WO2003087248A1 - Revetement en poudre dispersee dans l'eau, procede de production correspondant, et procede d'echantillonnage de la couleur - Google Patents

Revetement en poudre dispersee dans l'eau, procede de production correspondant, et procede d'echantillonnage de la couleur Download PDF

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Publication number
WO2003087248A1
WO2003087248A1 PCT/JP2003/004677 JP0304677W WO03087248A1 WO 2003087248 A1 WO2003087248 A1 WO 2003087248A1 JP 0304677 W JP0304677 W JP 0304677W WO 03087248 A1 WO03087248 A1 WO 03087248A1
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Prior art keywords
coating
water
paint
powder
dispersed
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PCT/JP2003/004677
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English (en)
Japanese (ja)
Inventor
Masakazu Teramoto
Tatuya Kawamura
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Kuboko Paint Co., Ltd.
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Priority claimed from JP2003011333A external-priority patent/JP2004224833A/ja
Application filed by Kuboko Paint Co., Ltd. filed Critical Kuboko Paint Co., Ltd.
Priority to AU2003236237A priority Critical patent/AU2003236237A1/en
Publication of WO2003087248A1 publication Critical patent/WO2003087248A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to a water-dispersible powder coating, a method for producing the same, and a toning method using the water-dispersible powder paint, and particularly to a coating having excellent coating workability and storage stability and having a smooth and excellent appearance.
  • the present invention relates to a toning method capable of finely adjusting the brightness and color to a desired brightness and color by a simple operation without causing color unevenness or the like.
  • a water-dispersed powder paint in which a powder paint component is dispersed in water is considered.
  • Japanese Patent Publication No. 11-34-34-32 and Japanese Patent Publication No. 11-150-34878 have been proposed.
  • Many of these water-dispersible powder coatings are prepared by melt-mixing a thermosetting resin or its pigment component at a temperature equal to or higher than the melting temperature but lower than the curing temperature, then coarsely pulverizing, and then finely pulverizing in a dry system. And a method of dispersing in water using a dispersing agent or the like, or a method of dispersing coarsely ground material in water together with a dispersing agent and then finely pulverizing by wet method.
  • the water-dispersible powder coatings disclosed in the prior art contain resin components constituting the water-dispersible powder coating in consideration of storage stability and uniformity of the coating film. It is said that the particle size of the particles is preferably small, and specifically, those having an average particle size (cumulative 50% particle size: D50) of 10 m or less are recommended.
  • the water-dispersed powder coating has poor storage stability because the resin powder, which is originally insoluble in water, is dispersed in water, and the powder components are liable to settle and separate during storage. In addition, cracking is likely to occur during heating and drying, and it is difficult to obtain a smooth coating film. For this reason, much research has been conducted on dispersants and surfactants for improving storage stability and coating film performance.
  • Japanese Unexamined Patent Publication (Kokai) No. 58-191 677 discloses a metal salt of a polycarboxylic acid, a diamine salt, an alkyl ether or an alkylphenyl ether of polyoxyethylene, a sorbitan fatty acid ester, or the like as a dispersant. Techniques for improving storage stability and coating film performance by adding an appropriate amount have been disclosed.
  • Japanese Patent Application Laid-Open No. 58-17757 discloses a nonionic surfactant having an HLB of 10 or less. A technique has been disclosed in which an agent is contained in an appropriate amount as a fluidity aid to suppress cracking and cracking.
  • H11-15034878 specifies the type of resin constituting the coating powder, a crosslinking agent, etc., as well as a nonionic thickener, a defoaming agent,
  • aqueous components including dispersants and water retention agents
  • Water-dispersible lacquers have been disclosed that provide transparent coatings of excellent performance for car bodies.
  • the solid content concentration of the paint is lowered to ensure fluidity, sagging and see-through of the substrate tend to occur, and the water-dispersed paint described in Japanese Patent Application Laid-Open No. 58-17557
  • the water resistance of the coating film is secured by using the selected surfactant, but the fluidity of the paint deteriorates as the powder particles become finer, and the surfactant is selected. Doing so alone does not ensure satisfactory liquidity.
  • the amount of the surfactant is increased to increase the fluidity, or the solid content concentration of the coating material is reduced, the puffiness is likely to occur as described above. Further, the addition of a large amount of a low HLB nonionic surfactant causes a serious defect that powder particles adhere to each other.
  • the transparent lacquer aqueous dispersion disclosed in Japanese Patent Application Laid-Open No. H11-5303478 can be used to convert a specific paint powder into a nonionic thickener, a surfactant and a dispersant. It is produced by wet dispersing in the coexistence of water, but it is pointed out that the finely divided coating powder tends to agglomerate, resulting in poor storage stability and poor water resistance of the coating film.
  • water-dispersed powder coatings are highly versatile and can be produced in a variety of small quantities, but when the color and lightness of the finished coating film is slightly different from the intended If the particle size and particle size distribution of the body paint are not precisely controlled, simply mixing the water-dispersed powder paint will cause color mixing and color unevenness, making it impossible to adjust the color. Therefore, in such a case, in order to readjust the color and brightness of the finished coating film, the water-dispersed powder coating is filtered or centrifuged to separate and dry the solid components. After blending the toning pigments and dyes, they must be heated and melted and then coarsely ground and finely ground again, which ultimately requires the same steps as preparing a new water-dispersed powder coating. become.
  • the present invention has been made by focusing on the problems of the prior art as described above. Eliminates the above-mentioned drawbacks of water-dispersed powder coatings, improves storage stability and coating workability as coatings, and is excellent in smoothness and gloss, and has no dullness
  • An object of the present invention is to provide a water-dispersed powder coating material that gives a beautiful coating film appearance and a useful production method thereof.
  • Another object of the present invention is to provide a toning method capable of easily performing toning using a water-dispersed powder coating even at a painting site or the like.
  • the water-dispersible powder coating material of the present invention which can solve the above-mentioned problems includes a coating resin, and has an average particle size (D50) of l to 30 ⁇ m, more preferably 5 to It is characterized in that the powder of 152 m is dispersed in water.
  • D50 average particle size
  • the particle size distribution of the powder in the water-dispersed powder coating material of the present invention is 50 m or more, more preferably 20% or more of the particles occupying 10 mass% or less, and 0.5 m or less, More preferably, the ratio of particles of 3 xm or less is 10% by mass or less.
  • the powder containing the coating resin having the above-mentioned particle size composition is prepared by adding water to an alkylene oxide adduct of a styrene / maleic acid copolymer and a surfactant.
  • the styrene / maleic acid copolymer is dispersed in an alkylene oxide.
  • Particularly preferred as an additive is a co-adduct of ethylene oxide and propylene oxide.
  • Non-ionic surfactants are particularly preferred as the surfactant, and among them, surfactants having an HLB in the range of 4 to 13 are preferred.
  • alkylene oxide adducts of alkyne diols having a weight-average molecular weight in the range of 300 to 300, and alkylene oxide addition of the alkyne diol.
  • Particularly preferred as the product is an ethylene oxide adduct of tetramethyldecinediol.
  • the content of the alkylene oxide adduct of the styrene / maleic acid copolymer is preferably from 0.1 to 1% by mass in terms of solid content with respect to the resin powder for coating, and the content of the surfactant is preferable. Is preferably in the range of 0.1 to 1% by mass in terms of solid content with respect to the resin powder for coating.
  • the preferred solid content concentration of the water-dispersed powder coating according to the present invention is 30 to 60% by mass, and the viscosity of the dispersion is 100 to 500 mPa ⁇ at 23 ° C. s,
  • the glass transition temperature of the paint resin powder is preferably in the range of 30 to 80 ° C.
  • the type of the resin for the coating material is not particularly limited, but is particularly preferably at least one selected from the group consisting of an epoxy resin, a polyester resin, and an acrylic resin.
  • a colored paint containing a pigment together with a paint resin may be used.
  • the production method of the present invention is positioned as a useful production method of a water-dispersed powder coating material having the above-mentioned properties.
  • the composition is constituted by melting and mixing raw material components for a coating material including a resin for a coating material and cooling the mixture. After the coarse pulverization, the coarsely pulverized material is dispersed in water in an amount of 0.3 to 2.3 times and treated with a circulation type bead mill to obtain a solid component having an average particle diameter (D50). Is 5 to 15 zm, the ratio of particles occupying 20 / m or more is 10% by mass or less, and the ratio of particles occupying 3m or less is 10% by mass or less. have.
