CN106010042A - Aqueous coloring basic paint composition - Google Patents

Abstract

The invention provides an aqueous coloring basic paint composition which is used for forming a repair coating film that has no disccomfortableness relative to a color film which is formed on vehicle body and the like. The aqueous coloring basic paint composition is a multi-component composition that includes a main agent component (I) and a diluent component (II) which are combined. The main agent component includes aqueous resin, a coloring pigment, and water; and the diluent component (II) includes polyether-modified polysiloxane compound, an adhesion regualtor and water. The invention also relates to a repair coating method with the aqueous coloring basic paint composition.

Description

Aqueous Color base coating composition

Technical field

The present invention relates to the aqueous used in body of a motor car etc. has set the Repair Coatings of film Color base coating composition.

Background technology

In recent years, from the viewpoint of environmental conservation, paint field it is also proposed coating Water-borne modification requirement.Water and other coating organic solvent are compared, and have as follows Specific physique: although to there is high boiling point, surface tension and dielectric normal for low-molecular-weight Number is the highest.Knowing, these factors produce considerable influence to the painting operation of water paint, Comparatively speaking, usual painting operation is poor, institute for the coating of water paint and organic solvent system The film obtained is not easy to become high glaze.

As improving the painting operation of water paint, forming the strategy of the finish of film, The most typically carry out is the method such as coating resin that uses in water paint of improvement.

But in the field of car repair application, depend on that Repair Coatings is on-the-spot, temperature, Bigger scope is there are, the painting changed at any time due to use on the painting environments such as humidity The water paint of the considerable influence of dress environment, thus be difficult to obtain stable finish outward appearance.

For such problem, patent documentation 1 is recorded following content: by having The organic solvent having specific HLB value is contained in water paint, pretends so that be coated with Industry is good, will not be affected by painting environment and make the finish forming film to become Well.

But, in the upper painting coating process in car repair application, generally based on putty, On the base treatment face of bonding layer surface agent etc., such by becoming the outward appearance identical with setting film The repairing of homology color the most periodically carry out application with painting Color base coating. And, usually proceed as follows: between each application, utilize compressed air as required Blow, thus accelerate being dried of each upper painting Color base film.

Using the water paint described in patent documentation 1 as repairing with being coated with color base Plinth coating and carry out 1 time coating, 1 time blow and periodically repeat coating time, then do Dry film is the most insufficient, sometimes in upper painting with the fusion of coated Color base coating The film that coating process obtains after terminating cause top layer coarse, uneven.

On the other hand, record in patent documentation 2～3: by making aqueous coating composition Thing is by host composition (I), viscosity adjusting agent composition (II) and viscosity adjusting agent composition (III) structure Become, and will each be set to specific composition, thus obtain the film not having the defect such as sagging.

According to these patent documentations, it is filled with wet touching even if being coated with in the stage of water-based paint compositions Wet (ウ ェ ッ ト オ Application ウ ェ ッ ト) mode is carried out continuously, it is possible to obtains and does not has defective film, Can significantly simple Repair Coatings operation, but even if be provided with back tender between stage application Sequence, is also found that in the film formed out that slight top layer is coarse, uneven, it cannot be said that It is to have reached to reappear the such purpose of tone having set film, has remained room for improvement.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2005-213274 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2001-316612 publication

Patent documentation 3: International Publication WO2013/002121 pamphlet

Summary of the invention

The problem solved is wanted in invention

It is an object of the invention to propose a kind of aqueous Color base coating composition, it is suitable for Do not have for the coloring film set etc. of body of a motor car etc. colours film in being formed The repairing film of sense of discomfort.

For solving the scheme of problem

Above-mentioned problem is conducted in-depth research by the present inventor, found that true as follows, Thus reached the present invention: by the aqueous Color base Coating material composition for Repair Coatings The diluent used in thing comprises organopolysiloxane compound, thus improves and be coated with in the stage Repeating in dress is coated with amalgamation.

That is, the present invention relates to the aqueous Color base coating composition of a kind of multicomponent system, its The water of the multicomponent system for host composition (I) and diluent components (II) are combined Property Color base coating composition, it is characterised in that host composition (I) comprises water-base resin Composition, coloring pigment and water, diluent components (II) comprises Siloxane-Oxyalkylene Copolymers Compound, viscosity adjusting agent and water；The invention still further relates to a kind of Repair Coatings method, it is special Levy and be to employ said composition.

The effect of invention

Water according to the multicomponent system with diluent components as constituent according to the present invention Property Color base coating composition so that painting operation is excellent, when having carried out stage application Repeat that to be coated with amalgamation good, can obtain do not have top layer coarse or uneven with set Film does not has the Color base film of the high finish outward appearance of sense of discomfort.

Detailed description of the invention

The aqueous Color base coating composition of the present invention be by by host composition (I) and The compositions of the multicomponent system that diluent components (II) is combined.

Host composition (I) in the present invention comprises water-base resin composition, coloring pigment and water.

As above-mentioned water-base resin composition, can list: emulsion acrylic resin, polyester breast The breast that liquid, epoxy resin latex, ester-polyurethane resin emulsion etc. are scattered in aqueous medium and obtain Liquid；Or water soluble acrylic resin, water-soluble polyester resin, water-soluble epoxy resin, The known composition such as the resin that water soluble polyurethane resin etc. are dissolved in aqueous medium and obtain.

In the present invention, water-base resin composition preferably comprises emulsion acrylic resin.

＜ emulsion acrylic resin ＞

In the present invention, emulsion acrylic resin refers to, will be by with containing (methyl) acryloyl The polymerism unsaturated monomer of base is that required composition, other polymerism as required are unsaturated The emulsion that the copolymer that monomer carries out copolymerization and obtains is dispersed in water.

Specifically, the mean diameter of emulsion acrylic resin is in the model of 0.01～1.0 μm In enclosing, it is preferably in the range of 0.05～0.5 μm.

In this manual, emulsion acrylic resin and carbamate resins described later breast The mean diameter of liquid refers to, utilizes coulter counter method to be measured measuring temperature 20 DEG C And the value of the volume average particle size obtained.Mensuration based on coulter counter method such as can be passed through " COULTER N4 type " (Beckman Coulter K.K. system, trade name) is used to carry out.

As such emulsion acrylic resin, the most preferably use: in water and dispersion In the presence of stabilizer, use polymerization initiator, gather above-mentioned with 1 stage or with the multistage The emulsion acrylic resin that conjunction property unsaturated monomer composition carries out emulsion polymerization and obtains.

In the present invention, as emulsion acrylic resin, can be single-layer type can also be core The multi-layered types such as shell mould, but consider from viewpoints such as repeating coating amalgamation, and single-layer type is preferred 's.

