CN106010203A - Aqueous metal based paint composition - Google Patents

Abstract

The invention provides an aqueous metal based paint composition. The paint composition is suitable for forming a repairing coating on an old metal coating, which has already been coated on the body of a vehicle, and no uncomfortable feeling is generated. The aqueous metal based paint composition comprises multiple components and is prepared by compounding a main agent component (I) and a diluent component (II). The main agent component (I) comprises resin emulsion (A) containing carbamate, acrylic resin emulsion (B), a bright pigment (C), and water. The diluent component (II) comprises a viscosity adjuster and water. The paint composition is characterized in that the composition comprises micro powder (D) made of resin particles or body pigments with an average particle size of 0.1 to 0.25 [mu]m.

Description

Water-based metal base coating composition

Technical field

The present invention relates to the Repair Coatings of metal deposit set at body of a motor car etc. uses Water-based metal base coating composition.

Background technology

Know, the metal obtained at the metallic pigments by being compounded with aluminum pigment as representative Base coating composition aspect, depend on these metallic pigments dispersity in coating or The state etc. of the orientation in film, thus occur occurring metal uneven or cannot obtaining The problem such as metallic luster sense of target, people propose various improvement to it and carry Case.

Such as Patent Document 1 discloses a kind of metal foundation coating composition, wherein, Mean diameter and mean diameter thickness is comprised for spy in the film formative resin of specified quantitative Determine the flake aluminum pigment of scope.

Patent Document 2 discloses one to be included in surface adsorption and have specific coupling agent The metal foundation coating composition of metallic pigments.

Patent documentation 3 is recorded, by optionally using three kinds of different flake aluminums Pigment, thus obtain and meet light sense, color travel, concealed metal foundation film.

According to patent documentation 1～3, can obtain and a kind of impart high light sense and prevent The film of the metal sense of the excellent appearance that metal is uneven.

In recent years, it is contemplated that environment, thus in the field of metal foundation coating composition also Propose the requirement of Water-borne modification.

It is known that the outward appearance of the film obtained based on water-based metal base coating composition Can be by the considerable influence of humidity, it is difficult to carried out application.

But, the object of the film that body of a motor car etc. is provided with high-quality carries out Repair Coatings In the case of, it is necessary to the repairing film formed out by Repair Coatings is set to and sets painting The finish outward appearance that film is equal.

In the case, owing to the body of a motor car completed to be implemented Repair Coatings, thus nothing Method at high temperature will according to the most affected mode of parts such as machine making fuselage interior Repair dried coating film.In terms of painting environment, it is compared to industrial paint line at management model For being stable situation, also it is the most different according to each Repair Coatings scene in enclosing, because of And need to make out in whole Repair Coatings scene that painting environment is different repairing Coating film and set the finish outward appearance not having sense of discomfort between film.

It addition, in the case of car repair application, in order to not make repairing portion and not repair The aberration on the border in portion is significantly changed, thus there are carry out gradual change application (ボ カ シ dress), I.e. for the scope in repairing portion to the portion of not repairing, enter according to the mode tilted to thin film from thick film The situation of row coating.

Therefore, the water-based metal base coating composition body of a motor car to having metallochrome is utilized In the case of carrying out Repair Coatings, painting environment also cannot manage, it is impossible at high temperature will repair Mend dried coating film.People are required of: be not only the fine tone of the metal deposit set, Even metal sense the most all must reappear on metal deposit repairing, and at above-mentioned mould In muddled dress, the most also make the metal sense unification of film section and thick film portion.

In patent documentation 1～3, describe and obtain the metal that metal sense or disguise etc. are excellent Film, but this is new in middle painting (middle り) or base material in the painting environment under management It is coated with the metal deposit taken on, does not disclose any content for the strategy of the description below: no Only on fine tone and also be connected in metal glitter sense on the most all make repair metal deposit With the metal deposit unification set, obtain the most not when having carried out fuzzy application further The natural look of suitable sense.

On the other hand, patent documentation 4 has been recorded a kind of aqueous coating compositions, its by The compositions containing special effect pigments comprising water reducible resin with comprise inorganic laminated silicon Hydrochlorate, water-dilutable polyurethane resin and water and the compositions without pigment are constituted, should The rheological behavior of aqueous coating compositions has suitable sagging resistance.

But the sagging resistance of the compositions described in patent documentation 4 is excellent, can be significantly Cut down drying time, but the metal of the film obtained uneven be significant, particularly Need to improve the finish of gradual change finish department.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 08-170034 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2012-1598 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2005-200519 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2001-316612 publication

Summary of the invention

The problem solved is wanted in invention

It is an object of the invention to propose a kind of water-based metal base coating composition, it is suitable for Do not have for the old metal deposits such as the metal deposit that formation has set relative to body of a motor car etc. 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 water-based metal base coating composition of specific composition Comprise the specific micropowder of the mean diameter with particular range, thus can obtain by thickness The film of the natural metal appearance that the poor sense of discomfort caused is few.

That is, the present invention relates to the water-based metal 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 metal foundation coating composition,

Host composition (I) comprises carbamate resins emulsion (A), emulsion acrylic resin (B), bright pigment (C) and water, diluent components (II) comprise viscosity adjusting agent and Water,

It is characterized in that, comprise the micropowder that mean diameter is 0.1～25.0 μm in the composition End (D), this micropowder (D) is resin particle or extender pigment；

The invention still further relates to a kind of Repair Coatings method, it is characterised in that it use aforementioned Compositions.

The effect of invention

Water-based metal base coating composition according to the present invention, can will be caused by film thickness difference The inconsistent of metal sense is set to Min., it is thus achieved that transparent feel, flatness and sense of glittering are excellent The metal foundation film of different outward appearance.

It addition, constitute the storage stability of each composition of this coating composition and mutual mixing Being good with property, the physical property such as the substrate disguise of the film of formation, resistance to water, tack is also Excellent.

Detailed description of the invention

The water-based metal base coating composition of the present invention is by host composition (I) and dilution The compositions of the multicomponent system that agent composition (II) is combined.

Host composition (I) in the present invention comprises carbamate resins emulsion (A), acrylic acid Resin emulsion (B), bright pigment (C) and water.

＜ carbamate resins emulsion (A) ＞

In the present invention, as carbamate resins emulsion (A), can make without restriction By carbamate resins emulsion well known in the art, include, for example out many by making The carbamate that isocyanates, polyhydric alcohol and carboxylic glycol carry out reacting is pre- The resin emulsion that polymers is dispersed in water and obtains.

