JP6497700B2 - Aqueous coloring base coating composition - Google Patents

Description

  The present invention relates to a water-based coloring base coating composition used for repair coating of an existing coating film such as an automobile body.

  In recent years, from the viewpoint of environmental protection, water-based paints are also required in the paint field. Compared to other organic solvents for paints, water has a unique property that it has a high boiling point for its low molecular weight and has a high surface tension and dielectric constant. These factors greatly affect the paint workability of water-based paints. Water-based paints are generally poorer in workability than organic solvent-based paints, and it is known that the resulting coatings are not likely to have high gloss. ing.

  As a measure for improving the paint workability of the aqueous paint and the finish of the formed coating film, for example, a method of improving the resin for paint used in the aqueous paint is generally performed.

  However, in the field of automotive repair coating, the coating environment such as temperature and humidity varies greatly depending on the repair coating site, and it is difficult to obtain a stable finished appearance by using a water-based paint that is greatly affected by the coating environment that fluctuates from time to time. It is said that.

  With respect to such problems, Patent Document 1 includes a water-based paint containing an organic solvent having a specific HLB value, so that the workability of painting is good and the finish of the formed coating film is not affected by the painting environment. It is described that it becomes good.

  By the way, in the top coating process in automotive repair coating, a base coating for repair with a similar color that has the same appearance as the existing coating film is applied to the ground-treated surface with a putty, primer surfacer, etc. in multiple steps. It is common to paint. And it is often performed that air blow is performed with compressed air as needed between each coating to speed the drying of each top-coated colored base coating film.

  When the water-based paint described in Patent Document 1 is used as a top coat colored base paint for repairing and one coat and one air blow are applied in stages, the familiarity of the dried paint film and the applied colored base paint is not sufficient. The coated film obtained after completion of the top coating process sometimes had skin roughness or unevenness.

  On the other hand, in Patent Documents 2 to 3, a water-based coating composition is composed of a main agent component (I), a viscosity modifier component (II) and a viscosity modifier component (III). It is described that a coating film having no defects such as can be obtained.

  According to these patent documents, a coating film having no defects is obtained even when the aqueous coating composition is continuously applied wet-on-wet, and the repair coating process can be greatly simplified. Even if a drying process is provided between the paintings, slight roughness or unevenness is observed in the formed coating film, and it cannot be said that it has reached the purpose of reproducing the color tone of the existing coating film, and is still improved. There is room for.

JP-A-2005-213274 JP 2001-316612 A International Publication WO2013 / 002121 Pamphlet

  An object of the present invention is to propose an aqueous colored base coating composition that is suitable for forming a repair coating film that does not feel uncomfortable with a colored coating film such as an existing colored coating film of an automobile body.

  As a result of intensive studies on the above-mentioned problems, the inventors of the present invention have improved coating compatibility in stage coating by including an organopolysiloxane compound in the diluent used in the aqueous coloring base coating composition used for repair coating. As a result, the present invention has been found.

That is, the present invention
A multi-component aqueous coloring base coating composition for preparing an aqueous coloring base coating composition by mixing the main component (I) and the diluent component (II) immediately before coating,
A multi-component aqueous coloring characterized in that the main component (I) contains an aqueous resin component, a coloring pigment and water, and the diluent component (II) contains a polyether-modified silicone compound, a viscosity modifier and water. The present invention relates to a base coating composition and a repair coating method using the composition.

  According to the multi-component water-based coloring base coating composition comprising the diluent component according to the present invention as a constituent, it has excellent workability in coating, good conformability in repeated coating, and rough skin. It is possible to obtain a colored base coating film that has no unevenness and has a highly finished appearance that does not feel uncomfortable with the existing coating film.

  The aqueous coloring base coating composition of the present invention is a multi-component composition obtained by combining the main component (I) and the diluent component (II).

  The main component (I) in the present invention includes an aqueous resin component, a color pigment, and water.

  Examples of the aqueous resin component include those dispersed in an aqueous medium such as acrylic resin emulsion, polyester emulsion, epoxy resin emulsion, polyurethane resin emulsion, or water-soluble acrylic resin, water-soluble polyester resin, water-soluble epoxy resin, water-soluble polyurethane resin, etc. Examples thereof include those dissolved in an aqueous medium.

  In the present invention, the aqueous resin component preferably contains an acrylic resin emulsion.

<Acrylic resin emulsion>
In the present invention, the acrylic resin emulsion comprises a (meth) acryloyl group-containing polymerizable unsaturated monomer as an essential component, and a copolymer obtained by copolymerizing other polymerizable unsaturated monomer as necessary. It is.

  Specifically, the average particle size of the acrylic resin emulsion is 0.01 to 1.0 μm, preferably 0.05 to 0.5 μm.

  In this specification, the average particle diameter of the acrylic resin emulsion and the urethane resin emulsion described later is a value of a volume average particle diameter measured by a Coulter counter method at a measurement temperature of 20 ° C. The measurement by the Coulter counter method can be performed using, for example, “COULTER N4 type” (trade name, manufactured by Beckman Coulter, Inc.).

  As such an acrylic resin emulsion, for example, those obtained by emulsion polymerization of the polymerizable unsaturated monomer component in the presence of water and a dispersion stabilizer in one step or in multiple steps using a polymerization initiator are suitable. Can be used for

  In the present invention, the acrylic resin emulsion may be a single-layer type or a multi-layer type such as a core-shell type, but a single-layer type is suitable from the viewpoint of coating compatibility.

  Examples of the polymerizable unsaturated monomer that can be a copolymer component of the acrylic resin emulsion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, Cycloaliphatic alkyl (meth) acrylates such as isobornyl (meth) acrylate; Aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxy ester Alkoxyalkyl (meth) acrylate such as ru (meth) acrylate; Perfluoroalkyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylate such as N, N-diethylaminoethyl (meth) acrylate; Acrylamide; (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1, 1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate , Polyallyl compounds having at least two polymerizable unsaturated groups in one molecule, such as diallyl terephthalate and divinylbenzene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxyalkyl (meth) acrylate such as loxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, ε-caprolactone modified product of the above hydroxyalkyl (meth) acrylate, containing polyoxyethylene chain whose molecular terminal is a hydroxyl group Hydroxyl group-containing polymerizable unsaturated monomers such as (meth) acrylate; carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate; (meth) acrolein, formylstyrol, C4-C7 vinyl alkyl ketone (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyethyl (meth) acrylate, acetoacetoxyallyl ester, diacetone Carbonyl group-containing polymerizable unsaturated monomers such as meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) ) Epoxy group-containing polymerizable unsaturated monomers such as acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether; isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc. Isocyanato group-containing polymerizable unsaturated monomers: vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane Alkoxysilyl group-containing polymerizable unsaturated monomers such as epoxy; epoxy group-containing polymerizable unsaturated monomers or reaction products of hydroxyl group-containing polymerizable unsaturated monomers and unsaturated fatty acids, dicyclopentenyloxyethyl (meth) acrylate, di Examples thereof include oxidatively curable group-containing polymerizable unsaturated monomers such as cyclopentenyloxypropyl (meth) acrylate and dicyclopentenyl (meth) acrylate, and these can be used alone or in combination of two or more.

