JP2002294140A - Coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material composition which is of a one-peak type, excels in workability, has a reduced influence on an undercoat and good lap coating properties, excels in initial drying properties, water resistance, and weatherability, and particularly excels in diluting properties on low- temperature operation as well. SOLUTION: This coating material composition comprises (A) an alkyd modified vinyl resin solution composed of (a) an alkyd modified vinyl polymer modified with an alkyd resin containing a (semi) drying oil and/or a (semi) drying oil fatty acid and an organic solvent and (B) a metallic drier, and has a dissolution index of a mineral spirit to the alkyd modified vinyl resin solution (A) [a value obtained by multiplying a numerical value obtained by dividing the volume (ml) of the mineral spirit having an aniline point of 45 deg.C necessary for the resin solution at 25 deg.C to become cloudy by dropwise adding the mineral spirit to the resin solution by a weight (g) of the resin solution (A) by 100] of >=100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type coating composition excellent in recoatability, initial drying property, water resistance and weather resistance. More specifically, a topcoat paint composition suitable for repairing any old paint film for building interior and exterior, or a topcoat for various substrates such as concrete, siding board, extruded plate, metal, glass, magnetic tile, plastic, etc. The present invention relates to a coating composition suitable for use.

[0002]

2. Description of the Related Art Although the market for building repairs is increasing, the field has good workability in winter, good weatherability and good coating properties, which were not available in conventional emulsion paints. In addition, it has the alkali resistance, weather resistance, and quick-drying properties not found in conventional alkyd paints, and has good paint workability with paint, such as spray, brush, and roller, which is usually used for repairs. So-called weak solvent-type acrylic paints using a vinyl resin, particularly an acrylic resin, as a binder dissolved or dispersed in a solvent containing a mineral spirit-based solvent having a low content as a main component are rapidly growing.

[0003] Among these weak solvent type acrylic paints, the conventional one-pack type weak solvent paints are good in terms of ease of use, but are inherently poor in solvent resistance, so they are applied twice or repaired. There is a serious drawback that a problem is likely to occur during recoating.

As a method for avoiding such a problem, a so-called weak solvent type acrylic urethane paint in which a hydroxyl group is introduced into an acrylic resin and cured with a polyisocyanate is used, but an old coating film has poor solvent resistance. Even if it is a coating film, it does not attack the old coating film, and the cured coating film has good coating performance such as weather resistance, water resistance, chemical resistance, and good solvent resistance. In addition, the demand for repair paints has been increased significantly in recent years in the repair market, because it has the performance required for repair paints, which does not cause coating film defects even if repaired with any paint on the next time. I've been.

[0005] However, although the weak solvent type acrylic urethane paint has good performance such as recoatability and weather resistance, it is a two-pack type, and its handling is complicated. Since there is only half a day from the time, the paint remaining after compounding cannot be used the next day, and there is a major problem in workability.

In general, paints for building interior and exterior are used after being diluted with a paint thinner mainly composed of mineral spirits. Therefore, it is necessary that the paint be well diluted with the paint thinner. However, a conventional one-pack type paint having excellent solvent resistance and excellent recoating property has poor dilutability in a paint thinner, and has been a problem particularly when used at a low temperature such as in winter.

[0007] Under such circumstances, the development of a one-pack type coating material having a small influence on an old coating film and having good recoatability, initial drying property, water resistance and weatherability, and having good dilutability in a paint thinner. Is desired.

[0008]

That is, the problem to be solved by the present invention is that it is a one-part type, has excellent workability, has little influence on the undercoat film, has good recoatability, and has good initial drying properties and water resistance. It is an object of the present invention to provide a coating composition which is excellent in water resistance and weather resistance, and particularly excellent in dilutability even at the time of low temperature operation.

[0009]

Means for Solving the Problems In order to achieve the targets of initial drying property, water resistance and weather resistance, the present inventors have developed a vinyl resin (acrylic resin) whose performance is essentially good. Selected as basic skeleton.

Furthermore, since the conventional one-pack type thermoplastic vinyl-based resin (acrylic resin) does not have good recoating properties, a (semi) drying oil having good oxidative polymerizability is required to improve it. And / or an alkyd resin containing a (semi) dry oil fatty acid, and an alkyd-modified vinyl resin solution comprising a vinyl copolymer containing a specific vinyl monomer as an essential component and a specific amount, and / or The crosslinked coating film obtained by oxidatively polymerizing a vinyl resin dispersion containing the same with a metal dryer is a one-pack type, has good recoatability, and has good initial drying properties, weather resistance, and water resistance. I found something.

Further, it has been found that by setting the solubility of the alkyd-modified vinyl resin solution in mineral spirit to a specific range, the above properties are maintained and the diluting property of the paint is excellent, and the present invention has been completed. Was.

That is, the present invention provides a coating composition comprising an alkyd-modified vinyl resin solution (A) and a metal dryer (B) as essential components, wherein the alkyd-modified vinyl resin solution (A) is used. An alkyd resin comprising an alkyd-modified vinyl polymer (a) and an organic solvent, wherein the alkyd-modified vinyl polymer (a) contains (semi) dry oil and / or (semi) dry oil fatty acid, A vinyl polymer obtained by using at least one kind of a vinyl monomer having a homopolymer solubility parameter of 9.0 or more as an essential component, and an alkyd-modified vinyl resin solution. Dissolution index of mineral spirit with respect to (A) [When a mineral spirit having an aniline point of 45 ° C is dropped into a resin solution, the resin solution is dissolved at 25 ° C. Is defined as a value obtained by multiplying a value obtained by dividing the volume (milliliter) of the mineral spirit required until cloudiness is obtained by dividing the volume (milliliter) by the weight (gram) of the resin solution (A) by 100]. It provides a composition.

