CN1673295A - Anion electroplating paint and finished articles - Google Patents
Anion electroplating paint and finished articles Download PDFInfo
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- CN1673295A CN1673295A CN 200510053994 CN200510053994A CN1673295A CN 1673295 A CN1673295 A CN 1673295A CN 200510053994 CN200510053994 CN 200510053994 CN 200510053994 A CN200510053994 A CN 200510053994A CN 1673295 A CN1673295 A CN 1673295A
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Abstract
This invention provides an anionic electrodeposition coating material which is excellent in weatherability, coating stability and die mark screening. The anionic electrodeposition coating material contains (A) a core/shell emulsion which is an emulsified polymer obtained by emulsion-polymerizing a polymerizable unsaturated monomer by a multi-step reaction in the presence of water and an emulsifier and contains 1-40 wt%, against the total monomer weight used in the multi-step reaction, an alkoxylsilyl group-containing polymerizable unsaturated monomer as the polymerizable unsaturated monomer, (B) an alkyl resin and (C) a hardener.
Description
Technical field
The present invention relates to the disguised good delustring anion electroplating paint of a kind of weathering resistance, paint stability, mould mark and cover with paint, lacquer, colour wash, etc. the article of this coating.
Background technology
Aluminium is because light and processing easily utilizes such character, particularly as the more use of the material of building materials aspect.
The hot-extrudable method of aluminium normally heats columniform aluminium block makes its fusion, then this melts is added forcing machine, is pressed in the mould in the hole with regulation section form, obtains having the section bar of regulation shape by the hole.
And usually aluminium section bar, generally will be covered with paint, lacquer, colour wash, etc. with the delustring anion electroplating paint and go up delustring and film behind the anodic oxidation treatment aluminium section bar because of itself erosion resistance, wearability, resistance to chemical reagents equal difference.
But electroplate under the situation of covering with paint, lacquer, colour wash, etc. above-mentioned delustring anion electroplating paint on the aluminium section bar of handling is filmed in anodic oxidation, the mould mark of raw material aluminium section bar is showy, thereby exists commodity value to hang down such problem.
Up to now, the invention that relates to the anion electroplating paint of the Emulgating polymers that contains alkoxysilyl has patent documentation 1, this Emulgating polymers is in the presence of water and emulsifying agent, the Emulgating polymers that uses polymerizability unsaturated monomer multistep processes emulsion polymerization to make, this polymerizability unsaturated monomer uses the unsaturated monomer contain alkoxysilyl for substep, and is 5～40 weight % with respect to the ratio of whole monomer weights.But the weathering resistance of patent documentation 1 and mould mark disguise are insufficient.
In addition, in order to improve weathering resistance, relating to the invention that contains the anion electroplating paint that UV light absorber and photostabilizer make in acrylic copolymer resin and aminoresin stiffening agent has patent documentation 2.As described in patent documentation 2, in the acrylic copolymer resin in conjunction with the words of UV light absorber and photostabilizer, consistency is insufficient, thereby and film after long-time middle-ultraviolet lamp absorption agent and photostabilizer can exhaust and can not get sufficient weathering resistance, the problem of long-term paint stability is also arranged.
Patent documentation 1: the spy opens the 2002-188044 communique
Patent documentation 2: the spy opens the 2002-38084 communique
Summary of the invention
The invention provides weathering resistance, paint stability, the disguised good delustring anion electroplating paint of mould mark.
The inventor studies intensively in order to address the above problem repeatedly, found that according to the anion electroplating paint that contains core/shell type emulsion (A) and can reach goal of the invention, thereby finish the present invention, this emulsion (A) has in nuclear part and is selected from the polymerizability unsaturated monomer (a) that contains alkoxysilyl, the free-radical polymerised unsaturated monomer (b) that contains the UV light absorber composition, contain the free-radical polymerised unsaturated monomer (c) of photostabilizer composition and at least a kind of free-radical polymerised unsaturated monomer and other the free-radical polymerised unsaturated monomers (e) in the free radical contained fluorine polymerizability unsaturated monomer (d) and carry out the polymkeric substance that radical copolymerization makes.
That is, the present invention relates to:
1) a kind of core/shell type emulsion (A) that contains, acrylic resin (B), the anion electroplating paint of stiffening agent (C), it is characterized in that: core/shell type emulsion (A) is to use the Emulgating polymers of polymerizability unsaturated monomer multistep processes emulsion polymerization preparation in the presence of water and emulsifying agent, this polymerizability unsaturated monomer uses the polymerizability unsaturated monomer that contains alkoxysilyl for substep, and the ratio with respect to whole monomer weights is 1～40 weight %, core/shell type emulsion (A) is in the aqueous solution of water and emulsifying agent, make and be selected from the free-radical polymerised unsaturated monomer (a) that comprises alkoxysilyl, the free-radical polymerised unsaturated monomer (b) that comprises the UV light absorber composition, comprise the free-radical polymerised unsaturated monomer (c) of photostabilizer composition and at least a kind of free-radical polymerised unsaturated monomer in the free radical contained fluorine polymerizability unsaturated monomer (d), with other free-radical polymerised unsaturated monomers (e), be included in the free-radical polymerised unsaturated monomer of the monomer (f) that contains 2 or more unsaturated groups in 1 molecule in case of necessity, in the presence of radical polymerization initiator, carry out the free radical emulsion polymerization reaction in the 1st step, after making free radical polyalcohol (I), then in the presence of above-mentioned free radical polyalcohol (I), make free-radical polymerised unsaturated monomer (a) with alkoxysilyl and other free-radical polymerised unsaturated monomer (e), the free-radical polymerised unsaturated monomer that is included in the monomer (f) that contains 2 or more unsaturated groups in 1 molecule in case of necessity carries out the free radical emulsion polymerization reaction in the 2nd step, the core/shell type emulsion that obtains.
2) as 1) anion electroplating paint of being put down in writing, it is characterized in that, in the core/shell type emulsion (A), with respect to the whole monomer weights that constitute core/shell type emulsion (A), be selected from the ratio that at least a kind of free-radical polymerised unsaturated monomer in the free-radical polymerised unsaturated monomer (b) that comprises the UV light absorber composition, the free-radical polymerised unsaturated monomer (c) that comprises the photostabilizer composition and the free radical contained fluorine polymerizability unsaturated monomer (d) accounts for 0.01～10 weight %.
