JP5674592B2 - Multi-component base coat paint, toning method and repair coating method - Google Patents

Description

  Multi-component base coat paint with good coating workability, no occurrence of unevenness, and capable of forming a repair paint film having color matching with existing paint film, toning method and repair paint method using the base coat paint About.

  In recent years, in the repair painting of vehicles such as automobiles, metallic base paints containing glitter pigments and metallic finishes that are repeatedly applied with clear paints have become mainstream, and when a lacquer type paint is used as the base coat, From the viewpoint of drying properties, paints using a film-forming component such as a blend of polyester resin and cellulose acetate butyrate (may be abbreviated as CAB), a blend of polyester resin and CAB in acrylic resin, etc. have been adopted. .

  For example, Patent Documents 1 and 2 describe coating compositions using CAB graft copolymers, polyester resins, and acrylic resins in specific ratios. According to the composition, the compatibility of each of these components is improved, and unevenness (so-called fukimura) that occurs when a metallic base coating is applied in metallic coating, occurs when a clear coating is applied over the metallic base coating. It is possible to form a coating film having good finish without causing unevenness (so-called "modular unevenness"). However, an organic solvent such as toluene or xylene is added to the paint and diluted thinner for adjusting the viscosity of the paint. A large amount was blended.

  Generally, a paint prepared by a paint manufacturer is not used as it is because of its high viscosity, and the paint manufacturer ships to a paint distributor together with a diluted thinner. The painter purchases both products from paint distributors and mixes the paint and dilution thinner for use in painting in order to adjust the viscosity and paint workability according to the purpose.

  In recent years, the impact of volatile organic compounds (VOC) on the environment has become a problem, and of course, high solidification is required in accordance with the low VOC of paints, and it has been usually blended in the past in the paint field. Organic solvents such as toluene and xylene are designated as environmental pollutants, for example, environmental pollutant release transfer registration (POLLUTANT RELEASE AND TRANSFER REGISTER (hereinafter, abbreviated as PRTR)), paints and diluted thinners. Both are required to reduce or substantially not contain these organic solvents.

  As a measure against such a problem, Patent Document 3 discloses cellulose derivative (A), acrylic resin (B), polyester resin (C), and at least one organic solvent (D) selected from ester organic solvents and ketone organic solvents. There is described a metallic base paint comprising a base paint comprising a diluent and a diluent (II) containing an aliphatic hydrocarbon organic solvent (E). According to such a composition, it is possible to form a coating film that is environmentally friendly and has an excellent finish that does not cause a phenomenon such as flaky unevenness or mottled unevenness, but it may be insufficient depending on the coating color and coating environment. There is still room for improvement.

  On the other hand, Patent Document 4 discloses a toner base containing an acrylic polyol, a cellulose resin, a polyester polyol and a pigment, a connector base containing at least one resin compatible with the resin contained in the toner base, and a solvent-based coating containing a diluent. Have been described. According to such a coating, not only has a good finish, but also the application range of the coating composition can be expanded depending on the composition and type of the connector base combined with the toner base.

  However, the coating described in Patent Document 4 contains an organic solvent that is a regulated object such as xylene, and in order to apply this to a composition corresponding to the recent environment, the organic solvent that is a regulated substance is changed to other substances. When replacing with organic solvents or reducing the VOC in the coating to make it highly solid, it is extremely difficult to suppress unevenness depending on the paint color such as gun metallic color (black iron color with gun-like luster). In addition, in order to eliminate this unevenness, a large number of times of coating is required, resulting in a problem that work efficiency is deteriorated.

JP 2000-178500 A JP 2002-129090 A JP 2006-152259 A JP-T-2004-513209

  An object of the present invention is to provide a multi-component base coat paint that can form a repair coating film having good coating workability, no unevenness, and color matching with an existing coating film, and a preparation using the base coat paint. It is to provide a color method and a repair coating method.

As a result of intensive studies to solve the above problems, the present inventors have divided the base coat paint into a metallic paint composition and a thickener composition containing a specific thickener, thereby providing a painting operation. The present inventors have found that it is possible to form a base coating film having excellent finishing properties and having excellent finishing properties that do not cause phenomena such as unevenness and modulation.
That is, the present invention
1.
A multi-component base coat paint comprising a combination of at least one metallic paint composition (I) and a thickener composition (II),
The metallic coating composition (I) contains a cellulose derivative (A1), an acrylic resin (B1), a polyester resin (C1), and a glitter pigment (D1).
The thickener composition (II) contains the cellulose derivative (A2), the acrylic resin (B2), the polyester resin (C2) and the thickener (E), and the thickener composition (II) in the thickener composition (II) Thickener (E) contains amide-based thickener (E1) and ethylene-vinyl acetate copolymer olefin-based thickener (E2) as a part of its components. Base coat paint,
2.
2. The multi-component base coat paint according to 1, wherein the cellulose derivative (A1) contained in the metallic paint composition (I) contains cellulose acetate butyrate and cellulose acetate butyrate-modified acrylic resin as a part of its components,
3.
The multi-component system according to claim 1 or 2, wherein the cellulose derivative (A2) contained in the thickener composition (II) contains cellulose acetate butyrate and cellulose acetate butyrate-modified acrylic resin as a part of the components. Base coat paint,
4).
The ratio of the amide-based thickener (E1) and the olefin-based thickener (E2) used is 95/5 to 5/95 in terms of the active ingredient mass ratio of the amide-based thickener (E1) / olefin-based thickener (E2). The multi-component base coat paint according to any one of items 1 to 3 within the range of
5.
The proportion of cellulose derivative (A2), acrylic resin (B2), and polyester resin (C2) used in the thickener composition (II) is based on the total solid content of (A2), (B2) and (C2). The multicomponent system according to any one of items 1 to 4, wherein (A2) is in the range of 5 to 75% by mass, (B2) is in the range of 5 to 90% by mass, and (C2) is in the range of 5 to 40% by mass. Base coat paint,
6).
The proportion of the metallic paint composition (I) and the thickener composition (II) used is 5 to 95 parts by weight of the thickener composition (II) with respect to 100 parts by weight of the metallic paint composition (I). The multi-component base coat paint according to any one of claims 1 to 5 ,
7).
7. The multi-component according to any one of 1 to 6 , further comprising at least one colored coating composition (III) in addition to the metallic coating composition (I) and the thickener composition (II). Base coat paint,
8).
Toning ratios of the metallic paint composition (I), the thickener composition (II) and the colored paint composition (III) to be prepared by the metallic paint composition (I) and the colored paint composition (III) The multi-component base coat paint according to 7 , wherein the thickener composition (II) is in the range of 5 to 95 parts by mass with respect to 100 parts by mass of the coating composition.
9.
A toning method for adjusting a coating color to a desired color using the base coat paint according to any one of items 1 to 8 ;
10.
The present invention relates to a repair coating method, characterized in that repair coating is performed using the base coat paint according to any one of items 1 to 8 .

