, In a composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component, further, a polyisocyanate is also blended, a non-aqueous dispersion paint Resin composition. 5. An organic solvent in which vinyl monomers are soluble but a polymer comprising the vinyl monomer is insoluble, in the presence of a polymer soluble in the organic solvent, A composition containing a non-aqueous dispersion type resin obtained by polymerizing a vinyl-based monomer as an essential film-forming component, further characterized by containing an amino resin, a non-aqueous dispersion paint Resin composition. 6. The above-mentioned vinyl polymer (A) which is insoluble in an organic solvent is used in an amount of 0 to about 60% by weight of a fatty acid adduct of an epoxy group-containing vinyl monomer, and another copolymerizable unsaturated diamine. The composition according to claims 1 to 5, which comprises about 40 to 100% by weight of the monomer having a heavy bond. 7. The above-mentioned vinyl polymer (B) soluble in an organic solvent is used in an amount of 0 to about 60% by weight of a fatty acid adduct of an epoxy group-containing vinyl monomer, and other copolymerizable unsaturated compounds. The composition according to claims 1 to 5, which comprises about 40 to 100% by weight of the monomer having a double bond. 8. The above-mentioned vinyl polymer (A) which is insoluble in an organic solvent is used as another monomer having a copolymerizable unsaturated double bond and has 1 or less carbon atoms in its side chain. The composition according to claims 1 to 5, which is obtained by using (meth) acrylic acid ester having an alkyl group of 2 and / or vinyl acetate as an essential monomer. 9. The above-mentioned vinyl polymer (B) soluble in an organic solvent is used as another monomer having a copolymerizable unsaturated double bond and has a side chain of 3 or more carbon atoms. 1 to 5 obtained by using (meth) acrylic acid ester having an alkyl group and / or styrene having an alkyl group in a side chain thereof in an amount of at least about 30% by weight based on the total amount of monomers. The composition as described. 10. The composition ratio of the vinyl polymer (A) that is insoluble in an organic solvent to the polymer (B) that is soluble in an organic solvent is the former polymer (A) / The latter polymer (B) is about 10/90 by weight based on the solid content.
6. The composition of claims 1-5, which is from about 90 / about 10.