3) as 1) item or 2) anion electroplating paint of being put down in writing, it is characterized in that the free-radical polymerised unsaturated monomer (b) that comprises the UV light absorber composition is 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole.
4) as 1) item or 2) anion electroplating paint of being put down in writing, it is characterized in that the free-radical polymerised unsaturated monomer (C) that comprises the photostabilizer composition is a 4-methacryloxy-1,2,2,6,6-pentamethyl-piperidines.
5) as 1) item or 2) anion electroplating paint of being put down in writing, it is characterized in that free radical contained fluorine polymerizability unsaturated monomer (d) is a 2-perfluoro capryl ethyl-methyl acrylate.
6) a kind of coated article, be by be coated with that jewelry is powering on that plating is covered with paint, lacquer, colour wash, etc. as 1)～5) in the hardened coating film that obtains of each anion electroplating paint of putting down in writing, it is 30 or still less according to the 60 degree mirror surface lusters of stipulating among the JISK-8741.
Anion electroplating paint of the present invention can obtain the disguised good delustring of weathering resistance, paint stability, mould mark film (according to the regulation 60 degree mirror surface lusters of JIS K-8741 30 or still less).About paint stability, even the problem that mechanical part does not have stability yet is installed on the paint line.
The reason that weathering resistance is good is because having added at least a kind in the nuclear partial polymer of core/shell type emulsion is selected from the free-radical polymerised unsaturated monomer that contains the UV light absorber composition, the free-radical polymerised unsaturated monomer that contains photostabilizer and free radical contained fluorine polymerizability unsaturated monomer etc. and has the monomer of weathering resistance effect, exposes illumination and does not also have these monomer components to separate out from film even for example will film.
The present invention is because mould mark disguise is good, can be effectively used to aspect the covering with paint of widely used aluminium section bar in building materials etc.
Embodiment
The good delustring anion electroplating paint of weathering resistance of the present invention and paint stability comprises core/shell type emulsion (A), acrylic resin (B), stiffening agent (C).Below be described in detail.
Core/shell type emulsion (A):
Core/shell type emulsion (A) is in the aqueous solution of water and emulsifying agent, make and be selected from the free-radical polymerised unsaturated monomer (a) that comprises alkoxysilyl, the free-radical polymerised unsaturated monomer (b) that comprises the UV light absorber composition, comprise the free-radical polymerised unsaturated monomer (c) of photostabilizer composition and at least a kind of free-radical polymerised unsaturated monomer in the free radical contained fluorine polymerizability unsaturated monomer (d), and the free-radical polymerised unsaturated monomer that contains other free-radical polymerised unsaturated monomers (e) carries out the free radical emulsion polymerization reaction in the 1st step by radical polymerization initiator, after making free radical polyalcohol (I), then in the presence of above-mentioned free radical polyalcohol (I), make free-radical polymerised unsaturated monomer (a) and other free-radical polymerised unsaturated monomers that contains free-radical polymerised unsaturated monomer (e) carry out the 2nd free radical emulsion polymerization reaction that goes on foot, the core/shell type emulsion that obtains with alkoxysilyl.
As the polymerizability unsaturated monomer (a) that contains alkoxysilyl, for example be divinyl dimethoxy silane, divinyl two-'beta '-methoxy Ethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three-'beta '-methoxy Ethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane etc., can use separately, also can two or morely be used in combination.
This polymerizability unsaturated monomer (a) that contains alkoxysilyl is fit to use with respect to 1～40 weight % multistep (for example 2 steps) of whole monomer weights, and preferred 3～35 weight % are more preferably in the scope of 5～25 weight %.Less than 1 weight %, extinction effect is insufficient, on the other hand, surpasses 40 weight %, and polymerization stability has the trend of reduction when synthetic, can produce problems such as gloss uneven simultaneously.
And core/shell type emulsion (A) internal crosslinking makes the stability of core/shell type emulsion (A) improve, and the alkoxysilyl deflection particle outside, in order to improve the extinction effect of filming, can use in the initial step during multistep is rapid and contain with respect to whole monomer weight 40 weight % or the compound (f) that in 1 molecule, has 2 or more polymerizability unsaturated groups still less, preferred 5～30 weight %.
As the compound (f) that in 1 molecule, has 2 or more polymerizability unsaturated groups, it for example is (methyl) allyl acrylate, two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) vinylformic acid TEG ester, two (methyl) vinylformic acid 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, two (methyl) vinylformic acid glyceryl ester, three (methyl) vinylformic acid glyceryl ester, two (methyl) vinylformic acid trishydroxymethyl propyl ester, three (methyl) vinylformic acid trishydroxymethyl propyl ester, two (methyl) vinylformic acid, five tetrahydroxybutane esters, three (methyl) vinylformic acid, five tetrahydroxybutane esters, four (methyl) vinylformic acid, five tetrahydroxybutane esters, five (methyl) vinylformic acid, two or five tetrahydroxybutane esters, three (methyl) vinylformic acid hydroxyl chlorinated isocyanurates, diacrylic acid pentyl diol ester, diacrylate 1,6-hexylene glycol ester, two (methyl) vinylformic acid glycerine allyl oxygen ester, two (methyl) vinylformic acid 1,1,1-three (methylol) ethyl ester, three (methyl) vinylformic acid 1,1,1-three (methylol) ethyl ester, triallyl isocyanurate, the trimellitic acid triallyl, the terephthalic acid diallyl, the phthalic acid diallyl, diallyl isophthalate, five tetrahydroxybutane diallyl ethers, Vinylstyrene etc.
As feature of the present invention, contain at least a free-radical polymerised unsaturated monomer that is selected from the free-radical polymerised unsaturated monomer (b) with UV light absorber composition, free-radical polymerised unsaturated monomer (c) and the free radical contained fluorine polymerizability unsaturated monomer (d) with photostabilizer composition.