  The base coat paint prepared by using the thickener composition used in the present invention has a very good painting workability and finish, and is coated with a paint color that is extremely difficult to suppress unevenness such as a gun metallic color. Even in this case, a coating film with little unevenness can be formed, so that a repair coating film having good color matching with an existing coating film can be easily formed. In addition, by configuring the base coat paint with a metallic paint composition and a thickener composition, it is possible to prepare an appropriate paint according to the coating environment, paint color, etc., as required, and to store at the painting site. The number of items can also be reduced.

The present invention is a multi-component base coat paint comprising a combination of at least one metallic paint composition (I) and a thickener composition (II).
≪Metallic paint composition (I) ≫
In the present invention, the metallic coating composition contains a cellulose derivative (A1), an acrylic resin (B1), a polyester resin (C1), and a glitter pigment (D1).

<Cellulose derivative (A1)>
In the present invention, the cellulose derivative (A1) is used to improve the drying property, adhesion property, and orientation of the glitter pigment of the coating film formed by the base coat paint of the present invention. Is contained as a compound. For example, a cellulose esterified product in which a hydroxyl group of cellulose is esterified with an acid such as fatty acid or nitric acid, and a polymerizable unsaturated group-containing cellulose esterified product obtained by introducing a polymerizable unsaturated group into the esterified product of cellulose. Examples thereof include modified cellulose esterified products obtained by reacting with unsaturated monomers.

  Examples of the esterified product of cellulose include nitrocellulose, cellulose acetate butyrate, cellulose acetate, and cellulose acetate propionate. Of these, cellulose acetate butyrate can be suitably used.

  Cellulose acetate butyrate is obtained by further butyl esterifying a partially acetylated product of cellulose. Preferably, the acetyl group content is generally 1 to 30% by weight and the butyl group content is generally 16 to 60% by weight. is there. Specifically, for example, “CAB-381-0.5”, “CAB-381-0.1”, “CAB-381-2.0”, “CAB-551-0.2”, “CAB-551”. -0.01 "," CAB-553-0.4 "," CAB-531-1 "," CAB-500-5 "," CAB-321-0.1 "(above, manufactured by Eastman Chemical Company, USA) , Product name).

  The number average molecular weight of the cellulose acetate butyrate is preferably in the range of 15,000 to 100,000, particularly 20,000 to 35,000. Within this range, while maintaining compatibility with the acrylic resin or the polyester resin, the uneven coating phenomenon and the uneven modulation phenomenon when the base coat coating composition of the present invention is applied are suppressed, and a coating film having a good finish is formed. be able to.

  In this specification, the number average molecular weight is a value obtained by converting the number average molecular weight measured with a gel permeation chromatograph (trade name, “HLC8120GPC” manufactured by Tosoh Corporation) based on the number average molecular weight of polystyrene. is there. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.

  In the present invention, the cellulose derivative (A1) includes cellulose acetate butyrate and / or a polymerizable unsaturated group-containing cellulose acetate butyrate obtained by introducing a polymerizable unsaturated group into the cellulose acetate butyrate and a polymerizable non-polymerizable group. It is desirable to use a modified cellulose acetate butyrate obtained by reacting a saturated monomer, and it is particularly desirable to use both in combination. By using these in combination, the compatibility of each resin contained in the metallic paint composition (I) and the thickener composition (II) described later is improved, and the finish of the coating film formed by the base coat paint is improved. Can be improved.

  Examples of the modified cellulose acetate butyrate include copolymerization of a polymerizable unsaturated group-containing cellulose acetate butyrate obtained by reacting cellulose acetate butyrate with an isocyanate group-containing polymerizable unsaturated monomer. Can be manufactured.

  As the polymerizable unsaturated monomer, any polymerizable monomer having an ethylenically unsaturated bond can be used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) Straight chain having 1 to 18 carbon atoms such as acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.) Or containing branched hydrocarbon groups Polymerizable unsaturated monomer to be polymerized; polymerizable unsaturated monomer having a cycloalkyl group such as cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate; isobornyl ( Polymerizable unsaturated monomers having an isobornyl group such as meth) acrylate; polymerizable unsaturated monomers having an adamantyl group such as adamantyl (meth) acrylate; aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene; -Acryloyloxyethyl) acid phosphate, (2-methacryloyloxyethyl) acid phosphate, (2-acryloyloxypropyl) acid phosphate, (2-methacryloyloxypropyl) ) Phosphoric acid group-containing polymerizable unsaturated monomers such as acid phosphate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meta ) C2-C8 hydroxyalkyl (meth) acrylate such as acrylate, allyl alcohol, (meth) acrylate having hydroxyl group such as ε-caprolactone modified form of the above C2-C8 hydroxyalkyl (meth) acrylate; molecular terminal is hydroxyl group Hydroxyl group-containing polymerizable unsaturated monomers such as (meth) acrylate having a polyoxyethylene chain; carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid, and β-carboxyethyl acrylate; Methoxysila Alkoxysilyl group-containing polymerizable unsaturated monomers such as vinyl triethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane Perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; polymerizable unsaturated monomers having a fluorinated alkyl group such as fluoroolefin; glycidyl (meth) acrylate; β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexyl Epoxy group-containing polymerizable unsaturated monomers such as pill (meth) acrylate and allyl glycidyl ether; polymerizable unsaturated monomers having a photopolymerizable functional group such as maleimide group; 1,2,2,6,6-pentamethylpiperidyl (Meth) acrylate, 2,2,2,6,6-tetramethylpiperidinyl (meth) acrylate, etc .; vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate; ) Acrylonitrile and the like; Amide group-containing polymerizable unsaturated monomers such as (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate Amino group-containing polymerizable unsaturated monomers such as adducts of glycidyl (meth) acrylate and amines; 2- (methacryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium bromide, methacryloylaminopropyl Quaternary grades such as trimethylammonium chloride, methacryloylaminopropyltrimethylammonium bromide, tetrabutylammonium (meth) acrylate, tetramethylammonium (meth) acrylate, trimethylbenzylammonium (meth) acrylate, 2- (methacryloyloxy) ethyltrimethylammonium dimethyl phosphate Ammonium base-containing polymerizable unsaturated monomer; polyoxyalkyl having a molecular terminal alkoxy group (Meth) acrylate having a ren chain; 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, sodium styrene sulfonate, sulfoethyl methacrylate and its polymerizable salt having a sulfonic acid group such as sodium salt or ammonium salt thereof Saturated monomer: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc. These carbonyl group-containing polymerizable unsaturated monomers can be used, and these can be used alone or in combination of two or more.

