JP2001279156A - Resin composition for flat coating material and coating material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for a flat coating material, excellent in film properties such as mattedness, water resistance, and weathering resistance and in storage stability and desirable for a flat coating material and to obtain a coating material. SOLUTION: Provided are a resin composition for a flat coating material, containing (A) a solvent based on an aliphatic hydrocarbon, (B) a nonaqueously dispersed resin, and (C) a copolymer obtained by copolymerizing styrene with a monomeric alkyl (meth)acrylate with a 4C or higher alkyl, wherein the mixing ratio (B)/(C) is 25/75 to 75/25 [wherein (B) is the weight of nonaqueously dispersed resin B, (C) is the weight of copolymer (C) and the total of (B) and (C) is 100 pts.wt.] and the mixing ratio (a)/(b) is 30/70 to 70/30 [wherein (a) is the weight of the styrene in copolymer (C), (b) is the weight of the monomeric alkyl (meth)acrylate in copolymer C, and the total of (a) and (b) is 100 pts.wt.] and a coating material using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a matte paint and a paint using the same.

[0002]

2. Description of the Related Art Many methods have been proposed for matting a coating film. For example, by adding an inorganic powder such as silica powder or an organic powder such as polyethylene powder, which is generally called a matting agent, to generate unevenness on the coating film surface and scatter light reflection to obtain a matting effect. It is.

[0003] However, these methods using a matting agent are inferior in the stability of the coating due to the sedimentation of the matting agent, fail to obtain a uniform matte coating film, and are inferior in coating durability such as weather resistance. There's a problem. In order to solve this problem, a resin composition manufactured by using a special polymerization method without adding a matting agent (for example, JP-A-3-81371, JP-A-6-21-2).
87235). However, there is a problem that the matting property of the coating film is not satisfactory, and the durability of the coating film such as water resistance is poor.

In recent years, attempts have been made to use a so-called "weak solvent" containing an aliphatic hydrocarbon as a main component as a solvent for a resin. The paint using this weak solvent has less odor and improves the work environment compared to paints using aromatic hydrocarbon solvents such as xylene and toluene and ester solvents such as butyl acetate and ethyl acetate, which have been mainly used in the past. It has an advantage that it does not cause a lifting phenomenon that damages an old coating film in the case of repair coating, and is used as a solvent for paints such as top coats for architectural exteriors. From such a viewpoint, there is a demand for the development of a resin composition for a coating material which comprises an aliphatic solvent as a main component and can obtain a matte coating film without adding a matting agent.

[0005]

DISCLOSURE OF THE INVENTION The first invention described below is to provide a resin composition which is excellent in matting property and storage stability and is suitable for a paint. A second invention described below provides, in addition to the effects of the first invention, a resin composition excellent in weather resistance of a coating film and suitable for a coating. A third invention and a fourth invention described below provide a matte paint having excellent chemical resistance and water resistance of a coating film.

[0006]

Means for Solving the Problems The present invention provides the following (1) to
The present invention relates to the invention (4). (1) In the presence of a solvent (A) and a non-aqueous dispersion type resin (B) mainly composed of an aliphatic hydrocarbon, and (A) and (B), styrene and an alkyl group have 4 or more carbon atoms. Contains a copolymer (C) obtained by polymerizing a (meth) acrylic acid alkyl ester monomer, and the mixing ratio of the non-aqueous dispersion resin (B) and the copolymer (C) is (B ) And (C) assuming 100 parts by weight, (B) / (C) =
25/75 to 75/25, the mixing ratio of styrene (a) in the copolymer (C) and the alkyl (meth) acrylate monomer (b) having 4 or more carbon atoms in the copolymer (C) is (a) )
(A) / (b), with the total amount of (b) and (b) being 100 parts by weight.
= 30/70 to 70/30, a resin composition for a matte paint (first invention).