  • the molten mixture is formed into a sheet, which is roughly pulverized or processed by the circulation type bead mill.
  • the pigment is melt-mixed and used, a water-dispersed colored powder coating can be obtained.
  • the powder containing the paint resin and the pigment as one body is made of water.
  • the average particle size (D50) of the powder is 5 to 15 m and the proportion of particles having a particle size of 20 m or more is 10 mass% or less.
  • One kind of toning paint is prepared, and at least one kind of the toning paint is mixed with the base paint in an appropriate amount in accordance with the brightness and Z or color of the base paint.
  • the feature is that the brightness and / or color of the base paint is finely adjusted.
  • the ratio (A / B) to (B) is preferably 1 or more and 5 or less, and the mixing amount of the toning paint with respect to the base paint is 0.1 mass based on the solid content. % Or more and 20% by mass or less.
  • FIG. 1 is a graph showing the relationship between the particle size of the resin powder for coating and the circulation time when a circulation type bead mill is used
  • FIG. 2 is a graph showing the number of passes when a multi-pass operation type bead mill is used.
  • 4 is a graph showing the relationship with the particle size of a coating resin powder.
  • the water-dispersed powder coating composition of the present invention contains a coating resin, and has an average particle size (D 50) of 1 to 30 m, more preferably 5 to 30 m. It is more preferable that the powder having a particle size of ⁇ 15 ⁇ is dispersed in water, and the particle size of the powder is 50 zm or more, more preferably 20 m or more. Is less than 10% by mass (more preferably 5% by mass or less, more preferably substantially 0%) and 0.5 // m or less, more preferably 3% or less. The proportion occupied by the fine particles is 10% by mass or less (more preferably 5% by mass or less, further preferably substantially 0%).
  • the styrene / maleic acid copolymer with an alkylene oxide adduct in combination with a surfactant to increase the fluidity as an aqueous dispersion.
  • a surfactant to increase the fluidity as an aqueous dispersion.
  • the average particle size (D 50) of the powder is too small, the above surfactant or the like must be added more than necessary, which may adversely affect the coating properties such as water resistance. .
  • the average particle diameter (D50) exceeds 30 and becomes excessively coarse, the powder components in the paint tend to settle during storage and the like, and not only does the handling of the paint deteriorate, but also the The texture of the film becomes coarse, making it difficult to obtain a smooth coating film appearance.
  • the particle size distribution of the powder affects the smoothness of the coating film, the filterability when preparing a water-dispersed paint, and the workability of coating, and occupies 50% of the solid component (powder).
  • the ratio of particles having a particle size of at least m is 10% by mass or less, and the ratio of particles having a particle size of 0.5 ⁇ m or less (more preferably 3m or less) is 10% by mass or less.
  • the ratio of particles falling within the preferred particle size range of 0.5 ⁇ 1! 1 or more and 50 ⁇ 111 or less, more preferably 3 m or more and 2 m or less, is preferably 8%. It is desirably 0% by mass or more.
  • the unevenness interval is short and the coated film has a large unevenness height difference, and it is difficult to obtain a uniform finished coated film.
  • the amount of coarse particles of 50 zm or more exceeds 10% by mass, the filter is likely to be clogged in the filtration step at the time of paint production, and 0.5% If the amount of fine particles of less than 10% by mass (more preferably 3 m or less) exceeds 10% by mass, the fluidity of the paint tends to decrease and the coating workability tends to deteriorate.
  • the proportion of particles having an average particle diameter (D50) of 1 m or more and 30 m or less and 50 / im or more (more preferably 20 m or more) is 10 mass% or less, and 0.5 im
  • D50 average particle diameter
  • the proportion of particles of less than 3 / xm (more preferably 3 / xm or less) is 10% by mass or less
  • problems such as deterioration of coating workability and handleability due to excessively high paint viscosity may occur.
  • No coating occurs, and the formed coating film has a more uniform and smoother appearance.
  • only impurities can be easily removed without causing clogging of the filter in the filtration step in the production of paint.
  • the solid content concentration of the water-dispersed powder coating used in the present invention is also a factor that affects coating workability and coating film characteristics, and is preferably 30 to 60. It is desirable to adjust to the range of mass%. By the way, the solid content concentration
  • the solid content concentration of the water-dispersed powder coating is preferably adjusted to 30% by mass or more and 60% by mass or less.
  • the water-dispersible powder coating of the present invention is obtained by dispersing a powder containing the coating resin in water in the presence of an alkylene oxide adduct of a styrene / maleic acid copolymer and a surfactant. It is preferred that
  • the alkylene oxide adduct of the styrene / maleic acid copolymer is a compound in which an alkylene oxide is added to a copolymer obtained by copolymerizing styrene and (anhydrous) maleic acid. Is a copolymer obtained by the method represented by the formula
  • r is an integer of 1 to 5
  • s is an integer of 5 to 20
  • t is an integer of 1 to 50
  • R is hydrogen, an alkyl alcohol residue having 1 to 20 carbon atoms, and a carbon number of the alkyl group.
  • Is 1 to 20 alkylphenol residues Group fatty acid residue with 8 to 40 carbon atoms, fatty acid amide residue with 8 to 40 carbon atoms, fatty acid amide residue with 8 to 40 carbon atoms, ester residue of glycerin or dalyserin and fatty acid Sorbitol or sorbitol or an ester residue of a fatty acid with sorbitol, a fatty acid alkanol amide residue having 8 to 40 carbon atoms, and the like.
  • This adduct is preferably a styrene / maleic acid skeleton constituting the main chain, an alkylene oxide chain added to an unneutralized carboxyl group and one of the carboxylic acid groups in the maleic acid unit contained in the skeleton, and particularly preferably.
  • a water-dispersed powder coating it provides high-quality coatings that have excellent storage stability and coating workability, are free from sagging, and have excellent performance in water resistance and coating smoothness.
  • the weight average molecular weight of the above-mentioned adduct should be in the range of 2,000 to 100,000, more preferably 100,000 to 50,000.
  • the molar ratio of styrene units to maleic acid units ranges from 0.2 to 1 for the former, and the co-addition molar ratio of propylene oxide ranges from 0.1 to 0.5 for ethylene oxide. It is better to use one.
  • the weight average molecular weight is too small, the adsorption ratio (carboxyl group ratio) to the powder particles and the alkylene oxide chain are small, so that the finely divided powder particles tend to aggregate and storage stability tends to deteriorate. If the weight-average molecular weight is too large, the alkylene oxide chain becomes too large to improve the storage stability, but the water resistance tends to deteriorate.
  • the proportion of ethylene oxide contained in the alkylene oxide chain becomes too large, the water resistance tends to decrease due to the increase in hydrophilicity.
  • the proportion of propylene oxide is too large, the hydrophobicity becomes too strong, the solubility in water is reduced, and the function as a dispersant is hardly exhibited effectively.
  • the ratio of styrene constituting the main chain increases, the fluidity of the coating material improves and the coating workability improves, but the adsorption ratio (the ratio of lipoxyl groups) to the powder particles and the alkylene oxide chain increase. As the particle size becomes smaller, the coating powder particles tend to agglomerate and storage stability decreases.
  • the ratio of maleic acid is too large, the number of alkylene oxide chains increases and the storage stability is improved, but the water resistance tends to be insufficient.
  • Alkylene oxide adducts of styrene / maleic acid copolymers satisfying these preferred requirements are, for example, trade names of Pick Chemical Co., Ltd.
  • the type of surfactant used in combination with the alkylene oxide adduct is not particularly limited, and various surfactants usable for general water-based paints, for example, anionic, cationic, amphoteric, and nonionic surfactants can be used. Various surfactants can be used.
  • anionic surfactants include fatty acid trienol amine amine salt, (linear) alkyl benzene sulfonate, ⁇ -sulfo fatty acid (methyl) ester alkali salt, and «-olefin sulfonate alkyl ether sulfate Alkali salts, monoalkyl phosphates Lauryl sulfate, acyl-methyl taurate, sodium salts of carboxylic acids, sulfate esters of higher alcohols, sulfated fatty acid esters, sulfated olefins, alkylnaphthalene sulfonates, para Examples thereof include a fin sulfonate and a higher alcohol phosphate, and as the above salts, a sodium salt and a potassium salt are preferably used.
