JP2003138215A - Coating resin composition and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for flatting coating materials which excels in coating properties such as flatting, water resistance, and weatherability and storage stability, and is suitable for coating materials, and a coating material. SOLUTION: The resin composition for flatting coating materials comprises (A) an organic solvent containing an aliphatic hydrocarbon and (B) a nonaqueous solvent dispersion type resin and is substantially free of a flatting agent, and the coating film to be obtained after coating this composition has a surface roughness of 1-10 μm, and the coating material comprises this composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for coatings, which provides a coating film excellent in mattness and is excellent in storage stability.
And paints containing it.

[0002]

2. Description of the Related Art Conventionally, many methods have been proposed as a method for delustering a coating film. For example, it is said that an inorganic powder such as silica powder generally referred to as a matting agent or an organic powder such as polyethylene powder is added to generate irregularities on the coating film surface and scatter light reflection to obtain a matting effect. It is a thing.

However, the method using these matting agents is inferior in the storage stability of the coating due to the sedimentation of the matting agent, and a uniform matting coating cannot be obtained, resulting in poor coating durability such as weather resistance. . In order to solve this problem, a resin composition produced by using a special polymerization method without adding a matting agent (for example, JP-A-3-81371, JP-A-6-61).
No. 287235) is proposed. However, the matte properties of the coating film obtained from these resin compositions are not satisfactory, and the durability of the coating film such as water resistance is poor. Further, since these resin compositions use toluene as a solvent, the resin composition has a strong odor during coating, and also causes a lifting phenomenon that attacks the underlying coating film during repair coating or overcoating. From such a point of view, a resin composition for a coating which has a low odor, uses an aliphatic hydrocarbon that does not attack the underlying coating film as a solvent, and can obtain a matte coating film without adding a matting agent. Development is desired.

[0004]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a resin composition which gives a coating film having excellent matte properties. A second object of the present invention is to provide a resin composition having excellent storage stability in addition to the first object. The third object of the present invention is, in addition to that,
It is intended to provide a resin composition which gives a coating film having excellent water resistance and weather resistance.

A fourth object of the present invention is to provide a coating material which gives a coating film having excellent matting properties, storage stability and weather resistance of the coating film.

[0006]

The coating composition of the present invention comprises:
(A) an organic solvent containing an aliphatic hydrocarbon and (B)
A coating resin composition containing a non-aqueous solvent-dispersed resin, which is substantially free of a matting agent, wherein the surface roughness of the coating film obtained by a method including a step of coating a coating material containing this as a main component is It is characterized by being 1 to 10 μm.

In the present invention, the (B) non-aqueous solvent dispersion type resin is (B-1) a copolymer soluble in (A), and a vinyl type resin in the presence of (B-1). (B-2) Dispersed particles insoluble in (A), obtained by polymerizing a monomer, wherein (B-1) contains (a) styrene or a cycloalkyl group or a cycloalkyl-alkyl group. 20 to 50% by weight of one or two or more vinyl-based monomers selected from monomers, (b) alkyl (meth) acrylate monomer 10 having an alkyl group having 8 to 20 carbon atoms 10 40% by weight and (c) 10 to 70% by weight of other vinyl-based monomer are copolymerized; and (B-2) is (d) methyl methacrylate 70.
~ 95 wt%, (e) 0.5 carboxyl group-containing monomer
˜15% by weight, (f) glycidyl group-containing monomer 0.5˜
It is obtained by copolymerizing 15% by weight and, if necessary, (g) less than 20% by weight of other vinyl-based monomers, and the weight of the (B-1) / the (B-2). Ratio is 30
/ 70 to 70/30; the (B-1) and the (B-
The present invention relates to the resin composition for paints, wherein part or all of 2) is chemically bonded.

The present invention also relates to a coating composition containing the above resin composition, particularly a coating composition containing polyisocyanate as a curing agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Used in the Present Invention
The organic solvent contains an aliphatic hydrocarbon, for example, a linear aliphatic hydrocarbon, a branched aliphatic hydrocarbon, an alicyclic hydrocarbon and the like. Examples of linear and branched aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane.
And branched isomers thereof, and examples of the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and the like. As the organic solvent (A), a mixed solvent of aliphatic hydrocarbons such as petroleum ether, petroleum spirit, white spirit, petroleum benzine, ligroin, aliphatic naphtha, mineral thinner and mineral terpene can be used. .

