CN100462413C - Coating composition - Google Patents
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- CN100462413C CN100462413C CNB2005101215779A CN200510121577A CN100462413C CN 100462413 C CN100462413 C CN 100462413C CN B2005101215779 A CNB2005101215779 A CN B2005101215779A CN 200510121577 A CN200510121577 A CN 200510121577A CN 100462413 C CN100462413 C CN 100462413C
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Abstract
To provide a coating composition which comprises a base coating (I) and a diluent (II). In this composition, the base coating (I) comprises a cellulose derivative (A), an acrylic resin (B), a polyester resin (C) and at least one organic solvent (D) selected from an ester-based organic solvent and ketone-based organic solvent, wherein the cellulose derivative (A) accounts for 5-75 wt.% of the total solids of the components (A), (B) and (C), and for the diluent (II), an aliphatic hydrocarbon-based organic solvent (E) accounts for 5-90 wt.% of the whole diluent (II), and the base coating (I) is preferably a metallic base coating.
Description
Technical field
The present invention relates to coating composition, it can be formed in the coating that aspects such as covering with paint property, drying property, hardness, adhesivity show premium properties, and be substantially free of the volatile organic compounds that Be Controlled is used owing to influence environment, for example toluene, dimethylbenzene etc.
Background technology
In the art, the dry coating aspect is considered under Air drying or the forced drying condition, and acrylic acid or the like varnish and acryl urea alkane coating composition are mainly used in vehicle repair paint compositions field.
Be used under the situation in above field at lacquer class coating composition, consider from the dried coating film aspect, used and comprised as the vibrin of main carrier component and the blend of cellulose acetate butyrate (being called CAB hereinafter), the coating composition of the blend of acrylic resin and vibrin and CAB etc., this has caused following problem: unsafty consistency may cause detrimentally affect to covering with paint property between each component, and in the metallicity coating, the coating that pigment occurs containing produces the phenomenon (being called spot hereinafter) of pigment orientation spot and occurs clear coating composition is coated to and contain the phenomenon that filming of pigment contained generation pigment orientation spot (spot after being called hereinafter) of filming of pigment after going up after applying, may reduce covering with paint.
In order to address the above problem, the applicant has proposed the coating composition that obtains than mixed C AB graft copolymer, vibrin and acrylic resin with specific blend in following references 1 and 2.Use aforementioned coating composition can improve each compatibility between components, show good for coated surface filming, even do not shown also that in the metallicity coating spot and back are wide thereby formed.Yet the thinner that aforementioned coating composition and being used to is controlled coating composition viscosity comprises organic solvent for example toluene, dimethylbenzene etc.
Usually, the coating composition viscosity of coating composition producer preparation is too high and can not directly apply, so the coating composition producer offers retail trader's coating composition together with thinner.In order to control viscosity on request and to apply workability, the paint person can buy aforementioned coating composition and thinner from retail trader, and can prepare aforementioned coating composition and thinner applies.
Recently, volatile organic compounds causes many problems to the influence of environment, be generally used for the organic solvent in coating composition field, for example toluene, dimethylbenzene etc. for example are defined as environmental pollutant in Pollutant Release andTransfer Register (being called PRTR hereinafter) etc.So it is a small amount of or be substantially free of above-mentioned organic solvent that the utmost point requires to contain the coating composition of above-mentioned organic solvent and thinner.
Relevant therewith, following references No.3 discloses a kind of car repair coating composition, it comprises specific (methyl) acrylic copolymer, polyisocyanate compound and the organic solvent of specified quantitative, and this organic solvent is aliphatic series or the aromatic hydrocarbon solvent with specific solubility parameter and specific boiling point.
Yet, use aforementioned coating composition to produce following problem: although use the clear coating composition of aforementioned coating composition on filming as metallicity can control the generation of a back spot and the metal finish with good appearance is provided, but use aforementioned coating composition causing unsafty film performance aspect covering with paint property, drying property and the adhesivity, and aforementioned coating composition contain organic solvent for example toluene, dimethylbenzene etc. as the basic coating composition.
On the other hand, in order to address the above problem, the primer coating compositions, the clear coating composition that for example for example are used for the metallicity coating in the art at coating composition, from coating composition or thinner, remove organic solvent for example toluene, dimethylbenzene etc. and be used in the coating composition can dissolving resin organic solvent, for example ester organic solvent etc. is replaced and the back can be occurred and play spot and play a spot phenomenon, film owing to the organic solvent of replacing can dissolve again when especially on metallicity is filmed, forming transparent coating, and reduced covering with paint significantly.
References 1: Japanese Patent Application Publication
Publication number 2000-178500
References 2: Japanese Patent Application Publication
Publication number 2002-129090
References 3: Japanese Patent Application Publication
Publication number 256715/94
Brief summary of the invention
An object of the present invention is to provide a kind of coating composition, it is substantially free of volatile organic matter and shows and show filming of superperformance demonstrating good performance aspect coating workability and the covering with paint property and can be formed in aspects such as water tolerance, adhesivity.
In order to address the above problem, the inventor finds through further investigation: a kind of specific coating composition can address the above problem, thereby finished the present invention, described coating composition contains: the basic coating composition (base coating composition) that comprises specific resin composition and specific organic solvent (I) and comprise the thinner (II) of the specific organic solvent of specified quantitative.
That is to say, the present invention relates to contain the coating composition of following component: comprise derivatived cellulose (A), acrylic resin (B), the basic coating composition (I) of vibrin (C) and at least a organic solvent (D) that is selected from ester class organic solvent and organic solvent of ketone and comprise the thinner (II) of aliphatic hydrocrbon organic solvent (E), the content of derivatived cellulose (A) is that 5-75wt% is (based on component (A), (B) and total solid content (C), by weight,), the content of aliphatic hydrocarbon solvent (D) in rare dose (II) is 5-90wt%, basic coating composition (I) is metallicity basic coating composition preferably, the invention still further relates to the coating method that uses this coating composition.
The present invention can provide following certain effects.
This coating composition is substantially free of the volatile organic matter of defined, thereby to environment and body harmless.
This coating composition demonstrates good storage stability, shows excellent compatibility because the basic coating composition comprises between specific resin and specific organic solvent and each component.