  • Examples of the cationic surfactant include ammonium chloride, monoalkyl ammonium chloride, dialkyl ammonium chloride, trialkyl ammonium chloride, and cetyl chloride.
  • Methylammonium, etc., and examples of the amphoteric surfactant include amino acid-type amphoteric surfactants, bayone-type amphoteric surfactants, sulfate ester-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphorus Acid ester salt-type amphoteric surfactants are exemplified.
  • nonionic surfactants include alkyl polydarcosides, fatty acid alkanolamides, polyoxyethylene alkyl ethers, glycerin fatty acid esters, fatty acid esters of sorbitan and sorbitan, and fatty acid esters of sucrose.
  • Propylene glycol fatty acid ester higher alcohol ethylene oxide adduct, alkyl phenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide Fatty acid amido ethylene oxide adduct, fatty acid ester of glycerol, fatty acid ester of pentaerythritol, alkyl ether of polyhydric alcohol, fatty acid amine of alkanolamines For example.
  • non-ionic surfactants are particularly preferably used in the present invention, and HLB having a HLB in the range of 4 to 13, more preferably 4 to 9 is preferred. Things.
  • nonionic surfactants particularly preferred are alkylene oxide adducts of alkynediols, and more specifically, ethylene oxide adducts of tetramethyldecinediol represented by the following general formula.
  • the average molecular weight is in the range of 300 to 300, more preferably in the range of 300 to 1000.
  • alkylene oxide adduct of alkynediol satisfying these requirements is For example, it can be obtained as a product name “Surfinol” series manufactured by Air Products.
  • the water-dispersed powder coating material of the present invention it is effective to use the above-mentioned alkylene oxide adduct of styrene / maleic anhydride copolymer and the above-mentioned surfactant in combination, and only one of them is used. In this case, it is difficult to obtain comprehensively excellent paint performance intended in the present invention.
  • the alkylene oxide adduct of the styrene / maleic acid copolymer and the surfactant are added to the resin powder for coating in a solid content.
  • each of them is contained in the range of 0.1 to 1% by mass in terms of conversion, and the use ratio of the alkylene oxide adduct of the styrene-maleic acid copolymer and the surfactant is the former 1 by mass ratio.
  • coating resin used in the present invention there are no particular restrictions on the type of coating resin used in the present invention, and known resins used for water-dispersed powder coatings, such as epoxy resins, polyester resins, acrylic resins, polyvinyl chloride resins, Polyethylene resin, polyamide resin, alkyd resin, amino alkyd resin, phenol alkyd resin, polybutadiene resin Silicone resin, isocyanate resin, melamine resin, fluorine resin, etc. can be used. These can be used alone or in combination of two or more as needed. .
  • resins used for water-dispersed powder coatings such as epoxy resins, polyester resins, acrylic resins, polyvinyl chloride resins, Polyethylene resin, polyamide resin, alkyd resin, amino alkyd resin, phenol alkyd resin, polybutadiene resin Silicone resin, isocyanate resin, melamine resin, fluorine resin, etc.
  • resins having a glass transition temperature of 30 ° C or higher, more preferably 40 ° C or higher, and 80 ° C or lower, more preferably 70 ° C or lower. is there.
  • the glass transition temperature of the resin is less than 30 ° C, not only the powder particles in the paint may cause blocking during storage or transportation, but also cause the fusion during mechanical pulverization to cause fine particles.
  • the glass transition temperature is too high, the fluidity at the time of baking is deteriorated, and the smoothness of the finished coating film tends to decrease.
  • the coating resin used in the present invention for example, the above-mentioned epoxy resin, polyester resin, acrylic resin, alkyd resin, polybutadiene resin, silicon resin, polyurethane resin, fluorine resin, etc.
  • a hydroxyl group-containing resin in which a hydroxyl group is introduced into the resin by a known method and a curing agent having a functional group that reacts with the hydroxyl group in the resin are combined, a curable paint by heat, ultraviolet light, or the like can be obtained.
  • suitable hardeners include amino resins (paints incorporating these are sometimes referred to as amino resin-curable paints), blocked polyisocyanate compounds (paints containing these are cured with isocyanates) Paints).
  • amino resin examples include those obtained by condensation or co-condensation of melamine, benzoguanamine, urea dicyandiamide, and the like with formaldehyde, and further modified with alcohols having 1 to 8 carbon atoms. Also, an amino resin containing a carboxylic acid group can be used.
  • Acids such as para-toluenesulfonic acid dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinoernaphthalenedisulfonic acid, and amine-neutralized products of these acids can be blended as a curing catalyst for the hydroxyl group and the amino resin.
  • the blocked polyisocyanate compound is a polyisocyanate compound obtained by blocking a free isocyanate compound with a blocking agent.
  • polyisocyanate compound having a free isocyanate group examples include aliphatic diisocyanates such as hexamethylene diisocyanate or trimethyl hexamethylene diisocyanate, and xylene diisocyanate.
  • organic diisocyanates such as cycloaliphatic diisocyanates such as isophorone diisocyanate, aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate
  • cycloaliphatic diisocyanates such as isophorone diisocyanate
  • aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate
  • blocking agent examples include oxime, phenol, alcohol, lactam, malonate, and mercapone.
  • a dissociation catalyst for the blocking agent a lead-based catalyst (such as lead 2-ethylethylhexanoate, lead benzoate, and lead oleate), and a tin-based catalyst (tetrabutyltin, tin octoate, tin oleate, tin tartrate) , Dibutyltin di (2-ethylhexylate), dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate, dibutyltin diisooctyl maleate, dibutyltin sulfide, dibutyltin dibutoxide, etc.)
  • a catalyst such as zinc naphthenate
  • an antimony-based catalyst such as antimony trichloride
  • the above-mentioned resins such as polyester resin, acryl resin, alkyd resin, polybutylene resin, silicon resin, polyurethane resin, fluorine resin, etc.
  • a carboxyl group-containing resin into which a carboxylic acid group is introduced by a known method and a curing agent having a functional group that reacts with the carboxylic acid group in the resin are blended, a curable paint by heat or ultraviolet light can be obtained.
  • a polyepoxy compound (a paint containing this compound may be referred to as an epoxy curable paint) may be used.
  • a polyepoxy compound is a compound having at least two epoxy groups in one molecule. Typical examples thereof include ethylene glycol. Diglycidyl ether, neopentyldaricol ⁇ diglycidyl ether, glycerin Polyglycidyl ether of polyhydric alcohols such as diglycidyl ether, glycerintriglycidyl ether, diglycerin 'triglycidyl ether, hydrogenated bisphenol Adiglycidyl ether or bisphenol Adiglycidyl ether Examples include vinyl-based polymers having an epoxy group in the side chain.
  • ethoxy dimethyl silane ethoxy ethoxyl silane, trimethoxy propyl silane, trimethoxy butyl silane, trimethoxy phenyl silane, tetraethoxy silane, r-N- (2-aminoethyl And silane compounds such as aminopropyltrimethoxysilane and aminocaptopropyltrimethoxysilane.
  • the above-mentioned epoxy resin bis (phenol) -type glycidyl ether type, (meth) acrylic (co) polymer having glycidyl (meth) acrylate as an essential component, Etc.
  • a curing agent having a functional group that reacts with the epoxy group paints containing these are sometimes called epoxy-curable paints. It can be used as a paint that can be cured by heat or ultraviolet light.
  • Cationic polymerization catalysts include, for example, aryldiazonium salts, arylodenium salts, arylsulfonium salts, and the like.
  • Curing agents include, for example, polycarboxylic acid resins (acrylic resins) Resins, polyester resins, etc.), phenolic resins (nopolac-type phenolic resins, resole-type phenolic resins, etc.), polycarboxylic compounds (eg, adipic acid, sebacic acid, trimellitic acid, dodecane diacid, phthalic acid) Phosphoric acid) and amides (such as dicyandiamide).
  • a curing agent in addition to the above resin for paint, a curing agent, a curing accelerator, a flow regulator, a foaming inhibitor, an antistatic agent, an ultraviolet absorber, an antioxidant, which may be added to ordinary powder coating materials. It is, of course, possible to further improve the properties of the coating film by blending an agent.