As the polymerism unsaturated monomer of the copolymer composition that can become emulsion acrylic resin, Such as list (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) acrylic acid Propyl ester, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid Pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) propylene Acid straight or branched alkyl (methyl) acrylic acid such as lauryl, (methyl) stearyl acrylate ester Ester；Ester ring type alkyl (the first such as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate Base) acrylate；Aralkyl (methyl) acrylate such as (methyl) benzyl acrylate；(methyl) Alkoxyalkyl (the first such as acrylic acid 2-methoxy acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester Base) acrylate；Perfluoroalkyl (methyl) acrylate；N, N-diethylamino ethyl (first Base) N, N-dialkyl aminoalkyl (methyl) acrylate as acrylate；(methyl) Acrylamide；(methyl) acrylonitrile；The vinyl ester such as vinyl acetate, propionate Compound；The vinyl aromatic compounds such as styrene, α-methyl styrene；(methyl) propylene Allyl propionate, ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, three hydroxyls Methylpropane three (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, new penta Glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, tetramethylolmethane Two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, glycerol two (methyl) Acrylate, 1,1,1-trimethylolethane two (methyl) acrylate, 1,1,1-trihydroxy methyl Ethane three (methyl) acrylate, 1,1,1-trihydroxy methyl propane three (methyl) acrylate, Triallyl isocyanurate, diallyl terephthalate, divinylbenzene etc. are 1 Molecule has many vinyl compounds of at least two polymerism unsaturated group；(methyl) Acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, Hydroxy alkyl (methyl) acrylate such as (methyl) hy-droxybutyl, 1-propenol-3, above-mentioned hydroxyl The 6-caprolactone modification body of base alkyl (methyl) acrylate, it is hydroxyl containing molecular end The polymerism unsaturated monomer of the hydroxyls such as (methyl) acrylate of polyethylene oxide chain； (methyl) acrylic acid, maleic acid .beta.-methylacrylic acid, β-carboxyethyl acrylate etc. are carboxylic Polymerism unsaturated monomer；(methyl) acrylic aldehyde, formoxyl styrene, carbon number 4～7 Vinyl alkyl ketone (such as, ethenyl methyl ketone, vinyl ethyl ketone, vinyl fourth Base ketone etc.), acetoacetoxyethyl (methyl) acrylate, acetoacetoxy groups allyl The polymerism unsaturated monomer containing carbonyl such as ester, diacetone (methyl) acrylamide；Shrink sweet Oil base (methyl) acrylate, Beta-methyl glycidyl (methyl) acrylate, 3,4-epoxy Cyclohexyl methyl (methyl) acrylate, 3,4-epoxycyclohexylethyl (methyl) acrylate, 3,4-epoxycyclohexyl propyl group (methyl) acrylate, allyl glycidyl ether etc. are containing ring The polymerism unsaturated monomer of epoxide；Isocyanatoethyl (methyl) acrylate, different The polymerism unsaturation list of the isocyanato group containings such as acrylic-bis (alpha, alpha-dimethylbenzyl) based isocyanate Body；Vinyltrimethoxy silane, VTES, γ-methacryloxypropyl Base propyl trimethoxy silicane, γ-methacryloxypropyl etc. are containing alkane The polymerism unsaturated monomer of epoxide silicyl；Polymerism unsaturated monomer containing epoxy radicals Or the polymerism unsaturated monomer of hydroxyl and the product of unsaturated fatty acid, dicyclo penta Alkenyloxy group ethyl (methyl) acrylate, dicyclo amylene epoxide propyl group (methyl) acrylate, Double cyclopentenyl (methyl) acrylate etc. are unsaturated containing the polymerism of oxidation curable group Monomers etc., they can individually use or combine two or more and use.

It addition, make emulsion acrylic resin carry out the dispersion stabilizer used during emulsion polymerization It is not particularly limited, include, for example out dialkyl sodium sulfosuccinate, detergent alkylate sulphur Acid sodium, sodium lauryl sulfate, polyethylene glycol oxide alkyl phenyl ether sodium sulfate and alkyl diphenyl The anionic emulsifiers such as base ether sodium disulfonate, polyoxyethylene higher alcohol ether and polyoxygenated Non-ionic emulsifiers such as vinyl alkyl phenyl ether and there is free-radical polymerised double bond Anionic property or the reactive emulsifier of cationic.

Reactive emulsifier refers to the most together have nonionic group, anionic property Group more than any one in group and cationic groups and polymerism unsaturated group Group emulsifying agent, as polymerism unsaturated group, specifically list (methyl) pi-allyl, (methyl) acryloyl group, acrylic, cyclobutenyl etc..As commercially available product, can list " Latemul " (trade name, Kao Corporation system), " Eleminol " (trade name, Sanyo Chemical conversion (strain) system), " Aqualon " (trade name, the first industrial pharmaceutical (strain) is made), " Adekalia Soap " (trade name, rising sun electrification (strain) system), " ANTOX " (trade name, Japan's emulsifying agent (strain) System) etc..

As polymerization initiator, always known polymerization initiator can be used without restriction, Include, for example out Cyclohexanone peroxides, 3,3,5 trimethyl hexanone peroxide, first Pentylcyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, normal-butyl-4,4-bis(t-butylperoxy) valeric acid Double (the uncle of ester, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro-peroxidase, 1,3- A butyl peroxy-isopropyl) benzene, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, Dicumyl peroxide, tert-butyl cumyl peroxide, decanol peroxide, Laurel Acyl peroxide, benzoyl peroxide, DCBP 2,4 dichlorobenzoyl peroxide, two uncles penta Base peroxide, double (tert-butylcyclohexyl) peroxy dicarbonate, tert-butyl hydroperoxide benzene Formic acid esters, 2,5-dimethyl-2,5-two (benzoylperoxy) hexane, peroxidating-2-ethyl The peroxide type polymerization initiators such as hecanoic acid t-butyl ester；2,2 '-azo double (isopropyl cyanide), 2,2 '- Azo two-2-methylbutyronitrile, 1,1 '-azo double (hexamethylene-1-formonitrile HCN), azocumene, 2,2 '- Azo double (2-methylbutyronitrile), 2,2 '-azo two-2,4-methyl pentane nitrile, the double (4-of 4,4 '-azo Cyanopentanoic acid), 2-(tert-butyl group azo)-2-dicyanopropane, double (the 2,4,4-trimethyl of 2,2 '-azo Pentane), 2,2 '-azo double (2-methylpropane), 2,2 '-azo double [2-methyl-N-(2-ethoxy)- Propionic acid amide .], dimethyl 2,2 '-azo double (2 Methylpropionic acid ester), double (the 1-hexamethylene of 1,1 '-azo Alkane-1-formonitrile HCN), 2,2 '-azo double [2-(2-imidazoline-2-base) propane], dimethyl-2,2 '-even The azo type polymerization initiators such as nitrogen diisobutyrate.

In the present invention, as emulsion acrylic resin contained in host composition (I), from From the viewpoint of the resistance to water of Color base film and middle rank abrasiveness (in grind ぎ), comprise Many vinyl compounds in 1 molecule with at least two polymerism unsaturated group are made Emulsion acrylic resin for copolymer composition is preferred.

As above-mentioned many second in 1 molecule with at least two polymerism unsaturated group Alkenyl compound, lists foregoing illustrative compound, can be used alone or combine two kinds Use above, as its copolymerization amount, complete with use in manufacturing at emulsion acrylic resin On the basis of the quality of portion's polymerism unsaturated monomer, the scope of 0.1～10 mass % can be set to In, preferably can be set in the range of 0.5～5 mass %.

It addition, about emulsion acrylic resin, from resistance to water, the repetition of Color base film From the viewpoint of coating amalgamation, in solid content acid number is the scope of below 5mgKOH/g, It is preferably in the scope of below 4mgKOH/g.

It addition, about above-mentioned water-base resin composition, comprise this point of carbamate resins emulsion, It is preferred from the viewpoint of the water-fast tack of Color base film.

About relevant carbamate resins emulsion, can use without restriction in this field Known carbamate resins emulsion, include, for example out by by make polyisocyanates, Polyhydric alcohol and carboxylic glycol carry out the carbamate prepolymer dispersion reacted Yu Shuizhong and the resin emulsion that obtains.

As polyisocyanates, can list: hexamethylene diisocyanate, trimethyl six The fat such as methylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate (cyclo) aliphatic diisocyanates compound；The biuret form addition product of these diisocyanate cpds, Isocyanurate ring addition product；Isophorone diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (hexamethylene Based isocyanate), hexahydrotoluene-2,4-(or-2,6-) diisocyanate, 1,3-(or 1,4-) Two (isocyanatomethyl) hexamethylene, 1,4-cyclohexane diisocyanate, 1,3-Pentamethylene. two The alicyclic diisocyanate compounds such as isocyanates, 1,2-cyclohexane diisocyanate；This A little the biuret form addition product of diisocyanate, isocyanurate ring addition products；Dimethylbenzene two Isocyanates, m xylene diisocyanate, tetramethylxylene diisocyanate, toluene Diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4- Naphthalene diisocyanate, 4,4 '-toluidine diisocyanate, 4,4 '-diphenyl ether isocyanates, (or to) phenylene diisocyanate, 4,4 '-biphenylene diisocyanate, 3,3 '-dimethyl -4,4 '-biphenylene diisocyanate, double (4-isocyanatophenyi) sulfone, isopropylidene are double Aromatic diisocyanate compounds such as (4-phenyl isocyanate)；These diisocyanate The biuret form addition product of compound, isocyanurate ring addition product；Triphenyl methane -4,4 ', 4 "-triisocyanate, 1,3,5-tri-isocyanato-benzene, 2,4,6-tri-isocyanato- Toluene, 4,4 '-dimethyl diphenylmethane-2,2 ', 5,5 '-tetraisocyanate etc. is in 1 molecule There is the polyisocyanate compound of the NCO of more than three；These polyisocyanates The biuret form addition product of compound, isocyanurate ring addition product；Become with NCO For excess ratio make polyisocyanate compound with, ethylene glycol, propylene glycol, 1,4-fourth Glycol, dihydromethyl propionic acid, poly alkylene glycol, trimethylolpropane, hexane triol etc. The hydroxyl of polyhydric alcohol carries out the urethane addition product reacted；These carbamic acids Esterification the biuret form addition product of addition product, isocyanurate ring addition product etc..