As polyisocyanates, can list: two Carbimide. hexa-methylene esters, trimethyl six Methylene two Carbimide. tri-methyl hexamethylene ester, dimer acid diisocyanate, lysine two The aliphatic diisocyanate compounds such as isocyanates；The contracting of these diisocyanate cpds Two urea type addition products, isocyanurate ring addition product；Isophorone diisocyanate, 4,4 '- Di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hexahydrotoluene-2,4-(or-2,6-) diisocyanate, 1,3-(or 1,4-) two (isocyanatomethyl) hexamethylene, 1,4-cyclohexane diisocyanate, Alicyclic two Carbimide .s such as 1,3-Pentamethylene. diisocyanate, 1,2-cyclohexane diisocyanate Ester compounds；The biuret form addition product of these diisocyanate, isocyanuric acid ester cycloaddition Thing；XDI, m xylene diisocyanate, tetramethyl xylene two are different Cyanate, toluene di-isocyanate(TDI), 4,4 '-'-diphenylmethane diisocyanate, 1,5-naphthalene two are different Cyanate, 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, The aromatic diisocyanate compounds such as isopropylidene double (4-phenyl isocyanate)；These are two years old The biuret form addition product of isocyanate compound, isocyanurate ring addition product；Triphenyl Methane-4,4 ', 4 "-triisocyanate, 1,3,5-tri-isocyanato-benzene, 2,4,6-tri-Carbimide. Root closes toluene, 4,4 '-dimethyl diphenylmethane-2,2 ', 5,5 '-tetraisocyanate etc. is at 1 point Son has the polyisocyanate compound of more than three NCOs；These polyisocyanic acid The biuret form addition product of ester compounds, isocyanurate ring addition product；With NCO The ratio becoming excess makes polyisocyanate compound and ethylene glycol, propylene glycol, 1,4-fourth Glycol, dihydromethyl propionic acid, poly alkylene glycol, trimethylolpropane, hexanetriol etc. are many The hydroxyl of unit's alcohol carries out the urethane addition product reacted；These carbamates Change 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；Through dicarboxylic acids (adipic acid, amber Amber acid, decanedioic acid, 1,3-propanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid etc.) and glycol (second Glycol, propylene glycol, 1,4-butanediol, 1,6-HD, 3-methyl isophthalic acid are 5-pentanediol, new Pentanediol, bishydroxymethyl hexamethylene etc.) polycondensation and obtain polyhydric alcohol, such as, poly- Glycol adipate, polytetramethylene glycol adipate ester, polyhexamethylene adipate ester, poly-new Amyl group adipate ester, poly-3-methyl amyl adipate ester, poly-ethylidene/butylidene adipic acid The PEPAs such as ester, poly-neopentyl/hexyl adipate ester；Polycaprolactone polyol, poly- -3-methylpent lactone polyols；Polycarbonate polyol；Ethylene glycol, diethylene glycol, three Ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, tetramethylene glycol, hexamethylene glycol, Decamethylene glycol, ethohexadiol, dihydroxymethyl tristane, hydrogenated bisphenol A, hexamethylene The low molecular weight diols classes etc. such as dimethanol, 1,6 hexanediol, can be used alone or and with two Use more than kind.

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 (A) can also be to utilize nertralizer to be neutralized The carbamate resins emulsion arrived.As nertralizer, if carboxyl can be neutralized Nertralizer be then 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 (A), due to the middle rank of metal foundation film Abrasiveness (in grind ぎ) is good, thus is preferably the ammonia in the molecule with circulus Carbamate resin emulsion.

It is further preferred that the polyisocyanates constituting carbamate resins emulsion (A) comprises Being derived from a compound part as its composition for alicyclic diisocyanate compound, this is Suitably.

It addition, about carbamate resins emulsion (A), water-fast from metal foundation film Property and repeat to be coated with from the viewpoint of amalgamation, solid content acid number is at below 20mgKOH/g In the range of, 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 be by making 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 measure, 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 at more than 0.05 and the scope less than 0.5 μm In.

In this manual, carbamate resins emulsion (A) and acrylic acid tree described later The mean diameter of fat liquor (B) is, at measuring temperature 20 DEG C, passes through coulter counter method Measure the value of the volume average particle size obtained.About mensuration based on coulter counter method, example Such as by using " COULTER N4 type " (Beckman Coulter K.K. system, trade name) Carry out.

＜ emulsion acrylic resin (B) ＞

In the present invention, emulsion acrylic resin (B) is: by will be with containing (methyl) propylene The polymerism unsaturated monomer of acyl group be required composition, other polymerism as required not The acrylic acid tree that the copolymer that saturated monomer carries out copolymerization and obtains is dispersed in water and obtains Fat liquor.

Specifically, the mean diameter of emulsion acrylic resin (B) is in 0.01～1.0 μm In the range of, preferably more than 0.05 and less than 0.5 μm in the range of.

As such emulsion acrylic resin (B), such as preferably use by water with And in the presence of dispersion stabilizer, use polymerization initiator by above-mentioned polymerism unsaturated monomer Composition is with 1 stage or the emulsion acrylic resin that obtains so that the multistage carries out emulsion polymerization.

In the present invention emulsion acrylic resin (B) can be single-layer type can also be core-shell-type Deng multi-layered type, but considering from viewpoints such as repeating coating amalgamation, single-layer type is suitable.