Under Air drying or forced drying condition, this coating composition can be formed on aspects such as covering with paint property, water tolerance, adhesivity and have filming of superperformance, because the coating composition that the basic coating composition is mixed with the thinner that comprises the specified quantitative specific solvent when causing being coated with can have the specific solvent composition.
When on metallicity is filmed, forming transparent coating, this coating composition can be controlled dissolving again and can form and show filming of good covering with paint property and can not produce metallic pigment orientation spot, though be easy to have taken place spot and after also be like this under the situation of metallicity coating of a spot.
Detailed description of the invention
Derivatived cellulose among the present invention (A) is to contain the unitary compound of cellulosic structure, can comprise, for example, use acid, for example the hydroxyl in the esterified cellulose such as lipid acid, nitric acid and the Mierocrystalline cellulose esterification product for preparing, by making the Mierocrystalline cellulose esterification product that contains the polymerizable unsaturated group and the multipolymer (F) of polymerizable unsaturated monomer prepared in reaction etc., the Mierocrystalline cellulose esterification product that wherein contains the polymerizable unsaturated group obtains by introduce the polymerizable unsaturated group in Mierocrystalline cellulose esterification product.
Mierocrystalline cellulose esterification product can comprise, for example soluble cotton, butyric acid rhodia, rhodia, propionic acid rhodia etc., wherein preferred butyric acid rhodia.
The butyric acid rhodia can prepare with the product of butyl esterification partial acetylation; and make that acetyl content is 1-30wt%; butyl content is 16-60wt%; specifically can comprise; for example CAB-381-0.5, CAB-381-0.1, CAB-381-2.0, CAB-551-0.2 (trade(brand)name is sold by Eastman Chemical Company) etc.
Derivatived cellulose (A) can be improved resulting drying property of filming and adhesivity, and comprises glitter (glitters) when coating composition of the present invention, for example aluminium powder the time, can improve the flash of light orientation of glitter in filming.
The butyric acid rhodia has 15,000-100,000, especially 20,000-35,000 number-average molecular weight.Number-average molecular weight in above-mentioned scope makes it possible to controlling spot and the back is risen in the spot and acrylic resin and vibrin maintenance excellent compatibility, shows filming of good covering with paint property thereby can form.
In this manual, number-average molecular weight is the value by using permeation chromatograph (being sold with trade(brand)name HLC8120GPC by Tosoh Corporation) to measure number-average molecular weight and obtain based on the cinnamic number-average molecular weight conversion of standard specimen.Above-mentioned measurement is carried out under the following conditions: 4 posts: TSK gel G-4000H * L, TSK gel G-3000H * L, TSK gel G-2500H * L, TSK gel G-2000H * L (trade(brand)name is all sold by Tosoh Corporation), moving phase: tetrahydrofuran (THF), measure temperature: 40 ℃, flow velocity/cc (ml)/min and detector RI.
In the present invention, derivatived cellulose (A) can comprise Mierocrystalline cellulose esterification product and multipolymer (F), and the latter introduces the Mierocrystalline cellulose esterification product that contains the polymerizable unsaturated group that the polymerizable unsaturated group obtains and polymerizable unsaturated monomer and reacts and prepare by making in Mierocrystalline cellulose esterification product.
In the present invention, being used in combination Mierocrystalline cellulose esterification product and multipolymer (F) especially can improve the consistency that is included in each interlaminar resin in the basic coating composition and can improve resulting covering with paint of filming.
Multipolymer (F) can so prepare: for example copolymerization contains the Mierocrystalline cellulose esterification product and the polymerisable unsaturated monomer of polymerizable unsaturated group, and the former obtains by reacting cellulase esterified prod and the polymerizable unsaturated monomer that contains isocyanate group.
Polymerizable unsaturated monomer can comprise any polymerisable monomer with ethylenic unsaturated bond, for example contains straight or branched C
1-18The polymerizable of alkyl is big gun and monomer not, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid dodecane ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, vinylformic acid iso stearyl ester (, selling) etc. by Osaka Organic Chemical Industry Ltd; The polymerizable unsaturated monomer that contains cycloalkyl is as (methyl) cyclohexyl acrylate, (methyl) vinylformic acid methyl cyclohexane ester, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) vinylformic acid cyclododecane ester etc.; The polymerizable unsaturated monomer that contains isobornyl is as (methyl) isobornyl acrylate etc.; The polymerizable unsaturated monomer that contains adamantyl is as (methyl) vinylformic acid diamantane ester etc.; Aromatic ethylene is a monomer, as vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.; The polymerizable unsaturated monomer that contains phosphate, as (2-acryloxy ethyl) phosphate ester acid, (2-methacryloxyethyl) phosphate ester acid, (2-acryloxy propyl group) phosphate ester acid, (2-methacryloxypropyl) phosphate ester acid etc.; (methyl) acrylate that contains hydroxyl, for example (methyl) vinylformic acid C
2-C
8Hydroxyalkyl is as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid hydroxy butyl ester etc., vinyl carbinol, (methyl) vinylformic acid C
2-C
8The 6-caprolactone modified product of hydroxyalkyl etc.; Contain the polymerizable unsaturated monomer of hydroxyl, as have (methyl) acrylate etc. of the polyethylene oxide chain of hydroxy terminal; The polymerizable unsaturated monomer that contains carboxyl is as (methyl) vinylformic acid, toxilic acid, Ba Dousuan, propenoic acid beta-carboxylic ethyl ester etc.; The polymerizable unsaturated monomer that contains alkoxysilyl is as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane etc.; (methyl) perfluoroalkyl acrylate is as (methyl) vinylformic acid perfluoro butyl ethyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester etc.; Polymerizable unsaturated monomer with fluorinated alkyl is as fluoroolefin etc.; The polymerizable unsaturated monomer that contains epoxy group(ing), as (methyl) glycidyl acrylate, (methyl) vinylformic acid Beta-methyl glycidyl ester, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl ethyl ester, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl propyl ester, glycidyl allyl ether etc.; Polymerizable unsaturated monomer with photopolymerization functional group such as dimaleoyl imino etc.; (methyl) vinylformic acid 1,2,2,6,6-pentamethyl-piperazine (piperizyl) ester, (methyl) vinylformic acid 1,2,2,2,6,6-tetramethyl-piperazine ester etc.; Vinyl compound such as N-vinyl pyrrolidone, ethene, divinyl, chloroprene, propionate, vinyl acetate etc.; (methyl) vinyl cyanide etc.; The polymerizable unsaturated monomer that contains amide group is as (methyl) acrylamide, dimethylaminopropyl (methyl) acrylamide etc.; Contain amino polymerizable unsaturated monomer, as (methyl) vinylformic acid N, N-dimethylaminoethyl, (methyl) vinylformic acid N, the adducts of N-lignocaine ethyl ester, (methyl) vinylformic acid uncle N-fourth amino ethyl ester, (methyl) glycidyl acrylate and amine etc.; The polymerizable unsaturated monomer that contains quaternary ammonium salt base, as 2-(methacryloxy) ethyl-trimethyl salmiac, 2-(methacryloxy) ethyl-trimethyl brometo de amonio, methacrylamidopropyltrimethyl trimethyl ammonium chloride, methacrylamido oxypropyl trimethyl brometo de amonio, (methyl) vinylformic acid TBuA, (methyl) vinylformic acid tetramethyl-ammonium, (methyl) vinylformic acid tri methyl benzyl ammonium, dimethyl phosphoric acid 2-(methacryloxy) ethyl trimethyl ammonium etc.; (methyl) acrylate with alkoxy end-capped polyoxyalkylene chain; Contain sulfonic polymerizable unsaturated monomer, as 2-acrylamide-2-methyl propane sulfonic acid, allyl sulphonic acid, Sodium styrene sulfonate, methacrylic acid sulphur ethyl ester, their sodium or ammonium salt etc.; The polymerizable unsaturated monomer that contains carbonyl is as propenal, diacetone-acryloamide(DAA), diacetone Methacrylamide, methacrylic acid methyl aceto acetate, formyl vinylbenzene, C
4-C
7Vinyl alkyl ketone, for example ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone etc.; These materials can be used singly or in combination.