The content of these aliphatic hydrocarbons is from 30 to 100 in the total (A) organic solvent, because the lifting phenomenon does not occur during repair work to the human body and the environment.
Wt% is preferable, 50 wt% or more is more preferable, 7
It is more preferably 0% by weight or more. Further, an organic solvent component other than the aliphatic hydrocarbon can be used as long as the amount of the aliphatic hydrocarbon compounded is within the above range and the curing reaction of the hydroxyl group and the isocyanate group described later is not hindered.

Examples of the organic solvent component other than the aliphatic hydrocarbons include aromatic hydrocarbons, esters, ketones, alcohols and the like. Examples of aromatic hydrocarbons include toluene, xylene, Solvesso 1
00 (Exxon Mobil Co., Ltd. trade name), Solvesso 150 (Exxon Mobil Co., Ltd. trade name), and the like. Examples of the esters include ethyl acetate, butyl acetate, etc .; , Acetone, methyl ethyl ketone, methyl isobutyl ketone and the like; alcohols include, for example, methanol, ethanol, isopropanol,
Examples include n-butanol, isobutanol and t-butanol. When components other than these aliphatic hydrocarbons, especially aromatic hydrocarbons, are used, the odor may become strong and a lifting phenomenon may occur during repair work. Further, the alcohols may hinder the curing reaction between the hydroxyl group of the non-aqueous solvent dispersion type resin (B) described later and the isocyanate group of the polyisocyanate which is the curing agent.
Therefore, it is necessary to use them without departing from the object of the present invention. These aliphatic hydrocarbons and components other than the aliphatic hydrocarbons can be used alone or in combination of two or more.

The non-aqueous solvent dispersion type resin (B) in the present invention is obtained by polymerizing a vinyl monomer in the presence of the (B-1) copolymer soluble in the above (A) to prepare the above ( A resin obtained by forming dispersed particles of a copolymer (B-2) insoluble in A), wherein the copolymer (B-2) is (B-1).
A dispersion dispersed therein is formed, and the dispersion is dispersed in the non-aqueous solvent as a whole. (B-1) and / or (B-2)
Each preferably have a hydroxyl group in the molecule, the weather resistance of the coating film is improved, and the storage stability of the resin is also good. Therefore, the hydroxyl value of (B) is 20 to 150 mgKOH / g.
Is more preferable.

The copolymer (B-1) (A) soluble in an organic solvent is one or more selected from (a) styrene or a cycloalkyl group- or cycloalkyl-alkyl group-containing monomer. The vinyl-based monomer (1), the (b) alkyl (meth) acrylate monomer having an alkyl group having 8 to 20 carbon atoms, and the other vinyl-based monomer (c) are copolymerized.

One or more vinyl-based monomers (a) selected from styrene or a cycloalkyl group- or cycloalkyl-alkyl group-containing monomer are combined with (b) described below to obtain ( B) A monomer that provides a structural unit that imparts matteness and stability to the resin. Examples of the (a) include styrene, and examples of the cycloalkyl group-containing monomer include cyclohexyl (meth) acrylate and methylcyclohexyl (meth).
Acrylate, cyclododecyl (meth) acrylate,
1,4-cyclohexanedimethanol mono (meth) acrylate and the like; cycloalkyl-alkyl group-containing monomers include cyclopentylethyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate and the like. Is mentioned. These styrenes or cycloalkyl group- or cycloalkyl-alkyl group-containing monomers can be used alone or in combination of two or more kinds.

(B) The (meth) acrylic acid alkyl ester monomer having an alkyl group having 8 to 20 carbon atoms is combined with the above-mentioned (a) to give the resin (B) a matte property and stability. It is a monomer that provides the constituent units to be provided. Examples of the (b) include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, eicosyl (meth) acrylate, and the like, and the number of carbon atoms of the alkyl group. Is preferably 8 to 12, and particularly preferably 8. These monomers are
They can be used alone or in combination of two or more.