As free-radical polymerised unsaturated monomer (b) with UV light absorber composition; it for example is 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole; 2-hydroxyl-4-(3-methacryloxy-2-propoxyl) benzophenone; 2-hydroxyl-4-(3-methacryloxy-2-propoxyl) benzophenone; 2; 2 '-dihydroxyl-4-(3-methacryloxy-2-propoxyl) benzophenone; 2,2 '-hydroxyl-4-(3-methacryloxy-2-propoxyl) benzophenone; 2 (N-methacryloyl) aminobenzophenone etc.
This wherein preferred 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole (commercial goods of the commodity that Otsuka Chemical Co., Ltd makes RUVA-93 by name).
As free-radical polymerised unsaturated monomer (c), 4-(methyl) acryloxy-1,2 can be arranged for example with photostabilizer composition; 2,6,6-pentamethyl-piperidines, 4-(methyl) acryloxy-2; 2,6,6-tetramethyl piperidine, 4-(methyl) acryl amino-2; 2; 6,6-tetramethyl piperidine, 4-(methyl) acryloxy-1,2; 2; 6,6-pentamethyl-piperidines, 4-(methyl) acryl amino-1,2; 2; 6,6-pentamethyl-piperidines, 4-amino-4-(methyl) acryl amino-2,2; 6,6-tetramethyl piperidine etc.
This wherein preferred 4-methacryloxy-1,2,2,6,6-pentamethyl-piperidines (commercial goods of the commodity that Hitachi Chemical Co., Ltd. makes FA-711MM by name).
In addition, (for example the Xylene Diisocyanate of hexamethylene diisocyanate or trimethyl hexamethylene diisocyanate, hydrogenation, isophorone diisocyanate, benzyl support vulcabond, 4 by polymeric polyisocyanate, 4 '-diphenylmethanediisocyanate) makes the following hydroxyl reaction that has UV light absorber (g) Yu the core/shell type emulsion (A) of alcoholic extract hydroxyl group, can in this emulsion (A), import thus.
Can have 2 for example as the UV light absorber that has alcoholic extract hydroxyl group (g), 2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(methylol) phenol], 2,2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(2-hydroxyethyl) phenol], 2,2 '-methylene-bis [6-(5-chloro-2H-benzotriazole-2-yl)-4-(2-hydroxyethyl) phenol], 2,2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(3-hydroxypropyl) phenol], 2,2 '-methylene-bis [6-(5-chloro-2H-benzotriazole-2-yl)-4-(3-hydroxypropyl) phenol], 2,2 '-methylene-bis [6-(5-bromo-2H-benzotriazole-2-yl)-4-(3-hydroxypropyl) phenol], 2,2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(2-hydroxypropyl) phenol], 2,2 '-methylene-bis [6-(5-chloro-2H-benzotriazole-2-yl)-4-(2-hydroxypropyl) phenol], 2,2 '-methylene-bis [6-(5-bromo-2H-benzotriazole-2-yl)-4-(2-hydroxypropyl) phenol], 2,2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(4-hydroxyl butyl) phenol], 2,2 '-methylene-bis [6-(5-chloro-2H-benzotriazole-2-yl)-4-(4-hydroxyl butyl) phenol] etc.
As fluorine-containing unsaturated monomer (d) vinylformic acid perfluoro butyl ethyl ester, the different nonyl ethyl ester of vinylformic acid perfluor, vinylformic acid 2-perfluoro capryl ethyl ester, methacrylic acid perfluoro butyl ethyl ester, methacrylic acid trifluoroethyl ester, the different nonyl ethyl ester of methacrylic acid perfluor, methacrylic acid 2-perfluoro capryl ethyl ester etc. can be arranged for example.This is preferable methyl vinylformic acid 2-perfluoro capryl ethyl ester wherein.
Free-radical polymerised unsaturated monomer (e) as other for example has (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, single (methyl) vinylformic acid (gathering) glycol ester, single (methyl) vinylformic acid (gathering) propylene glycol ester, the hydroxyl butyl vinyl ether, (methyl) vinyl carbinol, and above-mentioned hydroxyl vinyl monomer class and beta-propiolactone, the dimethyl propylene lactone, butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Xin Neizhi, γ-dodecyl lactone, 6-caprolactone, the reactant of lactone compounds such as δ-caprolactone etc., for example (ダ イ セ Le chemical company makes プ ラ Network セ Le FM1, trade(brand)name, (methyl) crylic acid hydroxy ester class of caprolactone modification), プ ラ Network セ Le FM2 (with a left side), プ ラ Network セ Le FM3 (with a left side), プ ラ Network セ Le FA-1 (with a left side), プ ラ Network セ Le FA2 (with a left side), プ ラ Network セ Le FA3 hydroxyl unsaturated monomers such as (with left sides);
For example (following all is that ダ イ セ Le chemical company makes for (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, toxilic acid, fumaric acid, プ ラ Network セ Le FM1A, carboxylic (methyl) Acrylic Acid Monomer class of caprolactone modification, trade(brand)name), carboxylic unsaturated monomers such as プ ラ Network セ Le FM4A, プ ラ Network セ Le FM10A;
It for example is methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, the vinylformic acid pentyl ester, the methacrylic acid pentyl ester, Ethyl acrylate, N-Hexyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid 2-(ethyl hexyl) ester, the monoesters class of 1～24 carbon list alcohols of acrylic or methacrylic such as dodecylacrylate and lauryl methacrylate acid, acrylic acid epoxy propyl ester and the free-radical polymerised unsaturated monomer that contains epoxypropyl, vinyl cyanide, acrylamide, N methacrylamide, N hydroxymethyl acrylamide, nitrogenous free-radical polymerised unsaturated monomers such as N-butoxymethyl acrylamide and dimethylaminoethyl acrylate methyl base amino-ethyl ester, vinylbenzene, (methyl) vinylformic acid phenylethylester, vinyl acetate between to for plastic, vinylchlorid etc., they can independent or two or more being used in combination.In addition allyl methacrylate(AMA), diacrylate 1 can be arranged for example, bridging property unsaturated monomers such as oneself (glycol) ester of 6-etc.