Be used for to comprise to the polymerizable unsaturated monomer that contains isocyanate group of Mierocrystalline cellulose esterification product introducing polymerizable unsaturated group, the vinyl monomer that for example contains isocyanato, as the vinylformic acid isocyanato ethyl ,-pseudoallyl-α, the adducts of the polymerizable unsaturated monomer of α-Er Jiajibianji isocyanic ester etc., vulcabond and above-mentioned hydroxyl etc.
The copolymerization that contains the Mierocrystalline cellulose esterification product of polymerizable unsaturated group and polymerizable unsaturated monomer can be at radical polymerization initiator, as carrying out according to solution polymerization process etc. under the existence of organic superoxide.
In the preparation of multipolymer (F), the weight ratio of mixture of polymerizable unsaturated monomer/Mierocrystalline cellulose esterification product is preferably 5/95-95/5, further preferred 10/90-90/10.
Acrylic resin (B)
In the present invention, acrylic resin (B) uses mainly as film-forming components, also uses as pigment dispersing resin, can comprise the resin of acquisition like this: in the presence of organic solvent, use polymerization starter to make the polymerizable unsaturated monomer copolymerization.
Above-mentioned polymerizable unsaturated monomer can be selected from those examples of multipolymer (F) Shi Suoju in the used derivatived cellulose (A) of preparation arbitrarily.
Among the present invention, consider from resulting adhesivity of filming and water-fast adhesivity aspect, acrylic resin (B) makes the multipolymer that is prepared by the polymerizable unsaturated monomer that constitutes acrylic resin (B) have 0-80 ℃, preferred 5-75 ℃ second-order transition temperature.
In this manual, the second-order transition temperature of representing with absolute temperature is the value of being calculated by following formula:
1/Tg＝W
1/T
1+W
2/T
2+---W
n/T
n
W wherein
1, W
2,---W
nRepresent each monomeric wt%, that is, and each monomeric weight/monomeric gross weight * 100 (%), T
1, T
2,---T
nRepresent the second-order transition temperature that each monomer homopolymer is represented with absolute temperature.The second-order transition temperature of each monomer homopolymer is the value on the polymer handbook (the 4th edition).The second-order transition temperature that is not disclosed in the monomer homopolymer in the above-mentioned handbook is measured as follows.Preparation has weight-average molecular weight about 50, the monomeric homopolymer of each of 000 is as each sample, then the sample DSC-50Q type differential scanning calorimeter instrument (trade(brand)name of packing into, sell by Shimazu Corporation) measuring cup in, vacuum take-off is to remove molten Ji fully, measure the variation of the amounts of showing in-100 ℃ to+100 ℃ scopes with 3 ℃/minute rate of heating, and to get initial baseline be second-order transition temperature at the change point of low temperature side.
Preferred comonomer can comprise the polymerizable unsaturated monomer of above-mentioned hydroxyl in the acrylic resin.Consider that from resulting adhesivity of filming and water tolerance aspect above-mentioned monomeric combined amount is 0.1-35wt%, preferred 1-30wt% is based on the gross weight of the polymerizable unsaturated monomer that is used to prepare acrylic resin (B).The copolymerization of above-mentioned comonomer can improve the adhesivity of filming that is formed by resulting coating composition, and can react with the solidifying agent that is included in the clear coating composition.
Consider that from resulting adhesivity of filming and pigment-dispersing aspect acrylic resin (B) can preferably contain the carboxylic polymerizable unsaturated monomer as comonomer.Carboxylic polymerizable unsaturated monomer is 0.05-10wt% in the combined amount of all polymerizable unsaturated monomers that are used for preparing acrylic resin (B), is preferably 0.07-5.0wt%.
Improvement from pigment-dispersing and outward appearance, especially the glossy appearance aspect that applies the multilayer film that clear coating composition goes up and forms to filming of being formed by coating composition of the present invention considers that acrylic resin (B) preferably comprises the polymerizable unsaturated monomer that contains amino.Containing amino polymerizable unsaturated monomer is 0.1-60wt% in the combined amount of all polymerizable unsaturated monomers that are used for preparing acrylic resin (B), is preferably 0.5-50wt%.
The polymerization starter that is used for preparing acrylic resin of the present invention (B) comprises any those initiators in the known use of solution polymerization process, for example organo-peroxide such as benzoyl peroxide, peroxidation decoyl, lauroyl peroxide, stearoyl etc.; Azo-compound such as Diisopropyl azodicarboxylate, azo two (2, the 4-methyl pentane nitrile) etc.These materials can be used singly or in combination.