(C) Other vinyl monomers include
A (meth) acrylic acid-based monomer having a hydrocarbon group having 4 to 7 carbon atoms, a hydroxyl group-containing (meth) acrylic acid-based monomer, or the like can be used.

As the above-mentioned (c), (B) the dispersion stability of the non-aqueous solvent-dispersed resin is excellent, and the hydroxyl group-containing (meth) acrylic acid ester-based monomer is a curing agent of polyisocyanate. Since the weather resistance of the coating film obtained when combined with the compound is excellent, the carbon number is 4 to 7
The (meth) acrylic acid alkyl ester-based monomer having an alkyl group or a polycyclic alkyl group is preferred. Examples of such a monomer include n-butyl (meth) acrylate, pentyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
(Meth) acrylic acid alkyl esters such as pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate; and (meth) acrylic acid such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate Examples include polycyclic hydrocarbon esters. These monomers can be used alone or in combination of two or more kinds.

The hydroxyl group-containing (meth) acrylic acid ester type monomer imparts reactivity with the polyisocyanate to the copolymer (B-1). Examples of such a monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolmethane mono (meth) acrylate, (Meth) acrylic acid hydroxyalkyl esters such as tetramethylolmethane mono (meth) acrylate; (poly) alkylene glycols such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Mono (meth) acrylates and the like; or the above monomers and, for example, ε-caprolactone, γ-
Adducts with lactones such as valerolactone can also be used. Among these hydroxyl group-containing (meth) acrylic acid esters and their adducts, from the viewpoint of polymerizability and reactivity, (meth) acrylic acid hydroxyalkyl esters, and (meth) acrylic acid hydroxyalkyl esters and lactones Is preferred. These monomers can be used alone or in combination of two or more kinds.

As the other copolymerizable vinyl-based monomer (c), various vinyl compounds other than the above can be used. For example, a (meth) acrylic acid alkyl ester having 3 or less carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate; glycidyl (meth) acrylate , An epoxy group-containing (meth) acrylic acid ester such as methyl glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate; N, N-diethylaminoethyl (meth ) Amino group-containing (meth) acrylic acid ester such as acrylate and N, N-dimethylaminopropyl (meth) acrylate; hindered amino group-containing (meth) acrylic acid ester; benzotriazole group-containing (meth) acrylic acid ester, etc. each (Meth) acrylic acid derivatives, acrylic acid, methacrylic acid, the carboxyl group-containing monomers such as maleic acid, vinyl toluene, alpha
-Styrene-based monomers other than styrene such as methylstyrene; vinyl-based compounds such as vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, and vinyl acetate can be used. These monomers, alone,
Alternatively, two or more kinds can be used in combination.

(B-1) (A) Vinyl monomer selected from styrene or a cycloalkyl group- or cycloalkyl-alkyl group-containing monomer in the organic solvent-soluble copolymer. , (B) the compounding ratio of the (meth) acrylic acid alkyl ester monomer having an alkyl group having 8 to 20 carbon atoms and (c) the other vinyl-based monomer,
Sufficient matte property of the coating film is obtained, and (B) the non-aqueous solvent dispersion type resin has excellent dispersion stability.
1) Based on the total amount of monomers used in the copolymer, (a) 1
5 to 50% by weight, (b) 10 to 40% by weight and (c)
It is preferably in the range of 10 to 75% by weight, (a)
25 to 45% by weight, (b) 15 to 30% by weight and (c) 15 to 60% by weight are more preferable.

As a method for synthesizing 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 polymerizing using a radical polymerization method, for example, the above-mentioned monomer and a polymerization initiator are mixed in the above-mentioned organic solvent (A) and heated at 50 to 200 ° C for 1 to 10 hours.
Examples of the polymerization initiator used for polymerization of the copolymer (B-1) include organic peroxides and azo compounds. Examples of the organic peroxide include isobutyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and octa. Noyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, dichlorobenzoyl 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- Chiruperuokishi) cyclohexane, 2,2-bis (t-butylperoxy)
Butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, t-butylperoxyisobutyrate, t-butylperoxy- 2-ethylhexanoate, 1,1,
3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate and the like can be mentioned. Further, as the azo compound, 2,2′-azobisisobutyronitrile, dimethylazodiisobutyrate, 2,2-azobis (2,2)
4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile),
(1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2,
2'-azobis (2,2,4-trimethylpentane),
2,2'-azobis (2-methylpropane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile and the like can be mentioned. These polymerization initiators can be used alone or in combination of two or more kinds.