Polymerism unsaturation list as the copolymer composition that can become emulsion acrylic resin (B) Body, such as, list: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) Propyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) Amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) The straight or branched alkyl (methyl) third such as lauryl acrylate, (methyl) stearyl acrylate ester Olefin(e) acid ester；The ester ring type alkane such as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate Base (methyl) acrylate；Aralkyl (methyl) acrylate such as (methyl) benzyl acrylate；(first Base) the alkoxyl alkane such as acrylic acid 2-methoxy acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester Base (methyl) acrylate；Perfluoroalkyl (methyl) acrylate；N, N-diethylamino second N, N-dialkyl aminoalkyl (methyl) acrylate as base (methyl) acrylate；(first Base) acrylamide；(methyl) acrylonitrile；The vinyl such as vinyl acetate, propionate Ester compounds；The vinyl aromatic compounds such as styrene, α-methyl styrene；(methyl) Allyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) propylene Acid esters, TEG two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, Trimethylolpropane tris (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, Neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, season penta Tetrol two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, glycerol two (first Base) acrylate, 1,1,1-trimethylolethane two (methyl) acrylate, 1,1,1-tri-hydroxyl first Base ethane three (methyl) acrylate, 1,1,1-trihydroxy methyl propane three (methyl) acrylic acid Ester, Triallyl isocyanurate, diallyl terephthalate, divinylbenzene etc. There are in 1 molecule 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- Hydroxy alkyl (methyl) acrylate such as hydroxypropyl acrylate, (methyl) hy-droxybutyl, 1-propenol-3, The 6-caprolactone modification body of above-mentioned hydroxy alkyl (methyl) acrylate, containing molecular end it is The polymerism of the hydroxyls such as (methyl) acrylate of the polyethylene oxide chain of hydroxyl is unsaturated Monomer；(methyl) acrylic acid, maleic acid .beta.-methylacrylic acid, β-carboxyethyl acrylate etc. contain The polymerism unsaturated monomer of carboxyl；(methyl) acrylic aldehyde, formoxyl styrene, carbon atom Vinyl alkyl ketone (such as, ethenyl methyl ketone, vinyl ethyl ketone, the second of several 4～7 Thiazolinyl butyl ketone etc.), acetoacetoxyethyl (methyl) acrylate, acetoacetyl oxygen The polymerism unsaturated monomer containing carbonyl such as base allyl ester, diacetone (methyl) acrylamide； Glycidyl (methyl) acrylate, Beta-methyl glycidyl (methyl) acrylate, 3,4-epoxycyclohexyl-methyl (methyl) acrylate, 3,4-epoxycyclohexylethyl (methyl) third Olefin(e) acid ester, 3,4-epoxycyclohexyl propyl group (methyl) acrylate, allyl glycidyl The polymerism unsaturated monomer containing epoxy radicals such as ether；Isocyanatoethyl (methyl) acrylic acid The polymerism of the isocyanato group containings such as ester, an isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate is not Saturated monomer；Vinyltrimethoxy silane, VTES, γ-methyl-prop Alkene acryloxypropylethoxysilane trimethoxy silane, γ-methacryloxypropyl Deng the polymerism unsaturated monomer containing alkoxysilyl；Polymerism insatiable hunger containing epoxy radicals With the product of the polymerism unsaturated monomer of monomer or hydroxyl and unsaturated fatty acid, Dicyclo amylene epoxide ethyl (methyl) acrylate, dicyclo amylene epoxide propyl group (methyl) propylene The polymerism containing oxidation curable group such as acid esters, double cyclopentenyl (methyl) acrylate is not Saturated monomers etc., they can individually use or combine two or more and use.

It addition, the dispersion making emulsion acrylic resin (B) carry out being used during emulsion polymerization is steady Determine agent to be not particularly limited, include, for example out dialkyl sodium sulfosuccinate, dodecyl Benzene sulfonic acid sodium salt, sodium lauryl sulfate, polyethylene glycol oxide alkyl phenyl ether sodium sulfate and alkyl The anionic emulsifiers such as diphenyl ether disulfonates, polyoxyethylene higher alcohol ether and poly- Non-ionic emulsifiers such as ethylene oxide alkyl phenyl ether and have free-radical polymerised double The anionic property of key 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..Can list as commercially available product " 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, Methyl cyclohexanone 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 (B) contained in host composition (I), From the viewpoint of the resistance to water of metal foundation film and middle rank abrasiveness, it is included in 1 molecule In there are many vinyl compounds of at least two polymerism unsaturated group as being copolymerized into The emulsion acrylic resin divided is suitable.

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, to make in the manufacture of emulsion acrylic resin (B) Whole polymerism unsaturated monomers quality on the basis of, 0.1～10 mass % can be set to In the range of, preferably can be set in the range of 0.5～5 mass %.

It addition, about emulsion acrylic resin (B), from the resistance to water of metal foundation film or From the viewpoint of repeating to be coated with amalgamation, solid content acid number is the model of below 5mgKOH/g In enclosing, in the scope of preferably below 4mgKOH/g.

＜ bright pigment (C) ＞

Bright pigment (C) is not particularly limited in the present invention, can use in paint field Known bright pigment.As object lesson, can list aluminum, aluminium oxide, copper, zinc, The metal light material that metal or the alloys etc. such as ferrum, nickel, stannum do not colour or coloured Material etc..It addition, metal evaporation film sheet, Muscovitum, carried out surface by metal-oxide The interference of light such as the Muscovitum of covering, micaceous iron oxide, graphite pigment, hologram pigment Pigment also may be included in bright pigment (C).The shape of bright pigment (C) limits the most especially System, can be coloured, it is also possible to further by various surface conditioning agents, dispersant etc. Process.These bright pigment can be used alone or use two or more.

Bright pigment (C) also suitably can carry out mixing with dispersant, dispersion resin and divide Dissipate, carry out paste and be compounded in coating composition.

The most in the present invention, as bright pigment (C), covering dioxy is preferably used The aluminum pigment of SiClx.This is because, there is the effect of the film that can obtain stable metal appearance Really.

As cover silicon dioxide aluminum pigment, can use " Hydrolan series " (trade name, ECKART company system), " Alumipaste EMR series " (trade name, Toyo Aluminium K.K. System) etc. commercially available product.

" host composition (I) "

In the present invention, host composition (I) comprises the carbamate tree as resinous principle Fat liquor (A) and emulsion acrylic resin (B) are as required composition, and both total amounts exist Resin solid content contained in host composition (I) is in the scope of more than 50 mass %, Being preferably in the scope of more than 80 mass %, this is from the initial attachment of metal foundation film It is preferred from the viewpoint of property and resistance to water.

It addition, making as carbamate resins emulsion (A) and emulsion acrylic resin (B) By ratio, carbamate resins emulsion (A)/emulsion acrylic resin (B) presses solid material Amount ratio be in the range of 95/5～5/95, in the range of preferably 80/20～20/80, this from It is suitable from the viewpoint of the water-fast tack of metal deposit.

It addition, as the compounding amount of bright pigment (C), with contained in host composition (I) On the basis of resin solid content, it is 1～60 mass %, in the range of preferably 5～50 mass %, This is suitable.