With respect to the whole monomeric solids component gross weight that constitutes core/shell type emulsion (A), above-mentioned free-radical polymerised unsaturated monomer (a) with alkoxysilyl, free-radical polymerised unsaturated monomer (b) with UV light absorber composition, having the free-radical polymerised unsaturated monomer (c) of photostabilizer composition and the blending ratio of free radical contained fluorine polymerizability unsaturated monomer (d) and other free-radical polymerised unsaturated monomers (e) is: the ratio with free-radical polymerised unsaturated monomer (a) of alkoxysilyl is 1～40 weight %, preferred 3～35 weight %, more preferably 5～25 weight %, be selected from free-radical polymerised unsaturated monomer (b) with UV light absorber composition, at least a kind of free-radical polymerized unsaturated monomer with the free-radical polymerised unsaturated monomer (c) of photostabilizer composition and free radical contained fluorine polymerizability unsaturated monomer (d) is 0.01～10 weight % with respect to the content of the whole monomer weights that constitute core/shell type emulsion (A), preferred 0.1～8 weight %, more preferably 0.5～5 weight %, the content of other free-radical polymerised unsaturated monomers (e) are preferably in the scope of 40～90 weight %.
The emulsifying agent that uses in the preparation of core/shell type emulsion (A) can use to have sulfate group, have sulfonic group, has the sodium salt or the ammonium salt of phosphate, and the reactive emulsifier that comprises them, the reason that this is wherein good for extinction effect and film performance is good preferably use the reactive emulsifier that has ammonium salt nuclear polymerizability unsaturated group in the molecule.
With respect to whole polymerizability unsaturated monomers that multistep in the preparation of core/shell type emulsion (A) is used, emulsification dosage is preferably in the scope of 0.5～5 weight %.And, the polymerization starter that may use can have persulfuric acid calcium, Sodium Persulfate, ammonium persulphate, 4 for example, 4 '-azo (4-cyanopentanoic acid), 2,2 '-azo organo-peroxide classes such as organonitrogen based compound, benzoyl peroxide, hydroperoxidation di-t-butyl such as [2-methyl-N-(2-hydroxyethyl) propionic acid amides] etc.
And this wherein also can use redox initiator simultaneously.With respect to the full polymerizability unsaturated monomer that multistep in the preparation of core/shell type emulsion (A) is used, these polymerization starters are preferably in interior use of scope of 0.1～1.0 weight %.
Be in the aqueous solution of water and emulsifying agent in the preparation of core/shell type emulsion (A), in the presence of radical polymerization initiator, make free-radical polymerised unsaturated monomer (a) with alkoxysilyl, free-radical polymerised unsaturated monomer (b) with UV light absorber composition, the radical copolymerization unsaturated monomer that has the free-radical polymerised unsaturated monomer (c) of photostabilizer composition and contain other free-radical polymerised unsaturated monomers (d) carries out the 1st step Raolical polymerizable, and the free radical emulsion polymerization reaction of for example carrying out under 90～110 ℃ 1～2 hour obtains free radical polyalcohol (I).Then, in the presence of free radical polyalcohol (I), carry out the free radical emulsion polymerization reaction of the 2nd step, the free radical emulsion polymerization reaction of for example carrying out under 90～110 ℃ 1～2 hour obtains core/shell type emulsion (A).
The free-radical polymerised unsaturated monomer (a) with alkoxysilyl that uses in the free radical emulsion polymerization reaction of the 2nd step can use with the 1st with other free-radical polymerised unsaturated monomers (e) and go on foot identical monomer in the reaction.
The hydroxyl value of core/shell type emulsion (A) is 5～100mgKOH/g, and median size (annotating 1) is 0.05～0.5 μ m, preferred 0.1～0.3 μ m.
Median size: use コ-Le one counter N4 (コ-Le one company makes, trade(brand)name) to measure.
Acrylic resin (B):
As acrylic resin (B) for example is (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, single (methyl) vinylformic acid (gathering) glycol ester, single (methyl) vinylformic acid (gathering) propylene glycol ester, the hydroxyl butyl vinyl ether, (methyl) vinyl carbinol, and above-mentioned hydroxyl vinyl monomer class and beta-propiolactone, the dimethyl propylene lactone, butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Xin Neizhi, γ-dodecyl lactone, 6-caprolactone, the reactant of lactone compounds such as δ-caprolactone etc., commodity are called プ ラ Network セ Le FM1, and (ダ イ セ Le chemical company makes, trade(brand)name, (methyl) crylic acid hydroxy ester class of caprolactone modification), プ ラ Network セ Le FM2 (with a left side), プ ラ Network セ Le FM3 (with a left side), プ ラ Network セ Le FA-1 (with a left side), プ ラ Network セ Le FA2 (with a left side), プ ラ Network セ Le FA3 hydroxyl unsaturated monomers such as (with left sides);
For example (following all is that ダ イ セ Le chemical company makes for (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, toxilic acid, fumaric acid, プ ラ Network セ Le FM1A, carboxylic (methyl) Acrylic Acid Monomer class of caprolactone modification, trade(brand)name), carboxylic unsaturated monomers such as プ ラ Network セ Le FM4A, プ ラ Network セ Le FM10A;
Methyl acrylate is arranged in addition for example, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, the vinylformic acid pentyl ester, the methacrylic acid pentyl ester, Ethyl acrylate, N-Hexyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid 2-(ethyl hexyl) ester, the monoesters class of 1～24 carbon list alcohols of acrylic or methacrylic such as dodecylacrylate and lauryl methacrylate acid, acrylic acid epoxy propyl ester and the free-radical polymerised unsaturated monomer that contains epoxypropyl, vinyl cyanide, acrylamide, N methacrylamide, N hydroxymethyl acrylamide, nitrogenous free-radical polymerised unsaturated monomers such as N-butoxymethyl acrylamide and dimethylaminoethyl acrylate methyl base amino-ethyl ester, vinylbenzene, (methyl) vinylformic acid phenylethylester, vinyl acetate between to for plastic, vinylchlorid etc.
They can be separately or 2 kinds or be used in combination more.Can have for example in addition and allyl methacrylate(AMA), diacrylate 1, the polymkeric substance of bridging property unsaturated monomers such as 6-hexylene glycol ester etc.Acrylic resin (B) preferably its hydroxyl value is 20～200mgKOH/g, and acid number is 20～200mgKOH/g, and weight-average molecular weight is 3,000～100,000.