The amount of the polymerization initiator used depends on the molecular weight of the desired copolymer (B-1), but the total amount of the polymerizable unsaturated monomers used for the polymerization of the component (B-1). Usually, 0.1 to 10.0% by weight is preferable with respect to 100 parts by weight. Moreover, you may adjust a molecular weight using a chain transfer agent as needed. As the chain transfer agent, for example, n-
Examples thereof include mercapto group-containing compounds such as dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl (methyl) dimethoxysilane, and 3-mercaptopropyltriethoxysilane.

The weight average molecular weight (value measured by GPC and converted into standard polystyrene) of the copolymer (B-1) in the present invention is practically a resin solution having a viscosity range which makes it easy to form a coating, In addition, since a coating film having excellent weather resistance and chemical resistance can be obtained, 10,000 to 400,000 is obtained.
0 is preferable and 20,000 to 200,000 is more preferable.

The non-aqueous solvent dispersion type resin (B) in the present invention is (d) methyl methacrylate in the presence of the organic solvent (A) and the copolymer (B-1) soluble in the (A). ,
Insoluble in the organic solvent (A) by copolymerizing (e) a carboxyl group-containing monomer, (f) a glycidyl group-containing monomer, and optionally (g) another vinyl-based monomer. It can be obtained by synthesizing the copolymer (B-2).

Among the above monomers, examples of the (e) carboxyl group-containing monomer include acrylic acid, methacrylic acid and maleic acid, which can be used alone or in combination of two or more kinds. .

Examples of the (f) glycidyl group-containing monomer include
Examples thereof include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. These can be used alone or in combination of two or more.

Further, (g) the other vinyl-based monomer is a mono-monomer exemplified as the monomers (a) to (c) used for synthesizing the above-mentioned copolymer (B-1). In the body, the monomers not included in the above (d) to (f) can be used alone or in combination of two or more kinds. Since the coating film properties such as weather resistance of the obtained coating film are improved, it is preferable to use a hydroxyl group-containing (meth) acrylic acid ester-based monomer as at least a part thereof.

The blending ratio of (d) methyl methacrylate in the copolymer (B-2) is such that a coating film excellent in matting property can be obtained, and therefore the total amount of the monomers used in the (B-2) is 70 to 95% by weight, preferably 80 to 95% by weight,
90% by weight is more preferred.

Further, in practice, a non-aqueous solvent dispersion type resin (B) having a viscosity range which can be easily made into a coating material can be obtained, and a coating film having excellent matte property can be obtained. The compounding ratio of the (e) carboxyl group-containing monomer is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the total amount of the monomers used. The mixing ratio of the (f) glycidyl group-containing monomer is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight. Also,
The blending ratio of (g) the other vinyl-based monomer is preferably less than 20% by weight because the matting property is not impaired.

The non-aqueous solvent dispersion type resin (B) synthesized and used in the present invention includes organic solvents (A) and (A).
In the presence of the copolymer (B-1) soluble in the above, a mixed solution of the above-mentioned monomer component and the polymerization initiator is added,
It can be obtained by heating to ° C for 1 to 10 hours. As the polymerization initiator used at this time, the same organic peroxides and azo compounds as described above can be used. The amount of the polymerization initiator is usually preferably 0.1 to 10.0% by weight based on 100 parts by weight of the total amount of the polymerizable unsaturated monomer used for the polymerization of the component (B-2).

If necessary, a chain transfer agent may be used to adjust the molecular weight. Examples of the chain transfer agent include mercapto group-containing compounds such as n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl (methyl) dimethoxysilane, and 3-mercaptopropyltriethoxysilane.

(B) In the non-aqueous solvent dispersion type resin (B-
The blending ratio of 1) and (B-2) is such that the non-aqueous solvent-dispersed resin (B) having excellent dispersion stability can be obtained and a coating film having excellent matte properties can be obtained. -1) / (B-
The ratio of 2) is preferably 30/70 to 70/30, more preferably 40/60 to 60/40.