The present invention also provides a coating composition comprising a vinyl resin dispersion (C) and a metal dryer (B) as essential components, wherein the vinyl resin dispersion (C)
Is a dispersion stabilizer (a) composed of an alkyd-modified vinyl polymer soluble in an organic solvent, dispersed particles composed of a vinyl polymer (b) insoluble in an organic solvent, and the organic solvent. Yes, the alkyd-modified vinyl polymer (a)
An alkyd resin containing a (semi) dry oil and / or a (semi) dry oil fatty acid and at least one vinyl monomer having a homopolymer solubility parameter of 9.0 or more are used as essential components. The solubility index of the mineral spirit in the alkyd-modified vinyl-based resin solution (A) [25 minutes when the mineral spirit having an aniline point of 45 ° C. is dropped into the resin solution; Volume of mineral spirit required for the resin solution to become cloudy at ℃ (milliliter)
Is divided by the weight (gram) of the resin solution (A) and multiplied by 100] is 100 or more.
Further, the present invention provides a coated article to which the above coating composition is applied.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on its embodiments. [1] (A) Alkyd-modified vinyl-based resin solution The alkyd-modified vinyl-based resin solution in the present invention comprises:
An alkyd resin containing a (semi) dry oil and / or a (semi) dry oil fatty acid and at least one vinyl monomer having a homopolymer solubility parameter of 9.0 or more are obtained as essential components. Alkyd-modified vinyl polymer (a) comprising a vinyl polymer to be obtained and an organic solvent.

First, the alkyd resin is typically obtained by esterifying (semi) dry oil or (semi) dry oil fatty acid, acid component and alcohol component according to a conventional method. It is mentioned as a thing.

As typical examples of such (semi) dry oils or (semi) dry oil fatty acids, only typical ones may be used, such as oleic acid, linoleic acid, linoleic acid, eleostearic acid or ricinoleic acid. Unsaturated fatty acids: "Pamoline 200 or 300" (synthetic dry oil fatty acid manufactured by Hercules, USA), Chinese nagiri oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid), cottonseed oil Various (semi) drying oils (fatty acids), such as (fatty acids), soybean oil (fatty acids), olive oil (fatty acids), safflower oil (fatty acids), castor oil (fatty acids) or rice bran oil (fatty acids). Examples include various oils or fatty acids. Further, non-drying oil or non-drying oil fatty acid such as hydrogenated coconut oil (fatty acid), coconut oil (fatty acid) or palm oil (fatty acid) can be used in combination as long as the effects of the present invention are not impaired. Such oils and fatty acids may be used alone or
It goes without saying that more than one kind may be used in combination.

On the other hand, only typical representative examples of the acid component include benzoic acid, p-tert-butylbenzoic acid, (phthalic anhydride), hexahydro (phthalic anhydride), phthalic acid and tetrahydrophthalic anhydride. Phthalic acid, tetrachloro (anhydride) phthalic acid, hexachloro (anhydride) phthalic acid, tetrabromo (anhydride) phthalic acid, trimellitic acid,
"Hymic acid" [product of Hitachi Chemical Co., Ltd .; "Hymic acid" is a registered trademark of the company. ], (Anhydride) succinic acid, (anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid, adipic acid, sebacic acid or oxalic acid.

Further, if only typical alcohol components are exemplified, ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, , 6-hexanetriol, pentaerythritol or sorbitol. In addition, various monoepoxy compounds represented by various fatty acid glycidyl esters, such as "Kajura E" (trade name of glycidyl ester of fatty acid, manufactured by Shell Co., The Netherlands) are also used as the above-mentioned acidic compounds. It can be used in the same manner as the alcohol component, as it reacts with the minute.

The acid component and the alcohol component may be used alone or in combination of two or more. In addition, the acid component and the alcohol component, particularly from the viewpoint of solubility and drying properties in organic solvents, coating film appearance, coating film properties such as weather resistance, etc., the amount of each component used and the combination thereof as necessary. It may be determined appropriately.

The oil length of the alkyd resin is 30 to
It is suitably in the range of 80% by weight, particularly preferably in the range of 40 to 70% by weight.

Next, as a vinyl monomer having a solubility parameter (hereinafter sometimes referred to as SP) of a homopolymer used for the vinyl polymer of 9.0 or more, a vinyl monomer having a hydroxyl group may be used. , A carboxyl group-containing vinyl monomer and methyl methacrylate are the most common and effective, but the homopolymer has a solubility parameter of 9.0.
Any vinyl-based monomer that satisfies the above conditions is not particularly limited to these. Here, the solubility parameter of the homopolymer is represented by Journal of Pain.
t Technology, Vol. 42, No. 541, p. 76 (1970). L. While the numerical values described in the literature described by Hoy are adopted, the calculated values obtained by the method of Hoy, the author of the above-mentioned reference literature, are calculated for the vinyl monomer having no literature value ( However, the density is assumed to be 1.0.).

The solubility parameter of the homopolymer is 9.0
As a vinyl monomer as described above, if a hydroxyl group-containing vinyl monomer, which is one of the most common and effective monomers, is exemplified,

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-monobutyl fumarate, polyethylene glycol or polypropylene glycol mono (meth) acrylate or an adduct thereof with ε-caprolactone, “Placel FM or FA monomer” Various hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids, such as [trade names of caprolactone-added monomers manufactured by Daicel Chemical Industries, Ltd.], and the like.