The combined amount of polymerization starter is 0.1-10wt%, and preferred 0.2-8wt% is based on the gross weight of all polymerizable unsaturated monomers that are used to prepare acrylic resin (B).
Consider that from resulting adhesivity of filming and pigment-dispersing aspect in the present invention, as above the acrylic resin of Huo Deing (B) has 5,000-80,000, preferred 6,000-70,000 weight-average molecular weight.
In this manual, weight-average molecular weight is the value by using permeation chromatograph (being sold with trade(brand)name HLC8120GPC by Tosoh Corporation) to measure weight-average molecular weight and obtain based on the cinnamic weight-average molecular weight conversion of standard specimen.Above-mentioned measurement is carried out under the following conditions: 4 posts: TSK gel G-4000H * L, TSK gel G-3000H * L, TSK gel G-2500H * L, TSK gel G-2000H * L (trade(brand)name is all sold by Tosoh Corporation), moving phase: tetrahydrofuran (THF), measure temperature: 40 ℃, flow velocity/cc (ml)/min and detector RI.
Vibrin (C)
In the present invention, vibrin (C) can comprise according to the ordinary method copolymerization and mainly contains the comonomer of polyprotonic acid and polyvalent alcohol and the resin for preparing.Polyprotonic acid comprises, for example hexanodioic acid, succsinic acid, m-phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride, maleic anhydride, trimellitic acid, hexahydrophthalic anhydride, 5-sulfoisophthalic acid sodium etc.Polyvalent alcohol comprises, for example ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP), neopentyl glycol, 1,6-hexylene glycol, tetramethylolmethane, Sorbitol Powder etc., randomly comprise, as the lipid acid of comonomer such as dehydrated castor oil fatty acid, linseed oil fatty acid, soy(a)-bean oil fatty acid, tall oil fatty acid etc., monoprotic acid such as phenylformic acid, grease etc.
In coating composition of the present invention, use vibrin (C) can improve adhesivity, especially can promote the infiltration of solidifying agent, thereby improved the adhesivity with transparent coating from the clear coating composition that contains this solidifying agent.
Consider that from resulting adhesivity of filming vibrin (C) has 5,000-100,000, preferred 10,000-70,000 weight-average molecular weight and 5-150mgKOH/g, the hydroxyl value of preferred 10-140mgKOH/g.
Vibrin (C) has-70 to 0 ℃, preferred-65 to-5 ℃ second-order transition temperature.The second-order transition temperature of vibrin (C) is measured in the following manner: the sample DSC-50Q type differential scanning calorimeter instrument (trade(brand)name of packing into, sell by Shimazu Corporation) measuring cup in, suction is desolvated to remove fully under pressure, measure the variation of heats in-100 ℃ to+100 ℃ scopes with 3 ℃/minute rate of heating, and to get initial baseline be second-order transition temperature at the change point of low temperature side.
Organic solvent (D)
In the present invention, organic solvent (D) can preferably include: to resulting drying property of filming and apply environment do not show deleterious effect organic solvent, can dissolve the resin derivatived cellulose (A) and can between each resin, show the organic solvent of excellent compatibility especially in the coating composition of the present invention, and can comprise for example at least a organic solvent that is selected from ester class organic solvent and organic solvent of ketone.
Ester class organic solvent in the organic solvent (D) can comprise, as ethyl acetate, butylacetate, isobutyl acetate, acetate 2-ethylhexyl, hexalin acetate, acetate 3-methoxyl group butyl ester, acetate propylene glycol monomethyl ether ester, acetate dipropylene glycol monomethyl ether ester, ethylene glycol monoethyl ether acetate ester, acetate diethylene glycol monoethyl ether ester etc.Organic solvent of ketone can comprise, for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethyl isoamyl ketone, diisobutyl ketone, methyl hexyl ketone, isophorone etc.These materials can be used singly or in combination.
The molecular weight of organic solvent (D) is preferably 58-220, especially 72-200.Specifically, ester class organic solvent be suitable for the storage stability that improves the basic coating composition and aspect the consistency of following aliphatic hydrocrbon organic solvent (E) display effect.
Organic solvent (D) can add with any state in preparation basic coating composition (I), and the strong solvent or the diluting solvent that also can be used as the resin that obtains in the preparation coating composition add.
Aliphatic hydrocrbon organic solvent (E)
The aliphatic hydrocrbon organic solvent comprises having high flash point and high boiling point and environment and human body are not shown the compound of deleterious effect, for example straight-chain paraffin such as normal butane, normal hexane, normal heptane, Skellysolve A, octane, positive nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, Pentadecane, n-hexadecane, n-heptadecane etc.; Branched paraffin such as 2-methylbutane, 2, the 2-dimethylpropane, the 2-methylpentane, the 3-methylpentane, 2, the 2-dimethylbutane, 2, the 3-dimethylbutane, the 2-methyl hexane, the 3-methyl hexane, 2, the 3-dimethylpentane, 2, the 4-dimethylpentane, 2,2, the 3-trimethylpentane, 2,2, the 4-trimethylpentane, 3,4-diethyl hexane, 2,6-dimethyl octane, 3,3-dimethyl octane, 3,5-dimethyl octane, 4,4-dimethyl octane, 3-ethyl-3-methylbutane, the 2-methylnonane, the 3-methylnonane, the 4-methylnonane, the 5-methylnonane, 2-methyl undecane, 3-methyl undecane, 2,2,4,6,6-five methylheptane etc.; Naphthenic hydrocarbon is as, pentamethylene, uncle's naphthalane, hexanaphthene, methylcyclohexane, ethylcyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, propyl cyclohexane, normenthane, 1,2-methylethyl hexanaphthene, 1,3-methylethyl hexanaphthene, 1,4-methylethyl hexanaphthene, 1,2,3-trimethyl-cyclohexane, 1,2,4-trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane etc.; These materials can be used singly or in combination.
When coating composition of the present invention is when comprising the metallic paints composition of glitter, from controlling resulting spot of filming and can improving covering with paint property aspect significantly and consider that organic solvent (E) preferably includes C
5-12, C especially
6-10Alkane, especially naphthenic hydrocarbon, more particularly alkyl cyclohexane.