  • acrylic acid-based copolymer copolymer of acrylic acid and acrylic ester
  • cellulose-based methylcellulose, hydroxyshethyl cellulose, propyl Cellulose, carboxymethylcellulose, etc.
  • polyurethane polyether-modified urethane compounds, etc.
  • polyamide polyamide
  • clay bentonite, heptrite, saponite, etc.
  • thickeners mineral oils and minerals
  • a defoaming agent such as a metal-based or silicon-based material, and also a heat-proofing agent that provides a stopping function to the metal to be coated (especially an iron-based alloy).
  • the water-dispersed powder coating of the present invention when a powder substantially consisting only of a coating resin is used, it becomes a coating for forming a so-called clear coating film.
  • a powder containing an appropriate amount of a pigment or a dye is used together with the resin for a coating, a colored coating having a color corresponding to the color tone or the like of the pigment or the dye can be obtained.
  • the pigments used here include coloring pigments and anti-pigmenting pigments.
  • coloring pigments include iron oxide such as red iron oxide, titanium oxide, titanium yellow, zinc white, zinc sulfide, lithium sulfide, antimony oxide, and cobalt.
  • Inorganic pigments such as blue and Rikiichi pump racks, quinacridone red, phthalocyanine blue, phthalocyanine green, permanent red, hanzaeroel, indian sable, brilliant
  • organic pigments such as first scarlet and variogen red. These can be used alone, or two or more can be used in combination as needed.
  • calcium carbonate, barium sulfate, barium carbonate, clay, talc, diatomaceous earth, silica powder, basic magnesium carbonate, alumina white, or the like may be used as an extender and an anti-glare agent.
  • the amount of the above pigments there is no limitation on the amount of the above pigments, and it may be arbitrarily selected according to the type of pigment to be used and the color tone, lightness, saturation, etc. required for the coating film. It is in the range of 1 to 80 parts by mass, more usually in the range of 2 to 70 parts by mass, per 100 parts by mass. It should be noted that when clear paint is used, the blending of the pigment is naturally omitted. If necessary, any dye may be used in addition to or instead of the pigment.
  • the water-dispersed powder coating of the present invention has excellent leveling properties and facilitates the formation of a coating film having higher smoothness, without causing the coating to be dull or transparent during spray coating. Therefore, the viscosity of the water-dispersed powder coating at 23 ° C. is not less than 100 mPas, more preferably not less than 200 mPas and not more than 500 mPas. It is more preferable to adjust the pressure to 400 mPas or less.
  • the paint viscosity is too low, the repelling property at the time of painting is good, but sagging occurs at the time of spray painting and cracking tends to occur at the time of heating and drying, making it difficult to obtain a uniform coating film. If the paint viscosity is too high, the sagging property will be good, but the workability of painting and the leveling property at the time of painting will deteriorate, and it tends to be difficult to obtain a smooth coating film.
  • the water-dispersed powder coating is a coating resin as a raw material or It is preferable to melt and mix the ingredients and dyes, cool and solidify, coarsely pulverize to an appropriate size (usually 1 mm or less), disperse them in an appropriate amount of water, and treat the aqueous dispersion with a circulation type bead mill or the like. Finely pulverize so as to satisfy the average particle size (D50) and the particle size distribution.
  • D50 average particle size
  • the recirculating bead mill circulates the coarsely ground dispersion liquid between a bead mill containing steel balls, ceramic balls, etc. as a crushing medium and a processing liquid tank to reduce the size of the powder in the dispersion liquid.
  • the progress of atomization depends on the material, size, filling amount, rotation speed of agitator / evening shaft, circulation flow rate of dispersion liquid, etc.
  • the degree of miniaturization can be arbitrarily adjusted by adjusting the operation time.
  • the powders in the aqueous dispersion may block (fuse) with each other. It is preferable to use a mold equipped with a cooling mechanism and to carry out the fine pulverization treatment while keeping the temperature of the processing solution low, since fine particles can be smoothly reduced without blocking. At this time, if the paint viscosity is too high, the temperature tends to rise during pulverization, which may cause blocking. Therefore, the paint viscosity is preferably suppressed to about 500 mPa ⁇ s or less at room temperature.
  • Fig. 1 is a graph showing the relationship between the circulating operation time and the particle size of the powder in the aqueous dispersion when performing the fine processing by the circulating bead mill. It is possible to easily obtain an aqueous dispersion having the following particle size configuration. On the other hand, even if a bead mill is used to refine the coarsely divided aqueous dispersion, when the multi-pass operation method is adopted, for example, the particle size changes stepwise with each pass, as shown in Fig. 2. It is difficult to adjust the particle size to a desired range. Therefore, in order to obtain the above-mentioned preferable average particle size (D50) and particle size distribution, it is desirable to use a circulation type bead mill.
  • D50 preferable average particle size
  • the particle size composition of the coarsely ground aqueous dispersion to be subjected to the circulation type bead mill is not particularly limited, and may be blended with the paint resin as necessary as described above.
  • the melt mixture of pigments may be used by appropriately pulverizing it.However, in order to narrow the particle size range after refining by a circulating bead mill as much as possible and to narrow the particle size distribution, the particle size range of the coarsely pulverized product It is also desirable to make the molten mixture as narrow as possible. For this purpose, it is preferable to use a coarsely crushed material obtained by processing the molten mixture into a sheet having an appropriate thickness (preferably around 1 mm) and then crushing it. desirable.
  • the coarsely crushed material when crushed after being formed into a sheet, the coarsely crushed material has a relatively uniform particle size as compared with crushed lump material, and it becomes easier to obtain coarsely crushed material having a narrow particle size distribution. As a result, the particle size composition of the finely pulverized product obtained by treating with a circulation type bead mill becomes more uniform.
  • a circulation type bead mill can be used to adjust the circulation time as appropriate according to the material, size, filling amount, rotation speed of the agitator shaft, circulation flow rate of the paint, etc. It is possible to easily obtain the water-dispersed powder coating material having the above-mentioned preferred particle size range and particle size distribution.
  • the alkylene oxide adduct of the styrene / maleic acid copolymer and the surfactant which are preferably blended when the resin powder for coating is dispersed in water, or other water-based additives, are used for coating. It may be contained in the compounding raw material when producing the resin powder, or added to the aqueous dispersion when coarsely pulverized, or may be added before or during the treatment by the circulating bead mill. Alternatively, it may be added after the bead mill treatment.
  • the thus obtained finely pulverized dispersion liquid is optionally pressurized in the final step.
  • the water-dispersed powder of the present invention is obtained by filtering foreign substances and impurities through a screen equipped with suction or an ultrasonic vibrating mechanism. Paint can be obtained.
  • the type of the object to be coated with the water-dispersed powder coating is not limited at all, and examples thereof include materials and parts used for automobiles, ships, trains, and the like, building materials such as outer panel materials, home electric appliances and office work. It is widely applied to the coating of materials such as components, outer shells, various containers, machine parts and members, pipes, various metal members used for cans and furniture, and plastic members. Can be
  • plastics examples include various known plastics irrespective of whether they are transparent or opaque, and specific examples thereof include polyolefins, polyesters, polyamides, polyurethanes, polyimides, and polycarbonates. These plastics can be appropriately surface-treated as necessary.
  • Metals include the most versatile iron-based metal materials such as steel and alloy steel, as well as non-ferrous metals and alloys such as aluminum, titanium, and brass, as well as zinc-plated steel and tin-plated steel.
  • Nozzle metal material chromate-treated phosphate-treated surface-treated steel material; applicable to aluminum or aluminum alloy materials that have been subjected to anodic oxidation, cathodic oxidation, sealing, etc. .
  • inorganic materials other than metal for example, it is also possible to apply to concrete, mortar, glass, etc., and it is possible to apply an appropriate surface treatment to these objects to be coated as necessary. .
  • the water-dispersed powder coating of the present invention often uses a thermosetting resin as a coating resin in order to enhance water resistance, chemical resistance, weather resistance, and scratch resistance.
  • baking treatment is performed.
  • any drying furnace such as an electric hot air drying oven, a gas hot air drying oven (indirect hot air a hot air blowing), a far infrared drying oven, or a jet heater drying oven is used.