Further, as a vinyl monomer having a homopolymer having a solubility parameter of 9.0 or more, a carboxyl group-containing vinyl monomer which is one of the most common and effective monomers is exemplified. Various unsaturated mono- or dicarboxylic acids such as, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid or dicarboxylic acid monoesters such as monoethyl fumarate, monobutyl maleate, or And the above-mentioned hydroxyl-containing (meth) acrylates, such as succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", and tetrachlorophthalic acid. Examples include adducts of various polycarboxylic acids with anhydrides.

In addition, a vinyl monomer having a homopolymer having a solubility parameter of 9.0 or more and other than a hydroxyl group-containing vinyl monomer, a carboxyl group-containing vinyl monomer, and methyl methacrylate Examples of vinyl monomers include methyl acrylate, vinyl acetate,
N, N-alkylaminoalkyl (meth) such as (meth) acrylonitrile, ethylene-di-methacrylate, and N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate ) Acrylates;

Vinyl monomers containing an amide bond such as (meth) acrylamide, butyl ether of N-methylol (meth) acrylamide, dimethylaminopropylacrylamide, etc .; dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) Phosphorus atom-containing vinyl monomers such as acryloyloxyalkyl acid phosphates, dialkyl [(meth) acryloyloxyalkyl] phosphites or (meth) acryloyloxyalkyl acid phosphites; and the like.

Further, regarding the effective amount of the vinyl monomer having a homopolymer having a solubility parameter of 9.0 or more, the alkyd-modified vinyl polymer may be used in the portion obtained by using the monomer. It is preferably 1 to 50% by weight in the solid content of (a), and more preferably 3 to 40 in view of the recoatability and the dissolution index of mineral spirits.
% By weight, more preferably 5 to 30% by weight.
It is.

The above-mentioned vinyl monomers having a solubility parameter of the homopolymer of 9.0 or more can be used alone or in combination.

The other vinyl monomers copolymerizable with the above-mentioned vinyl monomers having a solubility parameter of the homopolymer of 9.0 or more include the following groups (A) to (L): And the like, various compounds are particularly typical examples.

That is, (a) a styrene monomer such as styrene, vinyltoluene, p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene or p-tert-butylstyrene;

(B) Ethyl (meth) acrylate, propyl (meth) acrylate, iso (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 or lauryl (meth)
Acrylate, “Acryester SL” [trade name of C ₁₂ − / C ₁₃ methacrylate mixture, manufactured by Mitsubishi Rayon Co., Ltd.], alkyl (meth) acrylates such as stearyl (meth) acrylate; cyclohexyl (meth)
(Meth) acrylates having no functional group in the side chain, such as acrylate, 4-tert-butylcyclohexyl (meth) acrylate or isobornyl (meth) acrylate, adamantyl (meth) acrylate, and benzyl (meth) acrylate;

(C) various alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate or methoxybutyl (meth) acrylate;

(D) Representatives of maleic acid, fumaric acid or itaconic acid, such as dimethyl maleate, diethyl maleate, diethyl fumarate, di (n-butyl) fumarate, di (i-butyl) fumarate or dibutyl itaconate Diesters of various dicarboxylic acids and monohydric alcohols;

(E) Vinyl benzoate or "veova"
Various vinyl esters such as (vinyl esters of branched aliphatic monocarboxylic acids manufactured by Shell, The Netherlands);

(F) "Viscort 3F, 3FM, 8F,
8FM or 17FM "[manufactured by Osaka Organic Chemical Co., Ltd.
Trade names of fluorine-containing acrylic monomers], various (per) fluoroalkyls such as perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or N-isopropyl perfluorooctanesulfonamidoethyl (meth) acrylate Various fluorine-containing polymerizable compounds, such as -vinyl esters, -vinyl ethers,-(meth) acrylates or -unsaturated polycarboxylic esters, each containing a group;

(G) Various functional group-free halogenated olefins such as various olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride;

(H) vinylethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ-
(Meth) acryloxypropyltriethoxysilane, γ
-(Meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethoxydimethoxysilane, γ- (meth) acryloxypropylmethoxydiethoxysilane, γ- (meth) acryloxypropylmethoxydipropoxysilane, γ -(Meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane,
various silane monomers such as γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, and γ- (meth) acryloxypropyldimethylethoxysilane;

(Li) glycidyl (meth) acrylate,
Various unsaturated compounds containing a glycidyl group, such as β-methylglycidyl (meth) acrylate or (meth) allyl glycidyl ether, α, β-ethylenically unsaturated carboxylic acids or mono-2- (meth) acryloyloxymonoethyl phthalate And various types of unsaturated carboxylic acids such as equimolar adducts of various hydroxyl group-containing vinyl monomers with the above-mentioned various polycarboxylic anhydrides, as described in "Epiclon 200, 400, 44".
1,850 or 1050 "(trade names of epoxy resins manufactured by Dainippon Ink and Chemicals, Inc.)," Epicoat 828, 1001 or 1004 "(trade names of epoxy resins manufactured by Shell Inc.)," Araldite 60
71 or 6084 "(trade names of epoxy resins manufactured by Ciba Geigy, Switzerland)," Chissonox 2
21 "[trade name of epoxy compound manufactured by Chisso Corporation]
Or "Denacol EX-611" [Nagase & Co., Ltd.
Of epoxy compounds having at least two epoxy groups in one molecule and obtained by an addition reaction at an equimolar ratio. Containing polymerizable compound;
And the like.