Above-mentioned host composition (I) also can comprise: the water-base resin in addition to (A) and (B)； Pigment in addition to (C)；Viscosity adjusting agent, pigment dispersing agent, UV absorbent, Light stabilizer, dispersing aid, preservative, silane coupler, defoamer, curing catalysts, Organic solvent, nertralizer etc., when prepared by water paint, normally used coating adds Other composition such as agent.

As above-mentioned water-base resin, water soluble acrylic resin can be enumerated.In this manual, About water soluble acrylic resin, include, for example out: by the polymerization containing acidic group will be comprised Property unsaturated monomer, the polymerism unsaturated monomer of hydroxyl and other polymerism insatiable hunger Utilize in the presence of hydrophilic organic solvent with the polymerism unsaturated monomer composition of monomer The resin that polymerization initiator carries out being polymerized and obtains.

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 this The effect that amalgamation when bright compositions repeats coating improves.

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 tricyclodecyl 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 be by will 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.Chromatographic column uses " 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 be by will by chromatograph of gel permeation (east Cao (strain) make, " 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.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 Degree: 40 DEG C, flow velocity: 1ml/ minute, detector: carry out under conditions of RI.

About the hydrophilic organic solvent used in polymerization, although distinguish the most closely, but It is the organic solvent that include, for example out and dissolve at least 20g at 20 DEG C in water 100g, tool Body lists 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 as 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, in the following manner, host composition (I) is made to comprise viscosity adjusting agent: Host composition (I) is stably stored, can make by mixing with diluent components described later (II) Close and obtain water-based metal base coating composition, said composition can be formed do not occur uneven Or the film of sagging etc. good finish outward appearance.

As viscosity adjusting agent, always known viscosity adjusting agent can be used without restriction, Specifically list: sodium polyacrylate, polyacrylic acid-(methyl) acrylate copolymer etc. gather Acrylic compounds viscosity adjusting agent；Pulan Buddhist nun gram (Pluronic) polyethers, polyethers dialkyl, The polyethers viscosity adjusting agent such as polyethers dialkyl ether, the epoxide modified thing of polyethers；Carbamate Association type viscosity adjusting agent；Montmorillonite, beidellite, nontronite, saponite, Strese Hofmann's hectorite., The mineral-type viscosity adjusting agent such as humite, Muscovitum and bentonite；Carboxymethyl cellulose, first The cellulose derivative class viscosity adjusting agent such as base cellulose, hydroxyethyl cellulose；Casein, The protein-based viscosity adjusting agent such as sodium caseinate, ammonium caseinate；The Sargassums such as sodium alginate Acids viscosity adjusting agent；Polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl benzyl ether The polyethylene base class viscosity adjusting agent such as copolymer；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 Viscosity adjusting agent etc..

Among them, from the sight of the bright pigment (C) orientation metal foundation film Point considers, polyacrylic viscosity adjusting agent is good.

About 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 100mg/KOH and In the scope of below 300mg/KOH.As commercially available product, such as, list Rohm and Haas " Primal ASE60 ", " Primal TT615 ", " the Primal RM5 " of company (more than, trade name), " SN THICKENER 613 ", " SN THICKENER 618 ", " SN of San Nopco Limited THICKENER 630 ", " SN THICKENER 634 ", " SN THICKENER 636 " (more than, Trade name) etc..

In this manual, effective ingredient refers to that removal water, organic solvent etc. are dilute from sample The residue releasing agent and obtain.

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

The solid concentration of above-mentioned host composition (I) is generally adapted to 10～50 mass %, preferably Being adjusted in the range of 15～40 mass %, this is from painting operation and disguised and finish It is suitable from the viewpoint of 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 Yishi 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: sample is prepared as 10 points after 25 DEG C Within clock, use viscometer digital Vismetron viscometer VDA type (Shibaura Systems Co., Ltd. system) value that obtains so that rotating speed 60rpm is measured.

" diluent components (II) "

In the present invention, diluent components (II) comprises viscosity adjusting agent and water.

In the present invention, by diluent components (II) being mixed in before application State host composition (I), thus water-based metal basic coating group can be controlled according to painting environment The rheological behavior of compound, by so constituting water-based metal base coating composition, thus protects Hold the storage stability of each composition, can be formed and uneven etc. essence will not sagging and not occur The metal deposit of decorations excellent appearance.

As the viscosity adjusting agent that can comprise in diluent components (II), can be to above-mentioned master The viscosity adjusting agent exemplified in the explanation that viscosity adjusting agent contained in agent composition (I) is carried out Among suitably select and use.

In the present invention, among diluent components (II), mineral-type viscosity adjusting agent is suitable 's.

As relevant inorganic system 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 or water.

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

As the active constituent content of the mineral-type viscosity adjusting agent in diluent components (II), On the basis of diluent components (II) quality, it is in the range of 0.1～3.0 mass %, is preferably In the range of 0.3～2.0 mass %, this is suitable.

In above-mentioned diluent components (II), it is possible to comprise water-base resin, UV absorbent, Light stabilizer, polymer particles, surface conditioner, dispersing aid, preservative, silane are even Connection agent, defoamer, curing catalysts, organic solvent, nertralizer etc. are prepared at water paint Time other composition such as normally used additive for coatings.

It addition, the viscosity of above-mentioned diluent components (II) is not particularly limited, but from storage Stability and with the Combination of aforesaid host composition (II) etc. from the viewpoint of, Ke Yishi In the range of 10～300mPa sec, can be preferably in the range of 10～250mPa sec.

＜ micropowder (D) ＞

The water-based metal base coating composition of the present invention is characterised by, comprises mean diameter It it is the micropowder (D) in the range of 0.1～25 μm.

The shape of micropowder (D) can be spherical, granular, needle-like, fusiform, grain of rice shape, Flake, tabular, polyhedral and amorphous etc. in any one shape, but it is put down When all particle diameter is less than 0.1 μm, thickness based on metal foundation film and the light sense that causes Difference differ considerably, on the other hand, the mean diameter of micropowder (D) is more than 25 μm Time then metal foundation film uneven change notable, the most preferably.

The preferred mean diameter of micropowder (D) is in the range of 0.5～10 μm, preferably locates In the range of 1.0～8.0 μm.

In this manual, the mean diameter of micropowder (D) is the mean diameter of volume reference (D50), be to utilize laser diffraction formula particle size distribution device and the particle size distribution that measures The value of 50%.

As the micropowder (D) in the present invention, such as, list resin particle, extender pigment.

