WO2016017778A1 - Coating composition - Google Patents

Abstract

　The present invention addresses the problem of providing a matting coating film having excellent luster stability, alkali resistance, storage stability, and impact resistance. The present invention provides a coating composition including a film-forming resin (A) and a matting agent (B), and further including a nonaqueous polymer dispersion (C) comprising a skin component and a core component, and/or a block polyisocyanate compound (D), the coating composition characterized in that: the nonaqueous polymer dispersion (C) is a nonaqueous polymer dispersion containing an acrylic polymer and/or a self-condensate of a fatty acid having a hydroxyalkyl group in which the alkyl chain thereof has a carbon number of 10-25, and containing, as at least a portion of the skin component, a macromonomer having an average of one or more polymerizable unsaturated groups per molecule thereof; and the block polyisocyanate compound (D) is an active methylene block polyisocyanate compound in which the compound detached in a crosslinking reaction detaches a C3-12 monofunctional alcohol.

Description

Paint composition

[Cross-reference of related applications]
This application claims priority based on Japanese Patent Application No. 2014-154437, filed July 30, 2014, the entire disclosure of which is incorporated herein by reference. The present invention relates to a coating composition.

Conventionally, a glossy design is generally used for a coating film on a body of an automobile or the like, but recently, a so-called matte design in which the gloss is suppressed is attracting attention as a new design.

As means for forming a coating film exhibiting a matte design (hereinafter sometimes referred to as “matte coating film”), for example, Patent Document 1 discloses at least one hydroxyl group-containing compound and at least one hydroxyl group. A coating agent comprising a crosslinking agent having a reactive group and at least one silicate gel-based matting agent, wherein the matting agent is surface-modified with one or more waxes, and the coating agent comprises An organic solvent-based coating agent is described which additionally comprises at least one hydrophobic silicate-based rheology aid.

Patent Document 2 discloses a thermosetting two-component coating composition containing a specific amount of a hydroxyl group-containing resin, a polyisocyanate compound, barium sulfate having an average particle size of 1.0 to 15 μm, silica fine particles, and a rheology control agent. Is described.

Patent Document 3 includes a dispersion stabilizer made of a specific alkyd-modified vinyl polymer soluble in an organic solvent, dispersed particles made of a specific vinyl polymer insoluble in an organic solvent, and an organic solvent. And a non-aqueous dispersion type resin composition in which the ratio of the dispersion stabilizer to the dispersion particles is in a specific range.

Special table 2013-544301 gazette JP 2013-53304 A JP 2003-335947 A

On the other hand, a paint to be coated on an article to be coated such as an industrial product is required to have excellent storage stability and excellent coating film performance such as gloss stability, alkali resistance and impact resistance.
Here, the gloss stability in the present invention means that at least one of the following three conditions is satisfied.
(I) The gloss of the surface of a continuous coating film applied under the same coating conditions is uniform (ii) Even if the film thickness of the resulting coating film varies, the variation in gloss is small (iii) The coating conditions vary However, the variation in gloss is small even if the coating solid content varies. However, in the matte coating film formed by the paint described in Patent Document 1 to Patent Document 3, storage stability, gloss stability, alkali resistance And impact resistance (for example, gloss stability) was insufficient.

Therefore, an object of the present invention is to provide a coating composition capable of forming a matte coating film excellent in storage stability, gloss stability, alkali resistance and impact resistance.

The present inventors have intensively studied to solve the above problems. As a result, a coating composition containing a film-forming resin (A) and a matting agent (B) and further containing a specific non-aqueous polymer dispersion (C) and / or a specific block polyisocyanate compound (D) is provided. The present inventors have found that a matte coating film excellent in gloss stability, alkali resistance, storage stability and impact resistance can be formed, and completed the present invention.

That is, the present invention provides the following items:
Item 1. A coating composition comprising a film-forming resin (A) and a matting agent (B), and further comprising a non-aqueous polymer dispersion (C) and / or a block polyisocyanate compound (D) comprising a skin component and a core component Because
Non-aqueous polymer dispersion (C) contains an acrylic polymer and / or a self-condensate of a fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain, and one molecule of polymerizable unsaturated group A non-aqueous polymer dispersion containing, as an at least part of the skin component, a macromonomer having an average of 1 or more per hit,
A coating composition, wherein the block polyisocyanate compound (D) is an active methylene-based block polyisocyanate compound in which the compound eliminated in the crosslinking reaction is a monofunctional alcohol having 3 to 12 carbon atoms.

Item 2. Item 2. The coating composition according to Item 1, wherein the matting agent (B) is organically treated silica particles.

Item 3. Item 3. The coating composition according to Item 2, wherein the matting agent (B) is hydrophobic surface-treated silica particles.

Item 4. Item 4. The coating composition according to any one of Items 1 to 3, wherein the matting agent (B) has an average particle size of 1 to 10 μm and an oil absorption of 100 to 400 mL / 100 g.

Item 5. Item 5. The coating composition according to any one of Items 1 to 4, further comprising a crosslinking agent (E).

Item 6. Item 6. The coating composition according to Item 5, wherein the crosslinking agent (E) contains a polyisocyanate compound (E1).

Item 7. Claim | item 7. The coating method including the process of apply | coating the coating composition of any one of claim | item 1 thru | or 6 to to-be-coated article.

Item 8. Item 7. A coated article obtained by applying the coating composition according to any one of Items 1 to 6 to an object to be coated.

Item 9. Item 7. A coated article having a coating film obtained by curing the coating composition according to any one of items 1 to 6.

The coating composition of the present invention can form a matte coating film excellent in storage stability, gloss stability, alkali resistance and impact resistance on an object to be coated.

Hereinafter, the coating composition of the present invention will be described in detail. The coating composition of the present invention (hereinafter sometimes abbreviated as “present coating”) includes a film-forming resin (A) and a matting agent (B), and further contains a specific non-aqueous polymer dispersion (C And / or a specific block polyisocyanate compound (D).

Film-forming resin (A)
As the film-forming resin (A), a resin known per se that has been conventionally used in paints can be used. As a kind of resin, an acrylic resin, a polyester resin, an alkyd resin, a polyurethane resin etc. are mentioned, for example.

The film-forming resin (A) preferably has a crosslinkable functional group in order to react with the block polyisocyanate compound (D) and / or the crosslinking agent (E) described later to form a crosslinked coating film. Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, an epoxy group, a carbodiimide group, a carbonyl group, a hydrazide group, and a semicarbazide group. Of these, a hydroxyl group is preferred.

Examples of the film-forming resin (A) include a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, a hydroxyl group-containing polyurethane resin, and a hydroxyl group-containing epoxy resin. Preferred examples of the film-forming resin (A) include a hydroxyl group-containing acrylic resin. These film-forming resins (A) can be used alone or in combination of two or more.

Of these, the film-forming resin (A) is more preferably a hydroxyl group-containing acrylic resin from the viewpoint of excellent gloss stability, alkali resistance, impact resistance and the like of the resulting coating film.

The hydroxyl group-containing acrylic resin can be produced by copolymerizing the hydroxyl group-containing polymerizable unsaturated monomer (a1) and other polymerizable unsaturated monomers (a2) by a known method.

The hydroxyl group-containing polymerizable unsaturated monomer (a1) is a compound having at least one hydroxyl group and one polymerizable unsaturated group in one molecule. Specifically, the hydroxyl group-containing polymerizable unsaturated monomer (a1) is preferably a monoesterified product of acrylic acid or methacrylic acid and a dihydric alcohol having 2 to 10 carbon atoms, such as 2-hydroxyethyl. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Furthermore, examples of the hydroxyl group-containing polymerizable unsaturated monomer (a1) include ring-opening polymerization adducts of the above hydroxyalkyl (meth) acrylates and lactone compounds such as ε-caprolactone. Specific examples of the ring-opening polymerization adduct include, for example, “Plaxel FA-1”, “Plaxel FA-2”, “Plaxel FA-3”, “Plaxel FA-4”, “Plaxel FA-5”, “Plaxel FM-1,” “Plaxel FM-2,” “Plaxel FM-3,” “Plaxel FM-4,” “Plaxel FM-5” (all of these are trade names, manufactured by Daicel Chemical Industries), etc. be able to. These hydroxyl group-containing polymerizable unsaturated monomers (a1) can be used alone or in combination of two or more.

In this specification, “(meth) acrylate” means “acrylate or methacrylate”. “(Meth) acrylic acid” means “acrylic acid or methacrylic acid”. “(Meth) acrylamide” means “acrylamide or methacrylamide”.

Examples of the other polymerizable unsaturated monomer (a2) include monomers (a2-1) to (a2-8).

(A2-1) Acid group-containing polymerizable unsaturated monomer:
A compound having one or more acid groups and one polymerizable unsaturated group in one molecule, such as a carboxyl group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and maleic anhydride -Containing polymerizable unsaturated monomers; sulfonic acid group-containing polymerizable unsaturated monomers such as vinyl sulfonic acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate Acidic phosphoric acid ester-based polymerizable unsaturated monomers such as 2- (meth) acryloyloxy-3-chloropropyl acid phosphate and 2-methacryloyloxyethylphenyl phosphoric acid.

(A2-2) Monoesterified product of (meth) acrylic acid and a monohydric alcohol having 1 to 20 carbon atoms:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl acrylate (trade name, manufactured by Osaka Organic Chemical Industry), lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

(A2-3) a polymerizable unsaturated monomer having an alicyclic hydrocarbon group:
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, 3,5-dimethyladamantyl (meth) acrylate, 3-tetracyclododecyl methacrylate, 4-methylcyclohexyl Methyl (meth) acrylate, 4-ethylcyclohexylmethyl (meth) acrylate, 4-methoxycyclohexylmethyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclododecyl (meth) acrylate, tetrahydro Furfuryl (meth) acrylate and the like. Of these, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate are preferred from the viewpoint of acid resistance and stain resistance.

In addition, the polymerizable unsaturated monomer which has both an alicyclic hydrocarbon group and a hydroxyl group shall be contained in a hydroxyl-containing polymerizable unsaturated monomer (a1).

(A2-4) Aromatic polymerizable unsaturated monomer:
For example, styrene, α-methylstyrene, vinyl toluene and the like.

(A2-5) Glycidyl group-containing polymerizable unsaturated monomer:
A compound having one glycidyl group and one polymerizable unsaturated group in one molecule, specifically glycidyl acrylate, glycidyl methacrylate, and the like.

(A2-6) Nitrogen-containing polymerizable unsaturated monomer:
For example, (meth) acrylamide, dimethylacrylamide, N, N-dimethylpropylacrylamide, N-butoxymethylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide, N, N-dimethylaminoethyl (meth) acrylate , Vinyl pyridine, vinyl imidazole and the like.

(A2-7) Other vinyl compounds:
For example, vinyl acetate, vinyl propionate, vinyl chloride, versatic acid vinyl ester “Veoba 9”, “Veoba 10” (trade name, manufactured by Japan Chemtech Co., Ltd.) and the like.

(A2-8) Polymerizable unsaturated group-containing nitrile compound:
For example, acrylonitrile, methacrylonitrile and the like.

The other copolymerizable polymerizable unsaturated monomers can be used alone or in combination of two or more.

The amount of the hydroxyl group-containing polymerizable unsaturated monomer (a1) used is 15 to 50 parts by mass, preferably 20 to 45 parts by mass, based on 100 parts by mass of the polymerizable unsaturated monomer used for producing the hydroxyl group-containing acrylic resin. More preferably, the content is 25 to 40 parts by mass.

It is preferable that the amount of the hydroxyl group-containing polymerizable unsaturated monomer (a1) used is 15 parts by mass or more because predetermined alkali resistance and impact resistance are easily obtained by crosslinking in the cured coating film. On the other hand, by setting it to 50 parts by mass or less, compatibility with other polymerizable unsaturated monomer (a2) and / or copolymerization reactivity is improved, and further compatibility with other components in the paint is improved. Is preferable because the finished appearance of the coating film is improved.

In addition, from the viewpoint of excellent weather resistance, alkali resistance, impact resistance, and the like of the formed coating film, an acid group-containing polymerizable unsaturated monomer (a2-1) is used as at least one other polymerizable unsaturated monomer (a2). ) Is preferably used.

In this case, the acid group-containing polymerizable unsaturated monomer (a2-1) is used in an amount of 0.05 to 5 parts by mass, with 100 parts by mass of the polymerizable unsaturated monomer used for the production of the hydroxyl group-containing acrylic resin. The amount is preferably 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts by mass.

Further, from the viewpoint of the alkali resistance of the coating film to be formed, the coating film appearance, etc., the polymerizable unsaturated monomer (a2-) having an alicyclic hydrocarbon group as at least one other polymerizable unsaturated monomer (a2). It is preferable to use 3).