(N) For the purpose of further improving the weather resistance and the like of the film performance, for example, “NORBLOC” disclosed in US Pat. No. 4,528,311 is disclosed. Benzotriazole-based acrylic monomers such as "7966" (product of NORAMCO, USA); various polymerizable ultraviolet absorbers such as "ADEKA STAB T-37" (product of Asahi Denka Co., Ltd.); Such as ADK STAB LA-82 [Hindered amine-based acrylic monomer manufactured by Asahi Denka Co., Ltd.], and the like.

(G) Further, Japanese Patent Application Laid-Open No. 63-12800
2, "AA-6, AS-6, AN-6, AB"
-6 "[all manufactured by Toa Gosei Chemical Industry Co., Ltd.], various high molecular weight monomers (macromones or macromers) having a copolymerizable functional group terminal may also be used. I can do it.

The other copolymerizable vinyl monomers described above have solubility and drying properties in organic solvents, coating film appearance,
From the viewpoint of various properties of the coating film such as solvent resistance and weather resistance, the amount of each component used and the combination thereof may be appropriately selected and determined as necessary.

If necessary, the following various substances can be added and mixed, followed by copolymerization.

That is, the "Defensa" series or the "Mega Fac 170" series (products of Dainippon Ink and Chemicals, Inc.) and "Aron GF-150 or GF-300" (products of Toa Gosei Chemical Industry Co., Ltd.)
Products], "FA series, FM series or FS series" [Mitsubishi Yuka Corporation products], "Fluonate K-700" series [Dainippon Ink and Chemicals Co., Ltd. products], "Lumiflon" series [Asahi Glass Co., Ltd. products]
"Kyner ADS or SL" [US Penn
Fluororesins such as Orto products];

Various non-polymerizable ultraviolet absorbers such as a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a cyanoacrylate ultraviolet absorber, an oxalic anilide ultraviolet absorber, and a salicylate ester;

"Tinuvin 144, 292, 700 or 765" (product of Ciba Geigy, Switzerland);
Various non-reactive light stabilizers represented by hindered amine compounds, such as "Adekas Pig LA-52 or LA87" (products of Asahi Denka Co., Ltd.).
So-called highly weather-resistant raw materials can be mentioned. In the present invention, the alkyd-modified vinyl-based polymer (a) is prepared by subjecting the above-mentioned alkyd resin and the above-mentioned monomer used in the vinyl-based copolymer to, for example, peroxides and azo compounds. Such a radical polymerization initiator may be used to carry out various known and commonly used copolymerization reactions and graft copolymerization reactions.

In this case, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), t
tert-butyl perbenzoate (TBPB), ter
t-butyl hydroperoxide (TBHPO), di-
tert-butyl peroxide (DTBPO), cumene hydroperoxide (CHP) or o, o-ter
Various radical generators (radical generating polymerization catalysts or radical polymerization initiators) such as to- (1,2,2,6,6-pentamethyl-4-piperidinyl) monoperoxycarbonate are used alone Or a combination of two or more.

Further, as the solvent used at the time of polymerization, a solvent which does not easily attack the old coating film while maintaining the stability of the resin and has good workability of coating with a brush or a roller is preferable. . That is, generally, an aromatic hydrocarbon solvent having a boiling point range of about 160 ° C. to about 180 ° C. is preferable, and for example, “Solvesso 100” (a product of Exxon Chemical Co., Ltd.) is the most preferable solvent.

Further, as long as the characteristics of the present invention are not impaired, for example, aliphatic hydrocarbon solvents and / or aromatic
Aliphatic mixed solvents (typical examples of which are n-hexane, n-heptane, “Marcazole R or E” or “Swazol 310” [both are products of Maruzen Petroleum Co., Ltd.]; “LAWS”, “HAWS” "Or" Shellsol 70 or 71 "(both products of Shell, The Netherlands);" Diana Solvent No. 0 or No. 1 "[product of Idemitsu Kosan Co., Ltd.]," IP Solvent 1016, 1020 or 1620 "[ Id.]; "Shellsol D-40" (manufactured by Shell, The Netherlands), "A Solvent", "K Solvent" or "AF Solvent" (both manufactured by Nippon Oil Co., Ltd.); or "Exxon Naphtha No. 3" , No. 5 or No. 6 "," Exole D-30, D-40, D-
60 or D-70 "or" Isopar C, E,
G or H "[a product of Exxon Chemical Co., Ltd.], etc.);

Aromatic hydrocarbon solvents such as toluene, xylene and the like; acetate solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; propylene glycol ether Solvents, propylene glycol ether ester solvents or ethoxyethyl propionate can be used in combination.

The alkyd-modified vinyl resin solution (A) thus obtained has a solubility index of mineral spirit in the resin solution [in the case of dropping a mineral spirit having an aniline point of 45 ° C. into the resin solution at 25 ° C. Is defined as 100 times the value obtained by dividing the volume (milliliter) of mineral spirit required until the solution becomes cloudy by the weight (gram) of the resin solution (A)]. is there.

The mineral spirit having an aniline point of 45 ° C. used for measuring the solubility index is a high-boiling hydrocarbon solvent composed of about 30% of an aliphatic hydrocarbon and about 70% of an aromatic hydrocarbon. For example, Laws
(Shell), A Solvent (Nippon Oil), Naphtha N
o. 6 (Exxon) and Pegazol AN-45 (Mobile Oil).

When the dissolution index is 100 or more at 25 ° C., the stability of the coating material at low temperatures does not become poor, and excellent gloss and color mixing can be obtained even at low temperatures.

The dissolution index is more preferably in the range of 100 to 1,000, most preferably, in that the recoatability, which is a feature of the present invention, can be further improved while maintaining the above excellent characteristics. 20 for the range
0 to 1000.