  • Use for example, 120 to 350, more generally 140 to 25 O: 10 seconds to 60 minutes, and more generally, heat drying in about 5 minutes to 40 minutes do it. It is also effective to carry out preliminary drying prior to the above heat drying.
  • the method of applying the water-dispersed powder coating material of the present invention to an object to be coated or printed is not limited at all, and any of the conventionally known methods, electrostatic coating (rotary, air atomizing, airless, air assist, etc.) Type), electrodeposition coating, air spray coating, airless coating, natural roll coater coating, rib-roll coating, roller-coating, roller-coating, roller-coating, die coater coating, immersion coating, brushing Painting, screen Any method such as printing can be adopted.
  • the thickness of the coating film may be appropriately determined according to the performance and appearance required of the coating film, but is usually from 20 to 500 im, particularly preferably from 30 to 100 m. In the case of coating, it is of course effective to adopt a multilayer coating such as two-coating or three-coating.
  • the water-dispersed powder coating material of the present invention is obtained by uniformly and stably finely dispersing the resin powder for coating as described above.
  • the coating components other than the material to be coated are not included. Overspray is performed, but since redispersibility in water is good unless heat treatment is performed, powder paint sprayed with these bars is collected as powder at any time, or washed with water or the like. By collecting as a dispersion, it can be recovered.
  • the water-dispersed powder coating of the present invention can be used as an undercoat, an intermediate coating, or a top coating (including, for example, a coloring coating, a coloring base coating, and a clear top coating).
  • undercoat paint When used as an undercoat paint, besides the above-mentioned resin powder for paint, for example, coloring pigments, anticorrosion pigments, inorganic fillers, plasticizers, surfactants other than the above, defoamers, or other additives Agents (preservatives, solvents, etc.) can be added without any particular limitation.
  • coloring pigments, anticorrosion pigments, inorganic fillers, plasticizers, surfactants other than the above, defoamers, or other additives Agents can be added without any particular limitation.
  • the water-dispersed powder coating of the present invention is used as an intermediate coating, in addition to the above-mentioned resin powder for coating, for example, a coloring pigment, an inorganic filler, a plasticizer, a surfactant other than the above, Foaming agents and other additives (preservatives, solvents, etc.) can be added.
  • a coloring pigment for example, a coloring pigment, an inorganic filler, a plasticizer, a surfactant other than the above, Foaming agents and other additives (preservatives, solvents, etc.)
  • Foaming agents and other additives preservatives, solvents, etc.
  • the water-dispersed powder coating of the present invention is used as a top-coating colored coating, other than the above-mentioned coating resin powder, for example, a coloring pigment Inorganic fillers, plasticizers, surfactants other than the above, antifoaming agents, stabilizers, and other additives (such as anti-glazing agents, glazing agents, preservatives, anti-scratch agents, solvents, etc.) be able to.
  • a polyester resin-based curable paint acrylic resin-based curable paint from the viewpoints of weather resistance, finish properties, and the like.
  • the water-dispersible powder coating of the present invention is used as a clear top coating of a top coating type, other than the above-mentioned resin powder for coating, for example, a coloring pigment (to the extent that the base is not completely hidden), inorganic Fillers, plasticizers, surfactants other than the above, defoamers, stabilizers, and other additives (such as anti-glazing agents, glazing agents, preservatives, anti-scratch agents, solvents, etc.) may be added. it can.
  • a known curable coating, or a water-dispersible powder coating of the present invention is applied as a top coating
  • the top coat is cured at a predetermined baking temperature (when the undercoat and Z or the intermediate coat are not cured, they are cured simultaneously).
  • a known curable paint or the water-dispersible powder paint of the present invention is applied as a top coat
  • a baking treatment is performed at a predetermined temperature to cure the overcoat film (when the undercoat film and Z or the intermediate coat film are uncured, they are simultaneously cured).
  • a known curable paint is directly applied as an undercoat paint on the surface of a material such as metal,
  • a baking process is performed at a predetermined temperature to cure the top coat (or simultaneously cure the undercoat and / or intermediate coat if uncured).
  • curable paints used when carrying out each of the above film forming methods 1 to 3 include, for example, amino-curable resin paints, isocyanate-curable resin paints, acid epoxy-curable resin paints, and hydrolyzable resins.
  • Curable resin paints can be mentioned, and these can be used alone or in combination of two or more as needed if necessary.
  • curable paints may include additives conventionally incorporated into paints as needed, such as coloring pigments, extender pigments, metallic pigments, Color pearl pigments, flow control agents, anti-cissing agents, anti-sagging agents, ultraviolet absorbers, antioxidants, UV stabilizers, delustering agents, glazing agents, preservatives, curing accelerators, curing catalysts, An abrasion inhibitor, an antifoaming agent, a solvent and the like can be contained without particular limitation.
  • curable paints there is no particular limitation on the form of these curable paints, and any form of powder paint, solvent-free paint, water-based paint, organic solvent-based paint (including non-aqueous dispersion paint), etc. may be used. Absent.
  • curable coatings include, for example, electrostatic coating (rotary, air atomizing, airless, air assist, etc.), air spray coating, airless coating, brush coating, 'roll coating, dip coating, etc. It can be painted in any way.
  • top coat when made to be a clear finish, it is also possible to employ a three coat / three bake method, a three coat / two bake method, a three coat / one bake method, or the like.
  • the water-dispersed powder coating of the present invention has excellent storage stability, spray coating properties, and the like, and gives a coating film having a uniform, excellent surface appearance without unevenness or transparency. If the film is different from the intended color or lightness, or if the color or lightness is to be changed aggressively, the toning is performed in substantially the same manner as preparing a new paint as described above. It takes power.
  • a water-dispersed powder coating having the above characteristics is used as a base coating, and the color can be easily adjusted to any desired color and brightness without harming the above characteristics of the base coating. Also provides toning methods You.
  • the toning method defined as another configuration of the present invention is, as described above, a water-dispersed powder coating material in which a powder containing a coating resin and a pigment is dispersed in water, and an average particle size of the powder.
  • the diameter (D50) is 5 to 15 im and the proportion of particles of 20 m or more occupies 10 mass% or less, and the proportion of particles of 3 m or less occupies 10 mass% or less
  • the solid content concentration Is used as a base paint and as a method for finely adjusting the color and Z or lightness of the base paint
  • It is composed of a water-dispersed powder coating material in which a powder containing the same or different coating resin as the above-mentioned coating resin and a pigment is dispersed in water, and the powder has an average particle size (D50). 5 m or less (substantially free of coarse particles having a particle size of more than 10 m) and at least one toning containing white, black, red, blue or yellow pigments A paint is prepared in advance, and at least one of the toning paints is mixed with the base paint in an appropriate amount in accordance with the lightness and Z or color of the base paint. This is a toning method for finely adjusting the color.
  • the toning paint used in this case a water-dispersion type powder coating which is essentially the same as the above-mentioned base coating is used, but the minimum required characteristics required for the toning paint are used. It is preferable to use those having an average particle diameter (D 50) of the solid component contained in the coating material of 5 / m or less. The reason is that if the average particle size (D50) of the solid component contained in the toning paint exceeds 5 m, even if the amount of the toning paint is within an appropriate range, the toning after the toning is not possible. This is because a partial color tone difference (color unevenness) easily occurs on the coating film surface.
  • the average particle diameter (D50) In order to enhance the uniformity of the color and lightness of the paint after toning, it is desirable to use a paint having an average particle diameter (D50) of 5 m or less. However, if the average particle size (D50) is too small, the viscosity of the entire water-dispersed powder coating after toning becomes too high, which adversely affects the coating workability. Therefore, it is desirable to set the average particle diameter (D50) to about 2 m or more.
  • the average particle size (D 50) of the solid component in the toning paint is 5 m. Even if it is below, if more than 10 coarse particles are present in the solid component of the paint, color mixing will occur in the paint film after toning, and the particles of each color will be clearly distinguished and observed. It is difficult to obtain a toned coating film having a uniform color and brightness. Therefore, in order to obtain a uniform toned coating film without color unevenness or color mixture, it is required that the solid component of the coating material contains substantially no coarse particles exceeding 10%.