The component (B-1) and the component (B-2) may be chemically bonded. In this case, for example, the component (B-1) having an unsaturated double bond is used to polymerize the monomer (B-2) at the time of polymerization of the monomer for producing the copolymer (B-2). It is possible to use a method of forming a part by grafting (B-1) as a graft branch.

The hydroxyl value of the non-aqueous solvent-dispersed resin (B) thus obtained is preferably 20 to 150 mgKOH / g, and 30 to 30 because a coating film excellent in weather resistance and water resistance can be obtained. More preferred is 100 mg KOH / g. Further, the weight average molecular weight of the non-aqueous solvent-dispersed resin (B) is practically such that a resin having a viscosity range that is easily made into a paint can be obtained, and a coating film having excellent weather resistance and chemical resistance can be obtained. Therefore, usually, 20,000 to 500,000 is preferable, and 30,0
More preferably, it is from 00 to 300,000.

In order to improve the performance of a coating composition using the resin composition for coating composition of the present invention, a pigment dispersant, a leveling agent, a defoaming agent, an ultraviolet absorber, a light stabilizer and the like are added at the time of coating. Alternatively, it may be added after being made into a paint. However, the coating composition and coating material of the present invention do not substantially contain a powdery delustering agent such as silica powder or polyethylene powder that precipitates during storage.

The resin composition for a matte coating obtained as described above is applied to the surface of a substrate and then the solvent is volatilized as it is, or cured by an arbitrary curing mechanism, for example, by heating and / or an optional curing agent. , A coating film can be obtained. In particular, it is preferable to use polyisocyanate as a curing agent because a cured coating film can be obtained at room temperature and the coating film is excellent in weather resistance, water resistance and chemical resistance.

The polyisocyanate compound has 2 units in the molecule.
It is a compound containing one or more isocyanato groups. Examples of the polyisocyanate compound include, for example, hexamethylene diisocyanate, isophorone diisocyanate,
Aliphatic or alicyclic isocyanates such as lysine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methylcyclohexane diisocyanate, and isopropylidene bis (4-cyclohexyl isocyanate), and its trimerization And the like; and polyhydric alcohol compounds such as propanediol, butanediol, hexanediol, decanediol, dodecanediol, 12-hydroxystearyl alcohol, polyethylene glycol, trimethylolpropane, pentaerythritol, and dimer diol, or water. Examples thereof include compounds produced by the reaction with and prepolymers.

The blending amount of the polyisocyanate compound is such that the unreacted polyisocyanate compound does not remain in the coating film and the coating property is not deteriorated, and a coating film excellent in water resistance and weather resistance is obtained. Therefore, the total hydroxyl group / isocyanato group equivalent ratio of the non-aqueous solvent dispersion type resin (B) is 0.5 to
2.0 is preferable and 0.8-1.2 is more preferable. The matting resin composition of the present invention is preferably blended with the polyisocyanate compound immediately before coating and stirring and mixing.

The resin composition for a matte coating of the present invention may be blended with an inorganic pigment and / or an organic pigment to give an enamel coating. As the inorganic pigment, for example,
Examples thereof include titanium white and carbon black; examples of organic pigments include phthalocyanine blue and azo organic pigments. Also, if necessary, calcium carbonate,
An extender pigment such as barium sulfate can also be added. Further, a clear paint may be used without adding these pigments. As a method for preparing an enamel paint, for example,
Known means such as rolls, sand mills, dispersers, etc. can be used. Further, generally, when an enamel paint is prepared using a non-aqueous solvent-dispersed resin, a high shearing force is applied, and the resin may agglomerate. In such a case, the enamel paint can be prepared by adding a seed paint having good compatibility to the resin composition for paint obtained by the present invention.

The coating composition of the present invention is prepared according to the usual coating method.
For example, it can be used for coating various base materials such as wood, metal, slate, roof tile, etc., and the surface of articles. The coating can be performed, for example, by using an air spray device, an airless spray device, an electrostatic coating machine, a roll coating machine, a brush, or the like, or by dipping.