As resin particle, specifically can list olefine kind resin (polyethylene, polypropylene, Polybutene), acrylic resin, styrene resin, ABS resin, vinyl-based tree Fat, polyamide, polyester resin, carbamate resins, poly terephthalic acid second two Alcohol ester (PET), fluororesin, cellulosic resin, silicones, phenolic resin (phenol Resin), urea formaldehyde resin, melmac, allyl resin, furane resins, no Saturated polyester resin, epoxy resin, polyurethane, polyimides etc..

On the other hand, as extender pigment, list clay, calcium carbonate, barium sulfate, vitriol Soil white (alumina white), Talcum, zinc oxide, Kaolin and zirconium oxide etc..

The most above-mentioned micropowder (D) may be included in host composition (I) or diluent components (II) in any one in.

＜ contains micropowder composition (III) ＞

The water-based metal base coating composition of the present invention may be made as at above-mentioned host composition (I) and it is further combined (III) containing micropowder composition on the basis of diluent components (II) to form Multicomponent system, i.e. three component system.

And, this contains micropowder composition (III) and is in the form comprising above-mentioned micropowder (D), This considers from viewpoints such as light sense, the transparent feels of the metal foundation film formed, is preferred.

As the active constituent content containing the micropowder (D) in micropowder composition (III), to contain It is in the range of 1～50 mass % on the basis of micropowder composition (III) quality, preferably 3～40 In the range of quality %, this is suitable.

Preferably on the basis of micropowder (D), aqueous tree is also comprised containing micropowder composition (III) Fat.By making (III) containing micropowder composition comprise water-base resin, thus have so that containing micropowder The storage stability at end composition (III) 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 to State carbamate resins emulsion (A) contained in host composition (I) and acrylic resin breast The suitable resin emulsion selected among the material listed in the explanation that liquid (B) is carried out.

About the water-base resin in the case of comprising water-base resin at (III) containing micropowder composition Solid content, on the basis of micropowder (D) 100 mass parts, be in 1～300 mass In the range of Fen, being preferably in the range of 10～200 mass parts, this is suitable.

When amount containing water-base resin contained in micropowder composition (III) is too much, make the most sometimes The viscosity obtaining water-based metal basic coating uprises, when mixing each composition (I)～(III), sometimes Stirring can be made to become difficulty.

In the present invention, (III) containing micropowder composition comprise carbamate resins emulsion with And in the case of emulsion acrylic resin, as its ratio, by carbamate resins emulsion/ Emulsion acrylic resin solid ratio and be in the range of 5/95～95/5, be preferably in In the range of 30/70～70/30.

In the case of carbamate resins emulsion is less than this scope, at the beginning of metal foundation film Beginning tack is poor, on the other hand, makes dope viscosity uprise time too much the most sometimes, is being coated with Stirring is made to become difficulty when material is made sometimes.

(III) containing micropowder composition preferably comprises a viscosity adjusting agent part as its composition. Thus have the effect that and host composition (I) and the miscibility of diluent components (II) Well, and obtain the metal foundation film that light sense is excellent.

Relevant viscosity adjusting agent is not particularly limited, can be from institute to host composition (I) Suitably select among the viscosity adjusting agent exemplified in the explanation that the viscosity adjusting agent contained is carried out And use, but use poly-from the viewpoint of the storage stability containing micropowder composition (III) Acrylic compounds viscosity adjusting agent is suitable.

About the active constituent content containing the viscosity adjusting agent in micropowder composition (III), to contain On the basis of micropowder composition (III) quality, it is in the range of 0.1～20 mass %, is preferably In the range of 0.1～10 mass %, this is suitable.

It addition, (III) Han micropowder composition preferably comprises Siloxane-Oxyalkylene Copolymers compound. This is because, it is coated with repeating when being coated with water-based metal base coating composition is repeated several times On cloth amalgamation, there is effect.

As relevant Siloxane-Oxyalkylene Copolymers compound, list by polysiloxanes End and/or side chain in import polyether chain and the compound etc. that obtains, it is also possible to be to pass through The epoxy radicals in addition to polyether chain, amino, (methyl) third has been imported in the lump to polysiloxanes Organic group as enoyl-thus 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.

About above-mentioned Siloxane-Oxyalkylene Copolymers compound, with the quality of micropowder (D) as base Standard, uses, preferably in the scope of 2.0～20 mass % in the range of 0.5～40 mass % Interior use, this is suitable from the viewpoint of the initial tack of metal foundation film.

In the form that micropowder (D) is taken care of respectively with the form containing micropowder composition (III) In, it is suitable that above-mentioned (III) containing micropowder composition comprises organic solvent.This is in order at containing micro- The viewpoint of the storage stability of powdered ingredients (III).It addition, this is because, protecting sometimes The film caused by micropowder (D) is there is at the inlet of the pipe container containing micropowder composition (III) Attachment, the most therefore cause at the film obtained based on water-based metal basic coating Film aspect of making go wrong, but by make (III) containing micropowder composition comprise organic molten Agent thus this phenomenon can be improved.

As 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 containing the organic solvent in micropowder composition (III), with micropowder (D) On the basis of quality, it is in the range of 1～300 mass %, is preferably in 10～200 mass % In the range of.

Containing in micropowder composition (III), it is possible to comprise the granule in addition to micropowder (D), Water, UV absorbent, light stabilizer, dispersing aid, preservative, silane coupler, Defoamer, curing catalysts, nertralizer etc., normally used when prepared by water paint Other composition such as additive for coatings.

The above-mentioned viscosity containing micropowder composition (III) is not particularly limited, but from containing micropowder The storage stability of composition (III) and the painting operation of water-based metal base coating composition From the viewpoint of property, can be at, in the range of 10～8000mPa sec, preferably can be at In the range of 200～6000mPa sec.

" water-based metal base coating composition "

Host composition (I) and diluent components (II) and use as desired in the present invention (III) containing micropowder composition be to take care of respectively, application dealer will be will will be each before application Composition stirring mixing, utilizes water etc. to carry out viscosity adjustment as required, thus can prepare this Bright water-based metal base coating composition.Being explained, in this manual, what is called is i.e. Before application, it is impossible to define entirely according to application dealer or painting site, but such as Period till can listing before carry out application 3 hours.

About the host composition (I) in above-mentioned water-based metal 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 containing micropowder composition (III), it is however generally that, On the basis of host composition (I) 100 mass parts, diluent components (II) is 30～400 mass parts In the range of, in the range of preferably 40～350 mass parts, (III) containing micropowder composition is In the range of 0.01～105 mass parts, it is in the range of 0.1～50 mass parts, preferably 1～35 In the range of mass parts, this is to close from the viewpoint of the outward appearance and Physical properties of coating film of metal deposit Fit.