(2) The non-aqueous dispersion type resin (B) according to the first invention is insoluble and dispersed particles in the solvent (A) in the presence of the copolymer (B-1) soluble in the solvent (A). Has a hydroxyl value of 2 obtained by polymerizing a copolymer (B-2) which forms
A matte paint resin composition having a weight of 0 to 150 mgKOH / g (second invention). (3) A paint prepared by mixing a curing agent in any one of the first and second inventions (third invention). (4) A paint obtained by blending a polyisocyanate as a curing agent in the third invention (fourth invention).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The solvent (A) containing an aliphatic hydrocarbon as a main component in the present invention (hereinafter abbreviated as organic solvent (A))
Examples thereof include linear aliphatic hydrocarbons and cyclic aliphatic hydrocarbons. Examples of the linear aliphatic hydrocarbon include pentane, hexane, heptane, octane, nonane, and decane, and examples of the cyclic aliphatic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, and cycloheptane. .
As the organic solvent (A), a mixed solvent of aliphatic hydrocarbons, such as mineral spirit, mineral thinner,
Petroleum spirit, white spirit, mineral terpenes and the like can also be used.

The amount of these aliphatic hydrocarbons is preferably at least 50 parts by weight, more preferably at least 60 parts by weight, based on 100 parts by weight of the total organic solvent. If the amount is less than 50 parts by weight, it is not preferable because the safety to the human body and the environment is inferior and a lifting phenomenon occurs during the repair work. Further, the amount of the aliphatic hydrocarbon is within the above range, and as long as the curing reaction between the hydroxyl group and the isocyanate group described later is not inhibited, an organic solvent other than the aliphatic hydrocarbon can be used. .

The components other than the aliphatic hydrocarbons include, for example, aromatic hydrocarbons, esters, ketones and the like, and the aromatic hydrocarbons include, for example, toluene, xylene, Solvesso 100, Solvesso 150 and the like. Examples of the esters include ethyl acetate and butyl acetate, and examples of the ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Further, alcohols may be used as components other than the aliphatic hydrocarbons, but since they may inhibit the curing reaction between the hydroxyl group and the isocyanate group, they are used without departing from the object of the present invention. It is necessary. These aliphatic hydrocarbons and components other than the aliphatic hydrocarbons can be used alone or in combination of two or more.

The non-aqueous dispersion type resin (B) in the present invention comprises:
It is obtained by polymerizing a copolymer (B-2) which is insoluble in the organic solvent (A) and forms dispersed particles in the presence of the copolymer (B-1) soluble in the organic solvent (A). A resin having a hydroxyl value of 20 to 150 mgKOH / g is preferred. The copolymer (B-1) soluble in the organic solvent (A) is obtained by polymerizing an alkyl (meth) acrylate having 4 or more carbon atoms in the alkyl group and other ethylenically unsaturated monomers. Can be

Examples of the alkyl (meth) acrylate monomer having 4 or more carbon atoms in the alkyl group include, for example, n
-Butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth)
(Meth) acrylic acid alkyl esters such as acrylate, lauryl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, eicosyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; (Meth) acrylic acid cycloalkyl ester and the like.

Other ethylenically unsaturated monomers include, for example, hydroxyl-containing (meth) acrylates,
Examples include styrene-based monomers, alkyl (meth) acrylates having 3 or less carbon atoms in the alkyl group, other (meth) acrylic acid derivatives, unsaturated acids, and vinyl-based compounds.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, and trimethylolmethane monoester. (Meth) acrylate, hydroxyalkyl esters of (meth) acrylic acid such as tetramethylolmethane mono (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate (Poly) alkylene glycol mono (meth) acrylates, or adducts of the above compounds with lactones such as ε-caprolactone and γ-valerolactone. I can do it.

Examples of the styrene monomer include styrene, vinyl toluene, α-methylstyrene, chlorostyrene and the like. Examples of the alkyl (meth) acrylate having 3 or less carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate,
n-Propyl (meth) acrylate, iso-propyl (meth) acrylate and the like.

