CN106010042B - Aqueous pigmented base coating composition - Google Patents

Abstract

The present invention provides an aqueous colored base coating composition suitable for forming a repair coating film which does not give a sense of incongruity to a colored coating film such as an existing colored coating film of an automobile body or the like. The present invention relates to a multicomponent aqueous colored base coating composition comprising a combination of a main component (I) and a diluent component (II), wherein the main component (I) comprises an aqueous resin component, a coloring pigment and water, and the diluent component (II) comprises a polyether-modified polysiloxane compound, a viscosity modifier and water. The invention also relates to a repair coating method using the water-based coloring basic coating composition.

Description

Aqueous pigmented base coating composition

Technical Field

The present invention relates to an aqueous colored base coating composition used for refinish coating of an existing coating film on an automobile body or the like.

Background

In recent years, from the viewpoint of environmental protection, there has been a demand for the water-based coating materials in the field of coating materials. Compared with other organic solvents for coating, the water has the following special properties: although having a low molecular weight, a high boiling point, a high surface tension and a high dielectric constant are present. These factors have been known to greatly affect the coating workability of the aqueous coating material, and the aqueous coating material is generally inferior to an organic solvent-based coating material in coating workability, and the obtained coating film is not likely to have high gloss.

As a measure for improving the workability of coating of an aqueous coating material and the finish of a coating film, for example, a method of improving a coating resin used in an aqueous coating material has been generally performed.

However, in the field of automotive refinish coating, depending on the refinish coating site, there is a wide range of coating environments such as temperature and humidity, and since an aqueous coating material that is greatly affected by the coating environment that varies with time is used, it is difficult to obtain a stable finished appearance.

In order to solve such a problem, patent document 1 describes the following: by including an organic solvent having a specific HLB value in an aqueous coating material, the coating workability is improved, and the finish of the formed coating film is improved without being affected by the coating environment.

In the topcoat coating step in the automotive refinish coating, however, a refinish topcoat colored base paint having a color similar to the appearance of an existing coating film is usually applied to a base-treated surface of a base material such as a putty or a primer surface agent in multiple stages. Moreover, the following operations are often performed: between the respective coatings, air is blown with compressed air as necessary to accelerate drying of the respective colored base coating films.

When the water-based paint described in patent document 1 is used as a top-coat coloring base paint for repair and applied 1 time, and 1 time air blowing is performed and the coating is repeated in stages, the fusion of the dried coating film and the applied coloring base paint may be insufficient, and the surface layer may be rough or uneven in the coating film obtained after the top-coat coating step is completed.

On the other hand, patent documents 2 to 3 describe: by making the aqueous coating composition composed of the main agent component (I), the viscosity modifier component (II), and the viscosity modifier component (III), and setting each to a specific composition, a coating film free from defects such as sagging is obtained.

According to these patent documents, even if the step coating of the aqueous coating composition is continuously performed in a wet-on-wet manner (ウェット · オン · ウェット), a coating film having no defects can be obtained, and the repair coating process can be greatly simplified, but even if a drying process is provided between the step coating, slight surface roughness and unevenness are observed in the formed coating film, and it cannot be said that the purpose of reproducing the color tone of the existing coating film is achieved, and there is room for improvement.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-213274

Patent document 2: japanese patent laid-open No. 2001-316612

Patent document 3: international publication WO2013/002121 pamphlet

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide an aqueous colored base coating composition suitable for forming a repair coating film which does not give any unpleasant feeling to a colored coating film such as an existing colored coating film of an automobile body or the like.

Means for solving the problems

The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found the following facts, thereby achieving the present invention: the repeated coating fusibility in the stage coating is improved by including the organopolysiloxane compound in the diluent used in the aqueous colored base coating composition for the repair coating.

That is, the present invention relates to a multicomponent aqueous colored base coating composition comprising a main component (I) and a diluent component (II) in combination, wherein the main component (I) comprises an aqueous resin component, a coloring pigment and water, and the diluent component (II) comprises a polyether-modified polysiloxane compound, a viscosity modifier and water; the invention also relates to a repair coating method which is characterized by using the composition.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the multi-component aqueous colored base coating composition containing a diluent component as a constituent component of the present invention, a colored base coating film having a high decorative appearance without surface roughness or unevenness and having no discomfort with an existing coating film can be obtained, while having excellent coating workability and good repeated coating fusibility in the case of performing step coating.

Detailed Description

The aqueous colored base coating composition of the present invention is a multicomponent composition comprising a combination of a main component (I) and a diluent component (II).

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

Examples of the aqueous resin component include: emulsions obtained by dispersing acrylic resin emulsions, polyester emulsions, epoxy resin emulsions, polyurethane resin emulsions, and the like in an aqueous medium; or a resin obtained by dissolving a water-soluble acrylic resin, a water-soluble polyester resin, a water-soluble epoxy resin, a water-soluble urethane resin, or the like 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 is an emulsion in which a copolymer obtained by copolymerizing a polymerizable unsaturated monomer containing a (meth) acryloyl group as an essential component and, if necessary, another polymerizable unsaturated monomer is dispersed in water.

Specifically, the average particle diameter of the acrylic resin emulsion is in the range of 0.01 to 1.0. mu.m, preferably in the range of 0.05 to 0.5. mu.m.

In the present specification, the average particle diameter of the acrylic resin emulsion and the urethane resin emulsion described later means a volume average particle diameter measured by a coulter counter method at a measurement temperature of 20 ℃. The measurement by the COULTER counter method can be performed, for example, by using "COULTER N4 type" (manufactured by Beckman COULTER k.k., trade name).

As such an acrylic resin emulsion, for example, there can be preferably used: an acrylic resin emulsion obtained by emulsion polymerization of the polymerizable unsaturated monomer component in 1 stage or in multiple stages using a polymerization initiator in the presence of water and a dispersion stabilizer.