Stiffening agent (C): in order to obtain filming with the crosslinked of hydroxyl reaction of core/shell type emulsion (A), acrylic resin (B), stiffening agent (C) preferably uses melamine resin and/or block polyisocyanate.
For example using as melamine resin, the pure modification more than a kind or 2 kinds such as methyl alcohol, ethanol, propyl alcohol, butanols, octanol, 2-Ethylhexyl Alcohol obtains.Preferably obtain with C3 or pure modification more, particularly C4～18.And in the melamine resin with respect to average per 1 triazine ring, preferably contain and have an appointment 2.0 or, particularly about 2.0～5.0 more with the ether of C3 or more pure modification.
Can use known up to now isocyanic ester as the isocyanic ester that in block polyisocyanate, uses, for example benzyl supports vulcabond, the xylylene vulcabond, phenylene diisocyanate, ditan-2,4 '-vulcabond, ditan-4,4 '-vulcabond (being commonly referred to " MDI "), thick MDI, two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, aromatic series such as isophorone diisocyanate, aliphatics or alicyclic polymeric isocyanate compound; The cyclized polymer of these polyisocyanate compounds, isocyanic ester biuret body; The end that the low molecular compound reaction that makes ethylene glycol, propylene glycol, TriMethylolPropane(TMP), hexanetriol, castor-oil plant wet goods contain active hydrogen in these excessive polyisocyanate compounds obtains contains the compound of isocyanic ester etc.They can use separately, also can be used in combination more than 2 kinds or 2 kinds.
On the other hand, the block agent is contemplated to be the reagent that adds block on the isocyanate group of polyisocyanate compounds, it is stable at normal temperatures to add the block polyisocyanate compound that generates like this, but when being heated to the temperature of combustion of filming (being generally about 100～about 200 ℃), the block agent is decomposed, and regenerates the free isocyanate group.
The block agent of satisfying such condition can have lactan based compounds such as ε-Ji Neixianan, butyrolactam for example; Oxime compound such as methyl ethyl ketone oxime, cyclohexanone-oxime; Phenol based compounds such as phenol, p-tert-butylphenol, cresylol; Aliphatics such as propyl carbinol, 2-Ethylhexyl Alcohol alcohols; Aromatic series such as phenylcarbinol, methylbenzene methanol alcohols; Ether alcohol such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether based compound etc.
About anion electroplating paint:
The blending ratio of core/shell type emulsion (A), acrylic resin (B), stiffening agent (C) is fit in such scope in the anion electroplating paint of the present invention: core/shell type emulsion (A) is 1～40 weight %, preferred 5～20 weight %, acrylic resin (B) is 20～70 weight %, preferred 30～60 weight %, stiffening agent (C) is 20～60 weight %, preferred 30～50 weight %.
Anion electroplating paint of the present invention can be according to hardening catalyst, pigment, weighting agent, concrete pellet, pigment dispersing agent, wetting agent, defoamer, softening agent, organic solvent, sanitas, mould inhibitor, pH regulator agent, rust-preventive agent etc. such as the suitable selection of various purposes organo-tin compounds in conjunction with mixing.
As being coated with jewelry can be aluminium, aluminium alloy, protection against corrosion aluminium, iron and steel; Zinc-plated, zinc-plated, chromium plating, the electroplating steel plate of aluminizing etc.; Perhaps with chromic acid, phosphoric acid chemistry conversion process or on the metallic substance such as steel plate that catholyte is handled, be coated with.Be desirably in especially in the aluminium building materials field that uses painted or non-coloring anodic oxidation aluminium and be suitable for.
As coating process, for example can bathe (about 5～20 weight % of solid ingredient for example at anion electroplating paint, preferred about 6～12 weight %) after flooding aluminium in, make desciccator diaphragm thickness reach the such anion electroplating application of about 5～30 μ m, and after the washing (pipeline water, water permeable etc.), carry out the method for baking (for example descending about 20～40 minutes) as required at about 160～200 ℃.
Embodiment
Below the present invention will be described in more detail with embodiment.But the present invention is not limited to this.And " part " and " % " is expression " weight part " and " weight % ".
The preparation of preparation example 1 emulsion No.1
In the reaction vessel that has thermometer, thermostatted, agitator, reflux cooler and Dropping feeder, add 298 parts of deionized waters, be warmed up to 90 ℃.In reaction vessel, drop into then by 0.15 part of VA-086 (annotating 2), 9.85 parts of initiator solutions that deionized water forms, stirred 15 minutes.In another container, mix 1 part of SE-10N (annotating 3), 30 parts of deionized waters, 20 parts of vinylbenzene, 17 parts of n-butyl acrylates, 2 parts of vinylformic acid 2-hydroxyl ethyl esters, 5 parts of diacrylate 1,6-hexylene glycol ester, 4 parts of KBM-503 (annotating 4) and 2 parts of RUVA-93 (annotating 5), stirring makes monomer emulsification (1), is added drop-wise in the reaction vessel in 2 hours.
And, when dripping beginning, monomer emulsification (1) dripped the initiator solution that forms by 1 part " VA-086 " (annotating 2), 30 parts of deionized waters 5.5 hours, up to all processes end that comprises the aftermentioned reaction to reaction vessel.After monomer emulsification (1) drips, after 30 minutes, with another solution prepare by 1 part of SE-10N (annotating 3), 30 parts of deionized waters, 15 parts of vinylbenzene, 13 parts of n-butyl acrylates, 4 parts of vinylformic acid 2-hydroxyl ethyl esters, 3 parts of diacrylate 1, the monomer emulsification (2) that 6-hexylene glycol ester and 15 parts of KBM-503 (annotating 4) form added in 2 hours, after this grew up fully 1 hour, and obtained the emulsion No.1 of solids component 20%, median size 127 μ m.