  In addition, the dispersion stabilizer used when the acrylic resin emulsion is emulsion-polymerized is not particularly limited. For example, sodium dialkylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, polyoxyethylene alkylphenyl ether Anionic emulsifiers such as sodium sulfate and sodium alkyldiphenyl ether disulfonate, nonionic emulsifiers such as polyoxyethylene higher alcohol ether and polyoxyethylene alkylphenyl ether, and anionic or cationic reactive emulsifiers having radically polymerizable double bonds Can be mentioned.

  A reactive emulsifier is an emulsifier having both a nonionic group, an anionic group and a cationic group in the molecule and a polymerizable unsaturated group. Specific examples of the polymerizable unsaturated group include: (Meth) allyl group, (meth) acryloyl group, propenyl group, butenyl group etc. are mentioned. Commercially available products include “Latemuru” (trade name, manufactured by Kao Corporation), “Eleminol” (trade name, manufactured by Sanyo Chemical Co., Ltd.), “Aquaron” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Adekaria soap” (trade name, manufactured by Asahi Denka Co., Ltd.), “ANTOX” (trade name, manufactured by Nippon Emulsifier Co., Ltd.) and the like can be mentioned.

  As the polymerization initiator, conventionally known polymerization initiators can be used without limitation. For example, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butyl Peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxide) Oxy) hexane, diisopropylbenzene peroxide, tert-butylcumylperoxy Id, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-amyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate Peroxide polymerization initiators such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane and tert-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyrate) Nitrile), 2,2′-azobis-2-methylbutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2′-azobis (2-methylbutyronitrile), 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis (4-cyanovaleric ), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'- Azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], dimethyl 2,2'-azobis (2-methylpropionate), 1,1'-azobis (1-cyclohexane-1-carbonitrile ), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], dimethyl-2,2′-azobisisobutyrate, and the like.

  In the present invention, the acrylic resin emulsion contained in the main ingredient component (I) contains a polyvinyl compound having at least two polymerizable unsaturated groups in one molecule as a copolymerization component. It is suitable from the viewpoint of safety and sharpness.

  Examples of the polyvinyl compound having at least two polymerizable unsaturated groups in one molecule include the compounds exemplified above, and they can be used alone or in combination of two or more thereof. , Based on the mass of the total polymerizable unsaturated monomer used in the production of the acrylic resin emulsion, 0.1 to 10% by mass, preferably 0.5 to 5%.

  In addition, the acrylic resin emulsion preferably has a solid content acid value of 5 mgKOH / g or less, preferably 4 mgKOH / g or less, from the viewpoint of the water resistance of the colored base coating film and the coating compatibility.

  The aqueous resin component preferably includes a urethane resin emulsion from the viewpoint of the water-resistant adhesion of the colored base coating film.

  As such a urethane resin emulsion, those known in the art can be used without limitation, for example, a resin obtained by dispersing a urethane prepolymer obtained by reacting polyisocyanate, polyol and carboxyl group-containing diol in water. An emulsion can be mentioned.

  Examples of polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; burette-type adducts and isocyanurate ring adducts of these diisocyanate compounds; isophorone diisocyanate, 4,4 '-Methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or-2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate Alicyclic diisocyanate compounds such as 1,3-cyclopentane diisocyanate and 1,2-cyclohexane diisocyanate; Turret type adduct, isocyanurate ring adduct; 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 isocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, Aromatic diisocyanate compounds such as bis (4-isocyanatophenyl) sulfone and isopropylidenebis (4-phenylisocyanate); these diisocyanates -Burelet type adduct, isocyanurate ring adduct; triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-tri Polyisocyanate compounds having three or more isocyanate groups in one molecule such as isocyanatotoluene and 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate; burettes of these polyisocyanate compounds Type adducts, isocyanurate cycloadducts; ethylene glycol, propylene glycol, 1,4-butylene glycol, dimethylolpropionic acid, polyalkylene glycol, trimethylolpropane, hexanetriol and other isocyanate groups in excess of hydroxyl groups At a ratio of polyiso Urethane adduct obtained by reacting a Aneto compound; these urethane adducts of views - let type adducts can include an isocyanurate ring adducts.

  Examples of the polyol include polyether polyols such as polyethylene glycol, polypropylene glycol, polyethylene-propylene (block or random) glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol; dicarboxylic acid (adipic acid Succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, etc.) and glycol (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5) -Polycondensation polyols with pentanediol, neopentyl glycol, bishydroxymethylcyclohexane, etc., such as polyethylene adipate, polybutylene adipate, poly Polyester polyols such as xamethylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene / butylene adipate, polyneopentyl / hexyl adipate; polycaprolactone polyol, poly-3-methylvalerolactone polyol; polycarbonate polyol; ethylene Glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, octanediol, tricyclodecane dimethylol, hydrogenated bisphenol A, cyclohexane di Low molecular weight glycols such as methanol and 1,6 hexanediol; and the like. It is possible to use Te.

  Examples of the carboxyl group-containing diol include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutyric acid.

  The urethane prepolymer can be produced based on a conventionally known method.

  The urethane resin emulsion may be neutralized with a neutralizing agent. The neutralizing agent is not particularly limited as long as it can neutralize the carboxyl group. For example, sodium hydroxide, potassium hydroxide, trimethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol , Triethylamine, ammonia and the like.

  The urethane resin emulsion preferably has a cyclic structure in the molecule because it has good sharpening properties of the colored base coating film.

  More preferably, it is suitable that the polyisocyanate constituting the urethane resin emulsion contains a compound derived from an alicyclic diisocyanate compound as a part of the component.