As above-mentioned polyhydric alcohol, such as, list: Polyethylene Glycol, polypropylene glycol, poly-sub-second Base-propylidene (block or random) glycol, polytetramethylene ether diol, polyhexamethylene ether The polyether polyol such as glycol, poly-eight methylene ether glycol；By make dicarboxylic acids (adipic acid, Succinic acid, decanedioic acid, 1,3-propanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid etc.) with two Alcohol (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-HD, 3-methyl isophthalic acid, 5-pentanediol, Neopentyl glycol, bishydroxymethyl hexamethylene etc.) carry out polycondensation and obtain polyhydric alcohol, such as, Polyethyleneglycol adipate, polytetramethylene glycol adipate ester, polyhexamethylene adipate ester, poly- Neopentyl adipate, poly-3-methyl amyl adipate ester, poly-ethylidene/butylidene oneself two The PEPAs such as acid esters, poly-neopentyl/hexyl adipate ester；Polycaprolactone polyol, Poly-3-methylpent lactone polyols；Polycarbonate polyol；Ethylene glycol, diethylene glycol, Triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, tetramethylene glycol, hexa-methylene two Alcohol, decamethylene glycol, ethohexadiol, dihydroxymethyl tristane, hydrogenated bisphenol A, ring Hexane dimethanol, 1, the low molecular weight diols class etc. such as 6-hexanediol, can be used alone or also With two or more and use.

As above-mentioned carboxylic glycol, such as, list dihydroxymethyl acetic acid, dihydroxymethyl Propanoic acid, dimethylolpropionic acid etc..

About the manufacture of above-mentioned carbamate prepolymer, can be based on always known method Carry out.

Above-mentioned carbamate resins emulsion can also be to utilize nertralizer to be neutralized to obtain Carbamate resins emulsion.As nertralizer, if carboxyl can be neutralized Nertralizer, then be not particularly limited, include, for example out sodium hydroxide, potassium hydroxide, three Methylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, triethylamine, ammonia etc..

About above-mentioned carbamate resins emulsion, due to the middle rank grinding of Color base film Property be good, thus be preferably the carbamate resins breast in the molecule with circulus Liquid.

The polyisocyanates constituting carbamate resins emulsion more preferably comprises and is derived from fat The compound of ring (cyclo) aliphatic diisocyanates compound is as the polyisocyanic acid of a part for its composition Ester, this is preferred.

It addition, about carbamate resins emulsion, from the resistance to water of Color base film and From the viewpoint of repeating to be coated with amalgamation, solid content acid number is the model of below 20mgKOH/g In enclosing, in the range of preferably 5～18mgKOH/g.

Being explained, in this manual, solid content refers to nonvolatile component, expression be The residue removing the volatile ingredient such as water, organic solvent from sample and obtain, can pass through will The quality of sample is multiplied by solid concentration and calculates.About solid concentration, can make by inciting somebody to action About 3 grams of sample is before 105 DEG C of quality of residues being dried 3 hours and obtain are divided by being dried Quality, thus determine, it addition, there is also situation about representing with percentage rate.

As the mean diameter of above-mentioned carbamate resins emulsion (A), can be at In the range of 0.01～1 μm, particularly can be in the range of 0.05～0.5 μm.

It addition, water-base resin composition preferably further comprises water soluble acrylic resin.At this In description, about water soluble acrylic resin, include, for example out: contain by comprising The polymerism unsaturated monomer of acidic group, the polymerism unsaturated monomer of hydroxyl and other The polymerism unsaturated monomer composition of polymerism unsaturated monomer, at hydrophilic organic solvent In the presence of, utilize polymerization initiator to be polymerized, thus the resin obtained.

As the above-mentioned polymerism unsaturated monomer containing acidic group, such as, list acrylic acid, first Base acrylic acid .beta.-methylacrylic acid, maleic acid, itaconic acid, β-carboxyethyl acrylate etc. are containing carboxylic The polymerism unsaturated monomer of base；2-acrylamido-2-methyl propane sulfonic acid, pi-allyl Sulfonic acid, styrene sulfonic acid sodium salt, sulfoethyl methacrylate and its sodium salt or ammonium salt etc. Containing sulfonic polymerism unsaturated monomer；2-acryloyl-oxyethyl phosphate ester acid, 2- Methacryloxyethyl phosphate ester acid, 2-acryloxypropyl phosphate ester acid, The polymerism unsaturation list of the phosphorous acidic groups such as 2-methacryloxypropyl phosphate ester acid Bodies etc., they can use one or and with two or more and use.

Particularly, by and poly-with carboxylic polymerism unsaturated monomer and phosphorous acidic group Conjunction property unsaturated monomer is as the polymerism unsaturated monomer containing acidic group, thus has raising and exist Repeat to be coated with the confluent effect during present composition.

As the polymerism unsaturated monomer of above-mentioned hydroxyl, list (methyl) acrylic acid 2- Hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) The carbon numbers such as hy-droxybutyl 2～hydroxy alkyl (methyl) acrylate of 8；N- N-methylolacrylamide；1-propenol-3；Hydroxy alkyl (methyl) acrylic acid of carbon number 2～8 The 6-caprolactone modified acrylic acid monomer of ester；Diethylene glycol (methyl) acrylate, three second Glycol (methyl) acrylate, Polyethylene Glycol (methyl) acrylate, dipropylene glycol (methyl) Acrylate, tripropylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, Poly alkylene glycol (methyl) acrylate such as Polyethylene Glycol polypropylene glycol (methyl) acrylate Deng, they can use one or and with two or more and use.

As other polymerism unsaturated monomer above-mentioned, list (methyl) acrylic acid first Ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid isopropyl Ester, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid uncle Butyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 1-Octyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (methyl) acrylic acid 12 Arrcostab ((methyl) lauryl acrylate), (methyl) tridecyl acrylate, (methyl) Stearyl acrylate ester, the different stearyl ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (first Base) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid Cyclo-dodecyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (first Base) alkyl or cycloalkyl (methyl) acrylate such as acrylic acid tristane ester；(methyl) propylene The gathering containing aromatic ring such as acid benzyl ester, styrene, α-methyl styrene, vinyltoluene Conjunction property unsaturated monomer；Vinyltrimethoxy silane, VTES, second Thiazolinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxypropyl trimethoxy Silane, γ-(methyl) acryloxypropyl triethoxysilane etc. has alkoxy silicane The polymerism unsaturated monomer of base；Perfluoro butyl ethyl (methyl) acrylate, perfluoro capryl Perfluoroalkyl (methyl) acrylate such as ethyl (methyl) acrylate；Fluoroolefins etc. have fluorine The polymerism unsaturated monomer of substituted alkyl；There is the optical polymerism functional groups such as dimaleoyl imino Polymerism unsaturated monomer；NVP, ethylene, butadiene, neoprene The vinyl compounds such as diene, propionate, vinyl acetate；(methyl) acrylic acid alkene Propyl ester, ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, four Ethylene glycol bisthioglycolate (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, three hydroxyl first Base propane three (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, new penta 2 Alcohol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, tetramethylolmethane two (first Base) acrylate, tetramethylolmethane four (methyl) acrylate, glycerol two (methyl) acrylic acid Ester, 1,1,1-trimethylolethane two (methyl) acrylate, 1,1,1-trimethylolethane trimethacrylate (methyl) acrylate, 1,1,1-trihydroxy methyl propane three (methyl) acrylate, three allyls Base isocyanuric acid ester, diallyl terephthalate, divinylbenzene etc. are in 1 molecule There is the polymerism unsaturated monomer of at least two polymerism unsaturated group；(methyl) propylene Nitrile, (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylate, N, N- Diethylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) propylene The nitrogenous polymerisms such as the addition product of amide, glycidyl (methyl) acrylate and amine are not Saturated monomer；Glycidyl (methyl) acrylate, Beta-methyl glycidyl (methyl) Acrylate, 3,4-epoxycyclohexyl-methyl (methyl) acrylate, 3,4-epoxycyclohexyl second Base (methyl) acrylate, 3,4-epoxycyclohexyl propyl group (methyl) acrylate, pi-allyl The polymerism unsaturated monomer containing epoxy radicals such as glycidyl ether；2-isocyanatoethyl (methyl) acrylate, an isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate etc. are containing Carbimide. The polymerism unsaturated monomer of base；There is the polyethylene oxide chain that molecular end is alkoxyl (methyl) acrylate；Acrylic aldehyde, N-[2-(2-methyl-4-oxopentyl), diacetone methacrylamide, Acetoacetoxyethyl methacrylate, formoxyl styrene, to have 4～7 carbon former Vinyl alkyl ketone (such as, ethenyl methyl ketone, vinyl ethyl ketone, the vinyl of son Butyl ketone) etc. polymerism unsaturated monomer etc. containing carbonyl.These polymerism unsaturated monomers Can individually use or two or more combinations are used.