(annotating 2) VA-086: and the manufacturing of the pure pharmaceutical worker's industry of light company, trade(brand)name, nonionic is a water-soluble polymerization initiator, 2,2 '-azo [2-methyl-N-(2-hydroxyethyl) propionic acid amide]
(annotating 3) SE-10N: rising sun electrification company makes, trade(brand)name, and ammonium sulfate is reactive emulsifier
(annotating 4) KBM-503: chemical industrial company of SHIN-ETSU HANTOTAI makes, trade(brand)name, γ-methacryloxypropyl trimethoxy silane
(annotating 5) RUVA-93: Otsuka Chemical Co., Ltd makes trade(brand)name, 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole
(annotating 6) FA-711MM: Hitachi Chemical Co., Ltd. makes, trade(brand)name, 4-methacryloxy-1,2,2,6,6-pentamethyl-piperidines
(annotate 7) FAMAC: Japanese メ Network ト ロ Application company makes trade(brand)name, methacrylic acid 2-perfluoro capryl ethyl ester.
Preparation example 2～6
Except with mixing shown in the table 1, carry out with the method identical with preparation example 1, obtain emulsion No.2～No.6.
Table 1
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | Preparation example 6 | ||
| Emulsion | ??No.1 | ??No.2 | ??No.3 | ??No.4 | ??No.5 | ??No.6 | |
| Monomer emulsification 1 (nuclear) | SE-10N (annotating 3) | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| Deionized water | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | |
| Vinylbenzene | ??20 | ??20 | ??20 | ??20 | ??20 | ??22 | |
| N-butyl acrylate | ??17 | ??17 | ??17 | ??17 | ??17 | ??19 | |
| Vinylformic acid 2-hydroxyl ethyl ester | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | |
| Diacrylate 1,6-hexylene glycol ester | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | |
| KBM-503 (annotating 4) | ??4 | ??4 | ??4 | ??4 | ??4 | ||
| RUVA-93 (annotating 5) | ??2 | ??1 | |||||
| FA-711MM (annotating 6) | ??2 | ??1 | |||||
| FAMAC (annotating 7) | ??2 | ||||||
| Monomer emulsification 2 (shell) | SE-10N | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| Deionized water | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | |
| Vinylbenzene | ??15 | ??15 | ??15 | ??15 | ??15 | ??22 | |
| N-butyl acrylate | ??13 | ??13 | ??13 | ??13 | ??13 | ??21 | |
| Vinylformic acid 2-hydroxyl ethyl ester | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | |
| Diacrylate 1,6-hexylene glycol ester | ??3 | ??3 | ??3 | ??3 | ??3 | ??3 | |
| KBM-503 (annotating 4) | ??15 | ??15 | ??15 | ??15 | ??15 | ||
| Solids component (%) | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | |
| Particle diameter (nm) | ??127 | ??125 | ??124 | ??122 | ??124 | ??130 | |
The manufacturing of preparation example 7 acrylic resins (B)
In the reaction vessel that has thermometer, thermostatted, agitator, reflux cooler and Dropping feeder, add 100 parts of isopropyl acrylates, 150 parts of n-butyl acrylates, 100 parts of ethylene glycol butyl ethers, be warmed up to 85 ℃, monomeric mixture below in 3 hours, dripping, in reaction vessel, drop into the two methyl pentane nitriles of 5 parts of azos then, kept 3 hours down at 85 ℃, regulate solids component with organic solvent, obtain that acid number 46mgKOH/g, hydroxyl value 67mgKOH/g, weight-average molecular weight are about 50,000, the acrylic resin soln of solids component 60%.
50 parts of vinylbenzene
200 parts of methyl methacrylates
100 parts of n-butyl acrylates
50 parts of ethyl propenoates
70 parts of vinylformic acid 2-hydroxyl ethyl esters
30 parts in vinylformic acid
4 parts of azo dimethyl
Embodiment 1
45 parts of acrylic resin solns (solids component amount) that mixing is obtained by preparation example 7,40 parts of ニ カ ラ Star Network MX-430 (annotating 8) (solids component amount), with respect to the carboxyl 0.4 normal triethylamine of acrylic resin, the limit is stirred and is made its blending dispersion, the limit makes its resin solid composition reach 10%, so drips deionized water and carries out water-dispersion.
Add 15 parts of emulsion No.1 that preparation example 1 obtains, add the triethylamine of 0.4 neutralization equivalent again, regulate to make that the pH value is 8.2, the resin solid composition is 10%, obtain anion electroplating paint No.1.
Embodiment 2～5
According to the content of table 2, use anion electroplating paint No.2～5 that obtain embodiment 2～5 with embodiment 1 identical operations.
Comparative example 1～3
According to the content of table 2, use anion electroplating paint No.6～8 that obtain comparative example 1～3 with embodiment 1 identical operations.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | ||
| Coating No. | ??No.1 | ??No.2 | ??No.3 | ??No.4 | ????No.5 | ??No.6 | ??No.7 | ??No.8 | |
| Core/shell type emulsion (A) | Emulsion No.1 | ??15 | ????15 | ||||||
| Emulsion No.2 | ??15 | ||||||||
| Emulsion No.3 | ??15 | ||||||||
| Emulsion No.4 | ??15 | ||||||||
| Emulsion No.5 | ??15 | ??15 | |||||||
| Emulsion No.6 | ??15 | ||||||||
| Acrylic resin (B) | Acrylic resin soln | ??45 | ??45 | ??45 | ??45 | ????45 | ??45 | ??45 | ??45 |
| Stiffening agent (C) | ニ カ ラ Star Network MX-430 (annotating 8) | ??40 | ??40 | ??40 | ??40 | ????20 | |||
| デ ユ ラ ネ one ト TPA-B80 (annotating 9) | ????20 | ||||||||
| Hardening catalyst | SCAT-7 (annotating 10) | ????0.5 | |||||||
| Neutralizing agent | Triethylamine | 0.4 equivalent | ??← | ??← | ??← | ????← | ??← | ??← | ??← |
| UV light absorber | チ ヌ PVC Application 328 (annotating 11) | ??2 | |||||||
| Photostabilizer | チ ヌ PVC Application 292 (annotating 12) | ??1 | |||||||
| Neutralizing agent | Triethylamine | Be adjusted to pH=8.2 | ??←?? | ??← | ??← | ????← | ??← | ??← | ??← |
| Deionized water | Adjusting to solids component is 10% | ||||||||
Combined amount numeric representation solids component in the table.