  • substantially absent does not necessarily mean that there is no “absence”, but a small amount of contamination is permissible as long as it is recognized as uniform by visual observation as a toning coating film. However, it is desirable that the amount of coarse particles exceeding 10 m in the total amount of the solid components is suppressed to about 2% by mass or less, more preferably about 0.5% by mass or less.
  • the pigment to be blended by selecting a pigment to be blended, at least one selected from five types of white, black, red, blue, and yellow, preferably at least five types is selected.
  • white and black toning paints are used to fine tune the lightness and darkness of the base paint
  • red, blue and yellow toning paints are colors. These three primary colors are used for fine adjustment of color.
  • the base paint is gray and you only need to make fine adjustments to light and dark, prepare two types of toning paints, white and black, and use one or two of them. You just have to color it.
  • No special technology is required for the method of producing the above-mentioned toning paint, and if the particle size composition of the solid components is sufficiently understood, a method substantially similar to the above-mentioned method of producing the base paint is required.
  • the dispersant, emulsifier, anti-settling agent and the like disclosed as additives to the base paint can be similarly added to the toning paint.
  • the characteristics of the toning method are utilized more effectively to achieve the toning.
  • the ratio of the average particle diameter (A) of the powder contained in the base paint to the average particle diameter (B) of the powder contained in the toning paint It is desirable to adjust the average particle size of each solid component so that (A / B) is in the range of 1 to 5.
  • the particle size ratio (A / B) is less than 1 means that the particle size of the powder component in the toning coating is equal to or relative to the particle size of the powder component in the base coating. In this case, the coating film after toning is likely to cause color unevenness and color mixture. Conversely, the particle size ratio (A / B) exceeding 5 means that the particle size of the powder component in the toning coating is too small compared to the particle size of the powder component in the base coating. In this case, the handling of paint and the workability of coating tend to be poor.
  • the mixing ratio of the toning paint to the base paint cannot be determined uniformly because it varies depending on the lightness and color of the base paint to be fine-tuned.
  • color mixing occurs due to particles of the base paint, and it is difficult to obtain a uniform coating film.
  • an anti-glazing agent as an additive other than those described above to make the appearance of the coating film opaque.
  • an anti-glazing agent there are no special restrictions on the type of glossy agent.
  • All known matting agents such as calcium carbonate, barium sulfate, barium carbonate, clay, talc, diatomaceous earth, silica powder, basic magnesium carbonate, alumina white, wax, plastic beads, etc. They can be used alone or in combination of two or more as necessary.
  • the glossing agent can be added at any stage before or after the above-mentioned toning paint is blended with the base paint to be toned. Although it varies depending on the type and degree of the required matte state, it is usually about 0.1 to 20% by mass based on the solid content of the paint. In other words, if you want to make the toning film a matte finish, add an appropriate amount of the matting agent to the paint before toning, in the toning process, or after finishing the toning, It is possible to obtain a toned coating film in a correspondingly matt state.
  • a special method is not required for the coating method and baking conditions using the water-dispersed powder paint toned by the above method, and the methods described above, including the type of the object to be coated, are not required. All objects to be coated can be applied.
  • the average particle size (D50), particle size distribution, nonvolatile content, measurement method of paint viscosity, coating workability, and evaluation method of coating film performance used in the following experiments were as follows.
  • Each water-dispersed powder coating is mixed with water until the solid content concentration becomes 5% by mass or less. After dilution, this diluted solution is treated with an ultrasonic homogenizer "Ultrasonic homogenizer 1" manufactured by Nippon Seiki Seisaku-sho, Ltd., and then a particle size distribution analyzer manufactured by Nikkiso Co., Ltd.
  • the particle size distribution is measured using "Microtrack MT330 EL", and the cumulative 50% particle size is determined as the average particle size (D50) from the particle size distribution curve.
  • the glass transition temperature (T g) of the powder particles was measured using a differential scanning calorimeter “DSC 6200” manufactured by Seiko Instruments Inc.
  • Spray coating is performed three times in a row, spray-dried at a setting time of 20 minutes at 20 ° C, and baked and dried. Is evaluated on a 5-point scale based on the following criteria.
  • the spray gun and spray air pressure are the same as those adopted in the above-mentioned evaluation of coating workability.
  • a water-dispersed powder coating is applied in the same manner as in the above-mentioned dullness test, and the test piece is allowed to stand at 20 ° C for 10 minutes. Then, the size of the unevenness on the surface is visually evaluated in five steps.
  • Coating is performed in the same manner as in the sagging evaluation described above, and the paint state of the obtained coating film is evaluated on a 5-point scale according to the following criteria.
  • the spray gun and spray air pressure shall be the same as those adopted in the above-mentioned evaluation of coating workability.
  • Print area is less than 1 Z 4 of total coating area
  • the area where the peeling occurred was 1/4 or more of the total coating area, but less than 12 2: The area where the peeling occurred was 1/2 or more of the total coating area, and less than 3/4. 1: The area where the peeling occurred was 3/4 or more of the total coating area.
  • Benzoin Degassing agent manufactured by MIWON COMMERCIAL
  • Imidazole a curing accelerator manufactured by Shikoku Chemicals
  • AER6002 Epoxy resin manufactured by Asahi Kasei Epoxy Co., Ltd.
  • AER6004 Epoxy resin manufactured by Asahi Kasei Epoxy Co., Ltd.
  • Acronal 4F Flow modifier manufactured by BASF
  • Titanium oxide CR97 Titanium oxide manufactured by Ishihara Sangyo
  • ADEKINOL UH_540 Viscosity adjuster manufactured by Asahi Denka Kogyo Co., Ltd.
  • ADEKANOL UH_752 Viscous adjuster manufactured by Asahi Denka Kogyo Co., Ltd.
  • Sudfinol 420 Air Products Surfactant
  • Dispersant manufactured by BIC CHEMI
  • AD H curing agent manufactured by Otsuka Chemical Co., Ltd.
  • Almatex PD 7310 Acrylic resin manufactured by Mitsui Chemicals, Inc.
  • Decanedicarboxylic acid a curing agent manufactured by Ube Industries
  • a C E MA T T HK 460 silica particles manufactured by DeDasa AG, Inc.
  • the raw materials are used in the ratio shown in Formulation 1 below, uniformly mixed with a high-speed mixer, then hot-melt kneaded and extruded using a melt extruder. Cool and solidify into a sheet of about 1 mm. This sheet is coarsely crushed by passing through a crusher, and then passed through a filter having a sieve of 1.0 mm to obtain a coarsely crushed polyester resin.
  • Polyester resin coarse powder (Note) 50.0 (parts)
  • Example 11 the solid content concentration of the water-dispersed powder coating material, the total amount of the additives [components other than the coarsely pulverized product and the dispersion medium (water)], and the dispersion time by the circulating bead mill were determined.
  • a water-dispersed powder coating material is prepared in the same manner as in Example 11 except that each is changed as shown in Table 1 below.
  • Table 1 shows the average particle size (D50) and the particle size distribution of the paint powder contained in each paint.
  • Example 1 Using the epoxy resin coarse powder obtained above, a water-dispersed powder coating was obtained in the same manner as in Example 11 below. Table 1 shows the properties and characteristics of the obtained water-dispersed powder coating. The T g of the powder particles was 62. Example 1 1 7
  • Example 18 A total of 100.0 The water-dispersed powder coating was obtained in the same manner as in Example 11 above using the coarsely pulverized acrylic resin obtained above. Table 1 shows the properties and characteristics of the obtained water-dispersed powder coating. The T g of the powder particles was 60 ° C. Example 18
  • the raw materials are used in the ratio shown in Formulation 5 below, uniformly mixed with a high-speed mixer, and then hot-melt kneaded using a melt extruder.
  • the mixture is extruded and cooled and solidified into a sheet with a thickness of about 1 mm.
  • This sheet-like material is coarsely ground through a crusher, and then passed through a filter having a sieve of 1.0 mm to obtain a coarsely ground epoxy-polyester resin.
  • a water-dispersed powder coating was obtained in the same manner as in Example 11 below using the epoxy-polyester resin coarse powder obtained above.
  • Table 1 shows the properties of the obtained water-dispersed powder coating.
  • the T g of the powder particles was 65 ° C.