In such a case, the amount of the polymerizable unsaturated monomer (a2-3) having an alicyclic hydrocarbon group is 1 to 40, based on 100 parts by mass of the polymerizable unsaturated monomer used for producing the hydroxyl group-containing acrylic resin. The amount is preferably 5 parts by mass, preferably 5 to 30 parts by mass, and more preferably 10 to 25 parts by mass.

In addition, from the viewpoint of alkali resistance, impact resistance and the like of the coating film to be formed, the aromatic polymerizable unsaturated monomer (a2-4) is used as at least one other polymerizable unsaturated monomer (a2). It is preferable.

In such a case, the amount of the aromatic polymerizable unsaturated monomer (a2-4) used is 5 to 50 parts by weight, preferably 100 parts by weight of the polymerizable unsaturated monomer used for the production of the hydroxyl group-containing acrylic resin. The amount is preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass.

The copolymerization method for copolymerizing the above polymerizable unsaturated monomers to obtain a hydroxyl group-containing acrylic resin is not particularly limited, and a copolymerization method known per se can be used. Among them, a solution polymerization method in which polymerization is performed in the presence of a polymerization initiator can be preferably used.

Examples of the organic solvent used in the solution polymerization method include aromatic solvents such as toluene, xylene, and swazole 1000 (trade name, high-boiling petroleum solvent) manufactured by Cosmo Oil; ethyl acetate, 3-methoxybutyl Ester solvents such as acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propyl propionate, butyl propionate, ethoxyethyl propionate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, etc. Can be mentioned.

These organic solvents can be used alone or in combination of two or more. From the viewpoint of the solubility of the hydroxyl group-containing acrylic resin used in the coating composition of the present invention, it is preferable to use a high boiling ester solvent or ketone solvent. In addition, aromatic solvents having higher boiling points can be suitably used in combination.

Examples of the polymerization initiator that can be used in the copolymerization of the hydroxyl group-containing acrylic resin include 2,2′-azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, Mention may be made of radical polymerization initiators known per se, such as t-butyl peroctoate and 2,2′-azobis (2-methylbutyronitrile).

The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably in the range of 80 to 200 mgKOH / g, more preferably in the range of 100 to 170 mgKOH / g. When the hydroxyl value is 80 mgKOH / g or more, the desired weather resistance, alkali resistance, impact resistance, and coating film appearance are easily obtained because the crosslinking density is high. Moreover, since the water resistance of a coating film improves that it is 200 mgKOH / g or less, it is preferable.

The weight average molecular weight of the hydroxyl group-containing acrylic resin is in the range of 2500 to 40000, more preferably in the range of 4000 to 30000. A weight average molecular weight of 2500 or more is preferred because desired coating properties such as weather resistance, alkali resistance, impact resistance, and coating appearance can be easily obtained. Moreover, since the smoothness of a coating film improves that a weight average molecular weight is 40000 or less, a finishing property improves and it is preferable.

In addition, in this specification, a weight average molecular weight is the value which converted the weight average molecular weight measured with the gel permeation chromatograph (The Tosoh company make, "HLC8120GPC") on the basis of the weight average molecular weight of polystyrene. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (all manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: RI. The number average molecular weight is also a value measured under the same conditions as described above.

The glass transition temperature of the hydroxyl group-containing acrylic resin is usually in the range of −40 ° C. to 85 ° C., particularly preferably in the range of −30 ° C. to 80 ° C. When the glass transition temperature is −40 ° C. or higher, the desired coating film hardness can be obtained, and when it is 85 ° C. or lower, the coating surface smoothness of the coating film is improved.

The hydroxyl group-containing polyester resin that can be used as the film-forming resin (A) can be produced by a known method, for example, by an esterification reaction between a polybasic acid and a polyhydric alcohol.

The polybasic acid is a compound having two or more carboxyl groups in one molecule. For example, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexa Examples include hydrophthalic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof.

The polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, neopentyl glycol, 1,9-nonanediol, 1,4-cyclohexanediol, hydroxypivalic acid neopentyl glycol ester, Diol compounds such as 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethylpentanediol, hydrogenated bisphenol A, and trimethylolpropane, Trivalent or less trimethylolethane, glycerin, pentaerythritol, etc. Polyol component, and 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid, 2,2-dimethyloloctanoic acid And the like.

In addition, a monoepoxy compound such as propylene oxide and butylene oxide, a monoepoxy compound such as Cardura E10 (product name, glycidyl ester of a synthetic highly branched saturated fatty acid) such as Cardura E10 is reacted with an acid, A compound may be introduced into the polyester resin.

When a carboxyl group is introduced into a polyester resin, for example, an acid anhydride can be added to a hydroxyl group-containing polyester and half esterified.

The hydroxyl value of the hydroxyl group-containing polyester resin is preferably in the range of 80 to 200 mgKOH / g, more preferably in the range of 100 to 170 mgKOH / g. A hydroxyl value of 80 mgKOH / g or more is preferable because desired weather resistance, alkali resistance, impact resistance, coating film appearance, and the like are easily obtained. Moreover, the water resistance of a coating film improves that a hydroxyl value is 200 mgKOH / g or less, and is preferable.

The weight average molecular weight of the hydroxyl group-containing polyester resin is preferably in the range of 2500 to 40000, more preferably in the range of 5000 to 30000. A weight average molecular weight of 2500 or more is preferred because desired coating properties such as weather resistance, alkali resistance, impact resistance, and coating appearance can be easily obtained. Moreover, the coating surface smoothness of a coating film improves that a weight average molecular weight is 40000 or less, and is preferable.

The glass transition temperature of the hydroxyl group-containing polyester resin is usually in the range of −40 ° C. to 85 ° C., particularly preferably in the range of −30 ° C. to 80 ° C. A glass transition temperature of −40 ° C. or higher is preferable because a desired coating film hardness is easily obtained. Moreover, it is preferable that the glass transition temperature is 85 ° C. or lower because the smoothness of the coated surface of the coating film is improved.

The film-forming resin (A) includes so-called urethane-modified acrylic resins and urethane-modified polyester resins.

Examples of the hydroxyl group-containing polyurethane resin that can be used as the film-forming resin (A) include a hydroxyl group-containing polyurethane resin obtained by reacting a polyol and a polyisocyanate.

Examples of the polyol include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol and hexamethylene glycol, and trihydric alcohols such as trimethylolpropane, glycerin and pentaerythritol as low molecular weight substances. Can do. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, acrylic polyol, and epoxy polyol. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the polyester polyol include alcohols such as the aforementioned dihydric alcohols, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol, and dibasic acids such as adipic acid, azelaic acid, and sebacic acid. Lactone-based ring-opening polymer polyol such as polycaprolactone, polycarbonate diol, and the like. In addition, carboxyl group-containing polyols such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid can also be used.

Examples of the polyisocyanate to be reacted with the above polyol include aliphatic polyisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; and burette type addition of these polyisocyanates. , Isocyanurate cycloadduct; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) Alicyclic diisocyanates such as di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate Compounds; and burette-type adducts, isocyanurate cycloadducts of these polyisocyanates; xylylene diisocyanate, metaxylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5 -Naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl Aromatic dimers such as -4,4'-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenylisocyanate) Sorbocyanate compounds; and burette type adducts, isocyanurate cycloadducts of these polyisocyanates; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2, Polyisocyanate compounds having three or more isocyanate groups in one molecule such as 4,6-triisocyanatotoluene, 4,4′-dimethyldiphenylmethane-2,2 ′, 5,5′-tetraisocyanate; And polyisocyanate burette type adducts, isocyanurate ring adducts, and the like.

The hydroxyl value of the hydroxyl group-containing polyurethane resin is in the range of 80 to 200 mgKOH / g, more preferably in the range of 100 to 170 mgKOH / g. When the hydroxyl value is 80 mgKOH / g or more, desired weather resistance, alkali resistance, impact resistance, coating film appearance and the like can be obtained, and when it is 200 mgKOH / g or less, the water resistance of the coating film is improved. .

The weight-average molecular weight of the hydroxyl group-containing polyurethane resin is in the range of 2500 to 40000, more preferably in the range of 4000 to 30000. A weight average molecular weight of 2500 or more is preferred because desired coating properties such as weather resistance, alkali resistance, impact resistance, and coating appearance can be easily obtained. Moreover, the coating surface smoothness of a coating film improves that a weight average molecular weight is 40000 or less, and is preferable.

The glass transition temperature of the hydroxyl group-containing polyurethane resin is usually in the range of −40 ° C. to 85 ° C., particularly preferably in the range of −30 ° C. to 80 ° C. When the glass transition temperature is −40 ° C. or higher, the desired coating film hardness can be obtained, and when it is 85 ° C. or lower, the coating surface smoothness of the coating film is improved.

Matting agent (B)
As the matting agent (B), a matting agent known per se that has been conventionally used in paints can be used. Examples of the matting agent include inorganic fine particles and resin beads.

Examples of the inorganic fine particles include silica particles, alumina particles, titania particles, zirconia particles, zircon particles, tin oxide particles, magnesia particles, or a mixture thereof. In particular, the inorganic fine particles are preferably silica particles from the viewpoint of matting ability, storage stability, and the like. The shape of the silica particles is not particularly limited, and those having a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape can be used.

Examples of commercially available products that can be used as the silica particles include:
Siricia series (Silicia 350, Siricia 430, Siricia 435, Siricia 436, Sirisia 450, etc.), Silo Hovic series (Silo Hovic 100, Silo Hovic 200, Silo Hovic 702, Silo Hovic 100) , 4004, etc.), Cyros Sphere series (Cyros Sphere 1504, Cyros Sphere 1510, etc.),
SYLOID series (Syloid W300, Syloid W500, etc.) manufactured by Grace Japan,
ACEMATT series (ACEMATT HK460, ACEMATT HK400, ACEMATT OK412, ACEMATT TS100, ACEMATT 3200, ACEMATT 3300, ACEMATT 3600, etc.) manufactured by Evonik Degussa Japan
NIPGEL series (NIPGEL AZ-200, etc.) manufactured by Nippon Silica Kogyo Co., Ltd., NIPSIL series (NIPSIL E-200A, NIPSIL SS-50B, NIPSIL SS-178B, etc.)
Mizukasil series (Mizukasil P-73, P-526, etc.) manufactured by Mizusawa Chemical Co., Ltd.
Carplex series (Carplex CS-8 etc.) manufactured by Shionogi & Co.,
AEROSIL series (AEROSIL 200, AEROSIL R805, AEROSIL R972, etc.) manufactured by Nippon Aerosil Co., Ltd.
Radiolite series (Radiolite 100, Radiolite 200, Radiolite 500, Radiolite 500R, Radiolite 500RS, etc.) manufactured by Showa Chemical Industry Co., Ltd.
Etc.

The inorganic fine particles may be untreated inorganic fine particles and inorganic fine particles surface-treated with an organic compound or an inorganic compound. In particular, the inorganic fine particles are preferably subjected to organic treatment from the viewpoint of storage stability. Examples of the treatment with an organic compound include polyethylene treatment, polyethylene wax treatment, hydrophobic surface treatment, and the like. Of these, hydrophobic surface treatment is preferable from the viewpoint of storage stability, alkali resistance, and the like. As the hydrophobic surface treatment, a known method can be applied, and examples thereof include a treatment in which an organosilicon compound such as polydimethylsiloxane is chemically bonded to the hydroxyl group on the surface of the silica particles.

In the present invention, the inorganic fine particles have been subjected to a hydrophobic surface treatment as follows: “Put 5 mL of water into a test tube, and gently put 0.3 g of inorganic fine particles therein, and leave it for 12 hours. 75% or more of the water is floating on the water surface.

Examples of the resin beads include PMMA (polymethyl methacrylate) resin beads, MMA-EGDM (ethylene glycol dimethacrylate) copolymer resin beads, nylon resin beads, polytetrafluoroethylene resin beads, and the like.

Examples of commercially available products that can be used as the resin beads include “Tech Polymer Series (trade name)” manufactured by Sekisui Plastics Co., Ltd. and “Dinion Series (trade name)” manufactured by Sumitomo 3M Limited.

The matting agent (B) preferably has an average particle size of 1 to 10 μm, preferably 2 to 8 μm, more preferably 3 to 7 μm, from the viewpoint of matting ability, storage stability, and the like.

Here, in this specification, the average particle diameter of the matting agent refers to the D50 value of the particle size distribution measured by using the laser scattering method. The D50 value is a particle size at which the integrated particle size distribution from the small particle size side is 50% from the volume-based particle size distribution. In the present specification, the volume-based particle size distribution of the matting agent was measured using a laser diffraction / scattering particle size distribution measuring apparatus “Microtrack NT3300” (trade name, manufactured by Nikkiso Co., Ltd.). At that time, as a pretreatment, silica particles are added to a mixed solvent of acetone and isopropyl alcohol and dispersed by applying ultrasonic waves for 1 minute, and the matting agent concentration is adjusted to a concentration within a predetermined transmittance range set in the apparatus. did.