When the coating material of the present invention is used as a curable coating material, it is necessary to cure the coating film. for that reason,
After coating, it is preferable to stand at room temperature to 150 ° C. for about 1 minute to 10 days. When the coating composition of the present invention is applied as described above, the surface roughness of the obtained coating film is the surface roughness R
z is 1 to 10 μm, preferably 2 to 8 μm.
If Rz is less than 1 μm, the coating film will not be matte, and if it exceeds 10 μm, the appearance of the coating film will not be uniform.

[0042]

The present invention will be described in detail below with reference to examples. The invention is not limited by these examples. In addition, "part" shows a "weight part."

Production Examples 1 to 5 Production of (B-1) Copolymer Soluble in Organic Solvent (A) Mineral terpene 20 was placed in a flask equipped with a thermometer, a stirrer, a nitrogen gas blowing tube and a reflux condenser. And 20 parts of Solvesso 100 were charged, the temperature was raised to 100 ° C. in a nitrogen stream while stirring, and the mixed solution shown in Table 1 was added dropwise over 2 hours. Then, t-butylperoxy-2
-0.2 parts of ethyl hexanoate with 2 mineral terpenes
The solution dissolved in 0 part was added dropwise over 1 hour, and the temperature was kept for 3 hours. After cooling, mineral terpenes are added so that the heating residue is about 50%, and the copolymer solution (S-
1 to S-5) were obtained. The heating residue, hydroxyl value and weight average molecular weight of the obtained copolymer solution are shown in Table 1.

[0044]

[Table 1]

Production Examples 6 to 12 (B) Production of Non-Aqueous Solvent Dispersion-Type Resin The copolymers obtained in Production Examples 1 to 5 were blended in the synthesis apparatus used in Production Examples 1 to 5 by the formulation shown in Table 2. The solution was charged, the temperature was raised to 110 ° C. in a nitrogen stream while stirring, and the mixed solution having the formulation shown in Table 2 was added dropwise over 2 hours. Subsequently, a solution prepared by dissolving 0.2 parts of t-butylperoxy-2-ethylhexanoate in 20 parts of mineral terpene was added dropwise over 1 hour, and the mixture was kept warm for 3 hours. Then, the mixture was cooled, and mineral terpen was added so that the heating residue was about 50%. The obtained non-aqueous solvent dispersion type resin solution (N-1 to N-
Table 2 shows the heating residue, hydroxyl value and weight average molecular weight of 7).
Shown in.

[0046]

[Table 2]

Examples 1 to 3 and Comparative Examples 1 to 4 Nonaqueous solvent dispersion type resin solutions N- obtained in Production Examples 6 to 12.
1 to N-7, a polyisocyanate (duranate T) which is a curing agent so that the hydroxyl value of each copolymer is equimolar.
SA-100, a product name of Asahi Kasei Co., Ltd., is blended, and then a mineral terpene is used for 20 seconds (2
The paint was prepared by diluting it to 5 ° C. The paint is applied to a glass plate and a bonderite # 144-treated steel plate (Paltec Co., Ltd.) to which white enamel paint has been applied in advance by air spraying so that the dry film thickness becomes 30 μm, and then at room temperature for 1 week. It was cured to prepare a test plate.

(Evaluation) The prepared test plates were evaluated for surface roughness, gloss (matte resistance), water resistance and weather resistance according to the following methods (1) to (4), and the evaluation results are shown in Table 3. . For the evaluation, a test plate applied to a glass plate was used for the surface roughness, and a treated steel plate was applied for the gloss, water resistance, and weather resistance. Further, the storage stability of the non-aqueous solvent dispersion type resin solution was evaluated according to the method shown in (5). The evaluation results are shown in Table 3.

(1) Surface Roughness Rz of the manufactured test plate was measured by a surface roughness measuring device (SE-3).
400, Kosaka Laboratory Ltd. product name).

(2) Matting property (gloss value) The 60-degree specular reflectance of the test plate prepared was measured using a gloss meter (manufactured by Nippon Denshoku Co., Ltd.).