  Examples of isocyanate group-containing polymerizable unsaturated monomers for introducing polymerizable unsaturated groups into cellulose acetate butyrate include isocyanato such as isocyanatoethyl acrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate. A group-containing vinyl monomer or a product obtained by addition reaction of a diisocyanate and the above-mentioned hydroxyl group-containing polymerizable unsaturated monomer can be used.

  The copolymerization reaction of the polymerizable unsaturated monomer and the polymerizable unsaturated group-containing cellulose acetate butyrate can be performed by a solution polymerization method or the like in the presence of a radical polymerization initiator such as an organic peroxide.

  In the modified cellulose acetate butyrate, the use ratio of the polymerizable unsaturated monomer / cellulose acetate butyrate is preferably within the range of 5/95 to 95/5, preferably 10/90 to 90/10. .

  In the case where cellulose acetate butyrate and modified cellulose acetate butyrate are used in combination, the ratio of cellulose acetate butyrate used is 1/99 to 99/1, preferably 30/70, in terms of cellulose acetate butyrate / modified cellulose acetate butyrate solids mass ratio. It is preferable to be within the range of ~ 70/30.

  In this specification, solid content means a non-volatile component in a sample, and the solid content concentration is a residue obtained by leaving 3 grams of a sample in a dryer at 105 ° C. for 3 hours to dry. It can be a mass fraction.

<Acrylic resin (B1)>
In the present invention, the acrylic resin (B1) is a component that can be used mainly as a film-forming component and also as a pigment-dispersed resin for metallic pigments. A polymerizable unsaturated monomer is used as a polymerization initiator in the presence of an organic solvent. Examples thereof include resins obtained by copolymerization.

  As such a polymerizable unsaturated monomer, it can be used by appropriately selecting from the monomers listed in the description of the cellulose derivative (A1).

  As the polymerization initiator used in the production of the acrylic resin (B1) in the present invention, conventionally known polymerization initiators used in the solution polymerization method can be used without limitation. For example, benzoyl peroxide, octanoyl peroxide, lauroyl peroxide can be used. Examples thereof include organic peroxides such as oxide and stearoyl peroxide; azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). These can be used alone or in combination of two or more.

  The acrylic resin (B1) obtained as described above has a weight average molecular weight in the range of 5,000 to 80,000, preferably 6,000 to 70,000, from the viewpoints of adhesion of the formed coating film and pigment dispersibility. The solid content hydroxyl value is 150 mgKOH / g or less, preferably 50 to 120 mgKOH.

  In this specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on 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” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.

<Polyester resin (C1)>
In the present invention, examples of the polyester resin (C1) include resins that can be obtained by copolymerizing a polybasic acid and a polyhydric alcohol as main components according to a conventional method. Examples of the polybasic acid include adipic acid, succinic acid, isophthalic acid, terephthalic acid, phthalic anhydride, maleic anhydride, trimellitic acid, hexahydrophthalic anhydride, sodium 5-sulfoisophthalate, and the like. Examples thereof include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, pentaerythritol, and sorbitol. Furthermore, monobasic acids such as dehydrated castor oil fatty acid, linseed oil fatty acid, soybean oil fatty acid and tol oil fatty acid, benzoic acid, and fats and oils can be used as a copolymerization component.

  According to the base coat paint of the present invention, by containing the polyester resin (C1), the adhesion of the coating film formed by applying the base coat paint of the present invention, in particular, a curing agent from a clear paint containing a curing agent. The penetration of the components can be promoted, and the adhesion with the clear coating film can be improved.

  The polyester resin (C1) has a weight average molecular weight in the range of 5,000 to 100,000, preferably 10,000 to 70,000, and a hydroxyl value of 5 to 150 mgKOH from the viewpoint of adhesion of the formed coating film. / G, preferably in the range of 10 to 130 mg KOH / g.

<Darkness pigment (D1)>
In the present invention, the glitter pigment (D1) is a pigment that reflects received light and gives gloss to the coating film, and any pigment known in the paint field can be used without limitation. For example, aluminum powder, copper, Metal powders such as zinc and brass, metal flakes such as stainless steel flakes, mica, micacious iron oxide (MIO, flaky iron oxide), glass flakes, aluminum oxide coated with titanium oxide and iron oxide, titanium oxide and oxide One type or two or more types selected from the group such as mica coated with iron can be mentioned.

<Manufacture of metallic paint composition (I)>
In the present invention, the ratio of the cellulose derivative (A1), the acrylic resin (B1), and the polyester resin (C1) contained in the metallic coating composition (I) is the total solid content of (A1), (B1), and (C1). As a reference, (A1) is 5 to 75% by mass, preferably 10 to 60% by mass,
(B1) is 5 to 90% by mass, preferably 10 to 60% by mass,
It is preferable that (C1) is in the range of 5 to 40% by mass, preferably 5 to 30% by mass, from the viewpoint of the hardness and adhesion of the finally obtained base coating film.

  Further, the blending amount of the glitter pigment (D1) is in the range of 1 to 60% by mass, preferably 2 to 55% by mass, based on the resin solid mass in the metallic paint composition (I). Is preferred.

  The metallic coating composition (I) may further include an organic solvent, a pigment other than the bright pigment, an ultraviolet absorber, a light stabilizer, an antioxidant, a surface conditioner, a pigment dispersant, and a thickener as necessary. , Paint additives such as curing catalysts can be blended.