The matting agent (B) has an oil absorption of 100 to 400 mL / 100 g, preferably 100 to 380 mL / 100 g, more preferably 100 to 360 mL / 100 g, from the viewpoint of matting ability.

Here, in this specification, the oil absorption amount of the matting agent is a value measured according to JIS ５１０ K5101-13-2: 2004.

Non-aqueous polymer dispersion (C)
The non-aqueous polymer dispersion (C) consists of a skin component and a core component. Typically, it is a dispersion of polymer particles obtained by polymerizing at least one unsaturated monomer (C3) in the presence of a polymer dispersion stabilizer (C1) and an organic solvent (C2). The obtained non-aqueous polymer dispersion (C) has a skin part and a core part. The polymer dispersion stabilizer (C1) mainly forms the skin component, and the polymer particles (C4) obtained from the unsaturated monomer (C3) mainly form the core component.

In the present invention, the non-aqueous polymer dispersion (C) contains an acrylic polymer and / or a self-condensate of a fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain and is polymerizable unsaturated. This is a non-aqueous polymer dispersion containing a macromonomer having one or more groups on average per molecule as at least a part of the skin component.

The non-aqueous polymer dispersion (C) in the present invention typically has, as the polymer dispersion stabilizer (C1), an acrylic polymer (C1-1) and / or an alkyl chain having 10 to 25 carbon atoms. It is essential to contain a macromonomer (C1-2) containing a self-condensate of a fatty acid having a certain hydroxyalkyl group and having an average of one or more polymerizable unsaturated groups per molecule. That is, the non-aqueous polymer dispersion (C) contains an acrylic polymer (C1-1) and / or a self-condensate of a fatty acid having a hydroxyalkyl group in which the alkyl chain has 10 to 25 carbon atoms and is polymerizable. A non-aqueous polymer dispersion containing a macromonomer (C1-2) having an average of one or more unsaturated groups per molecule as at least a part of the skin component. Hereinafter, a macromonomer (C1-2) containing a self-condensate of a fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain and having an average of one or more polymerizable unsaturated groups per molecule May be abbreviated as “macromonomer (C1-2)”.

Polymer dispersion stabilizer (C1)
The polymer dispersion stabilizer (C1) contains an acrylic polymer (C1-1) and / or a self-condensate of a fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain and is polymerizable unsaturated. Contains a macromonomer (C1-2) having an average of one or more groups per molecule.

Acrylic polymer (C1-1)
The acrylic polymer (C1-1) is generally a polymer obtained by copolymerizing a long-chain unsaturated monomer optionally with another unsaturated monomer.

The long-chain unsaturated monomer used in the polymer can be appropriately selected according to the performance required for the coating film. Examples of the long-chain unsaturated monomer that can be preferably used from the viewpoints of copolymerizability, solubility in organic solvents, and the like can be exemplified.

For example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) C4-C18 alkyl or cycloalkyl esters of (meth) acrylic acid such as acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl ( Alkoxyalkyl ester of (meth) acrylic acid such as (meth) acrylate; ester of aromatic alcohol such as benzyl (meth) acrylate with (meth) acrylic acid; glycidyl (meth) acrylate or (meth) Adducts of hydroxyalkyl esters of crylic acid with monocarboxylic acid compounds such as capric acid, lauric acid, linoleic acid and oleic acid; adducts of (meth) acrylic acid with monoepoxy compounds such as “Cardiula E10”; styrene , Α-methylstyrene, vinyltoluene, p-chlorostyrene, pt-butylstyrene, etc. vinyl aromatic compounds; itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, etc. Mono or diester compounds of α, β-unsaturated carboxylic acids other than (meth) acrylic acid and monoalcohols having 4 to 18 carbon atoms such as butyl alcohol, pentyl alcohol, heptyl alcohol, octyl alcohol, stearyl alcohol; 8F "," Biscoat 8FM "," Biscoat F ”,“ Biscoat 3FM ”(both manufactured by Osaka Organic Chemical Co., Ltd., trade name, (meth) acrylate compound having a fluorine atom in the side chain), fluorine such as perfluorocyclohexyl (meth) acrylate, perfluorohexylethylene, etc. An atom containing compound etc. can be mentioned.

The unsaturated monomer other than the long-chain unsaturated monomer is not particularly limited as long as it is an unsaturated monomer other than the long-chain unsaturated monomer as listed above. For example, methyl (meth) acrylate, ethyl (meta ) Alkyl esters of (meth) acrylic acid such as acrylate and propyl (meth) acrylate having 1 to 3 carbon atoms; addition of glycidyl (meth) acrylate and monocarboxylic acid compounds having 2 to 3 carbon atoms such as acetic acid and propionic acid Products: α, β-unsaturated carboxylic acids other than (meth) acrylic acid such as itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid and carbon such as methyl alcohol and propyl alcohol Mono- or diester compounds with monoalcohols of 1 to 3; cyano groups such as (meth) acrylonitrile Examples thereof include unsaturated compounds; vinyl ester compounds such as vinyl acetate; vinyl ether compounds such as ethyl vinyl ether and methyl vinyl ether; α-olefin compounds such as ethylene, propylene, vinyl chloride, and vinylidene chloride. Examples of unsaturated monomers other than long-chain unsaturated monomers include those obtained by substituting the unsaturated monomers listed above with hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate.

Polymerization of the long-chain unsaturated monomer and the polymerization of the long-chain unsaturated monomer and the copolymerization with the other unsaturated monomer can usually be performed using a radical polymerization initiator. Examples of radical polymerization initiators include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl peroxide, and peroxide initiators such as t-butyl peroctoate and t-butyl peroxy-2-ethylhexanoate. These polymerization initiators can be used generally in the range of about 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the monomer used for polymerization. The reaction temperature during the polymerization is usually about 60 to 160 ° C., and the reaction time during the polymerization is usually about 1 to 15 hours.

In producing the component (C), the storage stability and mechanical properties of the non-aqueous polymer dispersion (C) are obtained by combining the acrylic polymer (C1-1) and the polymer particles (C4). Can be improved. Even when the acrylic polymer (C1-1) and the polymer particles (C4) are combined, there is almost no change in the dispersed state in appearance, and the average particle diameter of the polymer particles is hardly changed.

As a method for bonding the acrylic polymer (C1-1) and the polymer particles (C4), for example, in the stage of preparing the acrylic polymer (C1-1) in advance, a hydroxyl group, an acid group, an acid anhydride group, an epoxy A hydroxyl group or an acid group that reacts with the above functional group as a monomer component that forms a polymer particle by partially copolymerizing a monomer component having a functional group such as a group, a methylol group, an isocyanate group, an amide group, or an amino group. And a monomer having a functional group such as an acid anhydride group, an epoxy group, a methylol group, an isocyanate group, an amide group or an amino group. Examples of these combinations include an isocyanate group and a hydroxyl group, an isocyanate group and a methylol group, an epoxy group and an acid (anhydrous) group, an epoxy group and an amino group, an isocyanate group and an amide group, and an acid (anhydrous) group and a hydroxyl group. Can do.

Examples of the monomer having such a functional group include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and citraconic acid. Saturated carboxylic acids; glycidyl group-containing compounds such as glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, diacetone Carboxylic acid amide compounds such as acrylamide and N-methylol (meth) acrylamide; containing sulfonic acid amide groups such as p-styrenesulfonamide, N-methyl-p-styrenesulfonamide, and N, N-dimethyl-p-styrenesulfonamide Compound; (meth) act Amino group-containing compounds such as tert-butylaminoethyl silylate; condensates of 2-hydroxyethyl (meth) acrylate and phosphoric acid or phosphate ester compounds, glycidyl compounds having a glycidyl group such as glycidyl (meth) acrylate Phosphoric acid group-containing compounds such as those obtained by adding phosphoric acid or a phosphoric acid ester compound to the group; sulfonic acid group-containing compounds such as 2-acrylamido-2-methyl-propanesulfonic acid; m-isopropenyl-α, α- Examples include dimethylbenzyl isocyanate, isophorone diisocyanate or tolylene diisocyanate and hydroxy (meth) acrylate equimolar adducts, isocyanate group-containing compounds such as isocyanoethyl methacrylate, and the like.

As another method for bonding the acrylic polymer (C1-1) and the polymer particles (C4), an unsaturated monomer is polymerized in the presence of a polymer dispersion stabilizer having a polymerizable unsaturated group. Can be done.

Introducing a polymerizable unsaturated group into the acrylic polymer (C1-1) is, for example, using an acid group-containing monomer such as carboxylic acid, phosphoric acid or sulfonic acid as a copolymerization component of the resin, and glycidyl is added to the acid group. The reaction can be carried out by reacting a glycidyl group-containing unsaturated monomer such as (meth) acrylate or allyl glycidyl ether. Inversely, the glycidyl group can be contained in the acrylic polymer (C1-1) and reacted with an acid group-containing unsaturated monomer. These reactions can be performed according to known reaction conditions.

Further, as yet another method of bonding the acrylic polymer (C1-1) and the polymer particles (C4), functional groups that do not react with each other in the acrylic polymer (C1-1) and the polymer particles (C4). It can also be carried out by producing a non-aqueous polymer dispersion (C) into which is introduced and then reacting this with a binder that binds both.

Specifically, for example, a hydroxyl group-containing unsaturated monomer is polymerized alone or as a mixture with another unsaturated monomer in the presence of a hydroxyl group-containing acrylic polymer (C1-1) and an organic solvent (C2), After preparing a non-aqueous polymer dispersion (C) containing a polyisocyanate compound, etc., and reacting at room temperature for several hours to several days at about 60 to 100 ° C. for about 1 to 5 hours. Can do.

Any polyisocyanate compound may be used as long as it has two or more isocyanate groups in the molecule. For example, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, or hydrides thereof. An aliphatic diisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, dimer acid (dimer of tall oil fatty acid) diisocyanate; and an alicyclic diisocyanate such as isophorone diisocyanate.

In addition to the above, combinations of acrylic polymers (C1-1) and polymer particles (C4) containing acid groups and polyepoxides, acrylic polymers (C1-1) and polymer particles containing epoxy groups ( A combination of C4) and a polycarboxylic acid, an acrylic polymer (C1-1) containing an epoxy group or an isocyanate group, a combination of polymer particles (C4) and a polysulfide compound, or the like can also be used.

Examples of polyepoxides include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, epoxy group-containing acrylic resins, and the like. Examples of polycarboxylic acids include adipic acid, sebacic acid, azelaic acid, isophthalic acid, and the like; Examples of polysulfide include pentamethylene disulfide, hexamethylene disulfide, and poly (ethylene disulfide).

As described above, the acrylic polymer (C1-1) and the polymer particles (C4) can be chemically bonded. At this time, various functional groups and / or polymerizable unsaturated groups are bonded to the acrylic polymer. The amount introduced into the polymer (C1-1) and / or the polymer particles (C4) is on average at least about 0.1 per molecule in the acrylic polymer (C1-1) and / or polymer particles (C4). A single amount is sufficient.

The non-aqueous polymer dispersion (C) thus obtained has excellent storage stability because the acrylic polymer (C1-1) and the polymer particles (C4) are chemically bonded, and furthermore, The formed coating film can exhibit excellent chemical and mechanical properties.

Macromonomer (C1-2)
A macromonomer containing a self-condensate of a fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain and having an average of one or more polymerizable unsaturated groups per molecule (“macromonomer (C1- 2) ") can be exemplified as follows. By adding a glycidyl ester of (meth) acrylic acid to a carboxyl group in a self-condensed polyester resin of a fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain, about 1.0 per molecule Polyester macromonomer (C1-2a) obtained by introducing a polymerizable unsaturated group; a comb polymer obtained by polymerizing a polymerizable unsaturated monomer to the polymerizable unsaturated group in the macromonomer (C1-2a) ( C1-2b); a polymerizable unsaturated monomer containing a glycidyl ester of (meth) acrylic acid is polymerized to the macromonomer (C1-2a), and α, β-ethylenically unsaturated group is further added to the glycidyl group in the polymer. Comb polymer (C1-2c) in which a polymerizable unsaturated group is introduced by adding an acid.

The fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain is preferably 12 hydroxystearic acid.

The polymer dispersion stabilizer (C1) is preferably used in combination with an acrylic polymer (C1-1) and a macromonomer (C1-2) from the viewpoint of gloss stability, storage stability, and the like.

The molecular weight of the polymer dispersion stabilizer (C1) is usually in the range of about 2500 to 50000, preferably about 2500 to 25000 in terms of number average molecular weight. Use of a copolymer having a molecular weight in the above range as a dispersion stabilizer is preferable because stabilization of the dispersed particles can suppress aggregation and sedimentation and can provide a paint that is easy to handle without being too high in viscosity.