The vinyl resin dispersion (C) may be prepared in the presence of an organic solvent as described above and an alkyd-modified vinyl polymer (a) soluble in the organic solvent. A vinyl resin dispersion liquid (C) composed of vinyl polymer dispersion particles (b) insoluble in an organic solvent may be produced using a polymer and a radical polymerization initiator.

Here, it is necessary that the alkyd-modified vinyl polymer (a) is dissolved in the above-mentioned organic solvent, and the vinyl polymer dispersed particles (b) are insoluble in the organic solvent. The raw material used for the alkyd-modified vinyl polymer (a), in particular, the type of monomer used for obtaining the vinyl polymer may be appropriately selected so as to satisfy this condition. The raw materials used for the vinyl polymer dispersed particles (b) are also
What is necessary is just to select suitably from among the vinyl monomers mentioned above so as to satisfy the above conditions. The organic solvent may be appropriately selected depending on the alkyd-modified vinyl polymer (a) or vinyl polymer dispersed particles (b) to be used so as to satisfy the above conditions.

[2] Metal Dryer (B) Another essential component of the present invention is a cobalt-based, lead-based,
Known and conventional metal dryers such as zirconium-based or calcium-based are conventionally used. These may be used alone or in combination of two or more kinds. The preferred amount is 0.01% by weight to 10% by weight based on the solid content of the resin.
%, More preferably 0.1% to 5% by weight.

Within the above range, the recoating property does not become poor, the stability of the paint is good, there is no adverse effect such as discoloration of the paint and the coating film, and the water resistance and chemical resistance are further improved. And excellent weather resistance and the like.

[3] Other components The coating composition of the present invention is prepared by mixing various pigments such as titanium oxide and kneading them, or mixing dispersed pigments and processed pigments. It can be used as a so-called enamel paint, or as a metallic paint in which aluminum powder is dispersed, or as a so-called clear paint that does not use such pigments.

In the case of coating, for example, “Disper
pigment dispersants such as "byk-161, BYK-P104" [both are products of Big Chemie, Germany];
Leveling agents such as "BYK-302" (product of Big Chemie, Germany); for example, "BYK-065" (product of Big Chemie, Germany), "Dispalon OX-7"
0 "[product of Kusumoto Kasei Co., Ltd.] and the like;
"Dispalon 6820-20M" [Kusumoto Chemical Co., Ltd.]
Anti-sagging agents such as “Tinuvin P, 32
8 "[all manufactured by Ciba-Geigy, Switzerland]; UV absorbers; for example," Tinuvin 770, 76 "
5 "[all products of Ciba Geigy, Switzerland]; light stabilizers; various paints such as fungicides which are generally known and used in the art. Additives can be used in conventional amounts.

As an auxiliary crosslinking agent, aluminum-based, zirconium-based or titanium-based metal alkoxides, metal acylates or metal chelates (for example, “Acetop” [product of Hope Pharmaceutical Co., Ltd.], “Titacoat” [Japan] Soda Co., Ltd. products], “Plenact”
[Products of Ajinomoto Co., Inc.], “Orgatics TA Series, TC Series, ZA Series, ZB Series, ZC
Series or AL Series "[products of Matsumoto Pharmaceutical Co., Ltd.]," AIPD, AMD, ASBD or ALCH
Series "or" Aluminum chelate A, D or M "[products of Kawaken Fine Chemical Co., Ltd.] or" Tencalate TP series "(products of Tenka Polymer Co., Ltd.)) can be used as long as the effects of the present invention are not impaired. .

Further, in order to improve the performance of the coating composition of the present invention, other resins such as plasticizers, for example, acrylic copolymers, cellulose compounds, acrylated alkyd resins , Alkyd resins, silicone resins, fluororesins or epoxy resins, etc., may be used in combination as appropriate, but in that case, within the range not departing from the object of the present invention, or of the present invention Various kinds of the above-mentioned substances can be used within a range that does not impair the effect.

Thus, the coating composition according to the present invention comprises:
It can be applied to all old paint films, and has the best performance especially for repairing interior and exterior of buildings. However, it is mainly used for coating materials (substrates) as listed below. Can also be painted.

That is, if only typical examples of the above-mentioned base materials are given as examples, aluminum,
Metal products such as aluminum sashes and gates made of various metal materials, such as stainless steel, chrome plating, galvanized iron plate or tin plate; or tiles; and various types of buildings inside and outside such as building exterior walls and inorganic building materials Wearing materials;
And so on.

In the coating at that time, various known and commonly used means such as a spray, a brush or a roller can be used.

[0065]

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

Reference Example 1 [Preparation Example of Alkyd Resin] In a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a decanter, 650 parts of soybean oil, 137 parts of pentaerythritol and 0 parts of lithium hydroxide were added. .15 parts were charged and the temperature was raised to 250 ° C. After the transesterification was carried out at the same temperature for 1 hour, the temperature was lowered to 200 ° C., and 240 parts of phthalic anhydride and 30 parts of xylene were charged.
The temperature was raised to ° C. After dehydration at the same temperature under xylene reflux, the reaction was allowed to proceed for about 5 hours until the acid value became 6, and then diluted with "LAWS" so that the non-volatile content became 60%, and the oil length became 6
5% alkyd resin was obtained. Hereinafter, this alkyd resin solution is abbreviated as (S-1).