  In addition, the urethane resin emulsion has a solid content acid value of 20 mgKOH / g or less, preferably in the range of 5 to 18 mgKOH / g, from the viewpoint of the water resistance of the colored base coating film and the coating compatibility. .

  In addition, in this specification, solid content means a non-volatile content, means the residue remove | excluding volatile components, such as water and an organic solvent, from a sample, and multiplies the mass of a sample by solid content concentration. Can be calculated. The solid content concentration can be measured by dividing the mass of a residue obtained by drying about 3 grams of a sample at 105 ° C. for 3 hours by the mass before drying, and it may be expressed as 100 fraction.

  As an average particle diameter of the said urethane resin emulsion (A), it can exist in the range of 0.01-1 micrometer, especially 0.05-0.5 micrometer.

  The aqueous resin component preferably further contains a water-soluble acrylic resin. In the present specification, the water-soluble acrylic resin includes, for example, a polymerizable unsaturated monomer component containing an acid group-containing polymerizable unsaturated monomer, a hydroxyl group-containing polymerizable unsaturated monomer, and other polymerizable unsaturated monomers, a hydrophilic organic solvent. And a resin obtained by polymerizing with a polymerization initiator in the presence of.

  Examples of the acid group-containing polymerizable unsaturated monomer include carboxyl group-containing polymerizable unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and β-carboxyethyl acrylate; 2-acrylamide-2- Sulfonic acid group-containing polymerizable unsaturated monomers such as methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid sodium salt, sulfoethyl methacrylate and its sodium salt and ammonium salt; 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl Examples thereof include phosphoric acid group-containing polymerizable unsaturated monomers such as acid phosphate, 2-acryloyloxypropyl acid phosphate, and 2-methacryloyloxypropyl acid phosphate. It can be used in combination or more.

  In particular, the combined use of a carboxyl group-containing polymerizable unsaturated monomer and a phosphoric acid group-containing polymerizable unsaturated monomer as an acid group-containing polymerizable unsaturated monomer improves the compatibility when the composition of the present invention is applied repeatedly. There is.

  Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like having 2 to 2 carbon atoms. Eight hydroxyalkyl (meth) acrylates; N-methylolacrylamide; allyl alcohol; ε-caprolactone-modified acrylic monomers of hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms; diethylene glycol (meth) acrylate, triethylene glycol (meta ) Acrylate, polyethylene glycol (meth) acrylate, dipropylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, polypropylene glycol (meth) Acrylates, polyalkylene glycol (meth) acrylate and polyethylene polypropylene glycol (meth) acrylate and the like, which may be used in combination one or more.

  Examples of the other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl. (Meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate (Lauryl (meth) acrylate), tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate Alkyl, cycloalkyl (meth) acrylates such as benzoate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate; Aromatic ring-containing polymerizable unsaturated monomers such as benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meta ) Polymerizable unsaturated monomer having an alkoxysilyl group such as acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, Perfluoroalkyl (meth) acrylates such as fluorooctylethyl (meth) acrylate; Polymerizable unsaturated monomers having fluorinated alkyl groups such as fluoroolefins; Polymerizable unsaturated monomers having photopolymerizable functional groups such as maleimide groups Vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate; allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meta ) Acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc. Polymerizable unsaturated monomer having at least two saturated groups in one molecule; (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) a Relate, N, N-dimethylaminopropyl (meth) acrylamide, nitrogen-containing polymerizable unsaturated monomers such as adducts of glycidyl (meth) acrylate and amines; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate Epoxy group-containing polymerizable unsaturated monomers such as 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether Isocyanato group-containing polymerizable unsaturated monomer such as 2-isocyanatoethyl (meth) acrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate; has a polyoxyethylene chain whose molecular terminal is an alkoxy group (me ) Acrylate; 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. And carbonyl group-containing polymerizable unsaturated monomers. These polymerizable unsaturated monomers can be used alone or in combination of two or more.

  Moreover, as for the said water-soluble acrylic resin, it is desirable to neutralize an acid group with a neutralizing agent. Examples of the neutralizing agent include the compounds exemplified above.

  The water-soluble acrylic resin generally has a solid content acid value of 5 to 150 mgKOH / g, preferably 10 to 100 mgKOH / g, a solid content hydroxyl value of 10 to 150 mgKOH / g, preferably 20 to 100 mgKOH / g, and a weight average molecular weight. Is in the range of 5,000 to 10,000, preferably 8,000 to 70,000.

  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.

  The number average molecular weight is a value obtained by converting the number average molecular weight measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the number 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 name) These were carried out under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.

  The hydrophilic organic solvent used in the polymerization is not strictly distinguished, but examples thereof include organic solvents that dissolve at least 20 g in 100 g of water at 20 ° C., and specifically include methanol, ethanol, isopropanol. Alcohol organic solvents such as n-butanol and isobutanol; ether organic solvents such as dioxane and tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene Ethylene glycol ether organic solvents such as glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono tert-butyl ether; diethylene Diethylene glycol ether organic solvents such as recall 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 ether organic solvents such as propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol monoisopropyl ether; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono -Dipropylene glycol ether organic solvents such as propyl ether and dipropylene glycol monoisopropyl ether; and ester organic solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and 3-methoxybutyl acetate. Two or more types can be used in combination.

  When using the said water-soluble acrylic resin, as the compounding quantity, it can exist in the range of 1-30 mass% in the resin solid content contained in main ingredient component (I), Preferably it is in the range of 1-20 mass%. .

  In the present invention, conventionally known color pigments can be used without particular limitation. Specific examples thereof include metal oxide pigments such as titanium oxide and iron oxide, composite metal oxide pigments such as titanium yellow, carbon black, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, and perinones. Pigments, benzimidazolone pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, indigo pigments, etc .; aluminum (evaporation) (Including aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, glass flake, hologram pigment, etc. Pigments: clay, kaolin, barium sulfate, barium carbonate, potassium carbonate Siumu, talc, silica, extender pigments such as alumina white; and the like. These may be used alone or in combination depending on the color or coating film performance and its object.

  Further, when the glitter pigment is used, its shape is not particularly limited. For example, a flake shape is preferable, and it is hydrogen that it is dispersed and coated with a treatment agent containing a phosphate group or a sulfonate group. This is preferable from the viewpoint of suppressing gas generation. Conventionally known low molecular weight compounds and copolymers can be applied to the phosphoric acid group or sulfonic acid group-containing treatment agent without any particular limitation.