As the polymer dispersion stabilizer (C1), another dispersion stabilizer such as an alkyd resin can be used in combination as required.

Organic solvent (C2)
As the organic solvent (C2) used for the polymerization, although the dispersion polymer particles produced by the polymerization are not substantially dissolved, the polymer dispersion stabilizer (C1) and the unsaturated monomer (C3) are not dissolved. Can widely use known organic liquids that serve as good solvents. Specific examples of such organic liquids include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, and the like. Alcohol compounds; ether compounds such as cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketone compounds such as methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl hexyl ketone, ethyl butyl ketone; ethyl acetate, isobutyl acetate, amyl acetate, 2-ethylhexyl acetate And ester compounds such as These organic liquids may be used singly or in combination of two or more, but are generally composed mainly of aliphatic hydrocarbons, which are appropriately aromatic hydrocarbons, alcohol compounds, ethers. A combination of a compound, a ketone compound or an ester compound is preferably used.

Unsaturated monomer (C3)
The unsaturated monomer (C3) that forms the polymer particles (C4) is excellent in polymerizability and has a carbon number smaller than that of the monomer used as the monomer component of the polymer dispersion stabilizer (C1). It is preferable to use a saturated monomer because it is easy to form as dispersed polymer particles.

Examples of such unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. Carbon number of (meth) acrylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc. 1-18 alkyl or cycloalkyl esters; alkoxyalkyl esters of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate; Esters of aromatic alcohols such as ru (meth) acrylate with (meth) acrylic acid; glycidyl (meth) acrylate and mono-C 2-18 such as acetic acid, propionic acid, oleic acid, pt-butylbenzoic acid Adducts with carboxylic acid compounds; Adducts with (meth) acrylic acid and monoepoxy compounds such as “Kardura E10”; styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, pt-butyl Vinyl aromatic compounds such as styrene; itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid and other α, β-unsaturated carboxylic acids and methyl alcohol , Mono- or mono-alcohols having 1 to 18 carbon atoms such as butyl alcohol, hexyl alcohol, stearyl alcohol Ester compound; “Biscoat 8F”, “Biscoat 8FM”, “Biscoat 3F”, “Biscoat 3FM” (both manufactured by Osaka Organic Chemical Co., Ltd., trade name, (meth) acrylate compound having a fluorine atom in the side chain), Fluorine atom-containing compounds such as perfluorocyclohexyl (meth) acrylate and perfluorohexylethylene; cyano group-containing unsaturated compounds such as (meth) acrylonitrile; vinyl acetate, vinyl benzoate, “VEOVA” (Shell Co., Ltd.) Vinyl ester compounds such as n-butyl vinyl ether, ethyl vinyl ether, and methyl vinyl ether; 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene, etc. Polyvi Nyl compounds; α-olefin compounds such as ethylene, propylene, vinyl chloride, vinylidene chloride and the like can be mentioned.

As described above, the unsaturated monomer (C3) that forms the polymer particle (C4) has a particle component smaller than that of the monomer component of the polymer dispersion stabilizer (C1). It can be formed stably. From this viewpoint, a (meth) acrylic acid ester compound, a vinyl aromatic compound, (meth) acrylonitrile, or the like having 8 or less carbon atoms, preferably 4 or less carbon atoms can be suitably used. These unsaturated monomers can be used alone or in combination of two or more.

Polymerization of the unsaturated monomer (C3) is usually performed using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo-based initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl And peroxide initiators such as peroxide, t-butyl peroctoate, and t-butyl peroxy-2-ethylhexanoate. These polymerization initiators can be used generally in the range of about 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the monomer used for polymerization.

The use ratio of the polymer dispersion stabilizer (C1) and the unsaturated monomer (C3) to be present during the polymerization is usually the unsaturated monomer (C3) with respect to 100 parts by mass of the polymer dispersion stabilizer (C1). Is about 3 to 240 parts by mass, preferably about 5 to 82 parts by mass. Further, the total concentration of the polymer dispersion stabilizer (C1) and the unsaturated monomer (C3) in the organic solvent (C2) is usually about 30 to 70% by mass, preferably about 30 to 60% by mass.

The polymerization can be carried out by a method known per se, the reaction temperature during the polymerization is usually about 60 to 160 ° C., and the reaction time during the polymerization is usually about 1 to 15 hours.

By carrying out the polymerization reaction as described above, the liquid phase is a polymer in which the polymer dispersion stabilizer (C1) is dissolved in the organic solvent (C2), and the solid phase is a polymer in which the unsaturated monomer (C3) is polymerized. A stable non-aqueous polymer dispersion (C) that is particles (C4) can be obtained. The average particle size of the polymer particles (C4) is usually in the range of about 0.1 to 1.0 μm. By setting the average particle diameter of the polymer particles (C4) within the above range, the viscosity of the non-aqueous polymer dispersion (C) does not become too high, and the polymer particles (C4) swell during storage of the paint or Since aggregation can be suppressed, it is preferable.

Block polyisocyanate compound (D)
The blocked polyisocyanate compound (D) is a compound obtained by blocking an isocyanate group of a polyisocyanate compound having at least two isocyanate groups in one molecule with an active methylene-based blocking agent, and a compound that is eliminated in a crosslinking reaction. The active methylene block polyisocyanate compound is a monofunctional alcohol having 3 to 12 carbon atoms, preferably 6 to 8 carbon atoms.

In the present invention, the block polyisocyanate compound (D) is preferably a block polyisocyanate compound (D) in which an isocyanate group is blocked with the following (d1).

When the compound eliminated in the crosslinking reaction is a monofunctional alcohol having 2 or less carbon atoms, the matte property of the resulting coating film is inferior. On the other hand, when the compound eliminated in the cross-linking reaction is a monofunctional alcohol having 13 or more carbon atoms, the cross-linking reaction is difficult to occur, so that the resulting coating film is inferior in alkali resistance, water resistance, impact resistance and the like.

The active methylene-based block polyisocyanate compound (D) in which the compound eliminated in the crosslinking reaction removes the monofunctional alcohol having 3 to 12 carbon atoms is, for example, a compound in which the compound eliminated in the crosslinking reaction is 1 to 3 in carbon atoms. It can be obtained by reacting an active methylene compound (d1) (hereinafter abbreviated as “active methylene compound (d1)”) that removes a functional alcohol with a polyisocyanate compound (d2).

Active methylene compound (d1)
Examples of the active methylene compound (d1) include malonic acid diesters, acetoacetic acid esters, and isobutyrylacetic acid esters shown below.

Malonic acid diesters include di-n-propyl malonate, diethyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-sec-butyl malonate, di-t-butyl malonate, di-n malonate -Pentyl, di-n-hexyl malonate, di-2-ethylhexyl malonate, dioctyl malonate, diundecyl malonate, dihexadecyl malonate, di-9-octadecyl malonate, di (methylisopropyl) malonate, di (ethyl isopropyl malonate) Isopropyl), di (methyl n-butyl) malonate, di (ethyl n-butyl) malonate, di (methyl isobutyl) malonate, di (ethyl isobutyl) malonate, di (methyl sec-butyl) malonate, malon Acid di (ethyl sec-butyl), diphenyl malonate, dibenz malonate Di-2-methoxyethyl malonate, di-2-ethoxyethyl malonate, di-2-propoxyethyl malonate, di-2-isopropoxyethyl malonate, di-2-butoxyethyl malonate, di-2-isobutoxyethyl malonate Di-2-pentyloxyethyl malonate, di-2-hexyloxyethyl malonate, di-2-octyloxyethyl malonate, di-2-decyloxyethyl malonate, di-2- (2-methoxyethoxy) ethyl malonate, Di-2- (2-ethoxyethoxy) ethyl malonate, di-2- (2-propoxyethoxy) ethyl malonate, di-2- (2-butoxyethoxy) ethyl malonate, di-2- (2-benzyloxyethoxy malonate) ) Ethyl, di-2- [2- (2-methoxyethoxy) ethoxy] ethyl malonate, di-2- [2- (2-ethyl malonate) Xyloxy) ethoxy] ethyl, di-2- [2- (2-butoxyethoxy) ethoxy] ethyl malonate, di-1-methoxy-2-propyl malonate, di-1-ethoxy-2-propyl malonate, di1 malonate -Propoxy-2-propyl, di-1-butoxy-2-propyl malonate, di-1-pentyloxy-2-propyl malonate, di-1-hexyloxy-2-propyl malonate, di-1-octyloxy malonate- 2-propyl, di (2-methoxymethylethoxy) -1-propyl malonate, di-3- (3-ethoxypropoxy) -1-propyl malonate, di-1- (1-methyl-2-propoxyethoxy) malonate -2-propyl, di (2-butoxymethylethoxy) -1-propyl malonate, di-2- {2- [2-methoxy (methyl) ethoxy malonate Cis] (methyl) ethoxy} (methyl) ethyl, malonic acid di-1- [1-methyl-2- (1-methyl-2-propoxyethoxy) ethoxy] -2-propyl, and the like. And diesters of 3 to 12 monofunctional alcohols and malonic acid.

Examples of the acetoacetate include n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, n-pentyl acetoacetate, n-hexyl acetoacetate, 2-ethylhexyl acetoacetate, octyl acetoacetate, undecyl acetoacetate, hexadecyl acetoacetate, acetoacetate-9-octadecyl, phenyl acetoacetate, benzyl acetoacetate, 2-methoxyethyl acetoacetate, 2-ethoxyethyl acetoacetate, acetoacetate 2 -Propoxyethyl, 2-isopropoxyethyl acetoacetate, 2-butoxyethyl acetoacetate, 2-isobutoxyethyl acetoacetate, 2-pentyloxyethyl acetoacetate, 2-hexyloxyethyl acetoacetate, 2-octyl acetoacetate Ruoxyethyl, 2-decyloxyethyl acetoacetate, 2- (2-methoxyethoxy) ethyl acetoacetate, 2- (2-ethoxyethoxy) ethyl acetoacetate, 2- (2-propoxyethoxy) ethyl acetoacetate, 2-acetoacetate 2- (2-butoxyethoxy) ethyl, 2- (2-benzyloxyethoxy) ethyl acetoacetate, 2- [2- (2-methoxyethoxy) ethoxy] ethyl acetoacetate, 2- [2- (2-ethoxyethoxy) acetoacetate ) Ethoxy] ethyl, 2- [2- (2-butoxyethoxy) ethoxy] ethyl acetoacetate, 1-methoxy-2-propyl acetoacetate, 1-ethoxy-2-propyl acetoacetate, 1-propoxy-2-acetoacetate Propyl, 1-butoxy-2-propyl acetoacetate, 1-pentyloxy-2-propyl acetoacetate Pills, 1-hexyloxy-2-propyl acetoacetate, 1-octyloxy-2-propyl acetoacetate, (2-methoxymethylethoxy) -1-propyl acetoacetate, 3- (3-ethoxypropoxy) -1 acetoacetate -Propyl, acetoacetic acid 1- (1-methyl-2-propoxyethoxy) -2-propyl, acetoacetic acid (2-butoxymethylethoxy) -1-propyl, acetoacetic acid 2- {2- [2-methoxy (methyl)] Ethoxy] (methyl) ethoxy} (methyl) ethyl, 1- [1-methyl-2- (1-methyl-2-propoxyethoxy) ethoxy] -2-propyl acetoacetate, etc., preferably 3 carbon atoms And a diester of ˜12 monofunctional alcohol and acetoacetic acid.