  Among these, examples of the organic solvent include organic compounds having a molecular weight in the range of 58 to 220, particularly 72 to 200, and those known in the paint field can be used without limitation. An organic solvent capable of dissolving the resin contained in (I), in particular the cellulose derivative (A1), and compatibilizing each resin, is preferred. Specifically, an ester organic solvent and a ketone organic It is desirable to use at least one organic solvent selected from solvents.

  Examples of such ester organic solvents include ethyl acetate, butyl acetate, isobutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate. , Diethylene glycol monoethyl ether acetate and the like, and examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl isoamyl ketone, diisobutyl ketone, methyl hexyl ketone, and isophorone. It can be used alone or in combination of two or more.

  The use amount of at least one organic solvent selected from the ester organic solvent and the ketone organic solvent is 5% by mass or more, particularly 20% by mass or more in the total organic solvent contained in the metallic coating composition (I). It is desirable to be.

  In the present invention, other organic solvents other than the ester organic solvents and ketone organic solvents include n-butane, n-hexane, n-heptane, n-pentane, n-octane, n-nonane, n-decane, linear alkanes such as n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane; 2-methylbutane, 2,2-dimethylpropane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethyl Pentane, 2,2,4-trimethylpentane, 3,4-diethylhexane, 2,6-dimethyloctane, 3,3-di Tyloctane, 3,5-dimethyloctane, 4,4-dimethyloctane, 3-ethyl-3-methylheptane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2-methylundecane, 3-methylundecane Branched alkanes such as 2,2,4,6,6-pentamethylheptane; cyclopentane, t-decalin, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1 , 4-dimethylcyclohexane, propylcyclohexane, isopropylcyclohexane, 1,2-methylethylcyclohexane, 1,3-methylethylcyclohexane, 1,4-methylethylcyclohexane, 1,2,3-trimethylcyclohexane, 1,2 Aliphatic hydrocarbon organic solvents such as cyclic alkanes such as 4-trimethylcyclohexane and 1,3,5-trimethylcyclohexane; aromatic hydrocarbon organic solvents such as toluene and xylene; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Mono n-propyl ether, diethylene glycol monoisopropyl ether, Diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene Ether organic solvents such as glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol monoisopropyl ether, methanol, isopropanol, tert-butanol, secondary butanol, isobutanol, n-butanol, 2-ethylhexanol, n-Octanol, Ben Can be exemplified an alcohol-based organic solvents such as alcohol, it may be used within a range that does not impair the performance of the coating film formed of the coating environment and the base coat paint of the present invention.

  In the present invention, a composition containing toluene and xylene is not excluded, but it is desirable to keep the total content of toluene and xylene in the metallic coating composition (I) below 1% by mass in consideration of the environment.

  Examples of pigments other than the glitter pigment (D1) blended as necessary include pigments such as colored pigments and extender pigments that are usually used in the paint field. Specific examples of coloring pigments include white pigments such as titanium oxide; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and aniline black; yellow iron oxide, titanium yellow, monoazo yellow, and condensation Yellow pigments such as azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow; orange pigments such as permanent orange; red iron oxide, naphthol AS azo red, ansan Red pigments such as throne, anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyrrolopyrrole, watching red, permanent red; cobalt purple, quinacridone violet, dioxadi Purple pigments such as violet; blue pigments such as cobalt blue, phthalocyanine blue, and selenium blue; green pigments such as phthalocyanine green; and the like as extender pigments such as zinc powder, barita powder, precipitated barium sulfate, and carbonic acid Examples thereof include barium, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, mica powder, and the like.

  Further, the metallic paint composition (I) may contain a thickener in order to suppress pigment sedimentation in the storage stage and to obtain stable coating workability.

  As the thickener, a thickener known in the paint field can be used, and the same thickener as described later (E) can also be used. As the content of the thickener contained in the metallic paint composition (I), the amount of the active ingredient of the thickener is generally 30% by mass or less based on the resin solid content contained in the metallic paint composition (I). A range of 0.5 to 10% by mass is preferable.

  A preferable solid content concentration in the storage state of the metallic coating composition (I) is generally 80% by mass or less, preferably 1 to 50% by mass.

<Thickener composition (II)>
In the present invention, the thickener composition (II) is used to improve the coating workability of the base coat paint of the present invention, and to form a coating film having a good finish with little influence of fukimura, modrimura, etc. It is blended with respect to the composition (I).

  The said thickener composition (II) is a component containing a cellulose derivative (A2), an acrylic resin (B2), a polyester resin (C2), and a thickener (E).

<Cellulose derivative (A2)>
The cellulose derivative (A2) can be appropriately selected from the compounds described in the section of the cellulose derivative (A1) in the metallic coating composition (I).

  In addition, the cellulose derivative (A2) contained in the thickener composition (II) contains cellulose acetate butyrate and / or cellulose acetate butyrate-modified acrylic resin as a part of its components, preferably using both in combination. Containing it suppresses metallic unevenness of the finally formed coating film, which is suitable.

  Such cellulose acetate butyrate can be appropriately selected from the compounds described in the section of cellulose acetate butyrate in the metallic paint composition (I), and the number average molecular weight is as follows. It is preferably lower than the cellulose acetate butyrate contained in), and is preferably in the range of 5,000 to 100,000, particularly 15,000 to 30,000. Within this range, it is possible to form a coating film with good finish with little unevenness without excessively increasing the viscosity of the base coat coating composition of the present invention.

  In the present invention, when the thickener composition (II) contains cellulose acetate butyrate and cellulose acetate butyrate-modified acrylic resin, the proportion of both used is cellulose acetate butyrate / cellulose acetate butyrate-modified acrylic resin solid mass It is preferable that the ratio is in the range of 1/99 to 99/1, preferably 30/70 to 70/30, since the viscosity of the base coat paint does not increase excessively and the occurrence of unevenness is suppressed.

<Acrylic resin (B2)>
The acrylic resin (B2) contained in the thickener composition (II) can be used by appropriately selecting from the resins described in the section of the acrylic resin (B1) in the metallic coating composition (I).

  In particular, the weight average molecular weight of the acrylic resin (B2) contained in the thickener composition (II) is suitably lower than that of the acrylic resin (B1) contained in the metallic paint composition (I). It is preferable to be in the range of 000 to 20,000, preferably 6,000 to 10,000. Within this range, it is possible to form a coating film with good finish with little unevenness without excessively increasing the viscosity of the base coat coating composition of the present invention.