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

Examples of the polymerizable unsaturated monomer that can be a copolymerization component of the acrylic resin emulsion include linear or branched alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; alicyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; perfluoroalkyl (meth) acrylates; n, N-dialkylaminoalkyl (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate; (meth) acrylamide; (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and alpha-methylstyrene; allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 3-butanediol 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 tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1, 1-trimethylolethane tri (meth) acrylate, 1,1, 1-trihydroxymethylpropane tri (meth) acrylate, triallylisocyanurate, triallyl isocyanurate, and mixtures thereof, Polyvinyl compounds having at least two polymerizable unsaturated groups in 1 molecule, such as diallyl terephthalate and divinylbenzene; hydroxyl group-containing polymerizable unsaturated monomers such as hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, allyl alcohol, caprolactone-modified products of the hydroxyalkyl (meth) acrylates, and (meth) acrylates containing a polyoxyethylene chain having a hydroxyl group at the molecular end; carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid, and β -carboxyethyl acrylate; carbonyl group-containing polymerizable unsaturated monomers such as (meth) acrolein, formylstyrene, C4-7 vinyl alkyl ketones (e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyethyl (meth) acrylate, acetoacetoxyethyl allyl ester, diacetone (meth) acrylamide, etc.; epoxy group-containing polymerizable unsaturated monomers such as glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3, 4-epoxycyclohexylethyl (meth) acrylate, 3, 4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; isocyanate group-containing polymerizable unsaturated monomers such as isocyanatoethyl (meth) acrylate and m-isopropenyl- α, α -dimethylbenzyl isocyanate; alkoxysilyl group-containing polymerizable unsaturated monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma-methacryloxypropyltriethoxysilane; epoxy group-containing polymerizable unsaturated monomers or reaction products of hydroxyl group-containing polymerizable unsaturated monomers and unsaturated fatty acids, and oxidative curable group-containing polymerizable unsaturated monomers such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, and dicyclopentenyl (meth) acrylate, and they can be used alone or in combination of two or more.

The dispersion stabilizer used in the emulsion polymerization of the acrylic resin emulsion is not particularly limited, and examples thereof include anionic emulsifiers such as sodium dialkylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene alkylphenyl ether sulfate and sodium alkyldiphenylether disulfonate, nonionic emulsifiers such as polyoxyethylene higher alcohol ether and polyoxyethylene alkylphenyl ether, and anionic or cationic reactive emulsifiers having a radical polymerizable double bond.

The reactive emulsifier is an emulsifier having a polymerizable unsaturated group and at least one of a nonionic group, an anionic group and a cationic group in a molecule, and specific examples of the polymerizable unsaturated group include a (meth) allyl group, a (meth) acryloyl group, an propenyl group, and a butenyl group. Examples of commercially available products include "latex" (product name, manufactured by Kao Corporation), "elemin" (product name, manufactured by sanyo chemical Corporation), "Aqualon" (product name, manufactured by first industrial pharmaceutical company), "Adekalia Soap" (product name, manufactured by asahi electric company), "ANTOX" (product name, manufactured by japan emulsifier company).

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

In the present invention, an acrylic resin emulsion containing, as a copolymerization component, a polyvinyl compound having at least two polymerizable unsaturated groups in 1 molecule is preferable as the acrylic resin emulsion contained in the main component (I) from the viewpoints of water resistance and intermediate polishing properties (Zhongzhu ぎ properties) of the colored base coating film.

The polyvinyl compound having at least two polymerizable unsaturated groups in 1 molecule is exemplified by the above exemplified compounds, and can be used alone or in combination of two or more, and the copolymerization amount thereof can be set in the range of 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the mass of all polymerizable unsaturated monomers used in the production of the acrylic resin emulsion.

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

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

As the urethane resin emulsion, those known in the art can be used without limitation, and examples thereof include resin emulsions obtained by dispersing in water a urethane prepolymer obtained by reacting a polyisocyanate, a polyol and a carboxyl group-containing diol.

As the polyisocyanate, there can be mentioned: aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate, and the like; biuret-type adducts and isocyanurate cycloadducts of these diisocyanate compounds; alicyclic diisocyanate compounds such as isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), methylcyclohexane-2, 4- (or-2, 6-) diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclohexane, 1, 4-cyclohexane diisocyanate, 1, 3-cyclopentane diisocyanate, 1, 2-cyclohexane diisocyanate and the like; biuret-type adducts, isocyanurate cycloadducts of these diisocyanates; aromatic diisocyanate compounds such as xylene diisocyanate, m-xylene diisocyanate, tetramethylxylene diisocyanate, toluene diisocyanate, 4 '-diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether isocyanate, (m-or p-phenylene diisocyanate, 4' -biphenylene diisocyanate, 3 '-dimethyl-4, 4' -biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, and isopropylidene bis (4-phenylisocyanate); biuret-type adducts and isocyanurate cycloadducts of these diisocyanate compounds; polyisocyanate compounds having three or more isocyanate groups in 1 molecule, such as triphenylmethane-4, 4 ', 4 ″ -triisocyanate, 1,3, 5-triisocyanatobenzene, 2,4, 6-triisocyanatotoluene, and 4, 4' -dimethyldiphenylmethane-2, 2 ', 5, 5' -tetraisocyanate; biuret-type adducts and isocyanurate cycloadducts of these polyisocyanate compounds; a urethane adduct obtained by reacting a polyisocyanate compound with hydroxyl groups of a polyhydric alcohol such as ethylene glycol, propylene glycol, 1, 4-butanediol, dimethylolpropionic acid, polyalkylene glycol, trimethylolpropane or hexanetriol at a ratio at which an isocyanate group is excessive; biuret type adducts and isocyanurate cycloadducts of these urethanized adducts, and the like.

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, and octamethylene ether glycol; polyhydric alcohols obtained by polycondensation of dicarboxylic acids (adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, etc.) and diols (ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, dihydroxymethylcyclohexane, etc.), for example, polyester polyols such as polyethylene glycol adipate, polybutylene glycol adipate, polyhexamethylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene/butylene adipate, and polyneopentyl/hexyladipate; polycaprolactone polyols, poly-3-methylpentane polyols; a polycarbonate polyol; low molecular weight glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 4-butanediol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, octamethylene glycol, dimethylol tricyclodecane, hydrogenated bisphenol a, cyclohexanedimethanol, and 1, 6-hexanediol, and the like, and they may be used alone or in combination of two or more.

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

The production of the urethane prepolymer can be carried out by a conventionally known method.

The urethane resin emulsion may be a urethane resin emulsion obtained by neutralizing with a neutralizing agent. The neutralizing agent is not particularly limited as long as it is a neutralizing agent capable of neutralizing a carboxyl group, and examples thereof include sodium hydroxide, potassium hydroxide, trimethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, triethylamine and ammonia.

The urethane resin emulsion is preferably a urethane resin emulsion having a cyclic structure in the molecule because the colored base coating film has good middle-order polishing properties.