It addition, in the present invention, as required by polyisocyanate curing agent, end-blocking isocyanide Acid esters (block isocyanate) firming agent, melamine cured dose, oxazoline firming agent, The firming agent such as carbodiimide firming agent are contained in above-mentioned host composition (I), diluent components (II) And contain in any one in micropowder composition (III), or it also is used as individual components.

The solid of the water-based metal 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 suitable from the viewpoint of painting operation and disguise and finish outward appearance 's.

It addition, the viscosity during application of above-mentioned water-based metal base coating composition is the most especially Limit, but be in, in the range of 50～800mPa sec, being preferably in In the range of 100～600mPa sec, this is from the viewpoint of painting operation is good, It is suitable from the viewpoint of the finish outward appearance of metal foundation film further.

" application "

The water-based metal base coating composition of the present invention may utilize atomized spray painting, electrostatic coat The known application means such as dress, brush application, roller application carry out application, but from film Finish outward appearance from the viewpoint of preferably carry out atomized spray painting.

Application number of times can be once, but from taking into account finish outward appearance and concealed viewpoint is examined Consider, preferably carry out repeating coating with the most such as 2～6 degree by identical coating, thus enter Row application.

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

The application of water-based metal base coating composition terminate after dry be not particularly limited, Can be undried shape in the case of supernatant described later (top clear) is repeated coating State, but the most such as at 20～100 DEG C, preferably under the temperature conditions of 40～80 DEG C, dry Dry 5～60 minutes.Thickness suitably can adjust according to the state of coated surface, but generally speaking According to dry film thickness be in the range of 5～100 μm, especially for 10～60 μm in the range of It is suitable.

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., are additionally arranged at this base material Film be not particularly limited, include, for example out be arranged at car body etc. by based on The multilayer film that the basic film of color base coating composition and supernatant film are formed out, also Can be to be appropriately arranged with primer coating film, electrodeposition coating, middle painting in the lower floor of this basis film The films such as film and the multilayer film that obtains.

It addition, the water-based metal base coating composition of the present invention also is used as being directed to It is formed at the repairing coating of the film of above-mentioned coated surface.In the case, can advance with Coated surface is anticipated by putty or bonding layer surface agent etc..Additionally, it is possible to be coated with After above-mentioned water-based metal 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: will be containing cross-linking functional group such as hydroxyls Acrylic resin or fluororesin be set to host composition and containing blocked polyisocyanates, Polyisocyanates or melmac etc. are as the curable coating of firming agent, or with fibre Jaqan coating (the lacquer that acrylic resin is main component that dimension element acetate butyrate is ester modified Paint) etc..

Among them, it is preferably used and the one-tenth comprising the resin containing hydroxyl is divided into host Divide and be divided into by the one-tenth comprising polyisocyanate compound the double-formulation of curing agent component Coating, this is because desired appearance of film can be obtained, even and if in force drying Under the conditions of, it is possible to obtain the film of the physical properties excellent such as resistance to water.

In above-mentioned supernatant coating composition, pigment class, fibre can be contained the most as desired Dimension 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

In reaction vessel, by the polytetramethylene glycol adipate ester 115.5 of number-average molecular weight 2000 Part, the polycaprolactone glycol 115.5 parts of number-average molecular weight 2000, dihydromethyl propionic acid 23.2 Part, 1,4-butanediol 14.5 parts and isophorone diisocyanate 120.1 parts are incorporated in poly- Close container, under agitation in stream of nitrogen gas, obtain NCO 85 DEG C of reactions 7 hours The prepolymer of content 4.0%.Then this prepolymer is cooled to 50 DEG C, adds acetone 165 Part and dissolve equably, the most under agitation add triethylamine 15.7 parts, holding It it is less than 50 DEG C while adding deionized water 600 parts, by the aqueous dispersion that obtained at 50 DEG C Keep 2 hours, and the water reaction of propagation that finishes, the most under reduced pressure will below 70 DEG C Acetone distillation is removed, and utilizes triethylamine and deionized water that pH is adjusted to 8.0, it is thus achieved that The ammonia that solid content acid number is 17mgKOH/g, solid content 30%, mean diameter are 0.15 μm Carbamate resin emulsion (A-1).

The manufacture of ＜ emulsion acrylic resin: ＞

Manufacture example 2

Deionized water 100 parts, " Newcol 707SF " (Japan's breast is added in reaction vessel Agent company system, has the anionic emulsifier of polyethylene oxide chain, solid content 30%) 2.5 parts and monomer mixture (styrene 9 parts, n-butyl acrylate 39 parts, third Olefin(e) acid 2-Octyl Nitrite 40 parts, acrylic acid 2-hydroxyl ethyl ester 10 parts, methacrylic acid 1 part, Allyl methacrylate 1 part) among 1 part, utilize stream of nitrogen gas be stirred mixing, 3% ammonium persulfate aqueous solution 3 parts is added at 60 DEG C.Then, it is warming up to 80 DEG C, spends 4 Hour use dosing pump will comprise remaining 99 parts of aforementioned monomer mixture, " Newcol 707SF " 2.5 parts, the pre-emulsion of 3% Ammonium persulfate. 4 parts and deionized water 100 parts adds In reaction vessel, add and carried out ripening in 1 hour after terminating.Thereafter, deionized water is added 33 parts, dimethylethanolamine is utilized to be adjusted to pH7.5, it is thus achieved that glass transition temperature is -44 DEG C, mean diameter be the emulsion acrylic resin (B-1) of 0.1 μm, solid content 30%.

The manufacture of ＜ aluminum pigment paste: ＞

Manufacture example 3

Aluminum pigment paste " Hydrolan 2156 " (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 in the reaction vessel of cold-hot machine, add 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 hy-droxybutyl 7.5 parts, phosphorous acidic group, 2- Methacryloxyethyl phosphate ester acid 12.5 parts, isobutanol 10 parts, tert-butyl group mistake 121.5 parts of the mixture that oxidation caprylate 4 parts is constituted 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, stirring ripening 1 hour, thus obtain solid content 50% The resin solution of phosphorous acidic group.

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 After ethylene oxidic ester 42.5 parts, stirring ripening 1 hour further.Thereafter, isopropyl is added Alcohol 5.9 parts, thus obtain the polymerizable monomer solution of the phosphorous acidic group of solid content 50%.