  The acrylic resin (B2) has a solid content hydroxyl value of 120 mgKOH / g or less, preferably 50 to 100 mgKOH / g, from the viewpoint of adhesion of the base coat film.

<Polyester resin (C2)>
The polyester resin (C2) contained in the thickener composition (II) can be used by appropriately selecting from the resins described in the section of the polyester resin (C1) in the metallic paint composition (I).

<Thickener (E)>
In the present invention, the thickener composition (II) mixed with the metallic paint composition (I) contains the thickener (E), so that the viscosity of the paint can be effectively increased when the shear rate is low. It can act on the improvement of uneven coating of the film, and is characterized by containing an amide-based thickener (E1) as a part of its components.

  As such an amide-based thickener, those conventionally known in the paint field can be used without limitation, and the synthesis method, materials used, etc. are not particularly limited, and commercially available products can also be used. .

  Specifically, fatty acid monoamides synthesized by dehydration of fatty acid ammonium salts or ammonolysis of fats and oils (esters); condensation reaction of fatty acid amide and formaldehyde, heat condensation reaction of monocarboxylic acid and diamine, or dibasic acid and monoamine Fatty acid diamide (bisamide) synthesized by heat condensation reaction with diamine; obtained by polycondensation of dibasic acid and diamine, polycondensation of diamine derivative and dibasic acid, dimerization of diamine and dibasic acid derivative or unsaturated fatty acid And fatty acid polyamides obtained by polycondensation of dimer acid or ring-opening polymerization of lactam.

  Such an amide thickener may be diluted with a diluent medium such as an organic solvent, and the content of the active ingredient (component other than the diluent medium) of the amide thickener (E1) is increased. 0.1 to 15% by mass, preferably 0.1 to 5% by mass, based on the total solid content of components (A2), (B2) and (C2) contained in the adhesive composition (II) It is desirable to be in

  Further, as the thickener (E) contained in the thickener composition (II), in addition to the amide thickener (E1), an olefin thickener (E2) may be included in the orientation of the glitter pigment. It is suitable because it can improve the workability and improve the coating workability of the paint of the present invention.

  The olefin-based thickener (E2) is other than the amide-based thickener, and is a polyolefin homopolymer or copolymer, such as polyethylene, acid-modified polyethylene, polypropylene, ethylene / α-olefin copolymer. , Ethylene / α-olefin / non-conjugated diene copolymer, ethylene / non-conjugated diene copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid ester copolymer, ethylene / vinyl acetate copolymer, An ethylene-maleic acid copolymer, a propylene-butene copolymer, etc. are mentioned.

  The olefin-based thickener (E2) may be diluted with a diluent medium such as an organic solvent, and the content of the active ingredient (component other than the diluent medium) may be the thickener composition (II). In the range of 20% by mass or less, preferably 10% by mass or less, based on the total solid content of the components (A2), (B2) and (C2) contained in

The use ratio of the amide-based thickener (E1) and the olefin-based thickener (E2) in the thickener (E) is amide-based thickener (E1) / olefin-based thickener (E2) active ingredient mass. A ratio of 95/5 to 5/95, preferably 70/30 to 30/70, is desirable because the viscosity of the base coat paint can be moderated.
<Thickener composition (II)>
In the present invention, the use ratio of the cellulose derivative (A2), the acrylic resin (B2), and the polyester resin (C2) contained in the thickener composition (II) can be appropriately adjusted and is not particularly limited. In general, (A2), (B2) and (C2) are generally 5 to 75% by weight, preferably 10 to 60% by weight, based on the total solid content.
(B2) is 5 to 90% by mass, preferably 10 to 60% by mass.
It is suitable that (C2) is in the range of 5 to 40% by mass, preferably 5 to 30% by mass.

If the amount of (A2) in the thickener composition (II) is too large, the viscosity of the base coat paint will increase too much, and conversely if it is too small, the base coat coating film tends to become uneven.
If the amount of (B2) is too large, unevenness of the base coat film tends to occur, and conversely if too small, the viscosity of the base coat paint may increase too much.
If the amount of (C2) is too large, the mottling phenomenon may be likely to occur. Conversely, if the amount is too small, the coating performance such as adhesion after water immersion may be insufficient.

  In the present invention, the thickener composition (II) further includes an organic solvent, a pigment, an ultraviolet absorber, a light stabilizer, an antioxidant, a surface conditioner, a pigment dispersant, a curing catalyst, and the like, if necessary. Paint additives can be blended.

  Among these, the organic solvent can be appropriately selected from the organic solvents exemplified in the section of the metallic coating composition (I).

  The total amount of the ester organic solvent and the ketone organic solvent used in the thickener composition (II) is 5% by mass or more, particularly 20% by mass or more, based on the total organic solvent contained in the thickener composition (II). It is desirable that the total content of toluene and xylene in the thickener composition (II) is less than 1% by mass in the thickener composition (II).

  Further, when the thickener composition (II) contains a glitter pigment, the content thereof is lower than that of the metallic paint composition (I), preferably a clear composition which is substantially free of pigment. The specific bright pigment content is less than 2% by mass, preferably less than 1% by mass, based on the solid content of the resin contained in the thickener composition (II).

  The preferable solid content concentration in the storage state of the thickener composition (II) obtained as described above is generally 10 to 80% by mass, preferably 10 to 50% by mass.

<Base coat paint>
In the present invention, at least one metallic paint composition (I) and thickener composition (II) are stored separately, and both are mixed immediately before painting to produce a base coat paint and then applied.

  In the present specification, the term “immediately before painting” may include, for example, up to 3 hours before painting.

  The ratio of the metallic paint composition (I) and the thickener composition (II) used at this time varies depending on the coating environment and the desired appearance, but is generally based on 100 parts by weight of the metallic paint composition (I). The thickener composition (II) can be in the range of 5 to 95 parts by mass, preferably 5 to 50 parts by mass.

  The present invention also provides a multi-component base coat paint obtained by further combining at least one colored paint composition (III) in addition to the metallic paint composition (I) and the thickener composition (II). can do.

  That is, the thickener composition (II) in the present invention is not only mixed with the metallic coating composition (I) alone, but also at least one metallic coating composition (I) and at least one colored coating composition ( III) can be mixed to obtain a base coat paint, which is also extremely effective for a toning paint that is toned with a paint color that tends to cause uneven coating.