The polyisocyanate constituting the urethane resin emulsion is more preferably a polyisocyanate containing a compound derived from an alicyclic diisocyanate compound as part of its components, which is preferable.

Further, the urethane resin emulsion has a solid acid value of 20mgKOH/g or less, preferably 5 to 18mgKOH/g, from the viewpoint of water resistance and repeated coating fusibility of the colored base coating film.

In the present specification, the solid content means a nonvolatile component, and means a residue obtained by removing volatile components such as water and an organic solvent from a sample, and can be calculated by multiplying the mass of the sample by the solid content concentration. The solid content may be measured by dividing the mass of a residue obtained by drying a sample at 105 ℃ for 3 hours by about 3 g by the mass before drying, or may be expressed as a percentage.

The average particle diameter of the urethane resin emulsion (A) may be in the range of 0.01 to 1 μm, particularly 0.05 to 0.5. mu.m.

The aqueous resin component preferably further contains a water-soluble acrylic resin. In the present specification, examples of the water-soluble acrylic resin include: a resin obtained by polymerizing a polymerizable unsaturated monomer component containing an acid group-containing polymerizable unsaturated monomer, a hydroxyl group-containing polymerizable unsaturated monomer, and another polymerizable unsaturated monomer, in the presence of a hydrophilic organic solvent, with a polymerization initiator.

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; polymerizable unsaturated monomers containing sulfonic acid groups, such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, sodium styrenesulfonate, sulfoethyl methacrylate, and sodium or ammonium salts thereof; and a polymerizable unsaturated monomer containing a phosphoric acid group such as 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, and 2-methacryloyloxypropyl acid phosphate.

In particular, the use of a carboxyl group-containing polymerizable unsaturated monomer and a phosphoric acid group-containing polymerizable unsaturated monomer in combination as an acid group-containing polymerizable unsaturated monomer has the effect of improving fusibility when the composition of the present invention is repeatedly applied.

Examples of the hydroxyl group-containing polymerizable unsaturated monomer include hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; n-methylolacrylamide; allyl alcohol; a caprolactone-modified acrylic monomer of a hydroxyalkyl (meth) acrylate having 2 to 8 carbon atoms; polyalkylene glycol (meth) acrylates such as diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, dipropylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol (meth) acrylate, and the like, and they may be used singly or in combination of two or more.

Examples of the other polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-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, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, ethylene (meth) acrylate, propylene (meth) acrylate, alkyl or cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate, adamantyl (meth) acrylate, and tricyclodecanyl (meth) acrylate; aromatic ring-containing polymerizable unsaturated monomers such as benzyl (meth) acrylate, styrene, α -methylstyrene and vinyltoluene; polymerizable unsaturated monomers having an alkoxysilyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ - (meth) acryloyloxypropyltrimethoxysilane, and γ - (meth) acryloyloxypropyltriethoxysilane; perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; polymerizable unsaturated monomers having a fluoroalkyl group such as fluoroolefin; polymerizable unsaturated monomers having a photopolymerizable functional group such as a maleimide group; vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, and vinyl acetate; allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 3-butanediol 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 tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1, 1-trimethylolethane tri (meth) acrylate, 1,1, 1-trihydroxymethylpropane tri (meth) acrylate, triallylisocyanurate, triallyl isocyanurate, and mixtures thereof, Polymerizable unsaturated monomers having at least two polymerizable unsaturated groups in 1 molecule, such as diallyl terephthalate and divinylbenzene; nitrogen-containing polymerizable unsaturated monomers such as (meth) acrylonitrile, (meth) acrylamide, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylamide, and adducts of glycidyl (meth) acrylate and amines; epoxy group-containing polymerizable unsaturated monomers such as glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3, 4-epoxycyclohexylethyl (meth) acrylate, 3, 4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; isocyanate group-containing polymerizable unsaturated monomers such as 2-isocyanatoethyl (meth) acrylate and m-isopropenyl- α, α -dimethylbenzyl isocyanate; (meth) acrylate having a polyoxyethylene chain having an alkoxy group at the molecular end; and carbonyl group-containing polymerizable unsaturated monomers such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, and vinyl alkyl ketones having 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone). These polymerizable unsaturated monomers may be used alone or in combination of two or more.

In addition, the water-soluble acrylic resin is preferably obtained by neutralizing the acid groups with a neutralizing agent. Examples of the neutralizing agent include the compounds exemplified above.

The water-soluble acrylic resin generally has a solid acid value of 5 to 150mgKOH/g, preferably 10 to 100mgKOH/g, a solid hydroxyl value of 10 to 150mgKOH/g, preferably 20 to 100mgKOH/g, and a weight-average molecular weight of 5000 to 10,0000, preferably 8,000 to 70,000.

In the present specification, the weight average molecular weight refers to a value obtained by converting a weight average molecular weight measured by a gel permeation chromatograph ("HLC 8120 GPC" manufactured by tokyo corporation) into a weight average molecular weight of polystyrene. As the column, four columns of "TSKgel G-4000 HxL", "TSKgel G-3000 HxL", "TSKgel G-2500 HxL" and "TSKgel G-2000 HxL" (trade name, manufactured by Tosoh Co., Ltd.) were used, and in the mobile phase: tetrahydrofuran, measurement temperature: 40 ℃ and flow rate: 1 ml/min, detector: under the condition of RI.

The number average molecular weight is a value obtained by converting a number average molecular weight measured by a gel permeation chromatograph ("HLC 8120 GPC" manufactured by tokyo corporation) into a number average molecular weight of polystyrene. As the column, four columns of "TSKgel G-4000 HxL", "TSKgel G-3000 HxL", "TSKgel G-2500 HxL" and "TSKgel G-2000 HxL" (trade name, manufactured by Tosoh Co., Ltd.) were used, and in the mobile phase: tetrahydrofuran, measurement temperature: 40 ℃ and flow rate: 1 ml/min, detector: under the condition of RI.

The hydrophilic organic solvent used in the polymerization is not strictly distinguished, but examples thereof include organic solvents in which at least 20g of water is dissolved in 100g of water at 20 ℃, specifically, alcohol organic solvents such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ether organic solvents such as dioxane and tetrahydrofuran; glycol ether organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, and ethylene glycol mono-t-butyl ether; diethylene glycol ether organic solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, and diethylene glycol mono-t-butyl ether; propylene glycol ether organic solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene glycol mono-isopropyl ether; dipropylene glycol ether organic solvents such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-isopropyl ether; and ester-based organic solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and 3-methoxybutyl acetate, and these solvents may be used alone or in combination of two or more.