This alkyl cyclohexane comprises, as methylcyclohexane, ethylcyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, propyl cyclohexane, normenthane, 1,2-methylethyl hexanaphthene, 1,3-methylethyl hexanaphthene, 1,4-methylethyl hexanaphthene, 1,2,3-trimethyl-cyclohexane, 1,2,4-trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane etc.
Consider that preferred organic solvent (E) is included in the following thinner (II) and the content in thinner (II) is 5-90wt%, preferred 10-80wt% from the prolonged storage stability aspect of basic coating composition (I).When the content of organic solvent (E) in thinner (II) during, thinner (II) is mixed formed the filming of the coating composition that obtains to produce ununiformity with basic coating composition of the present invention aspect the covering with paint property by applying less than 5wt%.On the other hand, when greater than 90wt%, thinner (II) and the solvability deficiency of basic coating composition may reduce in order to control viscosity and to cover with paint, lacquer, colour wash, etc. performance and by mixing the stability of the coating composition that above-mentioned two components prepare.
Basic coating composition (I)
Among the present invention, basic coating composition (I) comprises component (A) as necessary component, (B), (C) and (D).At component (A), (B) and total solid content (C), by weight, in, the content of derivatived cellulose (A) is 5-75wt%, preferred 10-70wt%.
Component (A) may reduce the formed drying property of filming of coating composition of the present invention during less than 5wt%.On the other hand, when greater than 75wt%, may reduce adhesivity with coated base tree and transparent coating.
At component (A), (B) and total solid content (C), by weight, in, the content of acrylic resin (B) is 5-90wt%, preferred 10-85wt%; The content of vibrin (C) is 5-45wt%, preferred 10-40wt%.
Component (B) may reduction during less than 5wt% and the adhesivity of coated substrate and transparent coating.On the other hand, when greater than 90wt%, may reduce resulting drying property of filming.Component (C) can cause the linked perviousness of transparent coating insufficient during less than 5wt%.On the other hand, when greater than 45wt%, can reduce the hardness of filming.
In the present invention, basic coating composition (I) can be colo(u)r coating composition or clear coating composition.Wherein, the colo(u)r coating composition comprises that especially the coating composition of glitter can make effect of the present invention reach maximum.
The pigment that is used for the basic coating composition can comprise any pigment that is used for this area coating composition, not special restriction, for example glitter, coloured pigment, pigment extender etc.Glitter comprises, for example metallic pigment such as aluminium powder, bronze powder, copper powder, glass putty, tertiary iron phosphate etc.; The oxidized silicon chip that the alumina wafer that the mica powder that pearly pigment such as mica, metal oxide coat, metal oxide coat, metal oxide coat, mica shape ferric oxide etc.Coloured pigment comprises, for example white pigment such as titanium oxide etc.; Black pigment such as carbon black, acetylene black, dim, natural black (born black), graphite, iron oxide black, nigrosine etc.; Yellow ultramarine such as iron oxide yellow, titan yellow, monoazo yellow (monoazo yellow), polycondensation azophosphine, azomethine Huang, pucherite, benzimidazolone, isoindolinone, isoindoline (isoindolin), quinophthalone (quinophthalone), diarylide yellow, permanent Huang etc.; Orange pigments such as permanent orange etc.; Red pigment such as red iron oxide, naphthols AS azophloxine, three benzos [cd, jk] pyrene-5,10-diketone, anthraquinonyl are red, perylene maroon, quinacridine red, diketopyrrolopyrrolecocrystals, C lake red CAN'T (watchung red), permanent red etc.; Violet pigment such as cobalt violet, quinacridone violet, dioxazine violet etc.; Blue pigments such as cobalt blue, phthalocyanine blue, Threne blue (threne blue) etc.; Phthalocyanine such as phthalocyanine green etc.; Pigment extender comprises, for example zinc powder, barium oxide powder, precipitated barium sulfate, barium carbonate, lime carbonate, plaster, clay, silicon-dioxide, white carbon, diatomite, talcum, magnesiumcarbonate, white lake, gloss white, mica chalk.
The combined amount of pigment in coating composition of the present invention can determine that the resin solid content in the coating based composition by weight, is 1-250wt% usually, is preferably 2-240wt% according to the kind of pigment arbitrarily.For example, under the situation of the coating composition that contains glitter, the content of glitter is 1-60wt% based on the above, preferred 2-55wt%.
The optional additive that is used for this area coating composition that comprises of basic coating composition (I), for example thickening material, UV light absorber, photostabilizer, oxidation inhibitor, surperficial control agent, pigment dispersing agent, curing catalysts etc., also can comprise organic solvent (E) and other organic solvent, its area requirement does not show deleterious effect to the storage stability of basic coating composition (I) with to the drying property of coating composition of the present invention.
Other organic solvent can comprise and is different from organic solvent (D) and (E), as aromatic hydrocarbons organic solvent such as toluene, dimethylbenzene etc.; Ether organic solvent such as diox, tetrahydrofuran (THF), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl isopropyl ether, the glycol monomethyl n-butyl ether, the glycol monomethyl isobutyl ether, the glycol monomethyl tertbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary just-propyl ether, the diglycol monotertiary isopropyl ether, the diglycol monotertiary n-butyl ether, the diglycol monotertiary ethyl isobutyl ether, diglycol monotertiary butyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list n-propyl ether, the propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, dipropylene glycol list n-propyl ether, dipropylene glycol monoisopropyl ether etc.; With alcohol organic solvent such as methyl alcohol, Virahol, the trimethyl carbinol, sec-butyl alcohol, isopropylcarbinol, propyl carbinol, 2-Ethylhexyl Alcohol, n-Octanol, phenylcarbinol etc.On their consumption, require the film performance of filming that is formed by coating composition of the present invention is not shown deleterious effect.
Thinner (II)
In the present invention, thinner (II) mixes with basic coating composition (I) with the viscosity of control coating composition and improves the coating workability, and form to show a little or do not play spot or the back is played spot and shown filming of good covering with paint property.
In order to improve thinner (II) and the resin that is included in the basic coating composition, especially the formed covering with paint of filming of mixed stability of derivatived cellulose (A) and coating composition of the present invention, the amount that thinner (II) contains the aliphatic hydrocrbon organic solvent can be 5-90wt%, preferred 10-80wt%, the amount that contains ester class organic solvent is 8-85wt%, be preferably 10-80wt%, the amount that contains organic solvent of ketone is 2-35wt%, be preferably 5-30wt%, the amount that contains other organic solvent is 0-30wt%, preferred 0-25wt%.