Other (meth) acrylic acid derivatives include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate.
Amino group-containing (meth) acrylates such as acrylates, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate; Examples thereof include vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, hindered amino group-containing (meth) acrylate, and benzotriazole group-containing (meth) acrylate.

Examples of the unsaturated acid include (meth) acrylic acid, maleic acid, fumaric acid and the like. Examples of the vinyl compound include vinyl acetate and vinyl chloride.

The other ethylenically unsaturated monomers are used alone or in combination of two or more. Among these other copolymerizable unsaturated monomers, it is preferable to use a hydroxyl group-containing (meth) acrylic acid ester in combination with a curing agent, since the durability of the resulting coating film is improved. Among the hydroxyl group-containing (meth) acrylic acid esters, hydroxyalkyl esters of (meth) acrylic acid and hydroxyalkyl esters of (meth) acrylic acid and adducts of lactones are preferred from the viewpoint of polymerizability and reactivity. Preferred are mentioned.

The copolymer soluble in the organic solvent (A) (B-
In 1), the compounding ratio of the (meth) acrylic acid ester having 4 or more carbon atoms in the alkyl group is 30 to 95 parts by weight based on 100 parts by weight of the total amount of the monomers used for the copolymer (B-1). Is preferable in terms of dispersion stability of the obtained non-aqueous dispersion type resin (B).

The amount of the hydroxyl group-containing (meth) acrylate in the copolymer (B-1) is determined by the amount of the copolymer (B-1).
The hydroxyl value of -1) is preferably from 20 to 150 mgKOH / g, more preferably from 25 to 100 mgKOH / g, even more preferably from 30 to 70 mgKOH / g. When the hydroxyl value is less than 20 mgKOH / g, the matting properties and weather resistance tend to be poor, and when the hydroxyl value exceeds 150 mgKOH / g, the water resistance of the coating film tends to be poor.

The mixing ratio of other ethylenically unsaturated monomers can be appropriately used within a range in which the copolymer (B-1) becomes soluble in the organic solvent (A). As a method for producing the copolymer (B-1), for example, a usual radical polymerization method can be used, and the method is not particularly limited. As a method of performing polymerization using a radical polymerization method, a method of mixing the monomer and the polymerization catalyst in the presence of the organic solvent (A) and heating at 50 to 200 ° C. for 1 to 10 hours is used. Can be. Examples of the polymerization initiator used for the polymerization of the copolymer (B-1) include organic peroxides and azo compounds. Examples of the organic peroxide include isobutyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, and dichlorobenzoyl peroxide. Mil peroxide, di-t-butyl peroxide, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, diisobutylperoxydicarbonate, 2-diethylhexylperoxydicarbonate, 2,5- Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t
-Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butylperoxy-2-
Ethyl hexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, and the like. Can be Also,
As the azo compound, 2,2′-azobis-isobutyronitrile, dimethylazodiisobutyrate, 2,2-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (2-methylbutyronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 1'-azobis (1-cyclohexanecarbo Nitrile), 2,2'-azobis (2,2,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4
-Methoxyvaleronitrile, 2,2'-azobis (2-
Methylpropane) and the like. These polymerization initiators can be used alone or in combination of two or more.

The amount of the polymerization initiator used depends on the amount of the copolymer (B-
Although it is determined by the target molecular weight of 1), it is usually 0.1 to 10.3 based on 100 parts by weight of the total amount of the polymerizable unsaturated monomer used for the polymerization of the component (B-1).
It is preferably 0 parts by weight. Also, if necessary,
The molecular weight may be adjusted using a chain transfer agent. Examples of the chain transfer agent include n-dodecyl mercaptan, γ
-Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane and the like.