When the water-soluble acrylic resin is used, the amount of the water-soluble acrylic resin to be blended may be in the range of 1 to 30 mass%, preferably 1 to 20 mass% in the solid resin content contained in the main component (I).

In the present invention, conventionally known color pigments can be used without particular limitation as the color pigment. Specific examples thereof include coloring pigments such as 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, perinone pigments, benzimidazolone pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, and indigo pigments; bright pigments such as aluminum (including aluminum deposited), copper, zinc, brass, nickel, alumina, mica, alumina covered with titanium oxide or iron oxide, mica covered with titanium oxide or iron oxide, glass flakes, and hologram pigments (hologram pigments); and bulk pigments such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white, which may be used alone or in combination of two or more depending on the color and coating properties to be achieved.

In addition, the shape of the glitter pigment is not particularly limited, and for example, the glitter pigment is preferably in a form of a phosphor flake, and the glitter pigment is preferably coated by dispersing with a treatment agent containing a phosphoric group or a sulfonic group from the viewpoint of suppressing hydrogen gas generation. The treating agent containing a phosphoric acid group or a sulfonic acid group is not particularly limited, and conventionally known low molecular weight compounds and copolymers can be used.

Further, as the bright pigment, aluminum flakes covered with silica are preferably used. This is because a stable coating film with a metallic appearance can be obtained.

As the silica-coated aluminum pigment, commercially available products such as "Hydrolan series" (trade name, manufactured by ECKART corporation) and "Aluplate EMR series" (trade name, manufactured by Toyo aluminum K.K.) can be used.

The amount of the coloring pigment to be blended varies depending on the intended color of the coating, but is generally preferably in the range of 0.1 to 300 parts by mass, more preferably 0.5 to 200 parts by mass, per 100 parts by mass of the solid content of the resin contained in the main component, from the viewpoint of coating stability.

Main ingredient component (I)

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

The ratio of the acrylic resin emulsion to the urethane resin emulsion is preferably in the range of 95/5 to 5/95, more preferably in the range of 80/20 to 20/80 in terms of the solid matter ratio, from the viewpoint of the water-resistant adhesion of the colored base coating film.

The above-mentioned main agent component (I) may also contain a pigment other than the coloring pigment; viscosity modifiers, pigment dispersants, ultraviolet absorbers, light stabilizers, fine polymer particles, dispersion aids, preservatives, silane coupling agents, defoamers, curing catalysts, organic solvents, neutralizing agents, and other components such as coating additives generally used in the preparation of aqueous coatings.

In the present invention, the main component (I) contains the viscosity modifier so that the main component (I) can be stored stably and a coating film having a good finished appearance without unevenness, sagging, or the like can be formed from the aqueous colored base coating composition obtained by mixing with the diluent component (II) described later.

As the viscosity modifier, conventionally known viscosity modifiers can be used without limitation, and specific examples thereof include polyacrylic acid viscosity modifiers such as sodium polyacrylate and polyacrylic acid- (meth) acrylate copolymers; polyether viscosity modifiers such as Pluronic (Pluronic) polyether, polyether dialkyl ester, polyether dialkyl ether, polyether epoxy modifier, and the like; urethane associated type viscosity adjusting agents; inorganic viscosity modifiers such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, mica, and bentonite; cellulose derivative viscosity modifiers such as carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose; protein viscosity modifiers such as casein, sodium caseinate, and ammonium caseinate; alginic acid viscosity modifiers such as sodium alginate; polyvinyl type viscosity modifiers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl benzyl ether copolymer, etc.; maleic anhydride copolymer-based viscosity modifiers such as partial esters of vinyl methyl ether-maleic anhydride copolymers; polyamide viscosity modifiers such as polyamide amine salts.

Among them, polyacrylic acid-based viscosity modifiers are preferable from the viewpoint of the orientation of the colored pigment in the colored base coating film.

The acid value of the active ingredient of the polyacrylic acid-based viscosity modifier may be, for example, in the range of 30 to 350mg/KOH, and preferably may be more than 100 and 300mg/KOH or less. Examples of commercially available products include "Primal ASE 60", "Primal TT 615", "Primal RM 5" (trade name) manufactured by Rohm and Haas company, and "SN THICKENER 613", "SN THICKENER 618", "SN THICKENER 630", "SNTHICKENER 634" and "SN THICKENER 636" (trade name) manufactured by Sannopco Limited.

In the present specification, the effective component means a residue obtained by removing a diluent such as water or an organic solvent from a sample.

The amount of the polyacrylic acid-based viscosity modifier to be blended is about 0.5 to 20 mass%, preferably about 1 to 10 mass%, based on the resin solid content contained in the main component (I).

The solid content of the main component (I) is adjusted to be generally within a range of 10 to 50 mass%, preferably within a range of 15 to 40 mass%, which is preferable from the viewpoint of coating workability, concealing properties, and finished appearance.

The viscosity of the main component (I) is not particularly limited, but may be in the range of 100 to 3000mPa · sec, preferably 600 to 2000mPa · sec, from the viewpoint of storage stability and mixing property with the diluent component (II) and the like described later.

In the present specification, the viscosity is set as: the value obtained was measured at a rotation speed of 60rpm within 10 minutes after the sample was prepared at 25 ℃ using a viscometer model VDA of Vismetron viscometer (Shibaura Systems Co., Ltd.).

Dilution fraction (II)

In the present invention, the diluent component (II) contains a polyether-modified polysiloxane compound, a viscosity modifier, and water.

In the present invention, by mixing the diluent component (II) with the main component (I) immediately before coating and controlling the rheological characteristics of the aqueous colored base coating composition according to the coating environment, the aqueous colored base coating composition can be formed in such a manner that the storage stability of each component is maintained, and a colored base coating film having excellent finished appearance and good repeated coating fusibility can be formed without sagging, unevenness, and the like.

Examples of such polyether-modified polysiloxane compounds include compounds obtained by introducing a polyether chain into the terminal and/or side chain of polysiloxane, and co-modified polysiloxane compounds obtained by introducing an epoxy group, an amino group, and an organic group such as a (meth) acryloyl group in addition to the polyether chain into polysiloxane.