  The colored paint composition (III) here is a paint mainly composed of a colored pigment as a pigment, and the colored pigment can be appropriately selected from those described in the section of the metallic paint composition (I). If necessary, extender pigments may be used in combination.

  In this case, the metallic paint composition (I), the thickener composition (II), and the colored paint composition (III) are used according to the metallic paint composition (I) and the colored paint composition (III). The thickener composition (II) can be in the range of 5 to 95 parts by weight, preferably 5 to 50 parts by weight, with respect to 100 parts by weight of the toned coating composition.

  The base coat paint of the present invention may further contain a curing agent such as a polyisocyanate curing agent, a blocked isocyanate curing agent, or a melamine curing agent, if necessary, and the coating composition contains the above curing agent. In some cases, depending on the type of curing agent, it can be included in any of component (I), component (II) or component (III), or can be set separately as a curing agent component.

<Paint>
The base coat paint of the present invention can be applied by a known coating means such as spray coating, electrostatic coating, brush coating, roller coating after adjusting to a viscosity suitable for coating with dilution thinner as required. It is preferable to perform spray coating in view of the finished appearance.

  When coating is performed a plurality of times, steps such as flash-off (after coating is allowed to stand at room temperature), air blow, preheating, etc. may be provided between the coatings as necessary.

  Drying after the application of the base coat paint is completed is not particularly limited, and may be in an undried state when a top clear described later is applied. When drying for repair coating applications, it is preferable to dry for 5 to 60 minutes at a temperature of 20 to 100 ° C., for example. The film thickness can be appropriately adjusted according to the state of the surface to be coated, but generally a dry film thickness of 5 to 100 μm, particularly 10 to 60 μm is suitable.

  As the coated surface to be applied, a conventionally known substrate surface and a coating surface provided on the substrate can be exemplified, and the substrate is not particularly limited. Metals such as aluminum; Organic base materials such as plastics; Inorganic base materials such as concrete and wood; and the coating film provided on the base material is not particularly limited. A multilayer coating film formed from a base coating film and a top clear coating film formed from a colored base coating, and a primer coating film, an electrodeposition coating film, an intermediate coating film, etc. under the base coating film These coatings may be provided as appropriate.

  Further, since the base coat paint of the present invention can adjust the orientation of the glitter pigment and has excellent color matching with the target paint color, it is used as a repair paint for the coating film already formed on the coated surface. Is preferred. In this case, the surface to be coated can be previously treated with a putty, a primer surfacer or the like. Further, after the base coat paint is applied, a top clear paint may be applied on the paint film.

  As such a top clear coating, conventionally known ones can be used without any particular limitation. For example, acrylic resins or fluororesins containing a crosslinkable functional group such as a hydroxyl group are used as the main ingredients, and block polyisocyanates, polyisocyanates, melamine resins, etc. are cured. A curable paint contained as an agent or a lacquer paint mainly composed of cellulose acetate butyrate-modified acrylic resin can be suitably used. Further, if necessary, pigments, fiber derivatives, additive resins, UV absorbers Further, paint additives such as a light stabilizer, a surface conditioner, and a curing catalyst can be contained.

  The clear paint is preferably dried at a temperature of 20 to 100 ° C., preferably 40 to 100 ° C., for 5 to 60 minutes. The film thickness can be appropriately adjusted according to the state of the surface to be coated, but generally a dry film thickness of 5 to 100 μm, particularly 10 to 60 μm is suitable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to only these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

<Production of polyester resin solution>
Production Example 1
The following components were charged into a 4 liter reactor equipped with a reflux condenser equipped with a heating device, a thermometer, a stirrer, a rectifying column and a water separator, heated to 160 ° C., and heated from 160 ° C. to 230 ° C. over 3 hours. The temperature was raised to ° C.
Hexahydrophthalic anhydride 29.7 parts Adipic acid 25.4 parts Neopentyl glycol 5.3 parts 1,6-hexanediol 39.6 parts This was kept at 230 ° C. for 1 hour to produce condensed water (7.4 parts) Was distilled off using a rectification column. Subsequently, 5 parts of xylene was added, xylene and condensed water were refluxed, and water was removed using a water separator. Two hours after the addition of xylene, the acid value was measured, and when the acid value became 2 mgKOH / g or less, the pressure was reduced and xylene was distilled off almost completely. Thereafter, the mixture was cooled to 120 ° C. and diluted with butyl acetate to a solid content of 70% to obtain a butyl acetate solution of a polyester resin having a weight average molecular weight of 20,000 and a resin hydroxyl value of 32 mgKOH / g.

<Manufacture of acrylic resin solution>
Production Example 2
A reactor having a capacity of 4 liters equipped with a thermometer, a stirrer, a reflux condenser and a dropping pump was charged with 68 parts of butyl acetate, heated to 110 ° C. with stirring, and mixed with the following monomer mixture and polymerization initiator: Was added dropwise at a constant rate at 110 ° C. over about 3 hours.
Isobutyl methacrylate 59.75 parts Methyl methacrylate 10 parts “Isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.) 10 parts 2-hydroxyethyl acrylate 19 parts dimethylaminoethyl methacrylate 1 part methacrylic acid 0.25 parts Azobis (2,4-dimethyl) Valeronitrile) After completion of 0.2 part dropping, the temperature was kept at 110 ° C. for 1 hour and stirring was continued. Then, 0.5 parts of azobisdimethylvaleronitrile dissolved in 14 parts of butyl acetate as an additional catalyst was added dropwise at a constant rate over 1 hour. After completion of the dropwise addition, the reaction was terminated by maintaining at 110 ° C. for 1 hour, diluted with butyl acetate, an acrylic resin solution (A with a solid content of 49%, a weight average molecular weight of 50,000, and a resin hydroxyl value of 92 mgKOH / g) -1) was obtained.