  Further, as the glitter pigment, it is desirable to use aluminum flakes coated with silica. This is because a coating film having a stable metallic appearance can be obtained.

  As the silica-coated aluminum pigment, commercially available products such as “Hydrolan series” (trade name, manufactured by Ecart Co.) and “Alpaste EMR series” (trade name, manufactured by Toyo Aluminum Co., Ltd.) can be used.

  The blending amount of the color pigment varies depending on the pigment used depending on the intended coating color, but is generally within the range of 0.1 to 300 parts by mass with respect to 100 parts by mass of the total solid content of the resin contained in the main component. It is preferable that it is within the range of 0.5 to 200 parts by mass, more preferably from the viewpoint of coating stability.

≪Main ingredient component (I) ≫
In the present invention, when the aqueous resin component contains an acrylic resin emulsion and a urethane resin emulsion, the total amount of both is 50% by mass or more, preferably 80% by mass or more in the resin solid content contained in the main component (I). It is preferable from the viewpoint of initial adhesion and water resistance of the colored base coating film.

  The acrylic resin emulsion and the urethane resin emulsion are used in a ratio of 95/5 to 5/95, preferably 80/20 to 20/80 in terms of the solid mass ratio of the acrylic resin emulsion / urethane resin emulsion. It is suitable from the viewpoint of water resistance adhesion of the coating film.

  The main component (I) is a pigment other than a color pigment; a viscosity modifier, a pigment dispersant, an ultraviolet absorber, a light stabilizer, polymer fine particles, a dispersion aid, an antiseptic, a silane coupling agent, an antifoaming agent, and a curing agent. Other components such as a catalyst, an organic solvent, a neutralizing agent, and the like, which are usually used in the preparation of an aqueous paint, may be included.

  In the present invention, the main component (I) can be stably stored, and the aqueous colored base coating composition obtained by mixing with the diluent component (II) described below has a good finished appearance with no occurrence of unevenness or sagging. The main component (I) contains a viscosity modifier so that a coating film can be formed.

  As the viscosity modifier, conventionally known ones can be used without limitation. Specifically, polyacrylic acid viscosity modifiers such as polyacrylic acid soda, polyacrylic acid- (meth) acrylic acid ester copolymer; Polyether-based viscosity modifiers such as pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, polyether epoxy modified products; urethane-associated viscosity modifiers; montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, Inorganic viscosity modifiers such as mica and bentonite; Fibrin derivative viscosity modifiers such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; Protein viscosity modifiers such as casein, sodium caseinate, and ammonium caseinate; Alginate-based viscosity modifiers such as sodium formate; Polyvinyl-based viscosity modifiers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl benzyl ether copolymers; Maleic anhydride copolymers such as partial esters of vinyl methyl ether-maleic anhydride copolymers Polymer system viscosity modifiers; Polyamide viscosity modifiers such as polyamide amine salts.

  Among these, a polyacrylic acid viscosity modifier is good from the viewpoint of the orientation of the color pigment in the colored base coating film.

  The active component acid value of the polyacrylic acid viscosity modifier may be, for example, 30 to 350 mg / KOH, preferably more than 100 and 300 mg / KOH or less. Commercially available products include, for example, “Primal ASE60”, “Primal TT615”, “Primal RM5” (trade name) manufactured by Rohm and Haas, “SN thickener 613”, “SN thickener 618”, “manufactured by San Nopco” SN thickener 630 "," SN thickener 634 "," SN thickener 636 "(above, trade name) and the like.

  In this specification, an active ingredient means the residue remove | excluding diluents, such as water and an organic solvent, from a sample.

  As a compounding quantity of a polyacrylic-acid type viscosity modifier, it is 0.5-20 mass% on the basis of resin solid content contained in main ingredient component (I), Preferably it is about 1-10 mass%.

  The solid content concentration of the main component (I) is generally adjusted in the range of 10 to 50% by mass, preferably 15 to 40% by mass, from the viewpoint of coating workability and concealing property and finished appearance. Yes.

  The viscosity of the main component (I) is not particularly limited, but is preferably 100 to 3000 mPa · sec, in view of storage stability and miscibility with the diluent component (II) described later. Can be in the range of 600-2000 mPa · sec.

  In the present specification, the viscosity is a value measured at a rotational speed of 60 rpm using a viscometer digital bismetholone viscometer VDA type (manufactured by Shibaura System Co., Ltd.) within 10 minutes after the sample is prepared at 25 ° C. To do.

≪Diluent component (II) ≫
In the present invention, the diluent component (II) includes a polyether-modified silicone compound, a viscosity modifier, and water.

  In the present invention, by mixing the diluent component (II) with the main component (I) immediately before coating, the rheological properties of the aqueous coloring base coating composition can be controlled according to the coating environment. By configuring the colored base coating composition in this way, the storage stability of each component is maintained, there is no sagging, no unevenness is generated, and the colored base coating composition is excellent in finished appearance with good conformability. A film can be formed.

  Examples of such polyether-modified silicone compounds include compounds in which a polyether chain is introduced at the terminal and / or side chain of polysiloxane, and the epoxy group other than the polyether chain, amino group, (meth) It may be a co-modified silicone compound in which introduction of an organic group such as an acryloyl group is used in combination.

  Examples of the polyether-modified silicone compound include KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015. , KF-6004, X-22-4272, X-22-4952, X-22-6266, X-22-3667, X-22-4741, X-22-3939A, X-22-3908A [more; Shin-Etsu Manufactured by Chemical Industry Co., Ltd.], BYK-018, BYK-019, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-028, BYK-300, BYK-302, BYK- 306, BYK-320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, B K-375, BYK-377, BYK-UV3510, BYK-307, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-3455, BYK-UV3500, BYKUV3530 ( Above; manufactured by Big Chemie), SILWET L-77, SILWET L-720, SILWET L-7001, SILWET L-7002, SILWET L-7604, SILWET Y-7006, SILWET FZ-2101, SILWETFZ-2104, FZ-2105, SILWET FZ-2110, SILWET FZ-2118, SILWET FZ-2120, SILWET FZ-2122, SILWETFF-2123, SILWET FZ-2130, SILWET FZ- 154, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2163, SILWET FZ-2164, SILWET FZ-2166, SILWET FZ-2191, SILWET FZ-2203, SILWET FZ-2207, SILWET 2208, SILWET 2208, SILWET 2208 SILWET Y-7499, SILWET FZ-3789, SF8472, BY16-004, SF8428, SH3771, SH3746, BY16-036, SH3749, SH3748, SH8400, SF8410 (or more; Toray Dow Corning Silicone Co., Ltd.), L032 Commercially available products such as L051, L066 [above; manufactured by Asahi Kasei Wacker Silicone Co., Ltd.] can be used. It can be combined.