(annotate 8) ニ カ ラ Star Network MX-430: three and ケ ミ カ Le company make, trade(brand)name, 1 nucleome amount of have an appointment in each trimeric cyanamide nuclear 3 methyl, about 3 butyl are about 57% melamine resin, solids component 100%.
(annotating 9) デ ユ ラ ネ one ト TPA-B80: Asahi Kasei Corporation makes, trade(brand)name, the chlorinated isocyanurates type of hexamethylene diisocyanate, methyl ethyl ketone oxime block.
(annotating 10) SCAT-7: the synthetic Co., Ltd. of three total machines makes, trade(brand)name, the two thiohydroxy carboxylicesterss of dibutyl tin, hardening catalyst.
(annotating 11) チ ヌ PVC Application 328: チ バ ガ イ ギ one Co., Ltd. makes, trade(brand)name, UV light absorber.
(annotating 12) チ ヌ PVC Application 292: チ バ ガ イ ギ one Co., Ltd. makes, trade(brand)name, photostabilizer.
The making of test board
Make body lotion with the anion electroplating paint that obtains in embodiment and the comparative example, carry out alumite therein and handle (degreasing-etching-neutralization-anodic oxidation treatment-sealing), (silver-plated: size is 150 * 70 * 0.5mm) to the anodic oxidation aluminium that the about 10 μ m of oxide impregnation film are thick, electroplate and cover with paint, lacquer, colour wash, etc. so that desciccator diaphragm thickness reaches 10 μ m, after the washing, 180 ℃ of following roastings 20 minutes.
Carry out following test according to following test conditions.Test-results is shown in table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | ||
| Coating No. | ????No.1 | ?????No.2 | ????No.3 | ????No.4 | ????No.5 | ????No.6 | ????No.7 | ????No.8 | |
| Paint stability (annotating 13) | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????△ | |
| Weathering resistance | Gloss retention (annotating 14) | ????84 | ????94 | ????88 | ????89 | ????81 | ????37 | ????23 | ????58 |
| Aberration (Δ E) (annotating 15) | ????1.6 | ????0.9 | ????1.4 | ????1.0 | ????1.5 | ????4.5 | ????7.5 | ????12 | |
| Adhesivity (annotating 16) | ????○ | ????○ | ????○ | ????○ | ????○ | ????△ | ????△ | ????○ | |
| Pencil hardness (annotating 17) | ????4H | ????4H | ????4H | ????4H | ????3H | ????4H | ????4H | ????4H | |
| 60 ° of glossiness (annotating 18) | ????16 | ????17 | ????14 | ????14 | ????19 | ????25 | ????48 | ????24 | |
| Mould mark disguise (annotating 19) | ????○ | ????○ | ????○ | ????○ | ????○ | ????△ | ????× | ????△ | |
(annotating 13) paint stability: be filled into coating developmental tube (high 20cm, capacity 20m1), after leaving standstill 7 days under 20 ℃, be determined at the height of the residue of developmental tube bottom settlings.
Estimate:
Zero: residue is less than 0.5mm, and is good
△: residue is at 0.5～3mm, and is slightly bad
*: residue is more than 3mm, and is bad.
(annotating 14) weathering resistance (gloss retention):, shine 18 hours (exposure intensity 80mW/cm with the super atmospheric exposure test instrument (ダ イ プ ラ ウ イ Application テ ス company makes: metal dries up) that promotes of metal halide lamp mode
2) and condensation 6 hours as 1 cycle (24 hours), carry out the test of 15 cycles (360 hours).Gloss retention (%) is 60 degree mirror surface lusters according to JISK-8741 regulation, with the glossiness of glossiness before testing after as 100 o'clock test, represents with per-cent.
(notes 15) weathering resistance (aberration Δ E): the super atmospheric exposure test instrument that promotes of use metal halide lamp mode, (コ ニ カ ミ ノ Le company makes: CR-300) filming behind the mensuration pre-irradiation, the L of use JIS Z 8,730 6.1 with the color colour-difference meter
*a
*b
*Color specification system is calculated Δ E.
(annotating 16) weathering resistance (adhesivity): according to JIS H-8602 5.8, on the coated surface of test board, cut into 1mm 11 roads in length and breadth at interval, make 100 chessboard orders with cutting knife.On this, will firmly press with pointing according to the wide belt of 12mm of regulation among the JIS Z 1522, from stick beginning at once to directly over firmly peel off.
Zero is 100 (remaining numbers)/100
△ is 95～99 (remaining numbers)/100
* be less than 95 (remaining numbers)/100
(annotating 17) pencil hardness: according to JIS H-8602 5.9, contact with pencil-lead, on one side the degree that can not fracture with pen core firmly is pressed on the test coated plate face, Yi Bian move forward about 10mm with uniform acceleration to be about miter angle with respect to test coated plate face.Change the test place and repeat this operation 5 times, the pencil hardness mark that the situation of cannot not filming brokenly for 4 times is arranged is as pencil hardness.
(annotating 18) 60 ° of glossiness
As the gloss intensity of filming, measuring input angle and being subjected to firing angle respectively is 60 reflectivity when spending according to the 60 degree mirror surface lusters of stipulating among the JIS K-8741, is expressed as with the glossiness of the reference plane of the mirror surface luster percentage as 100 o'clock.
(annotating 19) mould mark disguise
With visual assessment.