The weight average molecular weight of the copolymer (B-1) in the present invention (value measured by GPC and converted into standard polystyrene) is preferably 10,000 to 400,000, and 20,000 to 200,000. Is more preferable. When the weight average molecular weight is less than 10,000, weather resistance and chemical resistance tend to decrease, and
If it exceeds 000, the viscosity of the resin increases, and it tends to be practically difficult to form a coating. The non-aqueous dispersion type resin (B) in the present invention is insoluble in the organic solvent (A) in the presence of the organic solvent (A) and the copolymer (B-1) soluble in the (A) to form dispersed particles. It can be obtained by copolymerizing the copolymer (B-2) to be formed.

As the monomer used for the copolymer (B-2), the monomer used for the above-mentioned copolymer (B-1) can be used. 2) is selected so as to be insoluble in the organic solvent (A). Usually, a (meth) acrylic acid ester having 2 or less carbon atoms in the alkyl group is used as the total amount of monomers used in the copolymer (B-2).
It is used in an amount of 30 to 95 parts by weight with respect to 0 parts by weight.

Further, among the monomers used for producing the copolymer (B-2), it is preferable to use a hydroxyl group-containing (meth) acrylic acid ester because the coating properties such as weather resistance are improved. At this time, the mixing ratio of the hydroxyl group-containing (meth) acrylate is such that the hydroxyl value of the copolymer (B-2) is 20 to 1
It is preferably 50 mgKOH / g, and 25 to 10
0 mgKOH / g, more preferably 30 to 7 mgKOH / g.
More preferably, it is 0 mgKOH / g. When the hydroxyl value is less than 20 mgKOH / g, the weather resistance tends to be poor, and when the hydroxyl value exceeds 150 mgKOH / g, the water resistance of the coating film tends to be poor.

The non-aqueous dispersion type resin (B) in the present invention comprises:
Organic solvent (A) and copolymer (B-1) soluble in (A)
, A mixed solution of the above-mentioned monomer and polymerization initiator is added, and the mixture is heated at 50 to 200 ° C. for 1 to 10 hours. As the polymerization initiator used at this time, the above-described organic peroxides, azo compounds, and the like can be used. The amount of the polymerization initiator is usually 0.1 to 10.0 parts by weight based on 100 parts by weight of the total amount of the polymerizable unsaturated monomers used for the polymerization of the component (B-2). preferable. Moreover, you may adjust a molecular weight using a chain transfer agent as needed. As the chain transfer agent, for example, n
-Dodecylmercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane and the like.

The non-aqueous dispersion type resins (B) (B-1) and (B-1)
The blending ratio of (B-2) is defined as (B-
1) / (B-2) = 10/90 to 60/40 is preferable, 20/80 to 50/50 is more preferable, and 25/7
5-40 / 60 is more preferred. Copolymer (B-1)
Is less than 10, the dispersion stability of the obtained non-aqueous dispersion resin (B) tends to decrease, and when (B-1) exceeds 60, the matting property tends to decrease. Further, the copolymer (B-1) and the copolymer (B-2) may be chemically bonded. In this case, for example, a method in which an unsaturated double bond is added to the copolymer (B-1) and grafting is performed at the time of producing the copolymer (B-2) can be used.

The non-aqueous dispersion type resin (B) thus obtained preferably has a hydroxyl value in the range of 20 to 150 mgKOH / g, and has a weight average molecular weight of usually 20,000 or less.
It is preferably set to 00 to 500,000.
More preferably, it is set to 00 to 300,000. If the weight average molecular weight is less than 20,000, weather resistance and chemical resistance tend to decrease, and if it exceeds 500,000, the viscosity of the resin tends to be high, and it tends to be difficult to make a coating material practically. The average particle size of the non-aqueous dispersion resin (B) (for example, a value obtained by measuring with an N4 type submicron particle analyzer manufactured by Coulter Inc. at a temperature of 20 ° C. in an INTENSITY mode) is about 100 to 2000 nm. Preferably, it is about 200-1500 nm, more preferably. If it is too small, the viscosity of the resin solution tends to be high. If it is too large, the particles tend to swell or aggregate during storage, resulting in poor stability.