  As the viscosity modifier that can be contained in the diluent component (II), it can be appropriately selected from those exemplified in the description of the viscosity modifier contained in the main agent component (I).

  In the present invention, an inorganic viscosity modifier is suitable for the diluent component (II).

  As such inorganic viscosity modifiers, those known in the art can be used without limitation, and examples thereof include minerals such as layered silicates, and these can be natural, synthetic, or processed products. May be. Specific examples include montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, mica and bentonite. These may be diluted with a diluting medium such as an organic solvent or water.

  “Bentone 27”, “Bentone 34”, “Bentone 38”, “Bentone SD-1”, “Bentone SD-2”, “Bentone SD-3”, “Bentone 52”, “Bentone 57” (all above) (Rheox, trade name), “Tixogel VP”, “Tixogel TE”, “Tixogel UN”, “Tixogel EZ100”, “Tixogel MP100”, “Tixogel MP250” (all of which are made by Sud Chemical) , “Craytone 40”, “Craytone 34”, “Claytone HT”, “Claytone APA”, “Claytone AF”, “Claytone HY” (all of which are Southern) manufactured by lay Products, trade name), "Laponite RD", "LaponiteRDS", "Laponite HW", "Laponite EP", "Laponite S482", "Laponite OG", "Laponite LV" , Product name) and the like.

As the proportion of polyether-modified silicone compound, viscosity modifier, and water used in the diluent component (II),
The polyether-modified silicone compound is 0.01 to 10.0% by weight, preferably 0.05 to 5.0% by weight, based on the weight of the diluent component (II).
The viscosity modifier is 0.1 to 3.0% by mass, preferably 0.3 to 2.0% by mass.
It is appropriate that the water content is in the range of 60 to 99.9% by mass, preferably 70 to 99.5% by mass.

  The diluent component (II) can contain a polyol compound having a polyalkylene skeleton for improving the storage stability of the diluent component (II).

  Examples of the polyol compound having a polyalkylene skeleton include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, polyethylene oxide, polypropylene oxide, and ethylene oxide / propylene. Polyalkylene polyol having at least one structure of block or random copolymerization of oxide; trimethylol ethane, trimethylol propane, polytrimethylol propane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, poly Polyalcohol such as tetramethylene glycol A polyhydric alcohol having a polyalkylene skeleton modified with lene; a condensation product of the polyalkylene polyol and a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid, etc. A certain polyester polyol; a caprolactone-modified polyol obtained by modifying a polyether polyol with caprolactone; and the like.

  The weight average molecular weight of the polyol compound having a polyalkylene skeleton is desirably in the range of 100 to 10,000, preferably 400 to 5,000.

  Moreover, as the usage-amount of the polyol which has the said polyalkylene frame | skeleton, 50-1000 mass parts on the basis of 100 mass parts as an active ingredient mass of the inorganic type thickener contained in diluent component (II), Preferably 100- It is desirable from the viewpoint of the water resistance of the metallic base coating film to be in the range of 500 parts by mass.

  The diluent component (II) is an aqueous resin, ultraviolet absorber, light stabilizer, polymer fine particle, surface conditioner, dispersion aid, preservative, silane coupling agent, antifoaming agent, curing catalyst, organic solvent, medium It may contain other components such as paint additives that are usually used in the preparation of water-based paints such as a compatibilizer.

  Among these, as the organic solvent, a hydrophilic solvent is suitable because it has an effect of further improving the coating compatibility with the polyether-modified silicone compound.

  Examples of the hydrophilic organic solvent include alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ether solvents such as dioxane and 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 mono Isopropyl ether, diethylene glycol Ethylene glycol ether solvents such as rumono 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 Propylene glycol ether solvents such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol monoisopropyl ether; ethyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, etc. And ester solvents, which are used alone or And use can be used.

The hydrophilic organic solvent that can be contained in the diluent component (II) preferably contains a propylene glycol ether solvent.
The amount of the hydrophilic solvent used is 0.1 to 50.0% by mass, preferably 0.5 to 30.0% by mass based on the mass of the diluent component (II). It is desirable to be able to suppress unevenness.

  The viscosity of the diluent component (II) described above is not particularly limited, but is 10 to 300 mPa · sec from the viewpoint of storage stability and miscibility with the main component (II). Preferably, it can be in the range of 10 to 100 mPa · sec.

<Particle component (III)>
The aqueous colored base coating composition of the present invention is a metallic base coating composition containing a glitter pigment, and further includes a particle component (III) in addition to the main component (I) and diluent component (II). A multi-component system in combination, that is, a three-component system may be used.

  And it is preferable that this particle | grain component (III) contains a silica particle and water from viewpoints, such as the glittering feeling of a colored base coating film formed, and a transparent feeling.

  Examples of such silica particles include finely divided silica, colloidal silica, and the like. “Syloid” series (trade name, manufactured by Grace Japan), “AEROSIL” series (trade name, manufactured by Nippon Aerosil Co., Ltd.), “ACEMATT” series (Trade name, manufactured by DEGUSSA), "Silicia" series, "Silo Hovic" series, "Syrosphere" series (above, product name, manufactured by Fuji Silysia Chemical Ltd.) "Quartron" series (trade name, Fuso “Fine Seal” series (trade name, manufactured by Tokuyama Corporation) “NIPSIL” series (trade name, manufactured by Tosoh Silica Corporation), “Mizukasil” series (trade name, Mizusawa Chemical Etc.).

  The average particle diameter of the silica particles is preferably in the range of 0.1 to 25 μm and 0.5 to 10 μm because the difference in glitter and unevenness due to the thickness of the colored base coating film is suppressed, which is preferable.

  In this specification, the average particle diameter of the silica particles is a volume-based average particle diameter (D50), which is a value of 50% of the particle size distribution measured by a laser diffraction particle size distribution measuring device.

  The effective component content of the silica particles in the particle component (III) is 1 to 50% by mass, preferably 3 to 40% by mass based on the mass of the particle component (III).

  The particle component (III) preferably contains an aqueous resin in addition to the silica particles. When the particle component (III) contains an aqueous resin, there is an effect that the storage stability of the particle component (III) is improved.