Examples of isobutyryl acetate include n-propyl isobutyryl acetate, isopropyl isobutyryl acetate, n-butyl isobutyryl acetate, isobutyl isobutylyl acetate, sec-butyl isobutyryl acetate, t-butyl isobutyryl acetate, n-pentyl isobutyryl acetate, n-hexyl isobutyryl acetate, Isobutyryl acetate 2-ethylhexyl, isobutyryl octyl acetate, isobutyryl acetate undecyl, isobutyryl acetate hexadecyl, isobutyryl acetate-9-octadecyl, isobutyryl acetate phenyl and isobutyryl acetate benzyl, isobutyryl acetate 2-methoxyethyl, isobutyryl acetate 2-ethoxyethyl, isobutyryl acetate 2 -Propoxyethyl, isobutyryl acetate 2-isopropoxyethyl, isobutyryl acetate 2-butoxyethyl Isobutyryl acetate 2-isobutoxyethyl, isobutyryl acetate 2-pentyloxyethyl, isobutyryl acetate 2-hexyloxyethyl, isobutyryl acetate 2-octyloxyethyl, isobutyryl acetate 2-decyloxyethyl, isobutyryl acetate 2- (2-methoxyethoxy) ) Ethyl, 2- (2-ethoxyethoxy) ethyl isobutyryl acetate, 2- (2-propoxyethoxy) ethyl isobutyryl acetate, 2- (2-butoxyethoxy) ethyl isobutyryl acetate, 2- (2-benzyloxyethoxy) isobutyryl acetate Ethyl, 2- [2- (2-methoxyethoxy) ethoxy] ethyl isobutyryl acetate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl isobutyryl acetate, 2- [2- (2-butoxyethoxy) ethyl isobutyryl acetate Xyl] ethyl, isobutyryl acetate 1-methoxy-2-propyl, isobutyryl acetate 1-ethoxy-2-propyl, isobutyryl acetate 1-propoxy-2-propyl, isobutyryl acetate 1-butoxy-2-propyl, isobutyryl acetate 1-pentyloxy -2-propyl, isobutyryl acetate 1-hexyloxy-2-propyl, isobutyryl acetate 1-octyloxy-2-propyl, isobutyryl acetate (2-methoxymethylethoxy) -1-propyl, isobutyryl acetate 3- (3-ethoxypropoxy) ) -1-propyl, isobutyrylacetic acid 1- (1-methyl-2-propoxyethoxy) -2-propyl, isobutyrylacetic acid (2-butoxymethylethoxy) -1-propyl, isobutyrylacetic acid 2- {2- [2-methoxy (Methyl) ethoxy] (Me Yl) ethoxy} (methyl) ethyl, isobutyrylacetic acid 1- [1-methyl-2- (1-methyl-2-propoxyethoxy) ethoxy] -2-propyl, and the like, preferably having 3 to 12 carbon atoms Examples include diesters of monofunctional alcohols and isobutyryl acetic acid.

The active methylene compound (d1) can be used alone or in combination of two or more.

Among them, from the viewpoint of gloss stability of the coating film to be formed, the active methylene compound (d1) is 1-methoxy-2-propyl malonate, 1-ethoxy-2-propyl malonate, 1-propoxy malonate. -2-propyl is preferred.

Polyisocyanate compound (d2)
The polyisocyanate compound (d2) is a compound having at least two isocyanate groups in one molecule, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, And polyisocyanate derivatives.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3. Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 2 , 6-Diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6 11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl Examples thereof include aliphatic triisocyanates such as octane.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, alicyclic diisols such as methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2 .1) Heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5- Di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) ) Heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanate) Natoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3 And alicyclic triisocyanates such as -isocyanatopropyl) -bicyclo (2.2.1) heptane.

Examples of the araliphatic polyisocyanate include methylene bis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate, or a mixture thereof, ω, ω′-diisocyanato- Aromatic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; 1,3 And araliphatic triisocyanates such as 5-triisocyanatomethylbenzene.

Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4- TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; , 4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and the like; 4,4′-diphenylmethane-2,2 ′ Fragrance such as 5,5'-tetraisocyanate Mention may be made of tetra-isocyanate, and the like.

Examples of the polyisocyanate derivatives include dimer, trimer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). And Crude TDI.

The above polyisocyanates and derivatives thereof may be used alone or in combination of two or more. Of these polyisocyanates, as the polyisocyanate compound (d2), the resulting block polyisocyanate compound (D) is unlikely to be yellowed when heated, so that aliphatic diisocyanates, alicyclic diisocyanates, and these The derivatives of are preferred. Of these, aliphatic diisocyanates and derivatives thereof are more preferable from the viewpoint of improving the flexibility of the formed coating film.

In addition, as the polyisocyanate compound (d2), a prepolymer obtained by reacting the polyisocyanate and its derivative with a compound capable of reacting with the polyisocyanate under an excess of isocyanate groups may be used. Examples of the compound capable of reacting with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group and an amino group. Specifically, for example, polyhydric alcohol, low molecular weight polyester resin, amine, water, etc. Can be used.

The polyisocyanate compound (d2) is a polymer of an isocyanate group-containing polymerizable unsaturated monomer or a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer and the isocyanate group-containing polymerizable unsaturated monomer. A copolymer with a monomer may be used.

The polyisocyanate compound (d2) has a number average molecular weight of 300 to 20 from the viewpoint of the reactivity of the resulting block polyisocyanate compound (D) and the compatibility between the block polyisocyanate compound (D) and other coating components. , Preferably in the range of 400 to 8,000, more preferably in the range of 500 to 2,000.

In addition, the polyisocyanate compound (d2) is an average per molecule from the viewpoint of the reactivity of the obtained block polyisocyanate compound (D) and the compatibility between the block polyisocyanate compound (D) and other coating components. The number of isocyanate functional groups is preferably in the range of 2-20. As a minimum, 3 is more preferable from a viewpoint of improving the reactivity of the block polyisocyanate compound (D) obtained. As an upper limit, 20 is more preferable from a viewpoint of preventing gelation at the time of manufacture of a block polyisocyanate compound (D).

In the blocking reaction of the isocyanate group with the active methylene compound (d1), a reaction catalyst can be used as necessary. Examples of the reaction catalyst include metal hydroxide, metal alkoxide, metal carboxylate, metal acetyl acetylate, hydroxide of onium salt, onium carboxylate, metal salt of active methylene compound, onium salt of active methylene compound, aminosilane compound Basic compounds such as amine compounds and phosphine compounds are preferred. Of these, ammonium salts, phosphonium salts, sulfonium salts and the like are suitable as the onium salt. The amount of the reaction catalyst used is usually preferably in the range of 10 to 10,000 ppm, based on the total solid mass of the polyisocyanate compound (d2) and the active methylene compound (d1). More preferably, it is in the range of 000 ppm.

The isocyanate group blocking reaction with the active methylene compound (d1) can be carried out at 0 to 150 ° C. The blocking reaction can be performed in a suitable solvent or without a solvent. As the solvent, an aprotic solvent is preferable, and esters, ethers, N-alkylamides, ketones and the like are particularly preferable. If the reaction proceeds as intended, an acid component may be added to neutralize the basic compound as a catalyst and stop the reaction.

In the isocyanate group blocking reaction with the active methylene compound (d1), the amount of the active methylene compound (d1) used is not particularly limited. It is suitable to use 0.1 to 3 moles, preferably 0.2 to 2 moles per mole of isocyanate groups in the polyisocyanate compound (d2). In addition, the active methylene compound that has not reacted with the isocyanate group in the polyisocyanate compound (d2) can be removed after completion of the blocking reaction.

Further, the active methylene-based block polyisocyanate compound (D) from which the compound eliminated in the crosslinking reaction removes the monofunctional alcohol having 3 to 12 carbon atoms is the active methylene compound (d1) and the polyisocyanate compound (d2) described above. In addition to the method of reacting with diisocyanate, diethyl malonate and polyisocyanate compound (d2) are reacted, and then the resulting reaction product is a monofunctional alcohol having 3 to 12 carbon atoms (preferably 6 to 8 carbon atoms). It can also be produced by a method of transesterification (sometimes simply indicated as a long-chain alcohol).

The reaction conditions in the reaction of diethyl malonate and polyisocyanate compound (d2) are the same as those for the active methylene compound (d1) and polyisocyanate compound (d2) described above except that diethyl malonate is used instead of the active methylene compound (d1). It can set suitably like the reaction conditions in this reaction.

In the transesterification with a long-chain alcohol for the reaction product of diethyl malonate and polyisocyanate compound (d2), a reaction catalyst can be used as necessary. Examples of the reaction catalyst include metal hydroxide, metal alkoxide, metal carboxylate, metal acetylacetonate, hydroxide of onium salt, onium carboxylate, metal salt of active methylene compound, onium salt of active methylene compound, aminosilanes And basic compounds such as amines and dried fins. The amount of the reaction catalyst used is usually preferably in the range of 10 to 10,000 ppm, based on the total solid mass of the reaction product of diethyl malonate and polyisocyanate compound (d2), preferably 20 to More preferably, it is in the range of 5,000 ppm.

The transesterification reaction can be performed at 0 to 150 ° C. The transesterification reaction can be performed in a suitable solvent or without a solvent. As the solvent, an aprotic solvent is preferable, and esters, ethers, N-alkylamides, ketones and the like are particularly preferable. If the reaction proceeds as intended, an acid component may be added to neutralize the basic compound as a catalyst and stop the reaction.

In the transesterification reaction, the amount of long-chain alcohol used is not particularly limited. It is suitable to use 0.1 to 100 mol, preferably 0.2 to 10 mol, per 1 mol of the reaction product of diethyl malonate and polyisocyanate compound (d2). Moreover, the long-chain alcohol that has not undergone the transesterification reaction can be removed after completion of the reaction.

In the present invention, monofunctional alcohols having 3 to 12 carbon atoms, preferably 6 to 8 carbon atoms that are eliminated from the block polyisocyanate compound (D) in the crosslinking reaction include, for example, propanol, isopropyl alcohol, butanol, pentanol, hexanol, Aliphatic alkyl alcohols such as octanol, 2-ethylhexanol, 4-methyl-2-pentanol, decanol, dodecanol and isomers thereof; 1-propoxy-2-propanol, 2-butoxyethanol, 1-butoxy-2-propanol And ether group-containing alcohols such as diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether.

Cross-linking agent (E)
In the coating composition of this invention, a crosslinking agent (E) can be contained as needed. The crosslinking agent (E) is a compound that can cure the coating composition of the present invention by reacting with a functional group such as a hydroxyl group, a carboxyl group, and an epoxy group in the film-forming resin (A). Examples of the crosslinking agent (E) include a polyisocyanate compound (E1), a block polyisocyanate compound other than the block polyisocyanate compound (D), an amino resin, an epoxy group-containing compound, and a carbodiimide group-containing compound. Of these, a polyisocyanate compound (E1) and an amino resin are preferable, and among them, a polyisocyanate compound (E1) is preferable. A crosslinking agent can be used individually or in combination of 2 or more types.

Polyisocyanate compound (E1)
The polyisocyanate compound (E1) is a compound having at least two isocyanate groups in one molecule, and includes, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, And polyisocyanate derivatives.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3. Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 2 , 6-Diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6 11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl Examples thereof include aliphatic triisocyanates such as octane.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, alicyclic diisols such as methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2 .1) Heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5- Di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) ) Heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanate) Natoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3 And alicyclic triisocyanates such as -isocyanatopropyl) -bicyclo (2.2.1) heptane.

Examples of the araliphatic polyisocyanate include methylene bis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate, or a mixture thereof, ω, ω′-diisocyanato- Aromatic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; 1,3 And araliphatic triisocyanates such as 5-triisocyanatomethylbenzene.

Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4- TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; , 4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and the like; 4,4′-diphenylmethane-2,2 ′ Fragrance such as 5,5'-tetraisocyanate Mention may be made of tetra-isocyanate, and the like.

Examples of the polyisocyanate derivatives include dimer, trimer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). And Crude TDI.

The above polyisocyanates and derivatives thereof may be used alone or in combination of two or more. Of these polyisocyanates, aliphatic diisocyanates and derivatives thereof can be suitably used from the viewpoint of impact resistance, weather resistance, and the like.

In addition, as the polyisocyanate compound (E1), the above polyisocyanate and derivatives thereof and a compound capable of reacting with the polyisocyanate, for example, a compound having an active hydrogen group such as a hydroxyl group, an amino group, etc. You may use the prepolymer formed by making it react. Examples of the compound that can react with the polyisocyanate include polyhydric alcohols, low molecular weight polyester resins, amines, and water.

The polyisocyanate compound (E1) can be used alone or in combination of two or more.

Block polyisocyanate compound other than the block polyisocyanate compound (D) Block polyisocyanate compound other than the block polyisocyanate compound (D) is a block obtained by blocking the isocyanate group in the polyisocyanate and its derivative with a blocking agent. Among the polyisocyanate compounds, a block polyisocyanate compound in which the compound eliminated in the crosslinking reaction is an alcohol compound having 1 to 2 or 13 carbon atoms or a polyfunctional alcohol can also be used.

Examples of the blocking agent include phenolic compounds such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and methyl hydroxybenzoate; ε-caprolactam, δ-valerolactam Lactam compounds such as γ-butyrolactam, β-propiolactam; aliphatic alcohol compounds such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoe Ether compounds such as ether, propylene glycol monomethyl ether, methoxymethanol; benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylol urea, methylol melamine, Alcohol compounds such as diacetone alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate; oxime compounds such as formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexane oxime; malonic acid Active methylene compounds such as dimethyl, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone Products; mercaptan compounds such as butyl mercaptan, t-butyl mercaptan, hexyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, ethylthiophenol; Acid amide compounds such as acetic acid amide, stearic acid amide, benzamide; imide compounds such as succinimide, phthalic acid imide, maleic imide; diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine Amine compounds such as butylamine, dibutylamine and butylphenylamine; imidazo such as imidazole and 2-ethylimidazole Urea compounds such as urea, thiourea, ethylene urea, ethylene thiourea and diphenyl urea; carbamate esters such as phenyl N-phenylcarbamate; imine compounds such as ethyleneimine and propyleneimine; bisulfite Examples thereof include sulfite compounds such as soda and potassium bisulfite; azole compounds and the like. Examples of the azole compounds include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5. -Pyrazole or pyrazole derivatives such as dimethylpyrazole, 3-methyl-5-phenylpyrazole; imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole; 2-methylimidazoline, And imidazoline derivatives such as 2-phenylimidazoline.