The matting resin composition of the present invention comprises a styrene and an alkyl (meth) acrylate having an alkyl group of 4 or more in the presence of an organic solvent (A) and a non-aqueous dispersion resin (B). It is obtained by polymerizing a monomer. The alkyl group used here has 4 carbon atoms.
The above (meth) acrylic acid alkyl ester monomer is
The foregoing are used. The mixing ratio of styrene and the alkyl (meth) acrylate monomer having 4 or more carbon atoms in the alkyl group is 100 parts by weight of the total amount, and the styrene / alkyl alkyl (meth) acrylate having 4 or more carbon atoms in the alkyl group is used. The monomer is preferably in the range of 25/75 to 75/25. Outside this range, the matting properties tend to decrease.

Further, in the presence of the organic solvent (A) and the non-aqueous dispersion type resin (B), styrene and an alkyl (meth) acrylate monomer having an alkyl group of 4 or more are polymerized. In the copolymer (C) obtained by the above, a monomer other than styrene and an alkyl (meth) acrylate monomer having 4 or more carbon atoms in the alkyl group may be polymerized, It is preferable that the total amount of the monomers used for the combination (C) is 100 parts by weight or less and 20 parts by weight or less. If the amount of the monomer other than the styrene and the alkyl (meth) acrylate having an alkyl group of 4 or more exceeds 20 parts by weight, the mattability tends to decrease.

This copolymer (C) is prepared by adding a mixture of the aforementioned monomer and polymerization initiator to an organic solvent (A) and a non-aqueous dispersion type resin (B), It can be obtained by holding for 10 hours. As the polymerization initiator used at this time, the above-described organic peroxides, azo compounds, and the like can be used. The amount of the polymerization initiator is usually 100% of the total amount of the polymerizable unsaturated monomer used for the polymerization of the component (C).
It is preferably 0.1 to 10.0 parts by weight based on parts by weight.

The mixing ratio of the non-aqueous dispersion type resin (B) and the copolymer (C) is (B) / (C) when the total amount is 100 parts by weight.
= 25/75 to 75/25.
When (B) is less than 25 or more than 75, the matting property tends to decrease. The weight average molecular weight of the resin composition comprising the non-aqueous dispersion type resin (B) and the copolymer (C) thus obtained is usually from 10,000 to 500,000.
0, preferably 20,000 to 300,00
More preferably, 0 is set. This weight average molecular weight is 1
If it is less than 000, the weather resistance and chemical resistance tend to decrease, and if it exceeds 300,000, the resin has a high viscosity, and it tends to be practically difficult to form a coating.

The resin composition for a matte paint obtained as described above is preferably added with a polyisocyanate as a curing agent because the weather resistance, water resistance and chemical resistance can be improved. As the polyisocyanate, 2
A compound having two or more isocyanate groups, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-
Aliphatic or alicyclic isocyanates such as trimethylhexamethylene diisocyanate, methylcyclohexane diisocyanate, isopropylidenebis (4-cyclohexyl isocyanate), trimers thereof, and the like; and isocyanates and propanediol, butanediol, hexanediol, Examples thereof include polyhydric alcohol compounds such as decanediol, dodecanediol, 12-hydroxystearyl alcohol, polyethylene glycol, trimethylolpropane, pentaerythryl, and dimer diol, and compounds generated by reaction with water.

The blending amount of the polyisocyanate should be 0.5 to 2.0 in terms of the total hydroxyl group / isocyanate group equivalent ratio of the non-aqueous dispersion resin (B) and the copolymer (C). More preferably, it is set to 0.8 to 1.2. If it is less than 0.5, the unreacted polyisocyanate compound remains in the coating film, so that the properties of the coating film tend to decrease. If it exceeds 2.0, the water resistance and weather resistance of the coating film tend to decrease. It is preferable that the matting resin composition of the present invention and the polyisocyanate are mixed immediately before coating and then mixed with stirring.