It addition, during acidic group is carried out by above-mentioned water soluble acrylic resin preferably by nertralizer With.As relevant nertralizer, foregoing illustrative compound can be enumerated.

About above-mentioned water soluble acrylic resin, it is however generally that solid content acid number is In the range of 5～150mgKOH/g, in the range of preferably 10～100mgKOH/g, Gu Shape thing hydroxyl value is in the range of 10～150mgKOH/g, preferably 20～100mgKOH/g In the range of, weight average molecular weight is 5000～10, in the range of 0000, is preferably In the range of 8,000～70,000.

In this manual, weight average molecular weight refers to, will be by chromatograph of gel permeation (east Cao (strain) makes, " HLC8120GPC ") weight average molecular weight that determines divides with the weight average of polystyrene The value carrying out converting on the basis of son amount and obtain.About chromatographic column, use " TSKgel G-4000H×L”、“TSKgel G-3000H×L”、“TSKgel G-2500H×L”、 " TSKgel G-2000H × L " (being east Cao (strain) system, trade name) these four, in flowing phase: Oxolane, mensuration temperature: 40 DEG C, flow velocity: the bar of 1ml/ minute, detector: RI Carry out under part.

It addition, number-average molecular weight refers to, will by chromatograph of gel permeation (east Cao (strain) system, " HLC8120GPC ") number-average molecular weight that determines with the number-average molecular weight of polystyrene is The value that benchmark carries out converting and obtains.About chromatographic column, use " TSKgel G-4000H×L”、“TSKgel G-3000H×L”、“TSKgel G-2500H×L”、 " TSKgelG-2000H × L " (being east Cao (strain) system, trade name) these four, in flowing phase: Oxolane, mensuration temperature: 40 DEG C, flow velocity: the bar of 1ml/ minute, detector: RI Carry out under part.

About the hydrophilic organic solvent used in polymerization, although distinguish the most closely, But the organic solvent such as dissolving at least 20g at 20 DEG C in water 100g can be listed, Specifically list the alcohol organic solvent such as methanol, ethanol, isopropanol, n-butyl alcohol, isobutanol； The ether organic solvent such as dioxane, oxolane；Glycol monoethyl ether, ethylene glycol monoethyl ether, Ethylene glycol list n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol list n-butyl ether, second two The gylcol ether organic solvents such as alcohol list isobutyl ether, ethylene glycol mono-tert-butyl ether；Diethyl two Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list n-propyl ether, diethylene glycol Dan Yi Propyl ether, diethylene glycol list n-butyl ether, diethylene glycol list isobutyl ether, diethylene glycol list The diethylene glycol ethers organic solvents such as tertbutyl ether；Propylene glycol monomethyl ether, dihydroxypropane single-ether, The propylene glycol ether organic solvents such as propylene glycol list n-propyl ether, propylene glycol monoisopropyl ether；Two Propylene glycol monomethyl ether, DPE, dipropylene glycol list n-propyl ether, dipropylene glycol The dipropylene glycol ethers organic solvents such as monoisopropyl ether；Ethyl acetate, butyl acetate, acetic acid The based organic solvent etc. such as isobutyl ester, 3-methoxybutyl acetas, they can be used alone Or combine two or more and use.

In the case of using above-mentioned water soluble acrylic resin, measure about its compounding, in host Resin solid content contained in composition (I) can be in the range of 1～30 mass %, preferably Can be in the range of 1～20 mass %.

In the present invention, as coloring pigment, can use always known with being not particularly limited Coloring pigment.As its object lesson, list the burning such as titanium oxide, ferrum oxide Thing pigment, the combined oxidation metallic pigments such as titan yellow, white carbon black, azo pigment, quinacridone Class pigment, diketopyrrolopyrroles pigment, class pigment, purple cyclic ketones (perinone) Class pigment, benzimidazoline ketone pigment, isoindoline class pigment, isoindolinone (isoindolinone) class pigment, metal chelation azo class pigment, phthalocyanine pigment, indigo anthracene The coloring pigments such as quinone (indanthrone) class pigment, two alkanes pigment, indigoid type pigment； Aluminum (comprising AM aluminum metallization), copper, zinc, pyrite, nickel, aluminium oxide, Muscovitum, by titanium oxide, The covered aluminium oxide of ferrum oxide, by titanium oxide, the covered Muscovitum of ferrum oxide, glass thin The bright pigment such as sheet, hologram pigment (hologram pigment)；Clay, kaolinite The extender pigments etc. such as soil, barium sulfate, brium carbonate, calcium carbonate, Talcum, Silicon stone, alumina white, They can be used alone or combine two kinds according to color, film performance as its target Use above.

It addition, its shape is not particularly limited in the case of use bright pigment, the most excellent Elect phosphorus lamellar as, from the viewpoint of suppression hydrogen produces preferably by containing phosphate or Sulfonic inorganic agent carries out dispersion process and covers.At phosphorous acidic group or sulfonic Inorganic agent aspect, can be without being suitable for limiting especially always known low molecular compound, altogether Polymers.

It addition, as bright pigment, be preferably used by the covered flake aluminum of silicon dioxide. This is because the film of stable metal appearance can be obtained.

As the aluminum pigment of covering silicon dioxide, " Hydrolan series " (commodity can be used Name, ECKART company system), " Alupaste EMR series " (trade name, Toyo The commercially available products such as Aluminium K.K..

As the compounding amount of coloring pigment, according to tinting as target, according to the face used Material and different, but the solid content conjunction of generally speaking contained relative in host composition resin Count 100 mass parts, in the range of preferably 0.1～300 mass parts, more preferably 0.5～200 In the range of mass parts, this from the standpoint of paint stability it is also preferred that.

" host composition (I) "

In the present invention, water-base resin composition comprises emulsion acrylic resin and carbamic acid In the case of ester resin emulsion, both total amounts are in host composition (I) contained tree In fat solid content in more than 50 mass % scope, it is preferably in the model of more than 80 mass % In enclosing, this is preferred from the viewpoint of the initial tack and resistance to water of Color base film 's.

It addition, as the use ratio of emulsion acrylic resin and carbamate resins emulsion Example, emulsion acrylic resin/carbamate resins emulsion is calculated as by solid quality ratio In the range of 95/5～5/95, in the range of preferably 80/20～20/80, this is from color base It is preferred from the viewpoint of the water-fast tack of plinth film.

Above-mentioned host composition (I) also can comprise the pigment in addition to coloring pigment；Viscosity is adjusted Whole dose, pigment dispersing agent, UV absorbent, light stabilizer, polymer particles, dispersion Auxiliary agent, preservative, silane coupler, defoamer, curing catalysts, organic solvent, in Mediating recipe etc. are other composition such as normally used additive for coatings when prepared by water paint.

In the present invention, according to host composition (I) stably can be stored, can make by with The aqueous Color base coating composition that diluent components described later (II) mixes and obtains is formed There is not the mode of the film of uneven, sagging etc. good finish outward appearance, make host composition (I) viscosity adjusting agent is comprised.

As viscosity adjusting agent, always known viscosity adjusting agent can be used without restriction, Specifically list sodium polyacrylate, polyacrylic acid-(methyl) acrylate copolymer etc. poly-third Olefin(e) acid class viscosity adjusting agent；Pulan Buddhist nun gram (Pluronic) polyethers, polyethers dialkyl, poly- The polyethers viscosity adjusting agent such as ether dialkyl ether, the epoxide modified thing of polyethers；Carbamate is formed Mould assembly viscosity adjusting agent；Montmorillonite, beidellite, nontronite, saponite, Strese Hofmann's hectorite., silicon The mineral-type viscosity adjusting agent such as magnesite, Muscovitum and bentonite；Carboxymethyl cellulose, methyl The cellulose derivative class viscosity adjusting agent such as cellulose, hydroxyethyl cellulose；Casein, cheese The protein-based viscosity adjusting agent such as protein acid sodium, ammonium caseinate；The alginic acid such as sodium alginate Class viscosity adjusting agent；Polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl benzyl ether are altogether The polyethylene base class viscosity adjusting agent such as polymers；Vinyl methyl ether-copolymer-maleic anhydride The copolymer-maleic anhydride class viscosity adjusting agent such as part ester；Polyamide amine salt etc. are polyamide-based viscous Property regulator etc..