Examples of the polyether-modified polysiloxane 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 [ or more; 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, BYK-375, BYK-377, BYK-UV3510, BYK-307, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-3455, BYK-UV3500, BYKUV3530 (see, W-Chemie Co., SILK-Inc.), SILK-L-SILT-SILK, SILWET-720, SILWET-7001, SILWET-7002, SILT-70004, SILWET-766, SILWET-Z-2104, TFF-2104, TFK-2104, and so on, FZ-2105, SILWET FZ-2110, SILWET FZ-2118, SILWET FZ-2120, SILWET FZ-2122, SILWET FZ-2123, SILWET FZ-2130, SILWET FZ-2154, 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 FZ-3736, SILWET Y-7499, SILWET FZ-3789, SF8472, BY16-004, SF8428, SH3771, SH3746, BY16-036, SH3749, SH3748, SH 3700, SF8410 or more [ SILWET 843; dow Corning Toray Silicone co., ltd. system ], L032, L051, L066[ above; WackerAhikasei Silicone Co., Ltd ], and the like, and they may be used singly or in combination of two or more.

The viscosity modifier contained in the diluent component (II) can be appropriately selected from among the viscosity modifiers exemplified in the description of the viscosity modifier contained in the main component (I) and used.

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

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

Commercially available Products include "Bentone 27", "Bentone 34", "Bentone 38", "Bentone SD-1", "Bentone SD-2", "Bentone SD-3", "Bentone 52", "Bentone 57" (all of which are trade names of Rheox Co., Ltd., "Tixogel VP", "Tixogel TE", "Tixogel UN", "Tixogel EZ 100", "Tixogel MP 250" (all of which are trade names of Sud Chemical Co., Ltd., "Claytone 40", "Claytone 34", "Claytone HT", "Claytone APA", "Claytone AF", "Claytone HY" (all of which are trade names of Southern Clay Products Co., Ltd., "LaponiteRD", "Laponite HW 482", "Laponite EP", "Laponite OG" (all of which are trade names of Southern Clay Products Co., Ltd., "Laponite", "Laponite RDS", and/or more trade names of Laponite).

The polyether-modified silicone compound, the viscosity modifier, and water in the diluent component (II) are preferably used in a proportion of 0.01 to 10.0% by mass, preferably 0.05 to 5.0% by mass, the polyether-modified (poly) siloxane compound in a proportion of 0.1 to 3.0% by mass, preferably 0.3 to 2.0% by mass, and the water in a proportion of 60 to 99.9% by mass, preferably 70 to 99.5% by mass, based on the mass of the diluent component (II).

In the diluent component (II), a polyol compound having a polyalkylene skeleton may be contained for the purpose of improving the storage stability of the diluent component (II).

Examples of the polyol compound having a polyalkylene skeleton include polyalkylene polyols having at least one structure of diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, polyethylene oxide, polypropylene oxide, and a block structure or a random structure of ethylene oxide/propylene oxide; a polyol having a polyalkylene skeleton, which is obtained by modifying a polyol such as trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerol, polyglycerol, and polytetramethylene glycol with a polyalkylene group; polyester polyols which are condensates of the above polyalkylene polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid; caprolactone-modified polyols obtained by modifying polyether polyols with caprolactone, and the like.

The weight average molecular weight of the polyol compound having a polyalkylene skeleton is in the range of 100 to 10000, preferably 400 to 5000.

The amount of the polyol having a polyalkylene skeleton is preferably 50 to 1000 parts by mass, more preferably 100 to 500 parts by mass, based on 100 parts by mass of the active ingredient of the inorganic thickener contained in the diluent component (II), from the viewpoint of water resistance of the metal base coating film.

The diluent component (II) may contain other components such as coating additives generally used in the preparation of aqueous coatings, for example, aqueous resins, ultraviolet absorbers, light stabilizers, fine polymer particles, surface conditioners, dispersing aids, preservatives, silane coupling agents, defoaming agents, curing catalysts, organic solvents, and neutralizing agents.

Among them, as the organic solvent, a hydrophilic solvent is preferable because it has an effect of further improving the fusibility by repeated coating together with the polyether-modified polysiloxane 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; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, and diethylene glycol mono-tert-butyl ether; propylene glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-isopropyl ether; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and 3-methoxybutyl acetate may be used alone or in combination.

The hydrophilic organic solvent that can be contained in the diluent component (II) preferably contains a propylene glycol ether-based solvent.

The amount of the hydrophilic solvent used is preferably in the range of 0.1 to 50.0 mass%, preferably 0.5 to 30.0 mass%, based on the mass of the diluent component (II), because the unevenness can be suppressed.

The viscosity of the diluent component (II) described above is not particularly limited, but may be in the range of 10 to 300mPa · sec, and preferably 10 to 100mPa · sec, from the viewpoint of storage stability and mixing property with the main component (II) and the like.

< particulate component (III) >

The aqueous colored base coating composition of the present invention may be a multi-component system, that is, a three-component system, in which the main component (I) and the diluent component (II) are further combined with the particulate component (III), particularly in the case of a metallic base coating composition containing a bright pigment.

The particulate component (III) preferably contains silica particles and water from the viewpoint of the gloss and transparency of the colored base coating film to be formed.

Examples of the Silica particles include Fine powder Silica, colloidal Silica, and the like, and include a "Syloid" series (trade name, manufactured by Grace Japan Corporation), "aersil" series (trade name, manufactured by Nippon AEROSIL co., ltd.), "ACEMATT" series (trade name, manufactured by DEGUSSA Corporation), "Sylysia" series, "sylphonic" series, "sylospere" series (trade name, manufactured by Fuji Silica Chemical ltd.), "Quartron" series (trade name, manufactured by hibian Chemical Corporation), "Fine Seal" series (trade name, manufactured by Tokuyama), "NIPSIL" series (trade name, manufactured by Tosoh Silica Corporation), "Mizukasil" series (trade name, manufactured by water Chemical Corporation), and the like.

The average particle diameter of the silica particles is preferably in the range of 0.1 to 25 μm, and in the range of 0.5 to 10 μm, since the difference in the brightness and the uneven feeling due to the film thickness of the colored base coating film are suppressed.

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

The content of the active ingredient in the silica particles in the particulate component (III) is preferably in the range of 1 to 50 mass%, preferably 3 to 40 mass%, based on the mass of the particulate component (III).

The particulate component (III) preferably further contains an aqueous resin in addition to the silica particles. By including the aqueous resin in the particulate component (III), the storage stability of the particulate component (III) is improved.