The resin composition for a matte coating in the present invention can be mixed with an inorganic pigment and an organic pigment to form an enamel coating. As the inorganic pigment, for example, titanium white,
Examples of the organic pigment include phthalocyanine blue and azo-based organic pigments.
In addition, extenders such as calcium carbonate and barium sulfate can be added. These are usually added to the base. It is also possible to make a clear paint without adding the pigment. As a method of making an enamel paint, for example,
A known method such as a roll, a sand mill, and a disperser can be used. In addition, when enamel coating with a non-aqueous dispersion resin, high shear force is applied, the resin may cause agglomeration, so a seed pen having good compatibility with the curable composition obtained by the present invention. It can also be used to create an enamel paint. Further, in order to improve the performance as a paint, a pigment dispersant, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer and the like can be added at the time of forming the paint or after the paint is formed.

The paint of the present invention is prepared according to a usual coating method.
It can be used for coating various substrates and surfaces of articles.
For coating, for example, an air spray machine, an airless spray machine, an electrostatic coater, a dipping, a roll coater, a brush or the like can be used. Examples of the substrate include wood, metal, slate, roof tile, and the like. When the coating composition of the present invention is used as a curing coating composition, it is necessary to cure the coating film.
It is preferable to leave it for about 10 days.

[0037]

The present invention will be described below in detail with reference to examples. Note that “parts” indicates “parts by weight”.

Production Examples 1-2 Production of Copolymer (B-1) Soluble in Organic Solvent (A) A mineral turpentine 30 was placed in a flask equipped with a thermometer, a stirrer, a nitrogen gas blowing tube and a reflux condenser. And 100 and 200 parts of Solvesso were charged and the temperature was raised to 100 ° C. by flowing nitrogen gas, and the mixture shown in Table 1 was added dropwise over 2 hours.
Subsequently, a mixture of 20 parts of a mineral terpene and 0.2 parts of t-butylperoxy-2-ethylhexanoate was added dropwise over 1 hour, and the mixture was further kept warm for 3 hours. Thereafter, the mixture was cooled, and a mineral terpene was added so that the heating residue was about 50% by weight to obtain copolymers (S-1 to S-2). Table 1 shows the heating residue, hydroxyl value, and weight average molecular weight of the obtained copolymer solution.

[0039]

[Table 1]

Production Example 3 Production of Non-Aqueous Dispersion Resin (B) Into the synthesizing apparatus used in Production Examples 1 and 2, 60 parts of the copolymer solution obtained in Production Examples 1 and 2 and 5 parts of a mineral terpene were charged. The temperature was raised to 110 ° C. by flowing nitrogen gas, and a mixture having the composition shown in Table 2 was added dropwise over 2 hours. Subsequently, a mixture of 20 parts of a mineral terpene and 0.2 part of t-butylperoxy-2-ethylhexanoate was added dropwise over 1 hour, and the mixture was further kept warm for 3 hours. After cooling, the heating residue is about 5
Mineral terpene was added so as to be 0% by weight. Table 2 shows the heating residue, hydroxyl value, and weight average molecular weight of the obtained non-aqueous dispersion type resin solution (N-1).

Production Examples 4 to 6 Production of Non-Aqueous Dispersion Resin (B) The copolymer solution obtained in Production Examples 1 to 2 with the composition shown in Table 3 using the synthesis apparatus used in Production Examples 1 and 2, 5 parts of mineral turpent was charged, and the temperature was increased to 110 ° C. by flowing nitrogen gas.
Was added dropwise over 2 hours. Subsequently, a mixed solution of 20 parts of a mineral terpene and 0.2 parts of t-butylperoxy-2-ethylhexanoate was added dropwise over 1 hour, and the temperature was further maintained for 3 hours. Thereafter, the mixture was cooled, and a mineral terpene was added so that the heating residue was about 50% by weight.
Table 2 shows the heating residue, hydroxyl value, and weight average molecular weight of the obtained non-aqueous dispersion type resin solutions (N-2 to N-4).