In performing the blocking (reacting the blocking agent), a solvent can be added as necessary. As the solvent used for the blocking reaction, those which are not reactive with isocyanate groups are preferable. For example, ketone compounds such as acetone and methyl ethyl ketone, ester compounds such as ethyl acetate, N-methyl-2-pyrrolidone (NMP) Can be mentioned.

Block polyisocyanate compounds other than the block polyisocyanate compound (D) can be used alone or in combination of two or more.

As the amino resin amino resin, a partially methylolated amino resin or a completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component can be used. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

Further, it is also possible to use those obtained by partially or completely etherifying the methylol group of the methylolated amino resin with an appropriate alcohol. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.

As the amino resin, a melamine resin is preferable. Specific examples of the melamine resin include methylol melamines such as dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine; alkyl etherified products or condensates of these methylol melamines; Examples thereof include condensates of alkyl ethers. The alkyl etherification of methylolmelamine can be carried out by a known method using monoalcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and the like.

The melamine resin preferably has a weight average molecular weight in the range of 600 to 6000, more preferably in the range of 800 to 5000, and still more preferably in the range of 1000 to 4000.

Commercial products can be used as the melamine resin. Commercially available product names include, for example, Cymel 303, Cymel 323, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 380, Cymel 385, Cymel 212, Cymel 251, Cymel 254, Mymel manufactured by Nippon Cytec Industries, Inc. Coat 776; Resimin 735, Resimin 740, Resimin 741, Resimin 745, Resimin 746, Resimin 747 manufactured by Monsanto; Summar M55, Summar M30W, Summar M50W manufactured by Sumitomo Chemical; Uban 20SB, Uban 20SE- 60, Yuban 28-60, etc.

The above melamine resins can be used alone or in combination of two or more.

Coating composition The coating composition of the present invention comprises the film-forming resin (A) and the matting agent (B), and further contains a specific non-aqueous polymer dispersion (C) and / or a specific block polyisocyanate compound. (D) is contained. The coating film obtained by applying the coating composition of the present invention has a matte property.

In the present specification, having a matte property means that the value of 60 ° specular gloss measured by the formed coating film based on JIS K 5600-4-7: 1999 is less than 60.

In the coating composition of the present invention, the blending ratio (solid mass) of each component is determined from the viewpoints of storage stability and matteness, glossiness stability, alkali resistance and impact resistance of the formed coating film. The following range is preferable.

The total amount of solid content of the film-forming resin (A), the non-aqueous polymer dispersion (C), the blocked polyisocyanate compound (D) and the crosslinking agent (E) used as necessary is 100 parts by mass,
Film-forming resin (A) (as solid content): 50 to 80 parts by mass, preferably 60 to 80 parts by mass, more preferably 60 to 75 parts by mass,
Matting agent (B): 5 to 50 parts by weight, preferably 5 to 45 parts by weight, more preferably 5 to 40 parts by weight,
Non-aqueous polymer dispersion (C) (as solid content): 0 to 10 parts by mass, preferably 0.1 to 8 parts by mass, more preferably 0.1 to 6 parts by mass,
Block polyisocyanate compound (D) (as solid content): 0 to 50 parts by weight, preferably 0 to 45 parts by weight, more preferably 0 to 40 parts by weight,
Crosslinking agent (E) (as solid content): 0 to 50 parts by weight, preferably 0 to 45 parts by weight, more preferably 0 to 40 parts by weight.
However, the non-aqueous polymer dispersion (C) and the block polyisocyanate compound (D) are not both 0 parts by mass at the same time.

The coating composition of the present invention is further used in the field of ordinary paints such as organic solvents, curing catalysts, pigments, pigment dispersants, leveling agents, ultraviolet absorbers, light stabilizers, and plasticizers, if necessary. Paint additives that can be added.

Examples of the curing catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, and dioctyl. Organometallic catalysts such as tin oxide and lead 2-ethylhexanoate; sulfonic acids such as tertiary amines, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid; salts of these acids with amines, etc. Can be mentioned. These can be used alone or in combination of two or more.

When the coating composition of the present invention contains a curing catalyst, the blending amount of the curing catalyst is in the range of 0.05 to 10 parts by mass based on 100 parts by mass of the solid content in the coating composition. Is preferably in the range of 0.1 to 5 parts by mass, and more preferably in the range of 0.2 to 3 parts by mass.

Examples of the pigment include titanium oxide, zinc white, carbon black, cadmium red, molybdenum red, chromium yellow, chromium oxide, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene. Colored pigments such as pigments; body pigments such as talc, clay, kaolin, barita, barium sulfate, barium carbonate, calcium carbonate, and alumina white; metallic pigments such as aluminum powder, mica powder, and mica powder coated with titanium oxide be able to. These can be used alone or in combination of two or more.

When the coating composition of the present invention is used as a clear coating and contains a pigment, the amount of the pigment is preferably an amount that does not hinder the transparency of the resulting coating film. Usually, it is preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.3 to 10 parts by weight, based on 100 parts by weight of the solid content in the coating composition. More preferably, it is in the range of 5 to 5 parts by mass.

Further, when the coating composition of the present invention is used as a colored coating and contains a pigment, the blending amount of the pigment is usually 1 based on 100 parts by mass of the resin solid content in the coating composition. It is preferably in the range of -200 parts by mass, more preferably in the range of 2-100 parts by mass, and still more preferably in the range of 5-50 parts by mass.

As the ultraviolet absorber, conventionally known ones can be used, and examples thereof include ultraviolet absorbers such as benzotriazole absorbers, triazine absorbers, salicylic acid derivative absorbers, and benzophenone absorbers. These can be used alone or in combination of two or more.

When the coating composition of the present invention contains an ultraviolet absorber, the blending amount of the ultraviolet absorber is within the range of 0.1 to 10 parts by mass based on 100 parts by mass of the solid content in the coating composition. It is preferably within a range of 0.2 to 5 parts by mass, and more preferably within a range of 0.3 to 2 parts by mass.

As the light stabilizer, conventionally known light stabilizers can be used, and examples thereof include hindered amine light stabilizers.

When the coating composition of the present invention contains a light stabilizer, the blending amount of the light stabilizer is within the range of 0.1 to 10 parts by mass based on 100 parts by mass of the solid content in the coating composition. It is preferably within a range of 0.2 to 5 parts by mass, and more preferably within a range of 0.3 to 2 parts by mass.

The paint composition of the present invention may be a one-component paint or a multi-component paint such as a two-component paint. In the coating composition of the present invention, when the non-blocked polyisocyanate compound (E1) is used as the crosslinking agent (E), from the viewpoint of storage stability, the film-forming resin (A), From a main agent containing a matting agent (B), a non-aqueous polymer dispersion (C) and / or a blocked polyisocyanate compound (D), and a crosslinking agent containing the non-blocked polyisocyanate compound (E1) It is preferable to use a mixture of the two just before use.

Coating Method The coating material to which the coating composition of the present invention (hereinafter may be abbreviated as “the present coating”) is not particularly limited, and examples thereof include cold-rolled steel sheets and galvanized steel sheets. Metal substrates such as steel plates such as zinc alloy plated steel plates, stainless steel plates and tin plated steel plates, aluminum plates and aluminum alloy plates; plastic substrates such as polyolefins, polycarbonates, ABS resins, urethane resins and polyamides; it can. Moreover, the vehicle body of various vehicles, such as a motor vehicle, a two-wheeled vehicle, a container formed by these, or its components may be sufficient.

Also, the object to be coated may be one in which a surface treatment such as a phosphate treatment, a chromate treatment or a complex oxide treatment is performed on the metal base or the metal surface of the vehicle body. Further, as the object to be coated, an undercoat film such as various electrodeposition paints may be formed on the metal substrate or the vehicle body, and the undercoat film and the intermediate coat film are formed. It may be an undercoating film, an intermediate coating film and a base coat film, or an undercoating film, an intermediate coating film, a base coat film and a clear coat film may be formed.

When the object to be coated is a plastic substrate, the plastic substrate may be appropriately subjected to degreasing treatment and / or surface treatment as necessary. Furthermore, after forming an undercoat film on the plastic substrate surface, the coating composition of the present invention may be applied.

The coating method of the paint is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, and the like. Can be formed. In these coating methods, electrostatic application may be performed as necessary. Of these, air spray coating or rotary atomization coating is particularly preferred. In general, the coating amount of the paint is preferably about 10 to 50 μm as a cured film thickness.

Also, when performing air spray coating, airless spray coating, and rotary atomization coating, the viscosity of this coating is adjusted to a viscosity range suitable for the coating, usually Ford Cup No. In a 4-viscosity meter, it is preferable to adjust appropriately using a solvent such as an organic solvent so that a viscosity range of about 15 to 60 seconds at 20 ° C. is obtained.

Curing of the wet coating film formed by applying the coating material to the object to be coated is performed by heating, and the heating can be performed by a known heating means, such as a hot air furnace, an electric furnace, an infrared induction heating furnace, etc. Any drying oven can be used. The heating temperature is not particularly limited, and is preferably in the range of 60 to 200 ° C., preferably 90 to 150 ° C., for example. The heating time is not particularly limited, and for example, it is suitably in the range of 10 to 60 minutes, preferably 15 to 30 minutes.

This paint is excellent in storage stability, and can obtain a matte coating film having excellent gloss stability, alkali resistance and impact resistance, and therefore can be suitably used as a top-coat top clear coat paint. This paint can be particularly suitably used as an automobile paint.

Multi-layer coating film forming method As a multi-layer coating film forming method in which this paint is applied as a top-top clear coat paint, at least one colored base coat paint and at least one clear coat paint are sequentially applied to an object to be coated. It is a method of forming a multilayer coating film by doing, Comprising: The multilayer coating-film formation method including apply | coating the coating composition of this invention as an uppermost clear coat coating material can be mentioned.

Specifically, for example, a base coat paint is applied on an object to which electrodeposition coating and / or intermediate coating is applied, and the solvent in the base coat paint is cured as necessary without curing the coating film. In order to promote volatilization, for example, preheating is performed at 40 to 90 ° C. for about 3 to 30 minutes, and after applying this paint as a clear coat paint on the uncured base coat film, the base coat and the clear coat are applied. Examples thereof include a method for forming a multilayer coating film of a two-coat one-bake method in which the coat is cured together.

Also, the paint can be suitably used as a top clear coat paint in a top coat of a 3-coat 2-bake system or a 3-coat 1-bake system.

As the base coat paint used in the above, a conventionally known normal thermosetting base coat paint can be used. Specifically, for example, a base resin such as an acrylic resin, a polyester resin, an alkyd resin, a urethane resin type, or the like. In addition, a coating material obtained by appropriately combining a reactive functional group contained in the base resin with a crosslinking agent such as an amino resin, a polyisocyanate compound, or a block polyisocyanate compound can be used.

Further, as the base coat paint, for example, water-based paint, organic solvent-based paint, powder paint, and the like can be used. Of these, water-based paints are preferable from the viewpoint of reducing environmental burden.

When two or more clear coats are applied in the multi-layer coating film forming method, conventionally known normal thermosetting clear coat paints can be used as the clear coat paint other than the uppermost layer.

Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. However, the present invention is not limited to these. In each example, “parts” and “%” are based on mass unless otherwise specified. Moreover, the film thickness of a coating film is based on a cured coating film. Furthermore, the compounding quantity in a table | surface is solid content mass.

Production Production Example 1 of Film Forming Resin (A)
31 parts of ethoxyethyl propionate was charged into a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet, and the temperature was raised to 120 ° C. under nitrogen gas flow. After reaching 120 ° C., nitrogen gas aeration was stopped, and a monomer mixture composed of the following monomer and polymerization initiator was added dropwise over 4 hours.
15 parts of styrene,
10 parts of methyl methacrylate,
11.5 parts of isobornyl acrylate,
20 parts of 2-ethylhexyl acrylate,
2-Hydroxyethyl acrylate 32.5 parts Acrylic acid 1 part 2,2′-Azobisisobutyronitrile 6 parts Next, after aging for 1 hour while bubbling nitrogen gas at 120 ° C., 2,2′-azo A mixture of 0.5 parts of bisisobutyronitrile and 5 parts of ethoxyethyl propionate is added dropwise over 1 hour, then aged at about 120 ° C. for 1 hour and diluted with 27.5 parts of ethoxyethyl propionate. As a result, a film-forming resin (A-1) solution which is a hydroxyl group-containing acrylic resin having a solid content of 60% was obtained. The obtained film-forming resin had a hydroxyl value based on the solid content of 140 mgKOH / g, a weight average molecular weight of about 8,000, and a glass transition temperature of 42 ° C.