As the aqueous resin, conventionally known aqueous resins can be used without limitation, but urethane resin emulsions and acrylic resin emulsions are preferably used. As the urethane resin emulsion and the acrylic resin emulsion, suitable resin emulsions from among the urethane resin emulsions and the acrylic resin emulsions listed in the description of the main component (I) can be used, respectively.

When the particulate component (III) contains an aqueous resin, the solid content of the aqueous resin is preferably in the range of 1 to 300 parts by mass, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the silica particles.

If the amount of the aqueous resin contained in the particulate component (III) is too large, the viscosity of the aqueous colored base paint may become high, and when the components (I) to (III) are mixed, stirring may become difficult.

When the particulate component (III) includes a urethane resin emulsion and an acrylic resin emulsion, the ratio of the urethane resin emulsion/acrylic resin emulsion in terms of solid content is in the range of 5/95 to 95/5, preferably in the range of 30/70 to 70/30.

If the urethane resin emulsion is less than this range, the initial adhesion of the colored base coating film may be poor, while if too much, the coating viscosity may be high, and stirring may be difficult in the case of preparing the coating.

In addition, the granular component (III) preferably contains a viscosity modifier as a part of its components. This provides the effect of providing a colored base coating film which has good miscibility with the main component (I) and the diluent component (II) and is excellent in the sense of brilliance.

The viscosity modifier is not particularly limited, and can be used by appropriately selecting from among the viscosity modifiers exemplified in the description of the viscosity modifiers contained in the main component (I), but the use of a polyacrylic viscosity modifier is preferable from the viewpoint of storage stability of the particulate component (III).

The content of the active ingredient of the viscosity modifier in the particulate component (III) is preferably in the range of 0.1 to 20 mass%, preferably 0.1 to 10 mass%, based on the mass of the particulate component (III).

In addition, the particulate component (III) preferably contains a polyether-modified polysiloxane compound. This is because the aqueous colored base coating composition has an effect on repeated coating fusibility when the aqueous colored base coating composition is repeatedly coated a plurality of times.

The polyether-modified polysiloxane compound can be suitably selected from the compounds listed in the description of the diluent component (II) above and used.

The polyether-modified polysiloxane compound is used in an amount of 0.5 to 40% by mass, preferably 2.0 to 20% by mass, based on the mass of the silica particles, and is preferably used from the viewpoint of initial adhesion of the colored base coating film.

In addition, the above-mentioned particulate component (III) contains an organic solvent, which is preferable. This is from the viewpoint of storage stability of the particulate component (III). This is because, although a silica film formed from silica particles may adhere to the inlet of the container for holding the particulate component (III) and a problem may be caused in the film formability of the coating film formed from the aqueous colored base coating material, the phenomenon can be improved by including the particulate component (III) with an organic solvent.

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

Examples of the solvent include alcohol organic solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol, and methoxypropanol; glycol ether organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-isopropyl ether; propylene glycol ether-based organic solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene glycol monoisopropyl ether, and the like, and these solvents may be used alone or in combination of two or more.

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

The particulate component (III) may contain particles other than silica particles, and other components such as additives for coating materials generally used in the preparation of aqueous coating materials, such as water, ultraviolet absorbers, light stabilizers, dispersion aids, preservatives, silane coupling agents, defoaming agents, curing catalysts, and neutralizing agents.

The viscosity of the particulate component (III) is not particularly limited, but may be in the range of 10 to 2000mPa · sec, preferably 10 to 1000mPa · sec, from the viewpoint of storage stability of the particulate component (III) and coating workability of the aqueous coloring base coating composition.

Aqueous colored base coating composition

In the present invention, the main component (I), the diluent component (II), and if necessary, the particulate component (III) are separately stored, and the coating manufacturer can prepare the aqueous colored base coating composition of the present invention by stirring and mixing the respective components immediately before coating and adjusting the viscosity with water or the like if necessary. In this specification, the term "immediately before coating" is not generally defined by the coating manufacturer and/or the coating site, but may be, for example, from 3 hours before coating.

Regarding the mass ratio of the main component (I) and the diluent component (II) in the above-mentioned aqueous colored base coating composition, the amount of the diluent component (II) is generally in the range of 30 to 400 parts by mass, preferably 40 to 350 parts by mass based on 100 parts by mass of the main component (I), or, the mass ratio of the main component (I), the diluent component (II) and the particulate component (III) is generally in the range of 30 to 400 parts by mass, preferably 40 to 350 parts by mass, and the particulate component (III) is in the range of 0.01 to 105 parts by mass, preferably 0.1 to 50 parts by mass, preferably 1 to 35 parts by mass, based on 100 parts by mass of the main component (I), which is preferable from the viewpoint of appearance of the colored base coating film and physical properties of the coating film.

In the present invention, if necessary, curing agents such as polyisocyanate curing agents, blocked isocyanate curing agents, melamine curing agents, oxazoline curing agents, and carbodiimide curing agents may be contained in any of the above-described main component (I), diluent component (II), and particle component (III), or may be used as individual components.

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

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

Coating (applications)

The aqueous colored base coating composition of the present invention can be applied by known coating means such as spray coating, electrostatic coating, brush coating, and roller coating, but is preferably applied by spray coating from the viewpoint of the finished appearance of the coating film.

The number of times of coating may be one, but from the viewpoint of achieving both finished appearance and concealing properties, it is preferable to coat the same paint by repeatedly applying the paint several times, for example, 2 to 6 times.

When the coating and painting are repeated, if necessary, a step of drying in the air (leaving the coating film after painting at room temperature), blowing at room temperature, or preliminary heating at 60 ℃ or less and 10 minutes or less may be provided between the respective paints.

The drying after the completion of the application of the aqueous coloring base coating composition is not particularly limited, and may be in an undried state when a supernatant described later is repeatedly applied, but is preferably performed, for example, for 5 to 60 minutes under a temperature condition of 20 to 100 ℃, preferably 40 to 80 ℃. The film thickness can be adjusted as appropriate depending on the state of the surface to be coated, but is generally preferably within a range of 5 to 100 μm, particularly 10 to 60 μm, as a dry film thickness.

Examples of the coated surface to be applied include conventionally known substrate surfaces or coating surfaces provided on the substrate, and the substrate is not particularly limited and includes, for example, metals such as iron and aluminum; organic substrates such as plastics; inorganic substrates such as concrete and wood, and the coating film provided on the substrate is not particularly limited, and examples thereof include a multilayer coating film provided on an automobile body or the like and formed from a base coating film and a clear coating film obtained from a colored base coating composition, and a multilayer coating film obtained by appropriately providing a coating film such as a primer coating film, an electrodeposition coating film, or an intermediate coating film on the lower layer of the base coating film.