  As the aqueous resin, conventionally known resins can be used without limitation, but it is preferable to use a urethane resin emulsion and an acrylic resin emulsion. As the urethane resin emulsion and the acrylic resin emulsion, suitable resin emulsions can be used from those listed in the description of the urethane resin emulsion and the acrylic resin emulsion contained in the main component (I).

  The solid content of the aqueous resin when the particle component (III) contains an aqueous resin is 1 to 300 parts by mass, preferably 10 to 200 parts by mass, based on 100 parts by mass of silica particles. Is suitable.

If the amount of the aqueous resin contained in the particle component (III) is too large, the viscosity of the aqueous colored base paint becomes high, and stirring may be difficult when the components (I) to (III) are mixed.
When the particle component (III) includes a urethane resin emulsion and an acrylic resin emulsion, the ratio is 5/95 to 95/5, preferably 30/70 to 70/30, as a solid content ratio of urethane resin emulsion / acrylic resin emulsion. It is desirable to be within the range.

  When the urethane resin emulsion is less than this range, the initial adhesion of the colored base coating film is inferior. On the other hand, when it is too much, the viscosity of the paint becomes high and stirring may be difficult at the time of preparing the paint.

  The particle component (III) preferably contains a viscosity modifier as a part of the component. Thereby, there exists an effect that the miscibility with the main ingredient component (I) and diluent component (II) is favorable, and the colored base coating film excellent in glitter is obtained.

  The viscosity modifier is not particularly limited, and can be appropriately selected from those exemplified in the description of the viscosity modifier contained in the main component (I). Use of an agent is suitable from the viewpoint of the storage stability of the particle component (III).

  The effective component content of the viscosity modifier in the particle component (III) is 0.1 to 20% by mass, preferably 0.1 to 10% by mass, based on the mass of the particle component (III). is there.

  The particle component (III) preferably contains a polyether-modified silicone compound. This is because there is an effect on the coating compatibility when the aqueous colored base coating composition is applied a plurality of times.

  Such a polyether-modified silicone compound can be used by appropriately selecting from the compounds listed in the description of the diluent component (II).

  The polyether-modified silicone compound is used in the range of 0.5 to 40% by mass, preferably 2.0 to 20% by mass, based on the mass of silica particles. Suitable from

  Moreover, it is suitable that the particle component (III) contains an organic solvent. This is from the viewpoint of the storage stability of the particle component (III). In addition, the spout of the container for storing the particle component (III) may have a silica film caused by silica particles, which causes a problem in the film-forming property of the coating film with the aqueous colored base paint. In some cases, the phenomenon is improved when the particle component (III) contains an organic solvent.

  As the organic solvent, a conventionally known organic solvent can be used. In particular, in the present invention, a hydroxyl group-containing organic solvent having a boiling point of 150 ° C. or lower and a water solubility of 10 or higher is preferable.

  Examples of such solvents include alcohol organic solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol, methoxypropanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol Ethylene glycol ether organic solvents such as monoisopropyl ether; propylene glycol ether organic solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether; These can be used alone or in combination of two or more.

  The content of the organic solvent in the particle component (III) is preferably 1 to 300% by mass, and more preferably 10 to 200% by mass, based on the mass of the silica particles.

  The particle component (III) includes water-based paints such as particles other than silica particles, water, UV absorbers, light stabilizers, dispersion aids, preservatives, silane coupling agents, antifoaming agents, curing catalysts, and neutralizing agents. Other components such as paint additives usually used in the preparation may be included.

  The viscosity of the particle component (III) is not particularly limited, but from the viewpoint of storage stability of the particle component (III) and coating workability of the aqueous colored base coating composition, 10 to 2000 mPa · sec, Preferably it can exist in the range of 10-1000 mPa * sec.

≪Water-based coloring base paint composition≫
In the present invention, the main component (I), the diluent component (II) and the particle component (III) used as necessary are stored separately, and the painter stirs and mixes each component immediately before painting. Then, the aqueous colored base coating composition of the present invention can be prepared by adjusting the viscosity with water or the like as necessary. In the present specification, the term “immediately before painting” cannot be generally defined by a painter or a painting site, but can include, for example, up to three hours before painting.

The mass ratio of the main component (I) and the diluent component (II) in the aqueous colored base coating composition can be appropriately adjusted depending on the coating environment and the like. Generally, the diluent is based on 100 parts by mass of the main component (I). The component (II) is in the range of 30 to 400 parts by mass, preferably in the range of 40 to 350 parts by mass, or the mass ratio of the main component (I), diluent component (II) and particle component (III) is generally the main component ( I) Diluent component (II) is 30 to 400 parts by weight, preferably 40 to 350 parts by weight, and particle component (III) is 0.01 to 105 parts by weight, 0.1 to 50 parts by weight, based on 100 parts by weight. In view of the appearance of the colored base coating film and the physical properties of the coating film, it is preferably within the range of 1 to 35 parts by mass.

  In the present invention, if necessary, curing agents such as polyisocyanate curing agent, block isocyanate curing agent, melamine curing agent, oxazoline curing agent, carbodiimide curing agent are used as the main component (I), diluent component (II) and particles. It can be included in any of the components (III) or used as a separate component.

  The solid content concentration of the aqueous colored base coating composition of the present invention obtained as described above is generally within the range of 5 to 50% by mass, preferably 10 to 40% by mass, and the coating workability and the concealing property and the finish. Suitable from the viewpoint of appearance.

  The viscosity of the aqueous colored base coating composition at the time of coating is not particularly limited, but the coating workability is within the range of 50 to 800 mPa · sec, preferably 100 to 600 mPa · sec. It is good and is suitable from the viewpoint of the finished appearance of the colored base coating film.

≪Painting≫
The aqueous coloring base coating composition of the present invention can be applied by known coating means such as spray coating, electrostatic coating, brush coating, roller coating, etc., but spray coating can be performed from the viewpoint of the finished appearance of the coating film. preferable.

  Although the number of times of coating may be one, it is desirable to coat the same paint a plurality of times, for example, 2-6 times, in order to achieve both the finished appearance and the hiding property.

  In the case of overcoating, steps such as flash-off between coatings (after coating is allowed to stand at room temperature), air blow at room temperature, and preheating at 60 ° C or less and 10 minutes or less are provided as necessary. May be.