Manufacture example 4

Aluminum pigment paste " Hydrolan 2156 " (ECKART is added in stirring mixing container Company's system, covers the flake aluminum pigment paste of silicon dioxide, pigment content 60%) 40.4 parts, " SPARWITE W-5HB " (note 5) 11.1 parts, propylene glycol monomethyl ether 31 parts, phosphorous acidic group Resin solution (note 1) 15.5 parts, be stirred mixing thus obtain aluminum pigment paste (C-2)。

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 mix by manufacturing the carbamate resins that example 1 obtains Emulsion (A-1) 150 parts and the emulsion acrylic resin obtained by manufacture example 2 further (B-1) 150 parts, interpolation " Primal ASE60 " (note 3) 17.8 parts, continue to stir 1 Hour, utilize dimethylethanolamine to add deionized water after have adjusted pH, it is thus achieved that solid The basic coating (I-1) of thing 20%.Method described in specifications measures this basic coating (I-1) viscosity, pH, result be respectively 1000mPa sec, 8.0.

(note 3) " Primal ASE60 ": trade name, Rohm and Haas company system, poly-third Alkene Acrylic associative thickener, 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 mix by manufacturing the carbamate resins that example 1 obtains Emulsion (A-1) 150 parts and the emulsion acrylic resin obtained by manufacture example 2 further (B-1) 150 parts, interpolation " Primal ASE60 " (note 3) 17.8 parts, continue to stir 1 Hour, utilize dimethylethanolamine to add deionized water after have adjusted pH, it is thus achieved that solid The basic coating (I-2) of thing 20%.Method described in specifications measures this basic coating (I-2) viscosity, pH, result be respectively 1500mPa sec, 8.0.

The manufacture of ＜ diluent: ＞

Manufacture example 7

995 parts of water, " Laponite RD " (note 4) 5 parts is added in stirring mixing container, It is stirred mixing and obtains 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.

Manufacture example 8

To stirring mixing container in, add 980 parts of water, " Laponite RD " (note 4) 5 parts, " SPARWITE W-5HB " (note 5) 15.0 parts, is stirred mixing and obtains diluent (II-2).Viscosity is 200mPa sec.

Manufacture example 9

To stirring mixing container in, add 980 parts of water, " Laponite RD " (note 4) 5 parts, " Epostar MA1002 " (note 6) 15.0 parts, is stirred mixing and obtains diluent (II-3).Viscosity is 200mPa sec.

The manufacture of the ＜ coating containing micropowder: ＞

Manufacture example 10

In stirring mixing container, mixing water 71 parts, the amino first obtained by manufacture example 1 Acid ester resin emulsion (A-1) 5 parts, sequentially adds propylene glycol list n-propyl ether 5 parts and by manufacturing The emulsion acrylic resin (B-1) 5 parts of example 2 acquisition, " KAOLIN HA-90T " (note 7) 10 Part, " Primal ASE60 " 3 parts, " BYK-348 " (note 13) 1 part, continue to stirring 1 hour, adjust pH with dimethylethanolamine, it is thus achieved that the coating (III-1) containing micropowder. Method described in specifications measure this containing micropowder coating (III-1) viscosity, PH, result be respectively 3800mPa sec, 8.0.

(note 5) " SPARWITE W-5HB ": trade name, SINO-CAN MICRONIZED PRODUCTS system, mean diameter 1.6 μm, barium sulfate,

(note 6) " Epostar MA1002 ": trade name, Japan's catalyst system, mean diameter 2.5 μm, polymethyl methacrylate class cross-linking agent,

(note 7) " KAOLIN HA-90T ": trade name, SHANXI JINGYANG system, Mean diameter 1.5 μm, Kaolin.

Manufacture example 11～19

Formula composition is set as shown in following table, in addition, with manufacture example 9 Similarly operate, thus obtain the coating (III-2) containing micropowder～(III-10).

Table 1

(note 8) " LPZINC-2 ": trade name, Mitsui Chemicals, Inc's system, mean diameter 2.0 μm, zinc oxide,

(note 9) " Sunlight SL-1500 ": trade name, the former chemical industry system of bamboo, average particle Footpath 2.0 μm, calcium carbonate,

(note 10) " SG-95 ": trade name, Nippon Talc Co., Ltd. system, mean diameter 2.5 μm, Talcum,

(note 11) " AEROSIL R-972 ": trade name, Nippon Aerosil Co., Ltd. System, mean diameter 0.02 μm, silicon dioxide,

(note 12) " MIN-U-SIL30 ": trade name, U.S.SILICA COMPANY system, Mean diameter 30.0 μm, silicon dioxide,

(note 13) " BYK-348 ": trade name, BYK-CHEMIE company system, polyethers changes Property polysiloxane compound, effective ingredient 100%.

The manufacture of ＜ dilution coating: ＞

Embodiment 1～16 and comparative example 1～3

By basic coating (I-1)～(I-2), diluent (II-1)～(II-3), coating containing micropowder (III-1)～(III-10) according to shown in following table formula form utilize hands stirring and fully Mixing, it is thus achieved that dilution coating (D-1)～(D-19).It addition, describe each in table in the lump The viscosity of dilution coating.About the mensuration of viscosity, to specifications described in method carry out, After basic coating and diluent and the coating containing micropowder are mixed, through 5 minutes After carry out.

What ＜ gradually changeable (ボ カ シ) was evaluated evaluates making of coated plate: ＞

With isopropanol, the door-plate (about 90 × 70cm) carrying out electrodeposition coating is carried out defat, By " Retan PG Hybrid Eco Filler " (trade name, Kansai Paint Co., Ltd. system, Double agent carbamate bonding layer surface agents) become the mode of 50 μm according to dry film thickness and spray It is coated on whole of door-plate, is dried 20 minutes at 60 DEG C, is ground with P600 paper, enters Go defat.Thereafter by commercially available organic solvent metalloid basic coating according to dry film thickness Become the mode atomized spray painting of 15 μm in whole of door-plate, 5 minutes intervals are set, by transparent Coating " Retan PG Eco Clear HX (Q) " (trade name, Kansai Paint Co., Ltd. System, the double agent carbamates comprising the resin containing hydroxyl and polyisocyanates are transparent Coating) become the mode atomized spray painting of 40 μm in whole of door-plate according to dry film thickness, 60 DEG C are dried 20 minutes, are made for the door-plate with old coating film.