Production Example 2
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and water separator, 20.1 g of trimethylolpropane (molecular weight 134), 83.2 g of neopentyl glycol (molecular weight 104), 1,2-cyclohexanedicarboxylic acid Charge 69.3 g of acid anhydride (molecular weight 154) and 65.7 g of adipic acid (molecular weight 146), raise the temperature from 160 ° C. to 230 ° C., and maintain at 230 ° C. while removing condensed water with a water separator. The film-forming resin (A-2), which is a hydroxyl group-containing polyester resin having a solid content of 60%, was reacted until the acid value reached 1 mg KOH / g, cooled to 120 ° C., and diluted with ethoxyethyl propionate. ) A solution was obtained. The hydroxyl value based on the solid content of the obtained film-forming resin was 90 mgKOH / g, and the weight average molecular weight was about 4400.

Production and production example 3 of polymer dispersion stabilizer (C1)
In a reaction vessel, 100 parts of xylene are heated to 130 ° C. and 50 parts of 2-ethylhexyl methacrylate, 33 parts of n-butyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, 2 parts of methacrylic acid, and 2,2′-azobisiso A mixture of 2 parts of butyronitrile was added dropwise at a uniform rate over 3 hours and further aged for 2 hours. The obtained acrylic resin had a solid content of 50% and a number average molecular weight of 7000.
Next, to 202 parts of the acrylic resin obtained above, 1 part of glycidyl methacrylate, 0.02 part of 4-t-butylpyrocatechol and 0.1 part of dimethylaminoethanol were added and stirred at 130 ° C. for 5 hours. A 50% polymer dispersion stabilizer (C1-1) solution was obtained. The obtained polymer dispersion stabilizer (C1-1) had an average of about 1.0 polymerizable unsaturated groups per molecule.

Production Example 4
12-Hydroxystearic acid was subjected to dehydration condensation under toluene reflux using methanesulfonic acid as a catalyst to condense to a resin acid value of 30 mgKOH / g. Polymer obtained by adding glycidyl methacrylate to the terminal carboxyl group of the resulting self-condensed polyester resin having a number average molecular weight of about 1,800 using dimethylaminoethanol as a catalyst to introduce a polymerizable unsaturated group, and having a solid content of 70% A dispersion stabilizer (C1-2) solution was obtained. The obtained polymer dispersion stabilizer (C1-2) had an average of about 1.0 polymerizable unsaturated groups per molecule.

Production Example 5
174 parts of butyl acetate was placed in the flask and heated to reflux, 297.0 parts of a 70% polymer dispersion stabilizer (C1-2) solution, 195.9 parts of methyl methacrylate, 18.5 parts of glycidyl methacrylate, 163. A mixture of 0 part and 9.6 parts of 2,2′-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours, followed by aging for 2 hours.
Next, a mixture of 0.05 part of pt-butylcatechol, 3.8 parts of methacrylic acid and 0.5 part of dimethylaminoethanol was added to the flask, and 140 ° C. until the resin acid value reached 0.5 mgKOH / g. The reaction was continued for about 5 hours to obtain a polymer dispersion stabilizer (C1-3) solution having a solid content of 50%. The obtained polymer dispersion stabilizer (C1-3) is a graft polymer having a first segment made of poly (12-hydroxystearic acid) and a second segment made of a copolymer of methyl methacrylate and glycidyl methacrylate. It had an average of about 4 polymerizable unsaturated groups in one molecule.

Production Example 6
The following reaction component mixture is placed in a normal polyester resin production reactor equipped with a stirrer, thermometer, rectifier, refluxer, etc., and a general dehydration / condensation reaction is carried out until an acid value of 4 mgKOH / g. Condensed.
Trimethylolpropane 46.5 parts Hexahydrophthalic acid 23.6 parts Isophthalic acid 25.5 parts Coconut fatty acid 35.8 parts To the resin solution thus condensed, 1.2 parts of isocyanate ethyl methacrylate was added, and isocyanate- The addition reaction was carried out until the trivalent value was 0.5 or less to obtain a polymer dispersion stabilizer (C1-4) solution. The number average molecular weight of this product was 15000, the hydroxyl value was 114, the oil length was 30%, the acid value was 4 mgKOH / g, and the solid content was 60%.

Production Example 7 of Nonaqueous Polymer Dispersion (C)
A four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 150 parts of n-heptane and 150 parts of xylene, and the temperature was raised to 100 ° C. while blowing nitrogen. 100 parts of a polymer dispersion stabilizer (C1-1) solution having a solid content of 50%, 50 parts of other dispersion stabilizer (C1-3) solution, 75 parts of methyl methacrylate, 18 parts of acrylonitrile, 70 parts of 2-hydroxyethyl acrylate Then, 7 parts of glycidyl methacrylate, 5 parts of methacrylic acid and 5 parts of 2,2′-azobisisobutyronitrile were added dropwise over 5 hours, followed by further aging for 2 hours to obtain a non-aqueous dispersion resin (C-1) A solution was obtained. The obtained non-aqueous dispersion resin (C-1) had a solid content of 40% and an average particle size of 146 nm.

Production Example 8
A four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 162 parts of n-heptane and 163 parts of xylene, and the temperature was raised to 100 ° C. while blowing nitrogen. 100 parts of a polymer dispersion stabilizer (C1-3) solution with a solid content of 50%, 86 parts of methyl methacrylate, 20 parts of acrylonitrile, 80 parts of 2-hydroxyethyl acrylate, 8 parts of glycidyl methacrylate, 6 parts of methacrylic acid, 2,2 ′ -2 parts of azobisisobutyronitrile was added dropwise over 5 hours and aged for 2 hours to obtain a non-aqueous dispersion resin (C-2) solution. The obtained non-aqueous dispersion resin (C-2) had a solid content of 40% and an average particle size of 330 nm.

Production Example 9
150 parts of n-heptane and 150 parts of xylene were charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet, and the temperature was raised to 100 ° C. while blowing nitrogen. 150 parts of a polymer dispersion stabilizer (C1-1) solution having a solid content of 50%, 75 parts of methyl methacrylate, 18 parts of acrylonitrile, 70 parts of 2-hydroxyethyl acrylate, 7 parts of glycidyl methacrylate, 5 parts of methacrylic acid, 2,2 ′ -5 parts of azobisisobutyronitrile was added dropwise over 5 hours and aged for 2 hours to obtain a non-aqueous dispersion resin (C-3) solution. The obtained non-aqueous dispersion resin (C-3) had a solid content of 40% and an average particle size of 157 nm.

Production Example 10
A four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 162 parts of n-heptane and 163 parts of xylene, and the temperature was raised to 100 ° C. while blowing nitrogen. Polymer dispersion stabilizer (C1-4) solution of 60% solid content 125 parts, methyl methacrylate 75 parts, acrylonitrile 18 parts, 2-hydroxyethyl acrylate 70 parts, glycidyl methacrylate 7 parts, methacrylic acid 6 parts, 2,2 ′ -2 parts of azobisisobutyronitrile was added dropwise over 5 hours and aged for 2 hours to obtain a non-aqueous dispersion resin (C-4) solution. The obtained non-aqueous dispersion resin (C-4) had a solid content of 40% and an average particle size of 400 nm.

Production and production example 11 of block polyisocyanate compound (D)
To a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dropping pump, etc., “Sumidule N-3300” (manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate, number average molecular weight of about 600, isocyanate (21.6% content) 605 g, diethyl malonate 413 g, and ethyl acetate 181 g were mixed, 7.0 g of a 28% sodium methoxide methanol solution was added under a nitrogen stream, and the mixture was kept at 60 ° C. for 12 hours. Thereafter, when the NCO value was measured, the isocyanate content was 0.2%. 99 g of ethyl acetate was added thereto to obtain a resin solution. The SP value of the resin solution was 10.8 (the number average molecular weight of the resin was about 3,000.

Next, 505 g of the resin solution obtained above and 450 g of propylene glycol monopropyl ether are placed in a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dropping pump, removal solvent simple trap, etc. The temperature rose. Under reduced pressure, the solvent was distilled off and removed over 2 hours while maintaining the system temperature at 80 to 90 ° C., and part of the isocyanate group was di (1-methyl-2-propoxyethyl) malonate. As a result, 642 g of a blocked polyisocyanate compound (D-1) solution was obtained.

The removal solvent simple trap contained 42 g of ethanol. The SP value of the block polyisocyanate and compound (D-1) was 10.1, and the sum average molecular weight was about 3,500. In the block polyisocyanate compound (D-1), an alcohol mixture containing propylene glycol monopropyl ether is eliminated by a crosslinking reaction.

Production Example 12
To a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dropping pump, etc., “Sumidule N-3300” (manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate, number average molecular weight of about 600, isocyanate (21.6% content) 605 g, diethyl malonate 413 g, and ethyl acetate 181 g were mixed, 7.0 g of a 28% sodium methoxide methanol solution was added under a nitrogen stream, and the mixture was kept at 60 ° C. for 12 hours. Thereafter, when the NCO value was measured, the isocyanate content was 0.2%. 99 g of ethyl acetate was added thereto to obtain a resin solution. The number average molecular weight of the resin was about 3,000.

Next, 505 g of the resin solution obtained above and 310 g of 1-propanol were placed in a 2 L flask equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a dripping pump, a removal solvent simple trap, etc., and the temperature was raised to 90 ° C. did. Under reduced pressure, the solvent was distilled off and removed over 2 hours while maintaining the temperature of the system at 80 to 90 ° C., and a blocked polyisocyanate compound in which a part of the isocyanate group was blocked with dipropyl malonate (D- 2) 560 g of solution was obtained. The removal solvent simple trap contained 43 g of ethanol. The number average molecular weight of the resin was about 3,100. In the block polyisocyanate compound (D-2), alcohol containing n-propanol is eliminated by a crosslinking reaction.

Production Example 13
To a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dropping pump, etc., “Sumidule N-3300” (manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate, number average molecular weight of about 600, isocyanate (21.6% content) 605 g, diethyl malonate 413 g, and ethyl acetate 181 g were mixed, 7.0 g of a 28% sodium methoxide methanol solution was added under a nitrogen stream, and the mixture was kept at 60 ° C. for 12 hours. Thereafter, when the NCO value was measured, the isocyanate content was 0.2%. 99 g of ethyl acetate was added thereto to obtain a resin solution. The number average molecular weight of the resin was about 3,000.

Next, 505 g of the resin solution obtained above and 395 g of isodecanol were placed in a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dripping pump, removal solvent simple trap, etc., and the temperature was raised to 90 ° C. Under reduced pressure, the solvent was distilled off and removed over 2 hours while maintaining the system temperature at 80 to 90 ° C., and a blocked polyisocyanate compound (D—) in which a part of the isocyanate group was blocked with diisodecyl malonate. 3) 690 g of solution was obtained. The removal solvent simple trap contained 41 g of ethanol. The number average molecular weight of the resin was about 3,800. In the block polyisocyanate compound (D-3), alcohol containing isodecanol is eliminated by a crosslinking reaction.

Production Example 14
To a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dropping pump, etc., “Sumidule N-3300” (manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate, number average molecular weight of about 600, isocyanate (21.6% content) 605 g and dipropylene glycol 337 g were blended and heated to 100 ° C. Thereafter, while stirring at 90 to 100 ° C., 308 g of 3,5-dimethylpyrazole was added little by little, and the mixture was further kept at 100 ° C. for 12 hours to block the polyisocyanate compound (D -4) A solution was obtained. When the NCO value was measured, the isocyanate content was 0.1%. The number average molecular weight of the resin was about 1,100.

Production Example 15
To a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dropping pump, etc., “Sumidule N-3300” (manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate, number average molecular weight of about 600, isocyanate (21.6% content) 605 g, diethyl malonate 413 g, and tetrahydrofuran 370 g were added, 7.0 g of 28% methanol solution of sodium methoxide was added under a nitrogen stream, and the mixture was kept at 60 ° C. for 12 hours. A blocked polyisocyanate compound (D-5) solution blocked with diethyl acid was obtained. When the NCO value was measured, the isocyanate content was 0.2%. The number average molecular weight of the resin was about 3,000.

Production Example 16
To a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dropping pump, etc., “Sumidule N-3300” (manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanurate structure-containing polyisocyanate, number average molecular weight of about 600, isocyanate (21.6% content) 605 g, diethyl malonate 413 g, and ethyl acetate 181 g were mixed, 7.0 g of 28% methanol solution of sodium methoxide was added under a nitrogen stream, and the mixture was kept at 60 ° C. for 12 hours. Thereafter, when the NCO value was measured, the isocyanate content was 0.2%. 99 g of ethyl acetate was added thereto to obtain a resin solution. The number average molecular weight of the resin was about 3,000.