Reference Example 2 [Preparation example of alkyd-modified vinyl resin solution (A1)] A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was obtained in Reference Example 1. 667 parts of the alkyd resin solution (S-1) and 401 parts of “Solvesso 100 (hereinafter abbreviated as S-100)” (exxon high-boiling aromatic solvent) were charged, and 120
The temperature was raised to ° C. At this temperature, 100 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as 2-HEMA), a vinyl monomer having a solubility parameter of 9.9, and other copolymerizable monomers , 200 parts of styrene (hereinafter abbreviated as St) and 265 of i-butyl methacrylate (hereinafter abbreviated as i-BMA).
Parts, 2-ethylhexyl acrylate (hereinafter referred to as 2-EHA
35 parts) and te as a polymerization initiator
rt-butyl peroxy (2-ethylhexanoate)
A mixture of 8 parts (hereinafter abbreviated as perbutyl O), 5 parts of tert-butyl peroxybenzoate (hereinafter abbreviated as perbutyl Z), and 150 parts of “S-100” was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 6 hours, 182 parts of "S-100" was charged, and an alkyd-modified vinyl polymer solution (A1) having a nonvolatile content of 50%
I got The resulting (A1) has a solubility index of 3 for mineral spirits (using “LAWS” from Shell) at 25 ° C.
The alkyd-modified vinyl resin solution was No. 00.

Reference Example 3 [Preparation Example of Alkyd-Modified Vinyl Resin Solution (A2)] 833 parts of the alkyd resin solution (S-1) obtained in Reference Example 1 was placed in a flask similar to the reaction apparatus used in Reference Example 2. And 335 parts of “S-100” were charged, and the temperature was raised to 120 ° C. At this temperature, 200 parts of methyl methacrylate (hereinafter abbreviated as MMA), a vinyl monomer having a solubility parameter of 9.2, and 50 parts of St as another copolymerizable monomer. , 150 of i-BMA
, 100 parts of 2-HEA, 8 parts of perbutyl O as a polymerization initiator, 5 parts of perbutyl Z, and "S-1
"00" was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 6 hours, and 182 parts of "S-100" was charged to obtain an alkyd-modified vinyl polymer solution (A2) having a nonvolatile content of 50%. Obtained (A2)
Is a mineral spirit at 25 ° C (Shell's “LAW
S ") was an alkyd-modified vinyl resin solution having a dissolution index of 350.

Reference Example 4 [Preparation Example of Alkyd-Modified Vinyl Resin Solution (A3)] 833 parts of the alkyd resin solution (S-1) obtained in Reference Example 1 was placed in a flask similar to the reactor used in Reference Example 2. And 335 parts of “S-100” were charged, and the temperature was raised to 120 ° C. At this temperature, the solubility parameter becomes 1
The vinyl monomer of 3.1, methacrylic acid (hereinafter referred to as M
AA), 200 parts of St, 180 parts of i-BMA, 2-H
100 parts of EA, 8 parts of perbutyl O as a polymerization initiator, 5 parts of perbutyl Z, and 1 part of “S-100”
50 parts of the mixture were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 6 hours, and 182 parts of “S-100” was charged to obtain an alkyd-modified vinyl polymer solution (A3) having a nonvolatile content of 50%. (A3) obtained was at 25 ° C.
Was an alkyd-modified vinyl resin solution having a solubility index of 400 of mineral spirit (using "LAWS" from Shell Co.).

Reference Example 5 [Preparation Example of Alkyd-Modified Vinyl Resin Solution (A4)] In a flask similar to the reactor used in Reference Example 2, 167 parts of the alkyd resin solution (S-1) obtained in Reference Example 1 And 601 parts of “S-100” were charged, and the temperature was raised to 120 ° C. When the temperature reached this temperature, 150 of 2-HEMA, a vinyl monomer having a solubility parameter of 9.9, was obtained.
Parts, as other copolymerizable monomers, 150 parts of St,
A mixture of 550 parts of i-BMA, 120 parts of 2-HEA, and 8 parts of perbutyl O as a polymerization initiator, 5 parts of perbutyl Z, and 150 parts of “S-100” was dropped over 3 hours. . After completion of the dropwise addition, the mixture was maintained at the same temperature for 6 hours, 182 parts of “S-100” was charged, and the nonvolatile content was 50%.
% Of an alkyd-modified vinyl polymer solution (A4). The obtained (A4) has a solubility index of mineral spirits (using Shell Corporation “LAWS”) at 25 ° C. of 150.
Alkyd-modified vinyl resin solution.

Reference Example 6 [Preparation Example of Alkyd-Modified Vinyl Resin Solution (A5)] In a flask similar to the reactor used in Reference Example 2, 1083 parts of the alkyd resin solution (S-1) obtained in Reference Example 1 And 234 parts of “S-100” were charged, and the temperature was raised to 120 ° C. At this temperature, 50 parts of 2-HEMA, a vinyl monomer having a solubility parameter of 9.9,
As other copolymerizable monomers, 100 parts of St, i-
A mixture of 200 parts of BMA, 8 parts of perbutyl O as a polymerization initiator, 5 parts of perbutyl Z, and 150 parts of “S-100” was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 6 hours, and 182 parts of "S-100" was charged to obtain an alkyd-modified vinyl polymer solution (A5) having a nonvolatile content of 50%. The obtained (A5) was obtained at 25 ° C.
Was an alkyd-modified vinyl-based resin solution having a solubility index of 650 of mineral spirit (using "LAWS" manufactured by Shell Co.).