  • each of the obtained water-dispersed powder coatings was applied three times to SPCC steel plates (same as above) using a spray gun “W-100” (nozzle diameter: 1.3 mm) manufactured by Annest Iwata. Spray-painted and then placed in a hot-air dryer.
  • W-100 spray gun
  • the raw materials are used in the ratio shown in Formulation 1 below, mixed uniformly with a high-speed mixer, then hot-melt kneaded and extruded using a melt extruder, and cooled and solidified into a sheet with a thickness of about 1 mm. After the sheet material is coarsely crushed by passing through a crusher, it is passed through a filter having a sieve of 1.0 mm to obtain a coarsely crushed material.
  • the average particle diameter (D50) of the powder particles is 13 m, and the content of coarse particles having a particle diameter of 50 m or more and fine particles having a particle diameter of 0.5 m or less is determined. Was also 0%.
  • the T g of the powder particles was 65 ° C.
  • Example 2-1 the surfactant shown in Table 3 was used in place of the surfactant "Safinol 420" used in the above Formulation 2, or "Disperbyk-19" in Formula 1 was used.
  • “Huichi Ichiren TG-7500 W” a dispersant manufactured by Kyoei Chemical Co., Ltd.
  • a polyester resin-based water-dispersible powder was used instead of “0”
  • Body paint was manufactured. The average particle size (D50), particle size distribution, and solid content of each water-dispersed powder coating material were adjusted to be the same as those in Example 2-1.
  • the surfactant used here is as follows:
  • An epoxy resin-based coarse powder is obtained in the same manner as in a-1) of Example 2-1 except that the raw materials are used in the ratio shown in the following formulation 3.
  • a water-dispersible powder coating was produced in the same manner as in Example 2-1 b-1), except that the raw material mixture used in the ratio shown in Formula 4 below was used.
  • Table 3 shows the properties and characteristics of the powder coating.
  • the average particle size (D 50) of the powder particles contained in the obtained powder coating material was 13 m, and the coarse particles having a particle size of 50 m or more and the particles having a particle size of 0.5 m or more were 0.5 m or more.
  • the content of fine particles below zm was 0% in all cases.
  • the T g of the powder particles was 62 ° C.
  • the average particle diameter (D50) of the body particles is 13 ⁇ m, and the content of coarse particles having a particle diameter of 50 ⁇ m or more and fine particles having a particle diameter of 0.5 / m or less
  • the powder particles had a T g of 62 ° C.
  • An acryl resin-based water-dispersed powder coating is obtained in the same manner as in Example 2-1 except that the raw material mixture having the ratio shown in the following formulation 6 is used.
  • Table 3 shows the properties and characteristics of the obtained water-dispersed powder coating.
  • the average particle size (D50) of the powder particles is 13 ⁇ m, and the content of coarse particles having a particle size of 50 m or more and fine particles having a particle size of 2.5 or less is determined. Was also 0%.
  • the T g of the powder particles was 60 ° C.
  • Coarse pulverized material (Note) 1 0 0.0 (Parts) Zion exchange water 1 0 0.0 "Adecanol UH—5 4 0" 0.4
  • Table 3 shows the properties and characteristics of the obtained water-dispersed powder coating.
  • the average particle size (D50) of the powder particles is 13 m, and the content of coarse particles having a particle size of 50 m or more and fine particles having a particle size of 0.5 m or less is as follows. All were 0%.
  • the T g of the powder particles was 60.
  • Paint 1 Production example (Polyester-based water-dispersed powder coating; for Examples) a-1) Production of coarsely ground polyester resin
  • the raw materials are used in the ratio shown in Formulation 1 below, uniformly mixed with a high-speed mixer, then hot melt kneaded and extruded using a melt extruder, extruded into a sheet with a thickness of about 1 mm, and cooled and solidified. Let it. This sheet is coarsely pulverized through a crusher, and then passed through a filter having a sieve of 1.0 mm to obtain a polyester resin coarse powder.
  • the raw material mixture used in the ratio shown in the following formulation 2 was mixed with a 100. O kg by a disperser, and the mixture was wet-circulated bead mill with a built-in cooling mechanism [dispersion media: Nitkato with a diameter of 1.0 mm Zirconiapole "YTZ" manufactured by one company was charged into a circulation tank connected to 80% (4.4 kg) of the vessel volume], and the agitator disk was rotated at a peripheral speed of 1 O mZ s Fine grinding is performed by circulating while rotating. Next, the mixture is filtered through a 502 m filter to obtain a polyester resin-based water-dispersed powder coating material 1. Table 5 shows the properties and characteristics of the obtained water-dispersed powder coating material 1.
  • the average particle size (D50) of the powder particles in the powder coating material 1 was 13 / m, and the coarse particles having a particle size of 50 ⁇ m or more and the particle size of 0.5 m or less were used. In each case, the content of fine particles was 0%.
  • the T g of the powder particles was 65.
  • Formula 2 Coarse pulverized polyester resin (Note) 1 0.0 0 (parts) Ion exchange water 100 0 0
  • a polyester resin-based water-dispersed powder coating material 2 was obtained in the same manner as described above, except that in the production example of the coating material 1, the following formulation 3 was used instead of the formulation 2.
  • Polyester resin coarsely pulverized product (Note) 10.0 (Parts) Ion-exchanged water 1 00.0
  • Polyester resin coarsely pulverized product obtained by the above formulation 1 Paint 3 Production example (Epoxy resin water-dispersed powder coating; for example) a-2) Epoxy resin Manufacture of coarse powder
  • a coarsely pulverized epoxy resin material is obtained in the same manner as in a-1) of the above-mentioned Production Example 1 for the coating material, except that the raw materials are used in the ratio shown in the following formulation 4.
  • An epoxy resin-based water-dispersed powder coating material 3 was produced in the same manner as in the above-mentioned coating material 1 Production Example b-1), except that the raw material mixture used in the ratio shown in the following formulation 5 was used.
  • Table 5 shows the properties and characteristics of the water-dispersed powder coating material 3.
  • the average particle size (D 50) of the powder particles contained in the obtained paint 3 was 13 m, coarse particles having a particle size of 50 m or more and particle sizes of 0.5 m or less. Was 0% in all cases.
  • the T g of the powder particles was 62 ° C.
  • Epoxy resin coarse pulverized product (Note) 10.0 (Parts) Deionized water 10.0
  • Epoxy resin-based coarsely pulverized product obtained by the above-mentioned formulation 4 Paint 4 Production Example (Epoxy resin-based water-dispersed powder paint; for Example) An epoxy resin-based water-dispersed powder coating material 4 was produced in the same manner except that the following formulation 6 was used instead of the formulation 5.
  • Epoxy resin coarse pulverized product (Note) 10.0 (parts) Ion exchange water 1 0 0 0
  • Acrylic resin-based water-dispersed powder coating material 5 is obtained in the same manner as in the above-mentioned coating material 1 production example, except that the raw material mixture having the ratio shown in the following formulation 8 is used.
  • Table 5 shows the properties and characteristics of the obtained water-dispersed powder coating material 5.
  • the average particle diameter (D 50) of the powder particles contained in the coating is 13 m, and the coarse particles having a particle diameter of 50 m or more and the fine particles having a particle diameter of 0.5 m or less are used. The contents were all 0%.
  • the T g of the powder particles was 60 ° C.
  • Acrylic resin-based coarse powder (Tg: 60 ° C) obtained by the above Formulation 7 Paint 6 Production example (Acrylic resin-based water-dispersed powder coating; for Examples) “Floren TG—750 W” (Kyoei Chemical Co., Ltd.) was used instead of “Disperbyk—190” used in Formulation 8 in the production of the acrylic resin-based water-dispersible powder coating 5 shown in 3).
  • Acrylic resin-based water-dispersible paint 6 was produced in exactly the same manner as in the above-mentioned Paint 5 Production Example, except that a dispersant manufactured by Co., Ltd. was used.
  • the average particle diameter (D 50) of the powder particles contained in the paint 6 is 13 m, and the coarse particles having a particle diameter of 50 m or more and the fine particles having a particle diameter of 0.5 m or less are used. The contents were all 0%.
  • the T g of the powder particles was 60 ° C. Paint 7 Production example (acrylic resin-based water-dispersed powder coating; for example) Admixture shown in Table 5 was adopted, and acryl resin-based water-dispersed powder-based coating was performed in the same manner as in the above-mentioned coating 1 Production Example. 7 was manufactured.