Among them, polyacrylic viscosity adjusting agent from coloring pigment at Color base film In orientation from the viewpoint of be good.

As the effective ingredient acid number of this polyacrylic viscosity adjusting agent, such as, can be In the range of 30～350mg/KOH, can be preferably more than 100 and at 300mg/KOH In following scope.As commercially available product, such as, list Rohm and Haas company " Primal ASE60 ", " Primal TT615 ", " Primal RM5 " (being above trade name), " the SN THICKENER 613 " of San Nopco Limited, " SN THICKENER 618”、“SN THICKENER 630”、“SN THICKENER 634”、“SN THICKENER 636 " (being above trade name) etc..

In this manual, effective ingredient refers to, removes water, organic solvent etc. from sample Diluent and the residue that obtains.

About the compounding amount of polyacrylic viscosity adjusting agent, with contained in host composition (I) Resin solid content on the basis of, be about 0.5～20 mass %, preferably 1～10 mass % Left and right.

The solid concentration of above-mentioned host composition (I) is generally adapted to the model of 10～50 mass % In enclosing, being preferably regulated as in the range of 15～40 mass %, this is from painting operation and hidden It is preferred from the viewpoint of property and finish outward appearance.

It addition, the viscosity of above-mentioned host composition (I) is not particularly limited, but steady from storage Qualitative and with the Combination of diluent components described later (II) etc. from the viewpoint of, Ke Yiwei In the range of 100～3000mPa sec, it can be preferably the scope of 600～2000mPa sec In.

In this manual, viscosity is set to: after sample is prepared as 25 DEG C 10 minutes Within, use viscometer digital Vismetron viscometer VDA type (Shibaura Systems Co., Ltd. system) value obtained is measured with rotating speed 60rpm.

" diluent components (II) "

In the present invention, diluent components (II) comprise Siloxane-Oxyalkylene Copolymers compound, Viscosity adjusting agent and water.

In the present invention, can be by diluent components (II) being mixed in before application Above-mentioned host composition (I), controls aqueous Color base coating composition according to painting environment Rheological behavior, by constituting aqueous Color base coating composition in this wise, thus can protect Hold the storage stability of each composition, can be formed will not sagging, not occur uneven etc. and Repeat to be coated with the Color base film of the good finish excellent appearance of amalgamation.

As relevant Siloxane-Oxyalkylene Copolymers compound, list the end at polysiloxanes The compound etc. importing polyether chain in end and/or side chain and obtain, it is also possible to be by poly- Siloxanes has imported in the lump the epoxy radicals in addition to polyether chain, amino, such as (methyl) Organic group as acryloyl group and the comodified polysiloxane compound that obtains.

As foregoing polyethers modified polyorganosiloxane compound, such as can use 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 than；SHIN-ETSU HANTOTAI Learn Industrial Co., Ltd system], 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 (more than；BYK-Chemie company system), 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、SILWETFZ-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, SH8400, SF8410 [with On；Dow Corning Toray Silicone Co., Ltd. system], L032, L051, L066 [with On；Wacker Asahikasei Silicone Co., Ltd system] etc. commercially available product, they can be independent Or combine two or more.

As the viscosity adjusting agent that can comprise in diluent components (II), can be from above-mentioned host Fit among the viscosity adjusting agent exemplified in the explanation of viscosity adjusting agent contained in composition (I) Use when selection.

In the present invention, in diluent components (II), mineral-type viscosity adjusting agent is preferred.

As relevant mineral-type viscosity adjusting agent, can use in this field public without restriction The mineral-type viscosity adjusting agent known, such as, list the mineral such as phyllosilicate, and they are permissible It is any one in natural product, composite, processed product.As object lesson, enumerate Go out montmorillonite, beidellite, nontronite, saponite, Strese Hofmann's hectorite., humite, Muscovitum and Bentonite etc..They can also be diluted by the diluent media such as organic solvent and/or water.

As commercially available product, " Bentone 27 ", " Bentone34 ", " Bentone can be listed 38”、“Bentone SD-1”、“Bentone SD-2”、“Bentone SD-3”、 " Bentone52 ", " Bentone 57 " (any above Dou Shi Rheox company system, commodity Name), " Tixogel VP ", " Tixogel TE ", " Tixogel UN ", " Tixogel EZ100 ", (any above is all Sud Chemical for " Tixogel MP100 ", " Tixogel MP250 " Company's system, trade name), " Claytone 40 ", " Claytone 34 ", " ClaytoneHT ", " Claytone APA ", " Claytone AF ", " ClaytoneHY " (any above are Southern Clay Products company system, trade name), " Laponite RD ", " Laponite RDS”、“Laponite HW”、“Laponite EP”、“Laponite S482”、 (any above is all Rochwood for " LaponiteOG ", " Laponite LV " AdditivesLimited company system, trade name) etc..

Adjust as the Siloxane-Oxyalkylene Copolymers compound in diluent components (II), viscosity The use ratio of agent and water, on the basis of diluent components (II) quality, polyether-modified (gathering) Silicone compounds is in the range of 0.01～10.0 mass %, preferably 0.05～5.0 mass % In the range of, viscosity adjusting agent is in the range of 0.1～3.0 mass %, preferably 0.3～2.0 In the range of quality %, water is in the range of 60～99.9 mass %, preferably 70～99.5 In the range of quality %, this is suitable.

It addition, in above-mentioned diluent components (II), in order to improve the storage of diluent components (II) Stability, can comprise the polyol compound with polyalkylene skeleton.

As having the polyol compound of polyalkylene skeleton, such as, list diethyl two Alcohol, triethylene glycol, TEG, Polyethylene Glycol, dipropylene glycol, polypropylene glycol, two fourths Glycol, polytetramethylene glycol, poly(ethylene oxide), poly(propylene oxide), there is oxirane/epoxy The polyalkylene polyhydric alcohol of at least one structure in the block of propane or random copolymerization；Logical Cross by trimethylolethane, trimethylolpropane, poly-trimethylolpropane, tetramethylolmethane, Polypentaerythritol, sorbitol, mannitol, glycerol, polyglycereol, polytetramethylene glycol etc. The polyhydric alcohol comprising polyalkylene skeleton that polyhydric alcohol carries out polyalkylene modification and obtains；Make For above-mentioned polyalkylene polyhydric alcohol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, The PEPA of the condensation substance of the polyprotic acid such as itaconic acid, adipic acid, M-phthalic acid；Will The caprolactone modification polyhydric alcohol etc. that polyether polyol carries out caprolactone modification and obtains.

About the weight average molecular weight of the above-mentioned polyol compound with polyalkylene skeleton, place In the range of 100～10000, it is preferably in the range of 400～5000.

It addition, about the consumption of the above-mentioned polyhydric alcohol with polyalkylene skeleton, with diluent Effective ingredient quality 100 mass parts of mineral-type thickening agent contained in composition (II) is base Standard, is in the range of 50～1000 mass parts, is preferably in 100～500 mass parts In the range of, this considers it is desired from viewpoints such as the resistances to water of metal foundation film.

It is steady that above-mentioned diluent components (II) also can comprise water-base resin, UV absorbent, light Determine agent, polymer particles, surface conditioner, dispersing aid, preservative, silane coupler, Defoamer, curing catalysts, organic solvent, nertralizer etc. are logical when prepared by water paint Other compositions such as the additive for coatings often used.

Among them, as organic solvent, owing to having and Siloxane-Oxyalkylene Copolymers chemical combination Thing the most further improves and repeats to be coated with confluent effect, thus hydrophilic solvent is excellent Choosing.