It is directed to the old coating film of this door-plate, grinds lightly with P1500 paper, utilize isopropyl Alcohol and carried out defat.Size (10cm × 10cm) is attached in the end of the length direction of door-plate White black hidden paper, it is assumed that for repair position.For being assumed to repair the part at position, It is the thickness (dry film thickness until the most hidden white black hidden paper according to its thickness About 15 μm), and the outer peripheral portion repairing position from white black hidden paper is until door Make the mode that thickness is the most thinning till part till about the 2/3 of plate length direction, make Carry out thickness with each dilution coating (D-1)～(D-19) and tilt application.Minimum thickness now It is about 2 μm.After application respectively dilutes coating (D-1)～(D-19), arrange between 5 minutes Every, by clear dope " Retan PG Eco Clear HX (Q) " (trade name, Kansai Paint Co., Ltd.'s system, comprises double agent carbamic acids of the resin containing hydroxyl and polyisocyanates Ester clear dope) become the mode atomized spray painting of substantially 40 μm in door-plate according to dry film thickness Whole, it is dried 20 minutes at 60 DEG C, is made for evaluating coated plate.

＜ evaluation test ＞

Embodiment 17～32 and comparative example 4～6

About the test coated plate being made for as described above, following projects are carried out Evaluation test.Show the result in table.

(1) light sense concordance: about by the repairing position (thick film part) of each evaluation coated plate And the light sense that the orientation difference of the aluminum of peripheral part (film portion) causes, in dark room Among between, utilize toning light source (trade name；Luminous, Kansai Paint Co., Ltd. system) assessment of exposure coated plate, from crooked direction, (ス カ シ direction) (tilted direction) is carried out Visual valuation.

◎: entirely without finding to repair the difference of the light sense of position and peripheral part.

Zero: a little difference finding to repair position with the light sense of peripheral part, but place In permissible range.

Δ: the difference repairing position with the light sense of peripheral part can be found, there is discomfort Sense.

×: repair the significant difference at position and the light sense of peripheral part, both light senses Entirely different.

(2) inhomogeneities: to the metal at the repairing position (thick film part) of each evaluation coated plate not Uniformly 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.

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

×: more it is found that the generation that metal is uneven.

(3) Δ E* value: for each evaluation coated plate, from right-hand member, be spaced with 3cm, use and divide Spectrocolorimeter CM-512m3 (trade name, Minolta company system), to be equivalent to crooked side Colour examining has been carried out to the acceptance angle for 75 °.Numerical value in table is to repair position and peripheral part The maximum of Δ E*.The value of Δ E* is the lowest the best, if within Δ E*=2.0, It is so there is no the scope of sense of discomfort by gradual change application, is suitable for the purpose of the present invention.

(4) IV value: (Kansai Paint Co., Ltd. system, swashs to use Alcope LMR-200 Light type metal sense determinator) the repairing Site Determination of each evaluation coated plate is gone out IV value.IV Be worth the lowest, then the light sense in front is the lowest, the aluminum obtained based on the coating containing micropowder The control effect of orientation is the biggest.

(5) 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.

Δ: have concavo-convex being coated with mask.

×: have big concavo-convex being coated with mask.

(6) disguised: during by the visual stage that 2 stage atomized spray paintings are respectively diluted coating Substrate disguise evaluated.

◎: the most hidden substrate.

Zero: slightly pass through and see substrate.

Δ: pass through and see substrate.

×: clearly pass through and see substrate.

(7) transparency: the fine tone (muddy) of each evaluation coated plate by visual valuation.

The transparency of ◎: film is high, and entirely without muddiness.

Zero: the transparency of film is slightly lower, it was observed that muddy a little.

Δ: the transparency of film is low, it is possible to find muddy.

×: the transparency of film is the most significantly low, and the muddy impact causing fine tone is relatively Greatly.

(8) 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.

Δ: film swelling.

×: film generation swelling, find the exceptions such as expansion/albefaction.

(9) initial tack: utilize cutting machine according to arriving base material (element in each evaluation coated plate Ground) mode implement incision, make 100 size 1mm × 1mm gridiron pattern, at it Surface attaches adhesion cellophane adhesive tape, after having peeled off this adhesive tape sharp at 20 DEG C, Investigate the extant number of gridiron pattern film.

◎: remaining 100.

Zero: remaining 99～90.

Δ: remaining 89～41.

×: remaining less than 40.

(10) repeat to be coated with amalgamation: for each dilution coating, carry out four atomized spray paintings also Then blowing until the operation that disappears of gloss, visual valuation repeats when being coated with The amalgamation of coating.

◎: glossy, wet painting face is smooth.

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

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

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

Claims (8)

1. a water-based metal base coating composition for multicomponent system, it is host to be become The water-based metal base of the multicomponent system that point (I) and diluent components (II) are combined Plinth coating composition, wherein,

Host composition (I) comprises carbamate resins emulsion (A), emulsion acrylic resin (B), bright pigment (C) and water, diluent components (II) comprise viscosity adjusting agent and Water,

It is characterized in that, comprise the micropowder that mean diameter is 0.1～25.0 μm in the composition End (D), this micropowder (D) is resin particle or extender pigment.

Compositions the most according to claim 1, wherein, emulsion acrylic resin (B) It is included in 1 molecule many vinyls chemical combination with at least two polymerism unsaturated group Thing is as copolymer composition.

Compositions the most according to claim 1 and 2, wherein, bright pigment (C) It is by the covered flake aluminum of silicon dioxide.

4., according to the compositions according to any one of claims 1 to 3, it is to become in host It is further combined (III) containing micropowder composition on the basis of dividing (I), diluent components (II) to form The water-based metal base coating composition of multicomponent system, wherein, containing micropowder composition (III) Containing micropowder (D) and water.

5. according to the compositions according to any one of claims 1 to 3, 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.

Compositions the most according to claim 4, wherein, about host composition (I), Diluent components (II) and the mass ratio containing micropowder composition (III), with host composition (I) 100 On the basis of mass parts, diluent components (II) is in the range of 30～400 mass parts, contains Micropowder composition (III) is in the range of 0.1～105 mass parts.

7. a Repair Coatings method, it is characterised in that it use claim 1～6 According to any one of compositions.

8. a Repair Coatings method, wherein, institute any one of application claim 1～6 The compositions stated, then carries out clear-coated.