Thinner (II) can be chosen wantonly and comprise the additive that is used for this area coating composition, for example thickening material, UV light absorber, photostabilizer, oxidation inhibitor, surperficial control agent, pigment dispersing agent, curing catalysts etc.
Coating composition
Coating composition of the present invention comprises basic coating composition (II) and thinner (II) and makes to be considered from coating workability and covering with paint property aspect, the consumption of organic solvent (D) is the 100-700 weight part, the consumption that is preferably 120-690 weight part and solvent (E) is the 20-340 weight part, be preferably the 25-330 weight part, based on the resin solid content in per 100 weight part basic coating compositions (I).
In the present invention, the consistency of interlaminar resin and formation show that well the aspect of filming of covering with paint property is considered from improve coating composition of the present invention, aliphatic hydrocrbon organic solvent (E) consumption is the 20-340 weight part, be preferably the 25-330 weight part, the consumption of ester class organic solvent is the 90-590 weight part, the consumption that is preferably 100-580 weight part and organic solvent of ketone is the 10-110 weight part, is preferably the 20-110 weight part.
The preparation of coating composition can be carried out in the following manner, for example mixes basic coating composition (I) and thinner (II) before being about to coating.In this manual, for example above-mentioned mixing can be carried out before applying in 3 hours.
In order to obtain above-mentioned solvent compositions, thinner (II) will make that with the ratio of mixture of basic coating composition (I) combined amount of thinner (II) is 20-250wt%, is preferably 30-200wt%, based on the weight of basic coating composition (I).
In the present invention, the type of coating composition is not particularly limited, but preferably includes the two-component-type composition of basic coating composition (I) and thinner (II).Coating composition of the present invention can be chosen wantonly and comprise solidifying agent such as polyisocyanate curing agent, end capped polyisocyanate curing agent, melamine solidifying agent etc.When coating composition comprises solidifying agent, according to the kind of solidifying agent, the type of coating composition at random is selected from: comprise basic coating composition (I), thinner (II) and solidifying agent three component type compositions, comprise basic coating composition (I) and solidifying agent mixture as the two-component-type composition of the composition of a component and thinner (II) and the mixture that comprises thinner (II) and solidifying agent as the composition of a component and the two-component-type composition of basic coating composition (I).
Apply
The invention provides a kind of coating method, it comprises coating composition of the present invention is coated on the coated substrate.
Coated substrate comprises base material known in the art and filming of forming on this base material.Base material is not particularly limited, and can comprise, for example metal such as iron, aluminium etc.; Organic substrate such as plastics etc.; Inorganic substrate such as concrete, timber etc.; Filming of forming on base material is not particularly limited, and can comprise multilayer film for example, the transparent coating etc. that it comprises the bottom coating that is formed by colored basic coating composition and is used for car body, vehicle such as train.Bottom coating can same bottom, and filming etc. as primer coating film, electrodeposition coating, centre combines.
The basis that forms by colored basic coating composition formed the filming of the coating composition that contains coloured pigment and/or glitter that ordinary representation applies in order to give beautiful outward appearance on coated substrate of filming.The transparent surface upper layer that ordinary representation can form transparent coating of filming is filmed.Electrodeposition coating forms by being used for the galvanic deposit applied coating composition.Ordinary representation is filmed bottom the filming between filming as bottom coating and transparent surface of filming as primer coating film and electrodeposition coating and external coating (EC) of filming in the middle layer.
The coating method that applies coating composition of the present invention is not particularly limited, and can comprise for example spraying, electrostatic coating, brushing, roller coat etc.Desiccating method comprises heat drying, forced drying and Air drying.In this manual, Air drying is to carry out under temperature is lower than 40 ℃ drying conditions.Forced drying is to be 40 ℃ or higher and be lower than under 80 ℃ the drying conditions and carry out in temperature.Heat drying is to carry out under temperature is 80 ℃ or higher drying conditions.
The invention provides a kind of coating method, it comprises and applies coating composition of the present invention and films with formation to coated substrate, applies then on clear coating composition films to this.
Film and before applying clear coating composition, to solidify and drying by what coating composition of the present invention formed, or uncured and form uncured filming, apply clear coating composition then and film to this and go up and form uncured transparent coating and dry two and film.
Be used for clear coating composition of the present invention and can comprise any those compositions known in the art, be not particularly limited, curable coating composition for example, it contains base resin as the acrylic resin that contains crosslinkable functional group such as hydroxyl and fluorocarbon resin and solidifying agent such as end capped polyisocyanates, polyisocyanates, melamine resin etc.; Contain paint coating composition as the butyric acid rhodia modified acroleic acid resinoid of main ingredient etc.Clear coating composition can be chosen wantonly and comprise the additive that is used for coating composition known in the art, for example pigment, derivatived cellulose, additive resin, UV light absorber, photostabilizer, surperficial control agent, curing catalysts etc.Wherein, when use comprises the clear coating composition of polyisocyanate curing agent, a part of polyisocyanate curing agent in the transparent coating can be from coating composition infiltration of the present invention be filmed, therefore when filming of coating composition of the present invention contained hydroxyl, the polyisocyanate curing agent that infiltrates and the reaction of hydroxyl make in coating composition unnecessary use solidifying agent or reduce use hardener dose therein, and can improve by the adhesivity between filming of forming of coating composition of the present invention and transparent coating.
The coating method that applies clear coating composition comprises for example spraying, electrostatic coating, brushing, roller coat etc.Drying means comprises heat drying, forced drying and Air drying.
Embodiment
The present invention explains in more detail that by following examples wherein ＂ part ＂ represents " weight part " and ＂ % " expression " wt% ".
The preparation of polyester resin solution
Preparation example 1
In the returned cold that is equipped with well heater, thermometer, agitator, fractional column and water trap has been installed is doubted 4 liters of reactors of device, add following component, then be warmed up to 160 ℃ and in 3 hours, be heated to 230 ℃ from 160 ℃.