As relevant hydrophilic organic solvent, such as list methanol, ethanol, isopropanol, The alcohols solvent such as n-butyl alcohol, isobutanol；The ether solvent such as dioxane, oxolane；Second two Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol list n-propyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol list n-butyl ether, ethylene glycol list isobutyl ether, ethylene glycol mono-tert-butyl ether, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list n-propyl ether, diethylene glycol list Isopropyl ether, diethylene glycol list n-butyl ether, diethylene glycol list isobutyl ether, diethylene glycol The glycol ethers solvents such as single tertbutyl ether；Propylene glycol monomethyl ether, dihydroxypropane single-ether, third Glycol list n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol The propylene glycol ethers such as single ether, dipropylene glycol list n-propyl ether, dipropylene glycol monoisopropyl ether Solvent；Ethyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetas etc. Esters solvent, they can be used alone, or can and with and use.

As the hydrophilic organic solvent that can comprise in diluent components (II), preferably comprise third Glycol ethers solvent.

About the consumption in the case of using above-mentioned hydrophilic solvent, with diluent components (II), on the basis of quality, it is in the range of 0.1～50.0 mass %, is preferably in In the range of 0.5～30.0 mass %, because inhomogeneities can be suppressed, thus preferably.

The viscosity of the diluent components (II) foregoing described is not particularly limited, but from storage Hide stability and with the Combination of aforesaid host composition (II) etc. from the viewpoint of, permissible It is in the range of 10～300mPa sec, can be preferably in the range of 10～100mPa sec.

＜ particulate component (III) ＞

About the aqueous Color base coating composition of the present invention, particularly comprising bright property In the case of the metal foundation coating composition of pigment, it is possible to be set to above-mentioned host composition (I) And on the basis of diluent components (II), it is further combined many one-tenth of particulate component (III) Point be, i.e. three component system.

And, this particulate component (III) comprises silica dioxide granule and water, and this is from being formed The light viewpoint such as sense, the transparent feel consideration of Color base film, be preferred.

As relevant silica dioxide granule, list micropowder silicon dioxide, colloidal state dioxy SiClxs etc., list " Syloid " series (trade name, Grace Japan company system), " AEROSIL " series (trade name, Nippon Aerosil Co., Ltd. system), " ACEMATT " Series (trade name, DEGUSSA company system), " Sylysia " series, " Sylophobic " Series, " Sylosphere " series (more than, trade name, Fuji Silysia Chemical LTD. System), " Quartron " series (trade name, Hibiscus rosa-sinensis's chemistry (strain) system), " Fine Seal " series (business The name of an article, (strain) Tokuyama system), " NIPSIL " series (trade name, Tosoh Silica Corporation system), " Mizukasil " series (trade name, marshy land chemistry (strain) system) etc..

About the mean diameter of relevant silica dioxide granule, it is in the scope of 0.1～25 μm In, it is in the range of 0.5～10 μm and can suppress to be caused by the thickness of Color base film The difference of light sense and uneven sense, thus preferably.

The mean diameter of silica dioxide granule is the average particle of volume reference in this manual The particle size distribution that footpath (D50) is to utilize laser diffraction formula particle size distribution device and measures 50% value.

About the active constituent content of the silica dioxide granule in particulate component (III), with granule It is in the range of 1～50 mass % on the basis of composition (III) quality, preferably 3～40 mass % In the range of, this is suitable.

Particulate component (III) preferably also comprises water-base resin on the basis of silica dioxide granule. By making particulate component (III) comprise water-base resin, thus there is the storage of particulate component (III) Stability becomes good effect.

As above-mentioned water-base resin, always known water-base resin can be used without restriction, But carbamate resins emulsion and emulsion acrylic resin are preferably used.As relevant Carbamate resins emulsion and emulsion acrylic resin, can use respectively above-mentioned master Saying of carbamate resins emulsion contained in agent composition (I) and emulsion acrylic resin Suitable resin emulsion among the resin emulsion listed in bright.

In the case of particulate component (III) comprises water-base resin, about the solid content of water-base resin Content, is in the scope of 1～300 mass parts on the basis of silica dioxide granule 100 mass parts In, it being preferably in the range of 10～200 mass parts, this is preferred.

When the amount of water-base resin contained in particulate component (III) is too much, then aqueous Color base The viscosity of coating uprises sometimes, and when mixing each composition (I)～(III), stirring becomes sometimes Difficulty.

Particulate component (III) comprises carbamate resins emulsion and emulsion acrylic resin In the case of, as its ratio, carbamate resins emulsion/emulsion acrylic resin is pressed Solid ratio is in the range of 5/95～95/5, is preferably in the model of 30/70～70/30 In enclosing.

In the case of carbamate resins emulsion is less than this scope, at the beginning of Color base film Beginning tack is the poorest, and time the most too much, then dope viscosity uprises sometimes, is being coated with When material is made, stirring becomes difficulty sometimes.

It addition, particulate component (III) preferably comprises viscosity adjusting agent as of its composition Point.Thus, have the miscibility with host composition (I) and diluent components (II) good, And obtain the effect of the excellent Color base film of light sense.

Relevant viscosity adjusting agent is not particularly limited, can be from contained host composition (I) Viscosity adjusting agent explanation in suitably select among the viscosity adjusting agent that exemplifies and use, But from the viewpoint of the storage stability of particulate component (III), use polyacrylic to glue Property regulator is preferred.

About the active constituent content of the viscosity adjusting agent in particulate component (III), become with granule It is in the range of 0.1～20 mass % on the basis of dividing (III) quality, preferably 0.1～10 mass % In the range of, this is suitable.

It addition, particulate component (III) preferably comprises Siloxane-Oxyalkylene Copolymers compound.This is Because melting the coating that repeats when being coated with aqueous Color base coating composition is repeated several times In conjunction property, there is effect.

As relevant Siloxane-Oxyalkylene Copolymers compound, can be from above-mentioned diluent components (II) explanation is drawn up and suitably selects among the compound and use.

On the basis of the quality of silica dioxide granule, above-mentioned Siloxane-Oxyalkylene Copolymers compound Use in the range of 0.5～40 mass %, preferably make in the range of 2.0～20 mass % With, this is preferred from the viewpoint of the initial tack of Color base film.

It addition, above-mentioned particulate component (III) comprises organic solvent, this is preferred.This is Viewpoint in the storage stability of particulate component (III).Additionally this is because, keeping granule The inlet of the container of composition (III) adheres to the dioxy caused by silica dioxide granule sometimes SiClx film, the most thus causes making film at the film formed by aqueous Color base coating Property aspect goes wrong, but can change by making particulate component (III) comprise organic solvent This phenomenon kind.

About organic solvent, always known organic solvent can be used, but particularly at this In invention, preferably boiling point is less than 150 DEG C and water solubility is the hydroxyl of more than 10 Organic solvent.

As relevant solvent, such as list methanol, ethanol, isopropanol, n-butyl alcohol, The alcohol organic solvent such as isobutanol, methoxypropanol；Glycol monoethyl ether, ethylene glycol list second The gylcol ether organic solvents such as ether, ethylene glycol list n-propyl ether, ethylene glycol monoisopropyl ether； Propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether, propylene glycol list isopropyl The propylene glycol ether organic solvents etc. such as base ether, they can be used alone or combine two or more And use.

About the content of the organic solvent in particulate component (III), with the matter of silica dioxide granule On the basis of amount, it is in the range of 1～300 mass %, is preferably in 10～200 mass % In the range of.

In particulate component (III), it is possible to comprise the granule in addition to silica dioxide granule, Water, UV absorbent, light stabilizer, dispersing aid, preservative, silane coupler, The normally used painting when prepared by water paint such as defoamer, curing catalysts, nertralizer Other compositions such as material additive.

The viscosity of above-mentioned particulate component (III) is not particularly limited, but from particulate component (III) Storage stability and the viewpoint of painting operation of aqueous Color base coating composition Consider, can be at, in the range of 10～2000mPa sec, preferably can be at In the range of 10～1000mPa sec.

" aqueous Color base coating composition "

Host composition (I) and diluent components (II) and use as desired in the present invention Particulate component (III) be to take care of respectively, application dealer is will be by each one-tenth before application Divide stirring mixing, utilize water etc. to carry out viscosity adjustment as required, thus the present invention can be prepared Aqueous Color base coating composition.Being explained, in this manual, what is called will Before application, it is impossible to define entirely according to application dealer and/or painting site, but example As can list carry out 3 hours of application before till between.