The aqueous colored base coating composition of the present invention can also be used as a repair coating material for a coating film already formed on the coated surface. In this case, the surface to be coated may be previously treated with putty, primer surface agent, or the like. Alternatively, the clear coating composition may be applied to the coating film after the aqueous colored base coating composition is applied.

As the related clear coating composition, conventionally known clear coating compositions can be used without particular limitation, and for example, the following can be preferably used: a curable coating material containing an acrylic resin or a fluororesin containing a crosslinkable functional group such as a hydroxyl group as a main component and a blocked polyisocyanate, a melamine resin or the like as a curing agent; or a lacquer coating (lacquer paint) containing an acrylic resin modified with cellulose acetate butyrate as a main component.

Among them, a two-component coating material in which a component containing a hydroxyl group-containing resin is used as a main component and a component containing a polyisocyanate compound is used as a curing agent component is preferably used because a desired coating film appearance can be obtained and a coating film having excellent physical properties such as water resistance can be obtained even under forced drying conditions.

The above-mentioned supernatant coating composition may further contain, as required, additives for coating such as pigments, cellulose derivatives, additional resins, ultraviolet absorbers, light stabilizers, surface control agents, and curing catalysts.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, "part(s)" and "%" represent "part(s) by mass" and "% by mass", respectively.

< production of urethane resin emulsion: [ solution ] A method for producing a polymer

Production example 1

115.5 parts of polytetramethylene glycol 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 were charged into a reaction vessel and reacted at 85 ℃ for 7 hours under a nitrogen stream with stirring to obtain a prepolymer having an NCO content of 4.0%. Then, the prepolymer was cooled to 50 ℃ and 165 parts of acetone was added and uniformly dissolved, then 15.7 parts of triethylamine was added with stirring, 600 parts of deionized water was added while keeping at 50 ℃ or lower, the obtained aqueous dispersion was kept at 50 ℃ for 2 hours and the water-extension reaction was completed, then acetone was distilled off under reduced pressure at 70 ℃ or lower, and the pH was adjusted to 8.0 using triethylamine and deionized water to obtain a urethane resin emulsion (A-1) having an acid value of 17mgKOH/g in solid content, 30% in solid content and an average particle diameter of 0.15. mu.m.

< production of acrylic resin emulsion: [ solution ] A method for producing a polymer

Production example 2

Into a reaction vessel, 2.5 parts of deionized water, "Newcol 707 SF" (anionic emulsifier having a polyoxyethylene chain, made by Nippon emulsifier Co., Ltd., solid content: 30%) and 1 part of a monomer mixture (9 parts of styrene, 39 parts of n-butyl acrylate, 40 parts of 2-ethylhexyl acrylate, 10 parts of 2-hydroxyethyl acrylate, 1 part of methacrylic acid and 1 part of allyl methacrylate) were charged, and the mixture was stirred and mixed by a nitrogen gas flow, and 3 parts of a 3% ammonium persulfate aqueous solution was added at 60 ℃. Subsequently, the temperature was raised to 80 ℃ and a pre-emulsion comprising the remaining 99 parts of the monomer mixture, "Newcol 707 SF" 2.5 parts, 3% ammonium persulfate 4 parts, and deionized water 100 parts was added to the reaction vessel using a metering pump for 4 hours, and aging was carried out for 1 hour after the addition was completed. Thereafter, 33 parts of deionized water was added thereto, and the pH was adjusted to 7.5 with dimethylethanolamine to obtain an acrylic resin emulsion (B-1) having a glass transition temperature of-44 ℃, an average particle diameter of 0.1 μm, and a solid content of 30%.

< production of aluminum pigment paste: [ solution ] A method for producing a polymer

Production example 3

To a stirring and mixing vessel, 45.5 parts of aluminum pigment paste "Hydrolan 2156" (silica-coated aluminum flake pigment paste manufactured by ECKART, pigment content 60%), 35 parts of propylene glycol monomethyl ether, and 17.5 parts of phosphoric acid group-containing resin solution (note 1) were added, and stirred and mixed to obtain aluminum pigment paste (C-1).

(Note 1) phosphoric acid group-containing resin solution: a mixed solvent of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol was charged into a 4 liter flask equipped with a stirrer, a temperature controller and a cooling and heating device, and heated at 110 ℃ for 4 hours, 121.5 parts of a mixture of 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, 15 parts of a polymerizable monomer containing a phosphoric acid group (Note 2), 12.5 parts of 2-methacryloyloxyethyl acid phosphate, 10 parts of isobutanol, and 4 parts of t-butylperoxy octanoate was added to the mixed solvent, and a mixture of 0.5 parts of t-butylperoxy octanoate and 20 parts of isopropanol was further added dropwise over 1 hour. Thereafter, the mixture was stirred and aged for 1 hour to obtain a phosphoric acid group-containing resin solution having a solid content of 50%.

(Note 2) polymerizable monomer containing phosphoric acid group: 57.5 parts of monobutyl phosphoric acid and 41.1 parts of isobutanol are added to a reaction vessel, 42.5 parts of glycidyl methacrylate is added dropwise over 2 hours under aeration of air, and then aging is further performed with stirring for 1 hour. Thereafter, 5.9 parts of isopropyl alcohol was added to obtain a phosphoric acid group-containing polymerizable monomer solution having a solid content of 50%.

< production of base coating: [ solution ] A method for producing a polymer

Production example 5

83.5 parts of the aluminum pigment paste (C-1) obtained in production example 3 was put in a stirring and mixing vessel and stirred for 1 hour, 150 parts of the urethane resin emulsion (A-1) obtained in production example 1 and 150 parts of the acrylic resin emulsion (B-1) obtained in production example 2 were further mixed, 17.8 parts of "Primal ASE 60" (Note 3) were added, stirring was further continued for 1 hour, pH was adjusted with dimethylethanolamine, and deionized water was added to obtain a base paint (I-1) having a solid content of 20%. The viscosity and pH of the base paint (I-1) were measured by the methods described in the specification, and the results were 1000 mPasec and 8.0, respectively.

(Note 3) "Primal ASE 60": the polyacrylic acid thickener has an acid value of 270mgKOH/g and an active ingredient of 28%, manufactured by Rohm and Haas company.