29.7 parts of hexahydrophthalic anhydrides
25.4 parts of oxalic acids
5.3 parts of neopentyl glycol
1,39.6 parts of 6-hexylene glycols
After this, keep 230 ℃ temperature one hour, then use fractional column to distillate formed water of condensation (7.4 parts), add 5 parts of dimethylbenzene, use water trap backflow dimethylbenzene and water of condensation to anhydrate to remove.Begin to measure acid number after 2 hours adding dimethylbenzene, when acid number becomes 2 or vacuumize almost entirely to distill out dimethylbenzene littler the time, cool to 120 ℃, making the content of nonvolatile substances with the N-BUTYL ACETATE dilution is 70%, thereby obtains vibrin N-BUTYL ACETATE solution.The weight-average molecular weight of resulting resin is 20,000, hydroxyl value is that 32mgKOH/g and second-order transition temperature are-52 ℃.
The preparation of acrylic resin solution
Preparation example 2
In 4 liters of reactors that are equipped with thermometer, agitator, reflux exchanger and dropping pump, add 68 parts of N-BUTYL ACETATEs, then stir and be warmed up to 110 ℃, with constant speed at the mixing solutions that in about 3 hours, drips following monomer mixture and polymerization starter under 110 ℃.
59.75 parts of Propenoic acid, 2-methyl, isobutyl esters
10 parts of methyl methacrylates
Vinylformic acid iso stearyl ester is (by 10 parts of Osaka Organic
Chemical Industry Ltd. sells)
19 parts of vinylformic acid 2-hydroxyl ethyl esters
1 part of dimethylaminoethyl methacrylate
0.25 part of methacrylic acid
0.2 part of azo two (2, the 4-methyl pentane nitrile)
After being added dropwise to complete, under condition of stirring, keep temperature be 110 ℃ one hour, then in 1 hour, drips and in 14 parts of N-BUTYL ACETATEs, has dissolved 0.5 part of solution that forms as the azo two (methyl pentane nitrile) of additional catalyst with constant speed, remain on 110 ℃ one hour so that react and to finish.More than Zhi Bei acrylic resin solution has 55.0% nonvolatile substances and is the solution of homogeneous transparent.The weight-average molecular weight of resulting resin is 50,000, hydroxyl value is that 92mgKOH/g and second-order transition temperature are 57 ℃.
The preparation of CAB grafted propylene acid resin solution
Preparation example 3
In 4 liters of reactors that are equipped with thermometer, agitator, reflux exchanger and dropping funnel, add following component, then in about 4 hours, under nitrogen atmosphere, be heated to 110 ℃.
600 parts of butylacetates
200 parts of CAB-381-0.5 (note 1)
Be heated to 110 ℃ to dissolve CAB-381-0.5 (note 1) fully, stop heating, vacuum distillates 133 parts of N-BUTYL ACETATEs, in reactor, add 11.1 parts of isophorone diisocyanates and vinylformic acid 2-hydroxyl ethyl ester etc. 90% butylacetate solution of mole addition reaction product, 0.02 part p-ten.-butylcatechol and 0.02 part of dibutyl tin laurate that forms catalyzer as carbamate as stopper, keeping the temperature in the reactor simultaneously is 87 ℃, the butyric acid cellulose acetate solution that contained unsaturated group under the dry air 87 ℃ of slakings in 7 hours with acquisition, be heated to 115 ℃, in 2 hours, drip the mixing solutions of following polymerizable unsaturated monomer and polymerization starter.
130 parts of butylacetates
58.2 parts of methyl methacrylates
2 parts of caproic acid t-butyl peroxy-2-ethyl ester
After above-mentioned being added dropwise to complete, then in 1 hour, drip the mixing solutions of 0.5 part of caproic acid t-butyl peroxy-2-ethyl ester and 20 parts of butylacetates, and under nitrogen atmosphere be 30% CAB-grafted acrylic resin solution with the acquisition nonvolatile substances 115 ℃ of slakings 1 hour.
(note 1) CAB-381-0.5: trade(brand)name, to sell by Eastman Chemical Company, butyric acid rhodia, butyl content are 38%, number-average molecular weight is 300,000.
The basic coating preparation of compositions
Preparation example 4-8
According to the prescription shown in the table 1, in reactor, add aluminium and stick with paste MC-606 (trade(brand)name, sell by Asahi KaseiMetals Ltd., aluminium powder paint, aluminium powder/mineral turpentine (mineral spirit)/C9 aromatic hydrocarbons organic solvent=60/19.5/19.5, weight ratio, amine is 1%) and preparation example 2 in 55% acrylic resin solution of preparation, then carry out dispersed with stirring, CAB551-0.2 solution (note 2) according to the interpolation of the prescription shown in the table 1 25%, the polyester resin solution of 70% in the preparation example 1 and 30% CAB-grafted propylene acid resin solution, add butylacetate according to the prescription shown in the table 1, thereby and stir with decollator and to obtain metallicity basic coating composition (I-1) to (I-5) in about 20 minutes.
Table 1
The CAB551-0.2 solution of (note 2) 25%: CAB551-0.2 (trade(brand)name, sold by EastmanChemical Company, butyric acid rhodia, butyl content are 55%, number-average molecular weight is 30,000) to be dissolved in the butylacetate to make solid content be 25% solution.
The preparation of thinner
Preparation example 9-26
Mix each solvent according to the prescription shown in the table 2, then stir and prepared thinner (II-1) in about 10 minutes to (II-18) with decollator.
The preparation of coating composition
Embodiment 1
The mixture that stirs 100 parts of metallic paints compositions (I-1) and 100 parts of thinners (II-1) obtains coating composition.
Embodiment 2-16 and Comparative Examples 1-9
Repeat embodiment 1, except according to each coating composition of each formulation shown in the table 3.
Apply
Apply KAR PRIMER-SURFACER GRAY (trade(brand)name, by Kansai Paint Co., Ltd. sell, the lacquer primer floating coat) to tinplate and to make build be 40 microns, then 20 ℃ of dryings 30 minutes, with #400 water-proof abrasive paper sand milling, spraying the coating composition of each embodiment and comparative example and make build on it is 30 microns, drying is 10 minutes under 20 ℃, spraying clear coating composition (note 3) and make build on it is 40 microns, and obtains test panel 20 ℃ of following dryings 24 hours.Before and after applying clear coating composition, each test panel is carried out following performance test.Test result is shown in the table 3.