Zero is that the mould mark is disguised good
△ is that the mould mark is disguised poor
* be that mould mark disguise is poor especially
Claims (6)
1. anion electroplating paint, it contains core/shell type emulsion (A), acrylic resin (B), stiffening agent (C); Core/shell type emulsion (A) is to use the Emulgating polymers of polymerizability unsaturated monomer multistep processes emulsion polymerization preparation in the presence of water and emulsifying agent, this polymerizability unsaturated monomer uses the polymerizability unsaturated monomer that contains alkoxysilyl for substep, and the ratio with respect to whole monomer weights is 1～40 weight %, it is characterized in that, core/shell type emulsion (A) is in the aqueous solution of water and emulsifying agent, make and be selected from the free-radical polymerised unsaturated monomer (a) that comprises alkoxysilyl, the free-radical polymerised unsaturated monomer (b) that comprises the UV light absorber composition, comprise the free-radical polymerised unsaturated monomer (c) of photostabilizer composition and at least a kind of free-radical polymerised unsaturated monomer in the free radical contained fluorine polymerizability unsaturated monomer (d), with other free-radical polymerised unsaturated monomers (e), be included in the free-radical polymerised unsaturated monomer of the monomer (f) that contains 2 or more unsaturated groups in 1 molecule in case of necessity, in the presence of radical polymerization initiator, carry out the free radical emulsion polymerization reaction in the 1st step, after making free radical polyalcohol (I)
Then under above-mentioned free radical polyalcohol (I), the free-radical polymerised unsaturated monomer that make free-radical polymerised unsaturated monomer (a) with alkoxysilyl and other free-radical polymerised unsaturated monomer (e), is included in the monomer (f) that contains 2 or more unsaturated groups in 1 molecule in case of necessity carries out the 2nd free radical emulsion polymerization that goes on foot and reacts the core/shell type emulsion that obtains.
2. as the anion electroplating paint of claim 1 record, it is characterized in that, core/shell type emulsion (A) is with respect to the whole monomer weights that constitute core/shell type emulsion (A), is selected from the ratio that at least a kind of free-radical polymerised unsaturated monomer in the free-radical polymerised unsaturated monomer (b) that comprises the UV light absorber composition, the free-radical polymerised unsaturated monomer (c) that comprises the photostabilizer composition and the free radical contained fluorine polymerizability unsaturated monomer (d) accounts for 0.01～10 weight %.
3. as the anion electroplating paint of claim 1 or 2 records, it is characterized in that the free-radical polymerised unsaturated monomer (b) that comprises the UV light absorber composition is 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole.
4. as the anion electroplating paint of claim 1 or 2 records, it is characterized in that the free-radical polymerised unsaturated monomer (c) that comprises the photostabilizer composition is a 4-methacryloxy-1,2,2,6,6-pentamethyl-piperidines.
5. as the anion electroplating paint of claim 1 or 2 records, it is characterized in that free radical contained fluorine polymerizability unsaturated monomer (d) contains 2-perfluoro capryl ethyl-methyl acrylate.
6. coated article, its by be coated with jewelry power on plating cover with paint, lacquer, colour wash, etc. as claim 1-5 in the hardened coating film that obtains of the anion electroplating paint of any one record to spend mirror surface lusters according to 60 of the regulation among the JISK-8741 be 30 or still less.
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| JP082735/2004 | 2004-03-22 | ||
| JP2004082735 | 2004-03-22 | ||
| JP359536/2004 | 2004-12-13 | ||
| JP2004359536A JP2005307161A (en) | 2004-03-22 | 2004-12-13 | Anionic electrodeposition coating material and coated artice |
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| CN100528989C CN100528989C (en) | 2009-08-19 |
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| DE602006011641D1 (en) | 2005-11-15 | 2010-02-25 | Valspar Sourcing Inc | BREAKFAST LATEX COATING COMPOSITION FOR FIBER ACCESSORIES |
| US9783622B2 (en) | 2006-01-31 | 2017-10-10 | Axalta Coating Systems Ip Co., Llc | Coating system for cement composite articles |
| EP1979426A1 (en) | 2006-01-31 | 2008-10-15 | Valspar Sourcing, Inc. | Coating system for cement composite articles |
| AU2007211045B2 (en) | 2006-01-31 | 2012-03-08 | Valspar Holdings I, Inc | Coating system for cement composite articles |
| WO2007090132A1 (en) | 2006-01-31 | 2007-08-09 | Valspar Sourcing, Inc. | Method for coating a cement fiberboard article |
| JP5207632B2 (en) * | 2006-02-13 | 2013-06-12 | エスケー化研株式会社 | Synthetic resin emulsion and aqueous coating composition using the same |
| MX2008014749A (en) | 2006-05-19 | 2009-02-04 | Valspar Sourcing Inc | Coating system for cement composite articles. |
| US7812090B2 (en) * | 2006-06-02 | 2010-10-12 | Valspar Sourcing, Inc. | High performance aqueous coating compositions |
| DE602007012700D1 (en) | 2006-06-02 | 2011-04-07 | Valspar Sourcing Inc | Aqueous high performance coating compositions |
| CA2656689C (en) | 2006-07-07 | 2017-01-03 | Valspar Sourcing, Inc. | Coating systems for cement composite articles |
| US8202581B2 (en) | 2007-02-16 | 2012-06-19 | Valspar Sourcing, Inc. | Treatment for cement composite articles |
| WO2008102822A1 (en) | 2007-02-20 | 2008-08-28 | Fujifilm Corporation | Polymer material containing ultraviolet absorbent |
| JP5276876B2 (en) | 2007-03-30 | 2013-08-28 | 富士フイルム株式会社 | UV absorber composition |
| US8070927B2 (en) * | 2007-08-15 | 2011-12-06 | Ppg Industries Ohio, Inc | Stabilizing aqueous anionic resinous dispersions with chelating agents |
| EP2177524A4 (en) | 2007-08-16 | 2011-12-14 | Fujifilm Corp | Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent |
| JP5250289B2 (en) | 2008-03-31 | 2013-07-31 | 富士フイルム株式会社 | UV absorber composition |
| JP5244437B2 (en) | 2008-03-31 | 2013-07-24 | 富士フイルム株式会社 | UV absorber composition |
| JP2009270062A (en) | 2008-05-09 | 2009-11-19 | Fujifilm Corp | Ultraviolet absorbent composition |
| MX2011001736A (en) | 2008-08-15 | 2011-05-10 | Valspar Sourcing Inc | Self-etching cementitious substrate coating composition. |
| US9133064B2 (en) | 2008-11-24 | 2015-09-15 | Valspar Sourcing, Inc. | Coating system for cement composite articles |
| JP6058191B1 (en) | 2016-05-27 | 2017-01-11 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Method for forming cured electrodeposition coating film |
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