About the host composition (I) in above-mentioned aqueous Color base coating composition and dilution The mass ratio of agent composition (II), suitably can adjust according to painting environment etc., but it is said that in general, On the basis of these host composition (I) 100 mass parts, diluent components (II) is 30～400 matter In the range of amount part, in the range of preferably 40～350 mass parts, or become about host Divide (I), diluent components (II) and the mass ratio of particulate component (III), it is however generally that with master On the basis of agent composition (I) 100 mass parts, diluent components (II) is in 30～400 mass parts In the range of, it is preferably in the range of 40～350 mass parts, particulate component (III) is in In the range of 0.01～105 mass parts, it is in the range of 0.1～50 mass parts, preferably locates In the range of 1～35 mass parts, this is from the outward appearance of Color base film and Physical properties of coating film It is preferred that viewpoint considers.

It addition, the most as required, it is possible to by polyisocyanate curing agent, end-blocking Isocyanate curing agent, melamine cured dose, oxazoline firming agent, carbodiimide solidification The firming agent such as agent are contained in above-mentioned host composition (I), diluent components (II) and particulate component (III) in any one in, or it also is used as individual components.

The solid of the aqueous Color base coating composition of the present invention obtained as described above Substrate concentration is typically in the range of 5～50 mass %, is preferably in 10～40 mass % In the range of, this is excellent from the viewpoint of painting operation and disguise and finish outward appearance Choosing.

It addition, viscosity during application above-mentioned aqueous Color base coating composition limits the most especially System, but be in, in the range of 50～800mPa sec, being preferably in 100～600mPa sec In the range of, this is good from painting operation, further from the finish of Color base film It is preferred from the viewpoint of sight.

" application "

About the aqueous Color base coating composition of the present invention, available atomized spray painting, quiet The known application means such as electropaining dress, brush application, roller application carry out application, but from Atomized spray painting is preferably carried out from the viewpoint of the finish outward appearance of film.

About application number of times, can be once, but from taking into account finish outward appearance and concealed Viewpoint considers, preferably by identical coating with repeatedly, the degree of such as 2～6 times carries out repeating to be coated with Cloth and application.

In the case of repeating to be coated with application, it is possible to arrange between each application as required and dry Air blowing under (after application, film being stood at normal temperatures), room temperature or less than 60 DEG C, 10 points The operations such as the preparation heating below clock.

The application of aqueous Color base coating composition terminate after dry be not particularly limited, In the case of supernatant described later is repeated coating, can be undried state, but such as Preferably 20～100 DEG C, be dried 5～60 minutes under the temperature conditions of preferably 40～80 DEG C. Thickness suitably can adjust according to the state of coated surface, but generally speaking as dry film thickness, In the range of 5～100 μm, particularly 10～60 be preferred in the range of μm.

As applicable coated surface, always known substrate surface or be arranged at this base can be exemplified The coated surface of material, this base material is not particularly limited, such as enumerate tap a blast furnace, the metal such as aluminum；Mould The organic substrates such as material；The inanimate matter base materials such as concrete, timber etc., additionally as being arranged at this The film of base material, is not particularly limited, include, for example out be arranged at car body etc., Formed out by basic film and the supernatant film obtained based on Color base coating composition Multilayer film, it is also possible to be to be appropriately arranged with primer coating film, electricity in the lower floor of this basis film The films such as electrodeposition coating film, middle painting film and the multilayer film that obtains.

It addition, the aqueous Color base coating composition of the present invention also is used as shape One-tenth is at the repairing coating of the film of above-mentioned coated surface.In the case, can advance with greasy Coated surface is anticipated by son or bonding layer surface agent etc..Additionally, it is possible on being coated with After stating aqueous Color base coating composition, application supernatant Coating material composition on this film Thing.

As relevant supernatant coating composition, can use always known with being not particularly limited Supernatant coating composition, the most preferably use: with containing cross-linking functional group such as hydroxyls Acrylic resin, fluororesin be host composition, and containing blocked polyisocyanates, many Isocyanates, melmac etc. are as the curable coating of firming agent；Or with fiber Jaqan coating (the lacquer that acrylic resin is main component that element acetate butyrate is ester modified Paint) etc..

Among them, use and the one-tenth comprising hydroxy-containing resin is divided into host composition, Jiang Bao One-tenth containing polyisocyanate compound is divided into the double-formulation coating of curing agent component, and this can obtain Even if obtaining desired appearance of film and also can obtaining water-fast under conditions of force drying The film of the physical properties excellent such as property, thus preferably.

In above-mentioned supernatant coating composition, pigment class, fiber can be contained the most as required Element derivatives class, add resin, UV absorbent, light stabilizer, surface conditioner, The additive for coatings such as curing catalysts.

Embodiment

Hereinafter, it is more particularly described the present invention by embodiment, but the present invention is not limited only to this A little embodiments.Being explained, " part " and " % " in following example represents " mass parts " respectively And " quality % ".

The manufacture of ＜ carbamate resins emulsion: ＞

Manufacture example 1

The polytetramethylene glycol adipate ester of number-average molecular weight 2000 is added in reaction vessel 115.5 parts, the polycaprolactone glycol 115.5 parts of number-average molecular weight 2000, dihydroxymethyl third Acid 23.2 parts, BDO 14.5 parts and isophorone diisocyanate 120.1 parts, Under agitation in stream of nitrogen gas, obtain NCO content 85 DEG C of reactions 7 hours The prepolymer of 4.0%.Then this prepolymer is cooled to 50 DEG C, adds 165 parts of acetone also And dissolve equably, the most under agitation add triethylamine 15.7 parts, remain 50 DEG C Following while adding deionized water 600 parts, the aqueous dispersion obtained is kept 2 at 50 DEG C Hour and the water reaction of propagation that finished, the most under reduced pressure below 70 DEG C by acetone steam Evaporate and remove, utilize triethylamine and deionized water that pH is adjusted to 8.0, it is thus achieved that solid content The carbamic acid that acid number is 17mgKOH/g, solid content 30%, mean diameter are 0.15 μm Ester resin emulsion (A-1).

The manufacture of ＜ emulsion acrylic resin: ＞

Manufacture example 2

Deionized water 100 parts, " Newcol707SF " (Japan's emulsifying is added in reaction vessel Agent company system, has the anionic emulsifier of polyethylene oxide chain, solid content 30%) 2.5 Part and monomer mixture (styrene 9 parts, n-butyl acrylate 39 parts, acrylic acid 2- Octyl Nitrite 40 parts, acrylic acid 2-hydroxyl ethyl ester 10 parts, methacrylic acid 1 part, methyl Allyl acrylate 1 part) among 1 part, utilize stream of nitrogen gas be stirred mixing, 60 DEG C add 3% ammonium persulfate aqueous solution 3 parts.Then, being warming up to 80 DEG C, cost 4 is little Time use dosing pump by by remaining 99 parts of aforementioned monomer mixture, " Newcol707SF " 2.5 parts, 3% Ammonium persulfate. 4 parts and deionized water 100 parts composition Pre-emulsion be incorporated in reaction vessel, add and carried out ripening in 1 hour after terminating.Thereafter, Add deionized water 33 parts, utilize dimethylethanolamine to be adjusted to pH7.5, it is thus achieved that glass Glass transition temperature is-44 DEG C, mean diameter is 0.1 μm, the acrylic acid of solid content 30% Resin emulsion (B-1).

The manufacture of ＜ aluminum pigment paste: ＞

Manufacture example 3

Aluminum pigment paste " Hydrolan2156 " (ECKART is added in stirring mixing container Company's system, covers the flake aluminum pigment paste of silicon dioxide, pigment content 60%) 45.5 parts, Propylene glycol monomethyl ether 35 parts, the resin solution (note 1) 17.5 parts of phosphorous acidic group, be stirred Mix and obtain aluminum pigment paste (C-1).

The resin solution of (note 1) phosphorous acidic group: to possess have agitator, thermoregulator with And the flask of 4 liters of cold-hot machine adds methoxypropanol 27.5 parts, isobutanol 27.5 parts Mixed solvent, be heated to be 110 DEG C, will be by styrene 25 parts, methyl-prop with 4 hours Olefin(e) acid N-butyl 27.5 parts, " the different stearyl ester of acrylic acid " (Osaka organic chemistry company system) 20 Part, the polymerizable monomer (note 2) 15 parts of hydroxy butyl acrylate 7.5 parts, phosphorous acidic group, 2-methacryloxyethyl phosphate ester acid 12.5 parts, isobutanol 10 parts, the tert-butyl group 121.5 parts of the mixture that peroxidation acid ester is 4 parts is incorporated in above-mentioned mixed solvent, enters One step has dripped with 1 hour and has comprised tert-butyl hydroperoxide caprylate 0.5 part and isopropanol 20 The mixture of part.Thereafter, stir ripening 1 hour thus obtain containing of solid content 50% The resin solution of phosphate.