Production example 6

83.5 parts of the aluminum pigment paste (C-2) obtained in production example 4 was put in a stirring and mixing vessel and stirred for 1 hour, and then 150 parts of the urethane resin emulsion (A-1) obtained in production example 1 and 150 parts of the acrylic resin emulsion (B-1) obtained in production example 2 were mixed, 17.8 parts of "Primal ASE 60" (Note 3) were added, and further stirring was continued for 1 hour, and after the pH was adjusted by dimethylethanolamine, deionized water was added to obtain a base paint (I-2) having a solid content of 30%. The viscosity and pH of the base paint (I-2) were measured by the methods described in the specification, and the results were 1500mPa sec and 8.0, respectively.

< production of diluent: [ solution ] A method for producing a polymer

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 mPasec.

(Note 4) "Laponite RD": trade name, (manufactured by Rochwood Additives Limited, inorganic thickener, synthetic hectorite,

(Note 5) "BYK-348": trade name of BYK-CHEMIE, polyether modified polysiloxane Compound, active ingredient 100%

Production examples 8 to 15

Diluents (II-2) to (II-9) were obtained in the same manner as in production example 7, except that the formulation compositions were set as shown in the following table.

TABLE 1

(Note 6) "Uniol D-2000": trade name, manufactured by Nichisu oil Co., Ltd., polypropylene glycol, weight average molecular weight 2000, active ingredient 100%

< production of particle-containing coating: [ solution ] A method for producing a polymer

Production example 16

In a stirring and mixing vessel, 71 parts of water, 10 parts of "Nipsil E-1009" (Note 7), 5 parts of propylene glycol mono-n-propyl ether, 5 parts of urethane resin emulsion (A-1), 5 parts of acrylic resin emulsion (B-1) and 1 part of "BYK-348" were stirred and mixed, 3 parts of "Primal ASE 60" were added, stirring was further continued for 1 hour, the pH was adjusted with dimethylethanolamine, and deionized water was then added to obtain a coating material (III-1) containing particles.

The viscosity and pH of the particle-containing coating material (III-1) were measured by the methods described in the specification, and the results were 1500 mPasec and 8.0, respectively.

(Note 7) "Nipsil E-1009": trade name, product name, made by Tosoh & SILICA, average particle size 1.5 μm, SILICA.

< production of Diluent dope: [ solution ] A method for producing a polymer

Examples 1 to 6 and comparative examples 1 to 3

The base paint (I-1), diluents (II-1) to (II-9) and particle-containing paint (III-1) were thoroughly mixed by hand stirring according to the formulation shown in the following Table to obtain diluted paints (D-1) to (D-9). The viscosity of each diluted paint is also shown in the table. The viscosity was measured by mixing the base paint, the diluent and the particle-containing paint according to the method described in the specification, and then after 5 minutes.

TABLE 2

< evaluation test: [ solution ] A method for producing a polymer

The following evaluation tests were carried out on the diluted paints (D-1) to (D-9) prepared as described above. The results are also shown in Table 2.

(1) Repeated coating fusibility: each diluted paint was spray-coated, and then the operation of blowing air was performed four times until the gloss disappeared, and the fusibility of the paint when repeatedly coated was visually evaluated.

Very good: glossy, wet coating surfaces are smooth.

O: glossy, but slightly uneven on the wet coated surface.

And (delta): slightly glossy, but uneven on the wet coated side.

X: it had no gloss and had large unevenness on the wet coated surface.

(2) Overview of coating: the film surface of each evaluation coated plate was evaluated visually.

Very good: the coated surface was smooth.

O: the coating surface had slight irregularities.

And (delta): the coating surface has irregularities.

(3) Water resistance: after each evaluation coated plate was immersed in warm water at 40 ℃ for 10 days, the coated film surface was observed.

Very good: is very good

O: good effect

And (delta): the coating film swells.

(4) Initial adhesion: each evaluation board was cut with a cutter so as to reach the backing material, 100 checkerboards 1mm × 1mm in size were prepared, cellophane tape was adhered to the surface of each checkerboard, the cellophane tape was peeled off vigorously at 20 ℃, and the number of remaining checkerboard coating films was examined.

Very good: there are 100 residues

O: 99 to 90 residues

And (delta): 89 to 41 residues

(5) Non-uniformity: the metal unevenness at the repaired portion (thick film portion) of each evaluation coated plate was visually evaluated.

Very good: no occurrence of metal unevenness was found at all.

O: the generation of metal unevenness was found a little bit, but within an allowable range.

And (delta): the generation of metal unevenness was found.

Claims (7)

1. A multi-component aqueous coloring base coating composition comprising a main component (I) and a diluent component (II) in combination, characterized in that,

the mass ratio of the main component (I) to the diluent component (II) is in the range of 30 to 400 parts by mass based on 100 parts by mass of the main component (I),

the main component (I) contains an aqueous resin component, a coloring pigment and water, and the diluent component (II) contains a polyether-modified polysiloxane compound, a layered silicate viscosity modifier and water;

wherein the aqueous resin component comprises an acrylic resin emulsion as a part of the component, the acrylic resin emulsion comprises a polyvinyl compound having at least two polymerizable unsaturated groups in 1 molecule as a copolymer component, and the acrylic resin emulsion has a solid acid value of 5mgKOH/g or less.

2. The composition according to claim 1, wherein the diluent component (II) comprises 0.01 to 10.0 mass% of the polyether-modified polysiloxane compound, 0.1 to 3.0 mass% of the layered silicate viscosity modifier, and 60 to 99.9 mass% of water, based on the mass of the diluent component (II).

3. The composition according to claim 1 or 2, wherein the colored pigment is an aluminum flake covered with silica.

4. The composition according to claim 1 or 2, which is a multi-component aqueous coloring base coating composition comprising a main component (I) and a diluent component (II), and further comprising a particulate component (III), wherein the particulate component (III) comprises silica particles and water.

5. The composition according to claim 4, wherein the mass ratio of the main component (I), the diluent component (II) and the particulate component (III) is in the range of 30 to 400 parts by mass of the diluent component (II) and 0.1 to 105 parts by mass of the particulate component (III) per 100 parts by mass of the main component (I).

6. A repair coating method characterized by using the composition according to any one of claims 1 to 5.

7. A repair coating method comprising applying the composition according to any one of claims 1 to 5 and then clear-coating the composition.