[0042]

[Table 2]

Production Example 7 Production of Copolymer (C) in the Presence of Organic Solvent (A) and Non-Aqueous Dispersion Resin (B) 140 parts of the obtained non-aqueous dispersion type resin solution (N-1) was charged, and heated to 110 ° C. under a nitrogen stream, and 20 parts of styrene, 10 parts of 2-ethylhexyl acrylate, and t-butylperoxy-2-ethylhexa were added. A mixed solution consisting of 0.2 part of noate was added dropwise over 1 hour. Then, mineral turpentine 10
And a mixture of 0.2 parts of t-butylperoxy-2-ethylhexanoate was added dropwise over 30 minutes, and the mixture was kept warm for 3 hours. Thereafter, the mixture was cooled, and a mineral terpene was added so that the heating residue was about 50% by weight. Table 2 shows the heating residue, hydroxyl value, and weight average molecular weight of the obtained copolymer resin solution (C-1).

Production Examples 8 to 10 Production of Copolymer (C) in the Presence of Organic Solvent (A) and Nonaqueous Dispersion Resin (B) Nonaqueous Dispersion Resin in Production Example 7 and Dropping Monomer Except that the mixture was changed to that shown in Table 3, it was produced in the same manner as in Production Example 7 to obtain copolymer solutions (C-2 to C-4). Table 3 shows the heating residue, hydroxyl value, and weight average molecular weight of the obtained copolymer solution.

[0045]

[Table 3]

Production Example 11 Production of Non-Polymer Solution D The same synthetic apparatus as in Production Examples 1 and 2 was used.
0 parts and 30 parts of Solvesso 100 were charged, and the temperature was raised to 110 ° C. under a nitrogen stream, and 67 parts of styrene, 33 parts of 2-ethylhexyl acrylate, and t-butylperoxy-2- were used.
A mixed solution consisting of 0.6 parts of ethyl hexanoate was added dropwise over 2 hours. Then, 20 parts of mineral turpen,
t-butyl peroxy-2-ethylhexanoate
The mixed solution consisting of 2 parts was added dropwise over 1 hour, and 3
Incubated for hours. Thereafter, the mixture was cooled, and a mineral terpene was added so that the heating residue was about 50% by weight. Thereafter, 30 parts of the obtained copolymer solution and the non-aqueous dispersion type resin solution (N-1) obtained in Production Example 3 were mixed at room temperature to obtain a non-polymer solution mixture D. The heating residue of the non-polymer solution D was 50.4% by weight, the hydroxyl value was 30, and the weight average molecular weight was 125,000.

Examples 1-4 and Comparative Examples 1-2 The copolymer solutions C-1 to C- obtained in Production Examples 7 to 10
4. Non-aqueous dispersion type resin solution (N-1) obtained in Production Example 3
And the copolymer solution mixture D obtained in Production Example 11 was mixed with a polyisocyanate (Duranate TSA-10 (trade name)) as a curing agent so as to be equimolar to the hydroxyl value of each copolymer.
0, manufactured by Asahi Kasei Corporation), and diluted with an Iwata cup using a mineral turpentine for 15 seconds (25 ° C.) to prepare a paint. The prepared paint was applied by air spray onto a Bonderite # 144 treated steel plate (manufactured by Nippon Test Panel Co., Ltd.) so that the dry film thickness became 30 μm.
After curing at room temperature for one week, a test plate was prepared.