(note 3) clear coating composition:
With thinner (II-1) dilution 100 weight part Retan PG Multi-Clear UX (Q) Base (trade(brand)names, by Kansai Paint Co., Ltd. sell, the clear coating composition that contains the acrylic resin of hydroxyl) and 50 weight part Retan PG Multi-Clear HX standard solidifying agent (trade(brand)names, by Kansai Paint Co., Ltd. sell the hexamethylene diisocyanate solidifying agent) mixture and obtain the clear coating composition that viscosity is 13-14 sec. (#4/25 ℃ in Ford cup).
(* 1) drying property
In thermostatic constant wet chamber, be that 20 ℃ and humidity are under 75% the condition in temperature, use scraper coated with coating composition to sheet glass and to make coating thickness be 100 microns, then measure the sticking needed time.Carry out following evaluation.◎: time of drying is less than 10 minutes, and zero: be 10 minutes or more but less than 12 minutes time of drying, △: 12 minutes or more but less than 15 minutes, *: 15 minutes or more.
(* 2) play spot
The pigment orientation spot that test panel is filmed before the range estimation coating clear coating composition.Test result is estimated as follows.◎: do not play spot and occur zero: a little plays the spot appearance, but can be practical, △: a little plays the spot appearance, *: spot appears rising significantly.
Spot is played in (* 3) back
Range estimation applies the pigment orientation spot that the also dry prepared test panel afterwards of clear coating composition is filmed.Test result is estimated as follows.◎: do not play spot and occur zero: a little plays the spot appearance, but can be practical, △: a little plays the spot appearance, *: spot appears rising significantly.
(* 4) adhesivity
By applying clear coating composition, then carry out drying and prepare test panel and carry out the adhesivity test as follows.On diagonal lines, carry out cross recess and arrive the base material of test panel with cutter, then carry out the separation property test with self adhesive tape.Test result is estimated as follows.Zero: do not separate △: a little separation, *: significantly separate.
The pollution substance content of (* 5) PRTR regulation
Measure the content of toluene and dimethylbenzene in the coating composition of each embodiment and Comparative Examples, and carry out following evaluation.Zero: the pollution substance content of PRTR regulation is less than 1%, *: the pollution substance content of PRTR regulation is 1% or more.
Claims (8)
1. coating composition, it comprises: contain derivatived cellulose (A), acrylic resin (B), vibrin (C) and be selected from ester class organic solvent and organic solvent of ketone at least a organic solvent (D) basic coating composition (I) and comprise aliphatic hydrocrbon organic solvent (E), the thinner of ester class organic solvent and organic solvent of ketone (II), described derivatived cellulose (A) is at least a compound that is selected from Mierocrystalline cellulose esterification product and multipolymer (F), described multipolymer (F) is introduced the Mierocrystalline cellulose esterification product that contains the polymerizable unsaturated group that the polymerizable unsaturated group obtains and polymerizable unsaturated monomer and is reacted and prepare by making in described Mierocrystalline cellulose esterification product, the content of derivatived cellulose (A) is based on component (A), (B) and total solid content (C), by weight, be 5-75wt%, the content of acrylic resin (B) is 5-90wt%, the content of vibrin (C) is 5-45wt%, the content of aliphatic hydrocrbon organic solvent (E) in thinner (II) is 5-90wt%, the content of ester class organic solvent in thinner (II) is 8-85wt%, the content of organic solvent of ketone in thinner (II) is 2-35wt%, and thinner (II) makes that with the ratio of mixture of basic coating composition (I) combined amount of thinner (II) is 20-250wt%.
2. according to the coating composition of claim 1, wherein basic coating composition (I) is a metallicity basic coating composition.
3. according to the coating composition of claim 1 or 2, wherein derivatived cellulose (A) is the butyric acid rhodia.
4. according to the coating composition of claim 1 or 2, wherein organic solvent (E) is an alkyl cyclohexane.
5. according to the coating composition of claim 1 or 2, wherein, based on resin solid content 100 weight parts in the basic coating composition (I), the content of organic solvent (D) is the 100-700 weight part, and the content of organic solvent (E) is the 20-340 weight part.
6. coating method, it is included in and applies on the coated substrate according to each coating composition in the claim 1 to 5.
7. coating method, it is included in to apply on the coated substrate and films with formation according to each coating composition in the claim 1 to 5, then applies clear coating composition on this is filmed.
8. the coated article that obtains according to the coating method of claim 6 or 7.
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| CN101191029B (en) * | 2006-12-01 | 2011-05-18 | 比亚迪股份有限公司 | Primer composition for metal substrate and its preparation method and multilayer coat |
| CN103237606B (en) * | 2010-12-03 | 2014-12-03 | 关西涂料株式会社 | Method for forming coating film |
| JP5674592B2 (en) * | 2011-08-18 | 2015-02-25 | 関西ペイント株式会社 | Multi-component base coat paint, toning method and repair coating method |
| CN103509412B (en) * | 2012-06-21 | 2017-04-12 | 关西涂料株式会社 | Brightness coating composition |
| CN102816487A (en) * | 2012-07-10 | 2012-12-12 | 华南理工大学 | Silver priming paint of 1K silver powder containing automobile refinishing coating and preparation method thereof |
| CN104325132B (en) * | 2014-10-23 | 2016-11-30 | 李烈熊 | A kind of powder used in metallurgy anticorrosive additive and preparation method thereof |
| JP6146529B1 (en) * | 2016-12-07 | 2017-06-14 | 藤倉化成株式会社 | Glitter paint |
| KR102050921B1 (en) | 2018-08-02 | 2019-12-03 | 에스케이이노베이션 주식회사 | Organic solvent composition and paint composition comprising the same |
| CN109439034B (en) * | 2018-11-10 | 2021-05-14 | 刘鹏 | Bi-component diatom ooze water-based paint with zero VOC (volatile organic compounds) emission |
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| JP2000178500A (en) * | 1998-12-14 | 2000-06-27 | Kansai Paint Co Ltd | Coating material composition and coating finish using the same |
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| JPH1046067A (en) * | 1996-08-02 | 1998-02-17 | Kansai Paint Co Ltd | Preparation of coating material |
| CN1189522A (en) * | 1997-05-21 | 1998-08-05 | 褚炎明 | Namometre automotive metal finish |
| JP2000178500A (en) * | 1998-12-14 | 2000-06-27 | Kansai Paint Co Ltd | Coating material composition and coating finish using the same |
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