Production Example 3
A reactor having a capacity of 4 liters equipped with a thermometer, a stirrer, a reflux condenser and a dropping pump was charged with 68 parts of butyl acetate, heated to 110 ° C. with stirring, and mixed with the following monomer mixture and polymerization initiator: Was added dropwise at a constant rate at 110 ° C. over about 3 hours.
Isobutyl methacrylate 59.75 parts Methyl methacrylate 10 parts “Isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.) 10 parts 2-hydroxyethyl acrylate 19 parts dimethylaminoethyl methacrylate 1 part methacrylic acid 0.25 parts Azobis (2,4-dimethyl) 4.8 parts of valeronitrile) After completion of dropping, the mixture was kept at 110 ° C. for 1 hour and stirring was continued. Then, 0.5 parts of azobisdimethylvaleronitrile dissolved in 14 parts of butyl acetate as an additional catalyst was added dropwise at a constant rate over 1 hour. Then, after completion of the dropwise addition, the reaction was terminated by maintaining at 110 ° C. for 1 hour and diluted with butyl acetate to obtain an acrylic resin solution having a solid content of 60.0%, a weight average molecular weight of 9,100, and a resin hydroxyl value of 92 mgKOH / g. A-2) was obtained.

<Manufacture of acrylic resin solution for pigment dispersion>
Production Example 4
A reactor equipped with a thermometer, a stirrer, a reflux condenser and a dropping pump was charged with 68 parts of butyl acetate, heated to 110 ° C. while stirring, and a mixture of the following monomer mixture and polymerization initiator was added at 110 ° C. At a constant rate over about 3 hours.
Isobutyl methacrylate 59.75 parts Methyl methacrylate 10 parts n-Butyl acrylate 10 parts Dimethylaminoethyl methacrylate 1 part 2-Hydroxyethyl methacrylate 19 parts Methacrylic acid 0.25 part t-Butylperoxy-2-ethylhexanoate 2.5 After completion of the dropwise addition, the temperature was kept at 110 ° C. for 1 hour and stirring was continued. Then, 0.5 parts of azobisdimethylvaleronitrile dissolved in 14 parts of butyl acetate as an additional catalyst was added dropwise at a constant rate over 1 hour. And after completion | finish of dripping, it hold | maintains at 110 degreeC for 1 hour, complete | finishes reaction, It dilutes with butyl acetate, Acrylic resin solution whose solid content is 60.0%, weight average molecular weight is 18,000, and resin hydroxyl value is 92 mgKOH / g (A-3) was obtained.

<Production of CAB graft acrylic resin solution>
Production Example 5
The following components were charged into a 4 liter reactor equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel, heated in a nitrogen gas atmosphere, and heated to 110 ° C. over about 4 hours.
Butyl acetate 600 parts “CAB-381-0.5” (Note 1) 200 parts After heating to 110 ° C., after confirming that “CAB-381-0.5” (Note 1) was completely dissolved, Heating was stopped and 133 parts of butyl acetate were distilled off under reduced pressure. The temperature in the reactor was 87 ° C. While maintaining this temperature, 11.1 parts of a 90% butyl acetate solution of an equimolar addition reaction product of isophorone diisocyanate and 2-hydroxyethyl acrylate, 0.02 part of pt-butylcatechol as a polymerization inhibitor, and urethane Dibutyltin dilaurate (0.02 part) was added to the reactor as a catalyst, and aged at 87 ° C. for 7 hours under dry air to obtain an unsaturated group-containing cellulose acetate butyrate solution. Next, the reaction temperature was raised to 115 ° C., and a mixed solution of the following polymerizable unsaturated monomer and polymerization initiator was added dropwise over 2 hours under a nitrogen atmosphere.
Butyl acetate 130 parts Methyl methacrylate 58.2 parts t-Butylperoxy-2-ethylhexanoate 2 parts After completion of dropwise addition, 0.5 part t-butylperoxy-2-ethylhexanoate, 20 parts butyl acetate Was added dropwise over 1 hour and aged at 115 ° C. for 1 hour in a nitrogen atmosphere. A CAB graft acrylic resin solution having a solid content of 30% was obtained.
(Note 1) “CAB-381-0.5”: trade name, manufactured by Eastman Chemical Co., Ltd., cellulose acetate butyrate, butyl group content 38%, number average molecular weight 30,000.
<Creation of metallic base paint>
Production Example 6
In the composition shown in Table 1, “Aluminum paste 96-0636” (trade name, manufactured by Toyo Aluminum Co., Ltd., aluminum content 70%) and the 49% acrylic resin solution obtained in Production Example 2 were added to the reaction vessel and dispersed with stirring. 40% “CAB551-0.2” solution (Note 2), 70% polyester resin solution obtained in Production Example 1 and 30% CAB graft acrylic resin solution obtained in Production Example 5, respectively, Butyl acetate was added in the formulation shown in the same table and stirred with a disper for about 20 minutes to prepare a metallic base paint (I-1).

Production Examples 7-8
Metallic base paints (I-2) to (I-3) were obtained in the same manner as in Production Example 6 except that the formulation composition in Table 1 was changed to Table 1.

(Note 2) 25% “CAB551-0.2” solution: “CAB551-0.2” (trade name, manufactured by Eastman Chemical Co., Ltd., cellulose acetate butyrate, butyl group content 55%, number average molecular weight 30,000) ) Was adjusted to a 25% solids solution with butyl acetate.
<Manufacture of color base paint>
Production Example 9
In Production Example 6, a black color base paint (II-1) was obtained in the same manner as in Production Example 6 except that the composition was as shown in Table 2.

<Manufacture of pigment dispersion paste>
Production Example 10
The 60% acrylic resin solution (A-3) obtained in Production Example 4 was blended in the blending amounts shown in Table 3 below, and “R5000U-3” (Note 4), “BYK-161” (Note 5), acetic acid Butyl was added in the formulation shown in Table 3, stirred for about 20 minutes with a disper, and then dispersed with a sand mill to obtain a 38% pigment dispersion paste.

(Note 4) “R5000U-3”: trade name, manufactured by Ciba Special Chemicals, carbon black,
(Note 5) “BYK-161”: trade name, manufactured by BYK-chemie, pigment dispersant, active ingredient 30%.

<Creation of thickener composition>
Production Examples 11 to 22
Each component was mix | blended with the mixing | blending composition of Table 4 at reaction container, and it stirred for about 20 minutes with the disper, and created the rheocon clears (IV-1)-(IV-12).