Next, 505 g of the resin solution obtained above and 500 g of isotridecanol are placed in a 2 L flask equipped with a thermometer, thermostat, stirrer, reflux condenser, dripping pump, simple solvent removal trap, etc., and the temperature is raised to 90 ° C. Warm up. This was attempted to distill and remove the solvent while maintaining the system temperature at 80 to 90 ° C. under reduced pressure conditions. However, it may be possible to distill and remove the solvent sufficiently because isotridecanol has a high boiling point. The production was discontinued. For this reason, the subsequent coating and various performance evaluations could not be performed.

Properties evaluation procedure of matting agents The average particle size, oil absorption and surface treatment characteristics of commercially available matting agents (B-1) to (B-6) were evaluated by the following procedures, and the results are summarized in Table 1. .

Average particle diameter: D50 value was measured using a laser diffraction / scattering particle size distribution measuring device “Microtrack NT3300” (trade name, manufactured by Nikkiso Co., Ltd.). At that time, as a pretreatment, silica particles are added to a mixed solvent of acetone and isopropyl alcohol and dispersed by applying ultrasonic waves for 1 minute, and the matting agent concentration is adjusted to a concentration within a predetermined transmittance range set in the apparatus. did.

Oil absorption: Measured according to JIS K5101-13-3: 2004.

Surface treatment characteristics: 5 mL of water was put into a test tube, 0.3 g of inorganic fine particles were gently put therein and allowed to stand, and the ratio of inorganic fine particles floating on the water surface after 12 hours was evaluated.

Production Examples and Comparative Examples of Coating Composition Each component was uniformly mixed so as to have the composition shown in Table 2. Next, a diluting solvent was added to the obtained mixture, and a Ford Cup No. 20 at 20 ° C. was added. A coating composition having a viscosity according to 4 of 25 seconds was obtained.

Table 2 shows the solid content, and (B-1) to (B-6) and (E-1) in Table 1 are as follows.
(B-1) “Silicia 436”: trade name, manufactured by Fuji Silysia, silica particles surface-treated with an organic compound (B-2) “Silo Hovic 200”: trade name, manufactured by Fuji Silysia, organosilicon compound Hydrophobic surface treated silica particles (B-3) “ACEMATT OK-412”: trade name, manufactured by Evonik Industries, Inc., silica particles surface treated with organic compounds (B-4) “Silo Hovic 702”: Products Name, manufactured by Fuji Silysia Co., Ltd., silica particles (B-5) hydrophobically treated with an organosilicon compound “ACEMATT 3300”: trade name, manufactured by Evonik Industries, Inc., silica particles hydrophobically treated with an organosilicon compound (B- 6) “Silicia 430”: trade name, manufactured by Fuji Silysia, untreated silica (E-1) Sumijour N3300: trade name, residence Bayer Urethane Co., Ltd., isocyanurate of hexamethylene diisocyanate, 100% solids, isocyanate group content of 21.8 percent

Preparation of test plates Examples 1 to 17 and Comparative Examples 1 to 4
On a 0.8 mm-thick dull steel plate having a size of 10 cm × 15 cm and subjected to zinc phosphate conversion treatment, “ELECRON GT-10” (trade name, thermosetting epoxy resin cation, manufactured by Kansai Paint Co., Ltd.) Electrodeposition coating is applied so that the cured film thickness is 20 μm, cured by heating at 170 ° C. for 30 minutes, and “TP-65-2” (manufactured by Kansai Paint, trade name, polyester) -Melamine resin-based automotive intermediate coating) was applied by air spray so as to have a cured film thickness of 35 μm, and cured by heating at 140 ° C. for 30 minutes. “WBC-713T No. 202” (manufactured by Kansai Paint Co., Ltd., acrylic-melamine resin water-based base coat for automobiles, black paint color) was applied to the coating film so as to have a film thickness of 15 μm and allowed to stand at room temperature for 5 minutes. Then, after preheating at 80 ° C. for 10 minutes, the coating compositions (1) to (17) and (20) to (23) shown in Table 2 are cured on the uncured coating film. Was coated at 20 μm and 40 μm, allowed to stand at room temperature for 10 minutes, and then heated at 140 ° C. for 20 minutes to cure both coating films together to obtain a test plate. The performance test results of the obtained coating film are also shown in Table 2.

Example 18
“Electron GT-10” (trade name, thermosetting epoxy resin-based cationic electrodeposition paint, manufactured by Kansai Paint Co., Ltd.) is cured on a 0.8 mm thick dull steel sheet that has been subjected to zinc phosphate conversion treatment. Electrodeposited to 20 μm, cured by heating at 170 ° C. for 30 minutes, and coated thereon with the coating composition (18) shown in Table 2 so that the cured film thickness was 20 μm and 40 μm. And left for 10 minutes, and then heated at 140 ° C. for 20 minutes to obtain a test plate. The performance test results of the obtained coating film are also shown in Table 2.

Example 19
Air-spray coating is applied to an ABS plate (black, degreased) with a primer “SOFLEX 1000” (trade name: manufactured by Kansai Paint Co., Ltd., polyolefin-containing conductive organic solvent type paint) to a dry film thickness of 15 μm. And preheating at 80 ° C. for 3 minutes. Further, “WBC-713T No. 202” was applied thereon so as to have a film thickness of 15 μm, left at room temperature for 5 minutes, and then preheated at 80 ° C. for 10 minutes. On top of that, the coating composition (19) was subjected to air spray coating so that the cured film thicknesses were 20 μm and 40 μm, and heated and cured at 80 ° C. for 30 minutes to obtain a test coated plate. The performance test results of the obtained coating film are also shown in Table 2.

Performance test method Gloss stability (gross difference due to film thickness fluctuation):
JIS K 5600-4-7: A 60 ° specular gloss value measured in accordance with JIS K 5600-4-7: 1999 is defined as a matte coating film, and the 60 ° specular gloss value when coated at a film thickness of 20 μm. And the difference between the 60 ° specular gloss value when coated with a film thickness of 40 μm. Evaluation was made according to the following criteria. S and A are acceptable.
S: difference is less than 5,
A: The difference is 5 or more and less than 10,
B: The difference is 10 or more.

In addition, when compared with the addition of the same amount of silica, it is preferable that the 60 ° C. gloss value itself is also small. Note that Comparative Examples 1 and 4 do not correspond to the coating film having “matte properties” defined above.

Gloss stability (gloss unevenness in the plate):
The 60 ° specular gloss at any 7 points on the surface of the test plate obtained above was measured and evaluated by the difference between the maximum value and the minimum value. Evaluation was made according to the following criteria. S and A are acceptable.
S: difference is less than 5,
A: The difference is 5 or more and less than 10,
B: The difference is 10 or more.

Alkali resistance:
After dropping 0.5 mL of 1% sodium hydroxide aqueous solution on the coating film surface of the test plate and leaving it in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65% for 24 hours, the coated surface is wiped with gauze and the appearance is visually observed. The evaluation was based on the following criteria. S and A are acceptable.
S: There is no abnormality on the surface of the coating film,
A: Discoloration (whitening) of the coating surface is observed,
B: Discoloration (whitening) of the coating film surface is remarkable.

Storage stability:
A coating composition prepared by diluting a mixture having the composition shown in Table 1 with “Swasol # 1000” (Note 4) so that the viscosity is 25 seconds / Ford Cup # 4/20 ° C. is used in an atmosphere of 50 ° C. For 72 hours. Then, it returned to 20 degreeC, the state of the coating material was observed visually, and the following reference | standard evaluated.
S: generation of sediment is not observed,
A: Sediment is generated, but if it is stirred for about 10 minutes, it returns to the state before storage.
B: A precipitate is generated and does not disappear even after stirring for 10 minutes or more.

Impact resistance:
After each multilayer coating is placed in a constant temperature and humidity chamber at a temperature of 20 ° C. ± 1 and a humidity of 75 ± 2% for 24 hours, it is specified in the DuPont impact tester specified in JIS K 5600-5-3 (1999). Attach a large cradle and striker, place the test plate with the coating surface facing upwards, and sandwich it between them, then drop a weight of 500g on the striker (1/2 inch) and paint by impact The drop height (cm) at which cracks and peeling occurred on the film (front surface) was measured.
S: 50 cm or more,
A: 45 cm or more and less than 50 cm,
B: Less than 45 cm.

Preparation of test plate (2)
Examples 20-21, Comparative Examples 5-6
On a 0.8 mm-thick dull steel plate having a size of 10 cm × 15 cm and subjected to zinc phosphate conversion treatment, “ELECRON GT-10” (trade name, thermosetting epoxy resin cation, manufactured by Kansai Paint Co., Ltd.) Electrodeposition coating is applied so that the cured film thickness is 20 μm, cured by heating at 170 ° C. for 30 minutes, and “TP-65-2” (manufactured by Kansai Paint, trade name, polyester) -Melamine resin-based automotive intermediate coating) was applied by air spray so as to have a cured film thickness of 35 μm, and cured by heating at 140 ° C. for 30 minutes. “WBC-713T No. 202” (manufactured by Kansai Paint Co., Ltd., acrylic / melamine resin-based aqueous base coat for automobiles, black paint color) was applied on the coating film to a film thickness of 15 μm and allowed to stand at room temperature for 5 minutes. Then, after preheating at 80 ° C. for 10 minutes, the coating compositions (1), (3), (21) and (22) shown in Table 3 are coated on the uncured coating film. The coatings were applied to give 52%, 62%, and 72% solids after 1 minute of adhesion, left at room temperature for 10 minutes, and then heated at 140 ° C. for 20 minutes. A test plate was obtained by curing. The coating solid content was adjusted by the mixing ratio of thinner (butyl acetate, ethyl-3-ethoxypropionate). The performance test results of the coating film obtained are shown together in Table 3.

Here, the coating solid content one minute after the coating composition shown in Table 3 adheres to the object is measured as follows.

Using the coating composition shown in Table 3 on a tin plate with a length of 45 cm x width 30 cm x thickness 0.8 mm, a rotary atomizing bell-type coating machine "ABB cartridge bell coating machine" (trade name, manufactured by ABB) The bell diameter is 70 mm, the bell rotation speed is 25000 rpm, the shaping air pressure is 2.0 kg / cm2, the discharge rate is 250 cc / min, the voltage is -75 kV, and the distance between the object to be coated and the metabell so that the dry film thickness is 40 μm. Was applied once under the condition of 30 cm, the coating composition shown in Table 3 was applied to the tinplate, and after 1 minute, a portion of the film was scraped with a spatula and collected at 110 ° C. for 1 hour. It can be obtained by measuring the solid content after drying. More precisely, the remaining heating amount after drying 1 ± 0.1 g of paint at 110 ° C. for 1 hour is measured, and this remaining heating amount is divided by the original paint weight (value in the range of 1 ± 0.1 g). Can be obtained.

Gloss stability (gross difference due to fluctuations in solid content of coating):
When the value of 60 ° specular gloss measured under JIS K 5600-4-7: 1999 is less than 60, it is defined as a matte coating, and the coating solid content is 52%. 60 ° specular gloss value,
Evaluation was made based on the difference from the value of 60 ° specular gloss when the coating was applied to 72%. Evaluation was made according to the following criteria. S and A are acceptable.
S: difference is less than 5,
A: The difference is 5 or more and less than 10,
B: The difference is 10 or more.

Claims (8)

A coating composition comprising a film-forming resin (A) and a matting agent (B), and further comprising a non-aqueous polymer dispersion (C) and / or a block polyisocyanate compound (D) comprising a skin component and a core component Because
Non-aqueous polymer dispersion (C) contains an acrylic polymer and / or a self-condensate of a fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain, and one molecule of polymerizable unsaturated group A non-aqueous polymer dispersion containing, as an at least part of the skin component, a macromonomer having an average of 1 or more per hit,
A coating composition, wherein the block polyisocyanate compound (D) is an active methylene-based block polyisocyanate compound in which the compound eliminated in the crosslinking reaction is a monofunctional alcohol having 3 to 12 carbon atoms. The coating composition according to claim 1, wherein the matting agent (B) is an organically treated silica particle. The coating composition according to claim 2, wherein the matting agent (B) is hydrophobic surface-treated silica particles. The coating composition according to any one of claims 1 to 3, wherein the matting agent (B) has an average particle diameter of 1 to 10 µm and an oil absorption of 100 to 400 mL / 100 g. The coating composition according to any one of claims 1 to 4, further comprising a crosslinking agent (E). The coating composition according to claim 5, wherein the crosslinking agent (E) contains a polyisocyanate compound (E1). A coating method comprising a step of coating the object to be coated with the coating composition according to any one of claims 1 to 6. A coated article having a coating film obtained by curing the coating composition according to any one of claims 1 to 6.