(3) Water resistance The prepared test plate was immersed in tap water and left for 240 hours, and the appearance (swelling, cracks, glossiness) of the coating film was visually observed and evaluated according to the following criteria. . ○: No abnormality in the coating △: Abnormality in part of the coating ×: Abnormality in the entire coating

(4) 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 (swelling, cracking, glossing, yellowing) ) Was visually evaluated according to the following criteria. ○: No abnormality in the coating △: Abnormality in part of the coating ×: Abnormality in the entire coating

(5) Storage stability of resin Non-aqueous solvent dispersion type resin solutions N-1 to N-7 were heated at a temperature of 50 ° C.
The sample was sealed and stored for 14 days, and the state change was visually observed and evaluated according to the following criteria. ○: No state change ×: Separation and / or aggregation

[0054]

[Table 3]

According to Table 3, the evaluation results of the storage stability of the coating resins obtained in Production Examples 6 to 8 and used in Examples 1 to 3 showed no change in state. Furthermore, Examples 1 to 1
The coating material obtained in No. 3 had a gloss value of 10 or less in terms of the evaluation of matte properties, and was excellent in matte properties. The water resistance and weather resistance evaluation results showed that the coating film was not abnormal. On the other hand, the paints obtained in Comparative Examples 1 to 4 have a gloss value of 60 or more as a result of the evaluation of the matte property, indicating that the paints are inferior in the matte property.

In addition, the coating obtained in Comparative Example 1 was evaluated for water resistance and weather resistance, and as a result, abnormalities were found in the entire coating film, showing that the coating was inferior in water resistance and weather resistance. ing. Further, the coating material obtained in Comparative Example 4 was found to have some abnormalities in the coating film as a result of the evaluation of water resistance and weather resistance, and further, the storage stability of the resin was evaluated, resulting in separation. However, the water resistance and weather resistance are poor, and the storage stability of the resin is also poor.

[0057]

Industrial Applicability According to the present invention, it is possible to obtain a coating resin composition which gives a coating having excellent storage stability and matting properties. Further, according to the present invention, in addition to the above effects, a resin composition having excellent water resistance and weather resistance of a coating film and suitable for a coating material can be obtained. The matte coating obtained by the present invention has excellent chemical resistance and water resistance of the coating film, and is particularly suitable as a coating for interior and exterior of buildings and a coating for plastics.

Continued front page    (72) Inventor Kei Sakamoto             Hitachi, Hasaki-machi, Kashima-gun, Ibaraki             Kasei Industry Co., Ltd. Yamazaki Office F-term (reference) 4J038 CC021 CG142 CH032 DG191                       DG261 GA03 GA06 GA07                       JA02 KA03 KA06 MA02 MA07                       NA01 NA03 NA04 NA26 PB05                       PC02 PC04 PC06

Claims (5)

[Claims] 1. A resin composition for a coating composition, which comprises (A) an organic solvent containing an aliphatic hydrocarbon and (B) a non-aqueous solvent dispersion type resin, and substantially does not contain a matting agent. A resin composition for paints, wherein the surface roughness of a coating film obtained by a method including a step of applying a paint contained as a component is 1 to 10 µm. 2. The non-aqueous solvent dispersion type resin (B) is (B)
-1) The copolymer soluble in (A), and the (B-
Obtained by polymerizing a vinyl monomer in the presence of 1),
(B-2) Dispersed particles insoluble in (A), wherein (B-1) is one or two selected from (a) styrene or a cycloalkyl group or a cycloalkyl-alkyl group-containing monomer. 15 to 5 or more vinyl monomers
0% by weight, (b) 10 to 4 (meth) acrylic acid alkyl ester monomers having an alkyl group having 8 to 20 carbon atoms
0% by weight, and (c) other vinyl monomers 10
It is obtained by copolymerizing about 75% by weight;
-2) is 70 to 95% by weight of (d) methyl methacrylate, 0.5 to 15% by weight of (e) carboxyl group-containing monomer, and (f) 0.5 to 15% by weight of glycidyl group-containing monomer. , And (g) if necessary, other vinyl-based monomers of less than 20% by weight are copolymerized, and the (B-1) / (B-2) weight ratio is 30. / 70
70/30 or less; The resin composition for coating according to claim 1, wherein a part or all of the (B-1) and the (B-2) are chemically bonded. 3. The coating resin composition according to claim 1, wherein the non-aqueous solvent dispersion type resin (B) has a hydroxyl value of 20 to 150. 4. A paint containing the resin composition according to claim 1. 5. The coating composition according to claim 4, further comprising polyisocyanate as a curing agent.