(Note 6) 40% “CAB551-0.01” solution: “CAB551-0.01” (trade name, manufactured by Eastman Chemical Co., Ltd., cellulose acetate butyrate, 55% butyl group content, number average molecular weight 16,000 ) Was adjusted to a 40% solids solution with butyl acetate.
(Note 7) “HPA-202N”: trade name, manufactured by Nagase Sangyo Co., Ltd., fatty acid amide, 20% active ingredient,
(Note 8) “Disparon 6900-20X” trade name, manufactured by Enomoto Kasei Co., Ltd., fatty acid polyamide, 20% active ingredient,
(Note 9) “CERATIX 8466”: trade name, manufactured by BYK-chemie, ethylene vinyl acetate copolymer, active ingredient 6%,
(Note 10) “Disparon 4200-10”: trade name, manufactured by Enomoto Kasei Co., Ltd., polyethylene wax, 10% active ingredient,
(Note 11) “BYK-410”: trade name, manufactured by BYK-chemie, urea / urethane compound, active ingredient 52%.

<Manufacture of base coat paint composition>
Example 1
30 parts by mass of Rheo Conc Clear (IV-1) with respect to 100 parts by mass of the metallic metallic toning paint prepared by 50 parts by mass of the metallic base paint (I-1) and 50 parts by mass of the color base paint (II-1) Were mixed and stirred to obtain a coating composition.

Examples 2-14 and Comparative Examples 1-10
A coating composition was obtained in the same manner as in Example 1 except that the blending composition was as shown in Table 5 in Example 1. In Example 3, it is a silver paint color that does not contain a color base paint.

<Paint>
“Letan PG Hybrid Eco-Filler” (trade name, Kansai Paint, Urethane-based Plasaf) was coated on the tin plate to a dry film thickness of 40 μm, dried at 60 ° C. for 30 minutes, and then with # 400 water-resistant abrasive paper Polished. On top of this, each of the coating compositions adjusted in the above Examples and Comparative Examples was spray-coated so that the dry film thickness was 30 μm, dried at 20 ° C. for 10 minutes, and then the clear coating (Note 12) on the coating surface. Was spray-coated to a dry film thickness of 40 μm and dried at a temperature of 60 ° C. for 20 minutes to obtain a test coated plate. The following performance test was performed on the test coating plate before and after applying the clear paint. The results are shown in Table 4.
(Note 12) Clear paint: “Letane PG Multiclear HX (Q) Base” (Kansai Paint Co., Ltd., hydroxyl group-containing acrylic resin-containing clear paint) 100 parts by weight “Letane PG Multiclear HX Standard Curing Agent” (Kansai A paint product (50 parts by weight of (hexamethylene diisocyanate-based curing agent) added) was diluted with a “PG hybrid thinner” for 13 to 14 seconds (Ford Cup # 4/25 ° C.) and adjusted to viscosity.
(* 1) Blowing unevenness
The orientation state of the pigment in the coating film of the test coating plate before applying the clear paint (Note 12) was visually observed. The results were evaluated as follows.
A: No unevenness,
○: Slight unevenness but practical level,
Δ: Slightly uneven,
X: Unevenness is remarkable.
(* 2) Modimura
The orientation state of the pigment in the coating film of the test coating plate coated with the clear paint (Note 12) and dried was visually observed. The results were evaluated as follows.
A: No unevenness,
○: Slight unevenness but practical level,
Δ: Slightly uneven,
X: Unevenness is remarkable.
(* 3) Coating workability The ease with which the coating composition produced in the examples and comparative examples was spread by spraying was evaluated according to the following criteria.
A: The paint spreads evenly on the workpiece immediately after spraying, and the coating surface state is very good.
◯: Immediately after spraying, the paint spreads evenly on the object to be coated, and the coating surface state is good.
Δ: The paint is slightly difficult to spread on the workpiece immediately after spraying, and the coating surface state is slightly poor.
X: The paint is difficult to spread on the object immediately after spraying, and the coating surface state is poor.

Claims (10)

A multi-component base coat paint comprising a combination of at least one metallic paint composition (I) and a thickener composition (II),
The metallic coating composition (I) contains a cellulose derivative (A1), an acrylic resin (B1), a polyester resin (C1), and a glitter pigment (D1).
The thickener composition (II) contains the cellulose derivative (A2), the acrylic resin (B2), the polyester resin (C2) and the thickener (E), and the thickener composition (II) in the thickener composition (II) Thickener (E) contains amide-based thickener (E1) and ethylene-vinyl acetate copolymer olefin-based thickener (E2) as a part of its components. Base coat paint. The multi-component base coat paint according to claim 1, wherein the cellulose derivative (A1) contained in the metallic paint composition (I) contains cellulose acetate butyrate and cellulose acetate butyrate-modified acrylic resin as part of its components. The multi-component system according to claim 1 or 2, wherein the cellulose derivative (A2) contained in the thickener composition (II) contains cellulose acetate butyrate and cellulose acetate butyrate-modified acrylic resin as part of its components. Base coat paint. The ratio of the amide-based thickener (E1) and the olefin-based thickener (E2) used is 95/5 to 5/95 in terms of the active ingredient mass ratio of the amide-based thickener (E1) / olefin-based thickener (E2). The multi-component base coat paint according to any one of claims 1 to 3, which falls within the range. The proportion of cellulose derivative (A2), acrylic resin (B2), and polyester resin (C2) used in the thickener composition (II) is based on the total solid content of (A2), (B2) and (C2). The multicomponent system according to any one of claims 1 to 4 , wherein (A2) is in the range of 5 to 75 mass%, (B2) is in the range of 5 to 90 mass%, and (C2) is in the range of 5 to 40 mass%. Base coat paint. The proportion of the metallic paint composition (I) and the thickener composition (II) used is 5 to 95 parts by weight of the thickener composition (II) with respect to 100 parts by weight of the metallic paint composition (I). The multi-component base coat paint according to any one of claims 1 to 5 , which falls within a range. The multicomponent according to any one of claims 1 to 6 , further comprising at least one colored coating composition (III) in addition to the metallic coating composition (I) and the thickener composition (II). Base coat paint. Toning ratios of the metallic paint composition (I), the thickener composition (II) and the colored paint composition (III) to be prepared by the metallic paint composition (I) and the colored paint composition (III) The multi-component base coat paint according to claim 7 , wherein the thickener composition (II) is in the range of 5 to 95 parts by mass with respect to 100 parts by mass of the coating composition. A toning method for adjusting a coating color to a desired color using the base coat paint according to any one of claims 1 to 8 . A repair coating method comprising performing repair coating using the base coat paint according to any one of claims 1 to 8 .