Reference Example 7 [Preparation Example of Alkyd-Modified Vinyl Resin Solution (A6)] In a flask similar to the reactor used in Reference Example 2, 667 parts of the alkyd resin solution (S-1) obtained in Reference Example 1 And 401 parts of “S-100” were charged, and the temperature was raised to 120 ° C. When this temperature is reached, i-BMA's 560
, 40 parts of 2-EHA, 8 parts of perbutyl O as a polymerization initiator, 5 parts of perbutyl Z, and "S-10
A mixture of 150 parts of "0" was added dropwise over 3 hours. After the completion of the dropping, the temperature was maintained at the same temperature for 6 hours, and 1
82 parts of an alkyd-modified vinyl polymer solution (A6) having a nonvolatile content of 50% was obtained. The obtained (A6)
Mineral spirit at 25 ° C (Shell “Laws”
Alkyd-modified vinyl resin solution having a solubility index of 1500.

Reference Example 8 [Preparation Example of Alkyd-Modified Vinyl Resin Solution (A7)] 333 parts of the alkyd resin solution (S-1) obtained in Reference Example 1 was placed in a flask similar to the reactor used in Reference Example 2. And 535 parts of “S-100” were charged, and the temperature was raised to 120 ° C. At this temperature, 550 parts of MMA, a vinyl monomer having a solubility parameter of 9.2, and 200 parts of i-BMA as other copolymerizable monomers,
-50 parts of EHA, 8 parts of perbutyl O as polymerization initiator, 5 parts of perbutyl Z, and 1 part of "S-100"
50 parts of the mixture were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 6 hours, and 182 parts of "S-100" was charged to obtain an alkyd-modified vinyl polymer solution (A7) having a nonvolatile content of 50%. The obtained (A7) was obtained at 25 ° C
Was an alkyd-modified vinyl resin solution having a dissolution index of 50 of mineral spirit (using "LAWS" from Shell Co.).

Reference Example 9 [Preparation Example of Alkyd-Modified Vinyl Resin Solution (A8)] In the same flask as the reaction apparatus used in Reference Example 2, “S-
668 parts of “100” were charged and the temperature was raised to 120 ° C. At this temperature, 100 parts of 2-HEMA, a vinyl monomer having a solubility parameter of 9.9, and 200 parts of St as other copolymerizable monomers, i-BMA
Of 540 parts, 130 parts of 2-EHA, and 8 parts of perbutyl O, 5 parts of perbutyl Z, and 150 parts of "S-100" as a polymerization initiator were added dropwise over 3 hours. After completion of the dropping, the temperature was maintained at the same temperature for 6 hours, and then "S-1
002 of "00" to obtain a vinyl polymer solution (A8) having a nonvolatile content of 50%. (A8) obtained was 2
It was an alkyd-modified vinyl resin solution having a solubility index of 250 of mineral spirits (using "LAWS" from Shell) at 5 ° C.

Reference Example 10 [Preparation Example of Vinyl Resin Dispersion (C1) Using Alkyd-Modified Vinyl Resin Solution (A1) as Dispersion Stabilizer] In a flask similar to the reaction apparatus used in Reference Example 2, 100 parts of the alkyd-modified vinyl resin solution (A1) obtained in Example 2 and 200 parts of "LOWS" were charged, and 100
The temperature was raised to ° C. At this temperature, MMA 2
A mixture of 00 parts, 240 parts of ethyl acrylate (hereinafter abbreviated as EA), 60 parts of 2-HEMA, 10 parts of perbutyl O as a polymerization initiator, and 300 parts of “LAWS” was dropped over 4 hours. The mixture was kept at the same temperature for 8 hours to obtain a non-aqueous dispersion (A9) using the alkyd-modified vinyl resin solution (A1) as a dispersion stabilizer. The obtained (A9) was a milky white resin dispersion having a nonvolatile content of 50.0% and a BM-type viscosity at 25 ° C of 6000 mPa · s.

Reference Example 11 [Non-aqueous dispersion (C) using alkyd-modified vinyl resin solution (A7) as a dispersion stabilizer
Preparation Example of 2)] Into a flask similar to the reaction apparatus used in Reference Example 2, 1000 parts of the alkyd-modified vinyl resin solution (A7) obtained in Reference Example 2 and 200 parts of “LAWS” were charged.
The temperature was raised to ° C. At this temperature, MMA 2
A mixture of 00 parts, 240 parts of ethyl acrylate (hereinafter abbreviated as EA), 60 parts of 2-HEMA, 10 parts of perbutyl O as a polymerization initiator, and 300 parts of “LAWS” was dropped over 4 hours. The same temperature was maintained for 8 hours to obtain a vinyl resin dispersion (A10) using the alkyd-modified vinyl resin solution (A1) as a dispersion stabilizer. The obtained (A10) had a nonvolatile content of 50.0%; 2
It was a milky white resin dispersion having a BM type viscosity of 3000 mPa · s at 5 ° C.

100 parts (50 parts solids) of the alkyd-modified vinyl resin solution (A1) obtained in Reference Example 2,
41 parts of Taipaque R-820 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) and glass beads were mixed, and the mixture was kneaded with a sand mill for 30 minutes.
A coating obtained by adding 3.0 parts of a mixed solution of 6% cobalt naphthenate / 12% zirconium naphthenate / anti-skinning agent (MEK oxime) = 1/1/1 was named "LAWS".
And adjusted so that the Stormer viscosity at 25 ° C. becomes 70 KU. This white paint is referred to as (W-A1).

Similarly, the alkyd-modified vinyl resin solutions (A2) to (A8) and the resin dispersions (C1) to (C1) using the alkyd-modified vinyl resin solution as a dispersion stabilizer
The white enamels prepared to 70 KU corresponding to 2) were respectively (W-A2) to (W-A8) and (W-C1) to (W-
C2), and the paint obtained by removing the metal dryer from (W-A1) is referred to as (W-A1 ′).