  Drying after the application of the aqueous colored base coating composition is not particularly limited, and may be in an undried state when the top clear described below is applied repeatedly, for example, 20 to 100 ° C., It is preferable to dry at a temperature of 40 to 80 ° 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.

  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 composition, and a primer coating film, an electrodeposition coating film, an intermediate coating film under the base coating film. A coating film such as a film may be appropriately provided.

  Moreover, you may use the aqueous | water-based coloring base coating composition of this invention as a coating material for repair with respect to the coating film already formed in the said to-be-coated surface. In this case, the surface to be coated can be previously treated with a putty, a primer surfacer or the like. Further, after the aqueous colored base coating composition is applied, a top clear coating composition may be applied on the coating film.

  As such a top clear coating composition, conventionally known ones can be used without particular limitation. For example, an acrylic resin or a fluororesin containing a crosslinkable functional group such as a hydroxyl group as a main component, and a block polyisocyanate, polyisocyanate or melamine resin. A curable paint containing, for example, a curing agent, or a lacquer paint mainly composed of an acrylic resin modified with cellulose acetate butyrate can be suitably used.

  Among these, it is possible to use a two-component coating material in which a component containing a hydroxyl group-containing resin is a main component and a component containing a polyisocyanate compound is a curing agent component, so that a desired coating appearance can be obtained and forced drying conditions can be used. It is preferable because a coating film having excellent physical properties such as water resistance can be obtained.

  The top clear coating composition may further contain coating additives such as pigments, fiber derivatives, additive resins, ultraviolet absorbers, light stabilizers, surface conditioners, and curing catalysts, if necessary. .

  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.

<Manufacture of urethane resin emulsion:>
Production Example 1
In a reaction vessel, 115.5 parts of polybutylene adipate having a number average molecular weight of 2000, 115.5 parts of polycaprolactone diol having a number average molecular weight of 2000, 23.2 parts of dimethylolpropionic acid, 14.5 parts of 1,4-butanediol and 120.1 parts of isophorone diisocyanate was charged in a polymerization vessel and reacted for 7 hours at 85 ° C. in a nitrogen stream with stirring to obtain a prepolymer having an NCO content of 4.0%. Next, the prepolymer was cooled to 50 ° C., and 165 parts of acetone was added and dissolved uniformly. Then, 15.7 parts of triethylamine was added with stirring, and 600 parts of deionized water was added while maintaining the temperature at 50 ° C. or lower. After maintaining the aqueous dispersion at 50 ° C. for 2 hours to complete the water elongation reaction, acetone was distilled off at 70 ° C. or less under reduced pressure, the pH was adjusted to 8.0 with triethylamine and deionized water, and solid acid A urethane resin emulsion (A-1) having a value of 17 mg KOH / g, a solid content of 30%, and an average particle size of 0.15 μm was obtained.

<Manufacture of acrylic resin emulsion:>
Production Example 2
In a reaction vessel, 100 parts of deionized water, “Newcol 707SF” (manufactured by Nippon Emulsifier Co., Ltd., 2.5 parts of an anionic emulsifier having a polyoxyethylene chain, solid content 30%) and a monomer mixture (styrene 9 parts, n-butyl acrylate 39) Part, 2-ethylhexyl acrylate 40 parts, 2-hydroxyethyl acrylate 10 parts, methacrylic acid 1 part, allyl methacrylate 1 part) and stirring and mixing in a nitrogen stream, 3% ammonium persulfate aqueous solution at 60 ° C Three parts were added. Then, the temperature was raised to 80 ° C., and a pre-emulsion consisting of the remaining 99 parts of the monomer mixture, 2.5 parts of “Newcol 707SF”, 4 parts of 3% ammonium persulfate and 100 parts of deionized water was added to the metering pump over 4 hours. In addition to the reaction vessel, aging was performed for 1 hour after the end of the addition. Thereafter, 33 parts of deionized water was added, the pH was adjusted to 7.5 with dimethylethanolamine, an acrylic resin emulsion (B-1) having a glass transition temperature of −44 ° C., an average particle size of 0.1 μm, and a solid content of 30%. Got.

<Manufacture of aluminum pigment paste:>
Production Example 3
Aluminum pigment paste "Hydrolan 2156" (silica coated aluminum flake pigment paste, pigment content 60%) 45.5 parts, propylene glycol monomethyl ether 35 parts, phosphate group-containing resin solution (Note 1) 17.5 parts were added and stirred and mixed to obtain an aluminum pigment paste (C-1).
(Note 1) Phosphate group-containing resin solution: A mixed solvent of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol is placed in a 4 liter flask equipped with a stirrer, a temperature controller and a refrigerator, and the mixture is heated to 110 ° C. Heat, 25 parts of styrene, 27.5 parts of n-butyl methacrylate, 20 parts of “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), 7.5 parts of hydroxybutyl acrylate, phosphate group-containing polymerizable monomer (Note 2) 121.5 parts of a mixture comprising 15 parts, 12.5 parts of 2-methacryloyloxyethyl acid phosphate, 10 parts of isobutanol and 4 parts of t-butylperoxyoctanoate was added to the above mixed solvent over 4 hours, and t A mixture of 0.5 part of butyl peroxyoctanoate and 20 parts of isopropanol was added dropwise over 1 hour. Thereafter, the mixture was aged and stirred for 1 hour to obtain a phosphate group-containing resin solution having a solid content of 50%.
(Note 2) Phosphoric acid group-containing polymerizable monomer: 57.5 parts of monobutyl phosphoric acid and 41.1 parts of isobutanol are placed in a reaction vessel, and 42.5 parts of glycidyl methacrylate are added dropwise over 2 hours under air flow. The mixture was aged with stirring for 1 hour. Thereafter, 5.9 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution having a solid content of 50%.

<Manufacture of base paint:>
Production Example 5
After 83.5 parts of the aluminum pigment paste (C-1) obtained in Production Example 3 was added to the stirring and mixing vessel and stirred for 1 hour, 150 parts of the urethane resin emulsion (A-1) obtained in Production Example 1 and further Mix 150 parts of the acrylic resin emulsion (B-1) obtained in Production Example 2, add 17.8 parts of “Primal ASE60” (Note 3), continue stirring for 1 hour, and adjust the pH with dimethylethanolamine. After that, deionized water was added to obtain a base paint (I-1) having a solid content of 20%. When the viscosity and pH of this base coating material (I-1) were measured according to the method described in the specification, they were 1000 mPa · sec and 8.0, respectively.
(Note 3) “Primal ASE 60”: trade name, manufactured by Rohm and Haas, polyacrylic acid thickener, acid value 270 mg KOH / g, active ingredient 28%.