The polymerizable monomer of (note 2) phosphorous acidic group: add monobutyl phosphoric acid in reaction vessel 57.5 parts, isobutanol 41.1 parts, with 2 hours dropping methacrylic acids under air vent Ethylene oxidic ester 42.5 parts, the most further stirring ripening 1 hour.Thereafter, add different Propanol 5.9 parts, thus obtain the polymerizable monomer solution of the phosphorous acidic group of solid content 50%.

The manufacture of ＜ basic coating: ＞

Manufacture example 5

The aluminum pigment paste (C-1) 83.5 parts obtained by manufacture example 3 is incorporated in stirring mixing In container, stir 1 hour, then by by manufacturing the carbamate resins breast that example 1 obtains Liquid (A-1) 150 parts and the emulsion acrylic resin that will be obtained by manufacture example 2 further (B-1) 150 parts mix, interpolation " Primal ASE60 " (note 3) 17.8 parts, further Continue stirring 1 hour, utilize dimethylethanolamine to add deionized water after have adjusted pH, Obtain the basic coating (I-1) of solid content 20%.The viscosity of this basic coating (I-1), pH Method described in specifications measures, result be respectively 1000mPa sec, 8.0.

(note 3) " Primal ASE60 ": trade name, Rohm and Haas company system, poly-third Olefin(e) acid system thickening agent, acid number 270mgKOH/g, effective ingredient 28%.

Manufacture example 6

The aluminum pigment paste (C-2) 83.5 parts obtained by manufacture example 4 is incorporated in stirring mixing In container, stir 1 hour, then by by manufacturing the carbamate resins breast that example 1 obtains Liquid (A-1) 150 parts and the emulsion acrylic resin that will be obtained by manufacture example 2 further (B-1) 150 parts mix, interpolation " Primal ASE60 " (note 3) 17.8 parts, further Continue stirring 1 hour, utilize dimethylethanolamine to add deionized water after have adjusted pH, Obtain the basic coating (I-2) of solid content 30%.The viscosity of this basic coating (I-2), pH Method described in specifications measures, result be respectively 1500mPa sec, 8.0.

The manufacture of ＜ diluent: ＞

Manufacture example 7

Stirring mixing container in, by 975 parts of water, " Laponite RD " (note 4) 5 parts, " BYK-348 " (note 5) 20 parts of stirring mixing, it is thus achieved that diluent (II-1).Viscosity is 15mPa·sec。

(note 4) " Laponite RD ": trade name, (Rochwood Additives Limited Company's system, mineral-type thickening agent, synthetic li-montmorillonite,

(note 5) " BYK-348 ": trade name, BYK-CHEMIE company system, polyether-modified Polysiloxane compound, effective ingredient 100%

Manufacture example 8～15

Formula composition is set as shown in following table, in addition, with manufacture example 7 Similarly operate and obtain diluent (II-2)～(II-9).

Table 1

(note 6) " Uniol D-2000 ": trade name, Japan Oil Co's system, polypropylene glycol, Weight average molecular weight 2000, effective ingredient 100%

The manufacture of the ＜ coating containing granule: ＞

Manufacture example 16

Stirring mixing container in, by 71 parts of water, " Nipsil E-1009 " (note 7) 10 parts, Propylene glycol list n-propyl ether 5 parts, carbamate resins emulsion (A-1) 5 parts, acrylic acid tree Fat liquor (B-1) 5 parts, " BYK-348 " 1 part of stirring mixing, add " Primal ASE60 " 3 Part, continue to stir 1 hour, utilize dimethylethanolamine to have adjusted pH, then Add deionized water, it is thus achieved that the coating (III-1) containing granule.

This contain the viscosity of coating (III-1) of granule, pH to specifications described in method Measure, result be respectively 1500mPa sec, 8.0.

(note 7) " Nipsil E-1009 ": trade name, east Cao's SILICA system, mean diameter 1.5 μm, silicon dioxide.

The manufacture of ＜ dilution coating: ＞

Embodiment 1～6 and comparative example 1～3

Basic coating (I-1), diluent (II-1)～(II-9), coating (III-1) containing granule are pressed Form according to the formula shown in following table, utilize hands stirring to be sufficiently mixed, it is thus achieved that dilute Release coating (D-1)～(D-9).It addition, describe the viscosity of each dilution coating in table in the lump. About the mensuration of viscosity, to specifications described in method carry out, by basic coating with dilute Release after agent mixes with the coating containing granule, carrying out after 5 minutes.

Table 2

＜ evaluation test: ＞

About the dilution coating (D-1) being made for as described above～(D-9), to following each Project has carried out evaluation test.Result is shown in the lump table 2.

(1) repeat to be coated with amalgamation: each dilution coating carries out atomized spray painting, then until The operation that gloss is blown till disappearing carries out four times, and visual valuation repeats painting when being coated with The amalgamation of material.

◎: glossy, wet painting face is smooth.

Zero: glossy, but slightly have concavo-convex in wet painting face.

△: the most glossy, but have concavo-convex at wet painting mask.

×: lackluster, have big concavo-convex at the wet mask that is coated with.

(2) film general survey: the coated surface of each evaluation coated plate by visual valuation.

◎: painting face is smooth.

Zero: slightly have concavo-convex in painting face.

△: have concavo-convex being coated with mask.

(3) resistance to water: each evaluation coated plate is immersed in the warm water of 40 DEG C after 10 days, observes Film coated surface.

◎: the best

Zero: good

△: film swelling.

(4) initial tack: utilize cutting machine that each evaluation is coated with according to the mode arriving bed material Plate is cut, and makes the gridiron pattern of 100 size 1mm × 1mm, attaches on its surface Adhesion cellophane adhesive tape, after 20 DEG C have been peeled off this adhesive tape tempestuously, has investigated chessboard The extant number of lattice film.

◎: remaining 100

Zero: remaining 99～90

△: remaining 89～41

(5) inhomogeneities: uneven to the metal at the repairing position (thick film part) of each evaluation coated plate Even carry out visual valuation.

◎: the generation uneven entirely without finding metal.

Zero: be found that the generation that metal is uneven a little, but be in permissible range.

△: be found that the generation that metal is uneven.

Claims (9)

1. an aqueous Color base coating composition for multicomponent system, it is host to be become The aqueous of the multicomponent system that point (I) and diluent components (II) are combined color base Plinth coating composition, it is characterised in that

Host composition (I) comprises water-base resin composition, coloring pigment and water, and diluent becomes (II) is divided to comprise Siloxane-Oxyalkylene Copolymers compound, viscosity adjusting agent and water.

Compositions the most according to claim 1, wherein, diluent components (II) comprises Siloxane-Oxyalkylene Copolymers compound 0.01～10.0 mass %, viscosity adjusting agent 0.1～3.0 Quality %, water 60～99.9 mass %.

Compositions the most according to claim 1 and 2, wherein, water-base resin composition Comprising an emulsion acrylic resin part as its composition, emulsion acrylic resin comprises Many vinyl compounds in 1 molecule with at least two polymerism unsaturated group are made For copolymer composition.

4. according to the compositions according to any one of claims 1 to 3, wherein, coloring face Material is by the covered flake aluminum of silicon dioxide.

5. according to the compositions according to any one of Claims 1 to 4, wherein, about master Agent composition (I) and the mass ratio of diluent components (II), with host composition (I) 100 mass parts On the basis of, diluent components (II) is in the range of 30～400 mass parts.

6., according to the compositions according to any one of Claims 1 to 4, it is to become in host It is further combined particulate component (III) many on the basis of dividing (I), diluent components (II) The aqueous Color base coating composition of composition system, wherein, particulate component (III) contains dioxy Silicon carbide particle and water.

Compositions the most according to claim 6, wherein, about host composition (I), Diluent components (II) and the mass ratio of particulate component (III), with host composition (I) 100 matter On the basis of amount part, diluent components (II) is in the range of 30～400 mass parts, granule Composition (III) is in the range of 0.1～105 mass parts.

8. a Repair Coatings method, it is characterised in that employ in claim 1～6 Compositions described in any one.

9. a Repair Coatings method, wherein, is coated with any one of claim 1～6 Described compositions, then carries out clear-coated.