As described above, (W-A1) to (W-A5) and (W-A5)
-C1) in Examples, (W-A6) to (W-A8) and (W-C2) and (W-A1 '), and a commercially available one-component weak solvent type acrylic paint, and a commercially available long oil alkyd type The paint is a comparative example.

Then, according to the test method shown below,
The storage stability, initial drying property, recoatability, and weather resistance were evaluated. The evaluation results are summarized in Tables 1 to 4.

Storage stability: The obtained paint was stored at 10 ° C. for 3 days, and the separated state of the paint was visually judged. ：: No separation ○: Slight separation △: Separation ×: Violent separation

[0082]

[Table 1]

Initial drying property: The above-mentioned white enamel was polished and brushed on a mild steel sheet so as to have a dry film thickness of 40 to 50 μm, and the drying property after standing for 6 hours was examined.

◎: No fingerprint is attached at all ○: Slight fingerprint is attached Δ: Fingerprint is attached ×: Paint adheres to finger

[0085]

[Table 2]

Coatability: The above-mentioned white enamel was applied to a tin plate at a wet film thickness of 100, 150, 200, 250.
μm, then 25 ℃ and 5 ℃
After the drying time was 6 hours and 24 hours, the same coating material was applied again. After drying, the dissolution of the coating film surface and the state of shrinkage were visually determined.

A: No abnormal appearance was observed at all. O: Slight dissolution or shrinkage was observed at a certain film thickness. Δ: Slight to moderate dissolution or shrinkage was observed depending on the film thickness. X: Severe at all film thicknesses. Dissolution or shrinkage is observed

[0088]

[Table 3]

Weather resistance: The above-mentioned white enamel was polished and brushed on a mild steel plate so as to have a dry film thickness of 40 to 50 μm, dried at 25 ° C. for 7 days, and then exposed outdoors for one year in the suburbs of Miyazaki City. Was done.

Gloss retention: The retention (%) determined by (60 ° mirror reflectance after outdoor exposure / 60 ° mirror reflectance before exposure) × 100.

[0091]

[Table 4]

[0092]

As apparent from the results shown in Tables 1 to 4, the present invention compensated for the disadvantages of the one-pack weak solvent type acrylic paint and the commercially available long oil alkyd white paint which were conventionally marketed on the market. This is an epoch-making invention having a very high practical utility value, which provides a coating composition having good storage stability, initial drying property, recoating property and weather resistance.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoshi Kishigami 3-1-1-503 Nakaicho, Kishiwada-shi, Osaka (72) Takashi Mukai 2-3-21-21-203 Futadamachi, Izumiotsu-shi, Osaka F-term ( 4J038 CC021 CD021 CF021 CF091 CG121 CG141 CG171 CH031 CH041 CH121 CH131 CH171 CH201 CL011 DB371 DD231 DG221 DL111 DL121 KA04 KA06 NA03 NA04 NA24 NA26 PA18 PB05 PB12 PC02 PC03 PC04 PC08

Claims (5)

[Claims] An alkyd-modified vinyl resin solution (A),
And a metal dryer (B) as an essential component, wherein the alkyd-modified vinyl polymer solution (A) comprises an alkyd-modified vinyl polymer (a) and an organic solvent. An alkyd-modified vinyl polymer (a) is a alkyd resin containing (semi) dry oil and / or (semi) dry oil fatty acid, and a vinyl monomer having a homopolymer solubility parameter of 9.0 or more. And a vinyl polymer obtained by using at least one of the above as an essential component, and a solubility index of mineral spirit in the alkyd-modified vinyl resin solution (A) [mineral having an aniline point of 45 ° C. When the spirit is dropped into the resin solution, the volume (milliliter) of the mineral spirit required until the resin solution becomes cloudy at 25 ° C. Solution weight of (A) (g) is defined with a number of 100 times the value obtained by dividing the] is 1
A coating composition having a molecular weight of at least 00. 2. A coating composition comprising a vinyl resin dispersion (C) and a metal dryer (B) as essential components, wherein the vinyl resin dispersion (C) is soluble in an organic solvent. A dispersion stabilizer comprising a modified vinyl polymer (a), dispersed particles comprising a vinyl polymer insoluble in an organic solvent, and the organic solvent, wherein the alkyd-modified vinyl polymer (a) comprises An alkyd resin containing a (semi) dry oil and / or a (semi) dry oil fatty acid and at least one vinyl monomer having a homopolymer solubility parameter of 9.0 or more are used as essential components. The solubility index of the mineral spirit in the alkyd-modified vinyl resin solution (A) [the mineral spirit having an aniline point of 45 ° C. is dissolved in the resin. When the solution is dropped, the volume (milliliter) of the mineral spirit required for the resin solution to become cloudy at 25 ° C. is divided by the weight (gram) of the resin solution (A) and multiplied by 100 to define the value. Is 100 or more. 3. In the alkyd-modified vinyl polymer (a), a portion obtained by using a vinyl monomer having a homopolymer solubility parameter of 9.0 or more is 1 to 50% in a resin solid content. 3. The coating composition according to claim 1, wherein the alkyd resin is 10% to 70% by weight of the resin solid content. 4. The homopolymer has a solubility parameter of 9.
The vinyl monomer having 0 or more is at least one selected from the group consisting of a hydroxyl group-containing vinyl monomer, a carboxyl group-containing vinyl monomer, and methyl methacrylate.
4. The coating composition according to claim 1, wherein the coating composition is of a kind. 5. A coated article to which the coating composition according to claim 1 is applied.