Production Example 6
After adding 83.5 parts of the aluminum pigment paste (C-2) obtained in Production Example 4 to the stirring and mixing vessel and stirring for 1 hour, 150 parts of the urethane resin emulsion (A-1) obtained in Production Example 1 and further Mix 150 parts of the acrylic resin emulsion (B-1) obtained in Production Example 2, add 17.8 parts of “Primal ASE60” (Note 3), continue stirring for 1 hour, and adjust the pH with dimethylethanolamine. After that, deionized water was added to obtain a base paint (I-2) having a solid content of 30%. When the viscosity and pH of the base paint (I-2) were measured according to the method described in the specification, they were 1500 mPa · sec and 8.0, respectively.

<Manufacture of diluent:>
Production Example 7
In a stirring and mixing vessel, 975 parts of water, 5 parts of “Laponite RD” (Note 4) and 20 parts of “BYK-348” (Note 5) were stirred and mixed to obtain Diluent (II-1). The viscosity was 15 mPa · sec.
(Note 4) “Laponite RD”: trade name, manufactured by Rochwood Additives Limited, inorganic thickener, synthetic hectorite,
(Note 5) “BYK-348”: trade name, manufactured by BYK-CHEMIE, polyether-modified silicone compound, active ingredient 100%
Production Examples 8-15
Diluents (II-2) to (II-9) were obtained in the same manner as in Production Example 7 except that the composition was as shown in the following table.

(Note 6) “Uniol D-2000”: trade name, manufactured by NOF Corporation, polypropylene glycol, weight average molecular weight 2000, active ingredient 100%
<Manufacture of particle-containing paint:>
Production Example 16
In a stirring and mixing container, 71 parts of water, 10 parts of “Nip seal E-1009” (Note 7), 5 parts of propylene glycol mono-n-propyl ether, 5 parts of urethane resin emulsion (A-1), acrylic resin emulsion (B- 1) 5 parts and 1 part of “BYK-348” were stirred and mixed, 3 parts of “Primal ASE60” was added, stirring was continued for another hour, pH was adjusted with dimethylethanolamine, deionized water was added, A particle-containing paint (III-1) was obtained.
When the viscosity and pH of the particle-containing paint (III-1) were measured according to the method described in the specification, they were 1500 mPa · sec and 8.0, respectively.
(Note 7) “Nip seal E-1009”: trade name, manufactured by Tosoh Silica, average particle diameter of 1.5 μm, silicon dioxide.

<Manufacture of diluted paint:>
Examples 1-6 and Comparative Examples 1-3
The base paint (I-1), the diluents (II-1) to (II-9), and the particle-containing paint (III-1) were sufficiently mixed by hand stirring with the blending composition shown in the following table, and the diluted paint (D -1) to (D-9) were obtained. The table also shows the viscosity of each diluted paint. Viscosity was measured according to the method described in the specification, and after 5 minutes had elapsed after mixing the base paint, diluent and particle-containing paint.

<Evaluation test:>
With respect to the diluted paints (D-1) to (D-9) prepared as described above, evaluation tests were performed on the following items. The results are also shown in Table 2.
(1) Applicability of repeated coating: Each diluted coating was spray-coated and then air blown four times until it was no longer glossy, and the conformability of the coating after repeated coating was visually evaluated.
A: Glossy and wet coated surface is smooth.
○: Glossy but slightly uneven on wet surface.
Δ: Slightly glossy, but wet coating surface has irregularities.
X: There is no luster and there is a large unevenness on the wet coated surface.
(2) Overview of coating film: The coating film surface of each evaluation coated plate was visually evaluated.
A: The coating surface is smooth.
○: The coating surface is slightly uneven.
Δ: There are irregularities on the coated surface.
(3) Water resistance: Each evaluation coated plate was immersed in warm water at 40 ° C. for 10 days, and then the coating surface was observed.
A: Very good B: Good B: The coating film is swollen.
(4) Initial adhesion: Cut each evaluation coating plate with a cutter so as to reach the substrate, make 100 goby meshes with a size of 1 mm x 1 mm, stick adhesive cellophane tape on the surface, and at 20 ° C The remaining number of the goby eye coating after the tape was abruptly peeled was examined.
；: 100 remaining ○: 99-90 remaining Δ; 89-41 remaining (5) Unevenness: Visual evaluation of metallic unevenness of the repaired portion (thick film portion) of each evaluation coated plate was performed.
A: No occurrence of metallic unevenness is observed.
○: Some metallic unevenness was observed, but it was within the allowable range.
Δ: Metallic unevenness was observed.

Claims (9)

A multi-component aqueous coloring base coating composition for preparing an aqueous coloring base coating composition by mixing the main component (I) and the diluent component (II) immediately before coating,
A multi-component aqueous coloring characterized in that the main component (I) contains an aqueous resin component, a coloring pigment and water, and the diluent component (II) contains a polyether-modified silicone compound, a viscosity modifier and water. Base paint composition. Diluent component (II) is a polyether-modified silicone compound 0.01 to 10.0% by mass
Viscosity modifier 0.1-3.0% by mass,
The composition according to claim 1, comprising 60 to 99.9% by weight of water. The aqueous resin component contains an acrylic resin emulsion as a part of the component, and the acrylic resin emulsion contains a polyvinyl compound having at least two polymerizable unsaturated groups in one molecule as a copolymer component. A composition according to 1. The composition according to any one of claims 1 to 3, wherein the color pigment is aluminum flakes coated with silica. Just before coating, a multi-component aqueous colored base coating composition for preparing an aqueous colored base coating composition by further mixing the particle component (III) in addition to the main component (I) and diluent component (II) The composition according to any one of claims 1 to 4, wherein the particle component (III) contains silica particles and water. The mass ratio of the main agent component (I) and the diluent component (II) is such that the diluent component (II) is in the range of 30 to 400 parts by mass based on 100 parts by mass of the main agent component (I). The composition of any one of these. The mass ratio of the main component (I), the diluent component (II) and the particle component (III) is 30 to 400 parts by mass of the diluent component (II) based on 100 parts by mass of the main component (I). The composition according to claim 5, wherein (III) is in the range of 0.1 to 105 parts by mass. A repair coating method using the composition according to any one of claims 1 to 7. A repair coating method comprising applying a clear coating after coating the composition according to any one of claims 1 to 7.