(Evaluation) The prepared test plates were evaluated for matting properties, water resistance, weather resistance and storage stability in accordance with the following methods. (1) Matting property The 60-degree specular reflectance (%) of the prepared test plate was measured with a gloss meter (manufactured by Nippon Denshoku Co., Ltd.). (2) Water resistance The prepared test plate was immersed in tap water and allowed to stand for 240 hours, and the appearance of the coating film (bulging, cracking, gloss return) was visually observed and evaluated according to the following criteria. ：: No abnormality in the coating film △: An abnormality occurred in a part of the coating film ×: An abnormality occurred in the entire coating film

(3) Weather Resistance The prepared test plate was tested for 500 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), and the appearance of the coating film (blow, crack, gloss return) was visually observed. Was evaluated according to the following criteria. ○: No abnormality in the coating film △: An abnormality occurred in a part of the coating film ×: An abnormality occurred in the entire coating film (4) Storage stability Copolymer resin solution C-1 to C-4, non-aqueous dispersion type resin solution (N-1) and the copolymer mixed solution D under the condition of 50 ° C.
It was stored tightly for 4 days, and the state change was visually observed and evaluated according to the following criteria. ：: No change in state ×: Separation and aggregation were observed.

[0050]

[Table 4]

According to Table 4, the evaluation result in the matting property column of the coating material of Comparative Example 1 was as high as 95 in gloss value, indicating that this coating material was inferior in matting property. In the paint of Comparative Example 2, the evaluation result in the stability column was x (separation), and the evaluation result in the water resistance and weather resistance column was Δ (abnormality occurred in a part of the coating film). This shows that this paint is inferior in storage stability, water resistance and weather resistance.

On the other hand, according to Table 4, Examples 1 to 4
In the paint obtained in the above, the evaluation result in the matte property column was as low as 10 or less in gloss value, and the evaluation result in the water resistance and weather resistance column was also ○ (no abnormality in the coating film). ,further,
The evaluation result in the column of stability of the paint is also ○ (no change in state). Thus, it is shown that the paints obtained in Examples 1 to 4 are excellent in matting properties, water resistance, weather resistance and storage stability.

[0053]

The first invention is excellent in matting properties and stability, and is suitable for a paint. The second invention has the effects of the first invention, is excellent in water resistance of a coating film, and is suitable for a paint. The third and fourth inventions have the effects of the first invention,
Suitable for matte paints with excellent chemical resistance and water resistance of the coating film.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5 / 00F // C09D 133/04 133/04 (72) Inventor Kei Sakamoto Ibaraki F-term (reference) in Kashima Plant, Hasaki-cho, Kashima-gun, Kashima-gun, Hitachi Chemical Co., Ltd. HC22 JA42 4J038 CC061 CG141 CG142 CH032 CH041 CH042 CH122 CJ031 CJ032 CJ062 CJ072 CJ092 CJ132 CP032 DG262 GA03 KA03 KA06 MA02 MA14 NA01 PC02 PC04 PC06

Claims (4)

[Claims] 1. The method according to claim 1, wherein the styrene and the alkyl group have carbon atoms in the presence of the solvent (A) containing the aliphatic hydrocarbon as a main component, the non-aqueous dispersion type resin (B), and (A) and (B). It contains a copolymer (C) obtained by polymerizing four or more alkyl (meth) acrylate monomers, and the compounding ratio of the non-aqueous dispersion resin (B) and the copolymer (C) is as follows: With the total amount of (B) and (C) being 100 parts by weight,
(B) / (C) = 25/75 to 75/25, styrene (a) in copolymer (C) and alkyl (meth) acrylate monomer having 4 or more carbon atoms in the alkyl group (b) )
Wherein the mixing ratio of (a) / (b) is 30/70 to 70/30, where the total amount of (a) and (b) is 100 parts by weight. 2. The non-aqueous dispersion type resin (B) is insoluble in the solvent (A) in the presence of the copolymer (B-1) soluble in the solvent (A) according to claim 1, and is dispersed particles. (B-
The hydroxyl value obtained by polymerizing 2) is 20 to 1
The matte coating resin composition according to claim 1, wherein the resin composition is 50 mgKOH / g. 3. A coating composition comprising the resin composition for coating composition according to claim 1 and a curing agent. 4. The paint according to claim 3, wherein the curing agent is a polyisocyanate.