  • the average particle size (D 50) of the powder particles contained in the paint 7 is 13 m, coarse particles having a particle size of 50 ⁇ m or more and fine particles having a particle size of 0.5 ⁇ m or less. The content of all substances was 0%.
  • the T g of the powder particles was 60 ° C.
  • Paint 8 Production Example (acrylic resin-based water-dispersed powder coating; for example) In the above-mentioned Paint 5 Production Example, an acrylic resin-based water-based Dispersion type powder coating 8 was produced.
  • the average particle diameter (D 50) of the powder particles contained in the paint 8 is 13 ⁇ m, the content of coarse particles having a particle size of 50 ⁇ m or more and the content of fine particles having a particle size of 0.511 or less were 0%.
  • the T g of the powder particles was 58 ° C. Paint 9 Production example (Polyester resin-based water-dispersed powder paint; for comparative example)
  • the formulation shown in Table 5 was adopted, and a polyester resin-based water-dispersed powder coating material 9 was manufactured in the same manner as in the above-mentioned coating material 1 manufacturing example.
  • the average particle size (D50) of the powder particles contained in the coating material 9 is 13 m, and the coarse particles having a particle size of 50 m or more and the fine particles having a particle size of 0.5 Xm or less are fine. The contents were all 0%.
  • the T g of the powder particles was 65 ° C., and the composition of the paint 10 was prepared as shown in Table 5 below.
  • An epoxy resin-based water-dispersed powder coating material 10 was produced in the same manner as in the coating material 1 production example.
  • the average particle diameter (D 50) of the powder particles contained in the paint 10 is 13 m, and the coarse particles having a particle diameter of 50 m or more and the fine particles having a particle diameter of 0.5 xm or less are fine. The contents were all 0%.
  • the T g of the powder particles was 62. Paint 11 Production Example (acrylic resin-based water-dispersed powder paint; for comparative example) The formulation shown in Table 5 was adopted. An acrylic resin-based water-dispersed powder coating material 11 was produced in the same manner as in the production example.
  • the average particle size (D50) of the powder particles contained in the coating material 11 is 13 ⁇ m, and coarse particles having a particle size of 50 m or more and fine particles having a particle size of 0.5 xm or less are provided. Was 0% in all cases.
  • the T g of the powder particles was 60 ° C.
  • the properties and characteristics of each of the obtained water-dispersed powder coating materials 1 to 11 are shown in Table 5. Table 5
  • Paint i "Rethane PG-80 Metallic” (Kansai Paint Co., Ltd.'s isocyanate-curable acryl resin paint, used as a two-component curable organic solvent-based colored topcoat.
  • Paint ii "Electron G T-10 Gray” (Kansai Paint Co., Ltd. block isocyanate curable epoxy resin cationic electrodeposition paint, used as undercoat.
  • Paint iii Mix 140 parts of neutralized aqueous acrylic resin (1) with 50% solids and 34 parts of Cymel 370 (88% water-soluble melamine resin solution manufactured by Mitsui Cytec) Then, 25 parts of “Aluminum Paste 891 K” (manufactured by Toyo Aluminum Co., Ltd.) was added and dispersed, and the solid content was adjusted to 35% with deionized water to obtain a colored base paint.
  • a number-average molecular weight: about 100,000 acryl resin solution (solid content: 60%) is prepared, di'methylaminoethanol is added to this solution, neutralized, and then solidified with isopropyl alcohol. Diluted to 50% per minute.
  • Paint iv Acrylic resin neutralization solution with 50% solids (same as 1 * above) 140 parts and “Cymel 370” (88% water-soluble melamine resin solution manufactured by Mitsui Cytec) 3 Mix 4 parts and adjust to a solid content of 35% with deionized water. Use as a clear top coating.
  • Paint V Acrylic resin neutralization solution with 50% solids (same as 1 * above) 140 parts and “Symel 370” (88% water-soluble melamine resin solution manufactured by Mitsui Cytec) 3 Four parts are mixed, 55 parts of titanium white and 2 parts of carbon black are added and dispersed, and then adjusted to a solid content of 35% with deionized water, and used as a colored overcoat.
  • Neo-Amirac # 600 White (Kansai Paint Co., Ltd., an organic solvent-based, acrylic melamine-cured paint, colored top coat Used as a paint.
  • Polyester resin (neopentyldaricol; ⁇ 56 parts; trimethylolpropane; 109 parts; hexahydrofuric acid; 370 parts; adipic acid; 292 parts and isofuric acid; Put 398 parts in a reaction vessel and react at 220 ° C for 6 hours, then add trimellitic anhydride; 45 parts, and react at 170 ° C for 30 minutes.
  • the polyester resin obtained has a number average molecular weight of about 800, an acid value of 2 O mg KOH / g. A hydroxyl value of 95 mg KO HZ g) 100 parts (solid equivalent, hereinafter the same).
  • Material A (zinc phosphate-treated steel sheet) was spray-coated with the above-mentioned “Paint 4” as an undercoat paint to a dry film thickness of 40 zm, and then baked at 180 ° C for 20 minutes. After the treatment, the above “paint i” was spray-coated as a colored overcoat paint so as to have a dry film thickness of 80 xm, and was cured by heating at 80 ° C for 30 minutes.
  • the coating film obtained is a two-layer multi-layer coating film consisting of an undercoat film and a colored overcoat film, and the coating method is ⁇ 2 coats and 2 coatings, 2 coating films and 2 baking times ''.
  • Example 3 is an example of the present invention in which an epoxy resin-based water-dispersed powder coating is applied as an undercoat.
  • the bath temperature of the electrodeposition bath is 15 to 35 ° C
  • the load voltage is 100 to 400 V
  • the film thickness is 40 / m was applied between the object to be coated and the electrode to perform cationic electrodeposition coating.
  • excess electrodeposition paint was washed with industrial water to prevent the electrodeposition paint from remaining on the surface of the coating.
  • Tables 6 to 8 collectively show the configurations and coating film performances of the coating films formed in Example 3-1 to 3-24 and Comparative Example 3-1 to 3-6.
  • “2C1B” means 2 coats and 1 bake
  • “3C2B” means 3 coats and 2bake
  • “3C3B” means 3 coats and 3bake
  • “4C2B” Means 4 coats 2 bake
  • 4 C 4 B means 4 coats 4 bake
  • material A is zinc phosphate treated steel sheet
  • material B is molten zinc plated steel sheet
  • material C is material “SP” means spray painting
  • ED means electrodeposition coating, which is used as a painting method to represent “phosphoric aluminum plate”.
  • Baking 180 180 Coating type iv 8 8 Coating method SP SP SP Top-coat clear coating Dry film thickness (im) 80 80 80 80 Drying (° C, 10 minutes)
  • Baking 140 180 180 Number of layers 2 2 2 3 2 3 4 2 2 3 Undercoat a a a a a a a a a a a a a a a a a a
  • Membrane a Use of invention product Colored top coat b b b b a a a a
  • Coloring base b a b Clear b a Baking process 2G2B 2G1 B 2C2B 2G2B 2C2B 3C3B 4G3B 2C1 B 2C2B 3C2B
  • Baking 180 180 180 180 Number of multilayer films 3 2 2 2 2 2 2 3 3 4 3 Undercoating a a a a a b b b b b b b Coating process Intermediate coating a Film a: Use of invention
  • Baking 180 180 140 140 140 140 140 140 140 Number of layers 3 3 3 4 2 2 3 3 4 Undercoat b b b b b b b b b b b b Intercoat b a b b b Coating coating
  • the raw materials are used in the ratio shown in Formulation 1 below, mixed uniformly with a high-speed mixer, melt-kneaded using a melt extruder, and extruded into a sheet with a thickness of about 1 mm to be cooled and solidified.
  • This sheet material is coarsely crushed through a crusher, and then passed through a filter having a sieve of 1.0 mm to obtain a coarsely crushed material.
  • a coarsely pulverized product is obtained in the same manner as above except that the following formulation 3 is used.
  • a coarse powdered material was obtained by the same raw material blend as shown in the above-mentioned blend 1, and this was used in the same blend ratio as in the above-mentioned blend 2, except that the circulation time for the fine grinding treatment was reduced to 30 minutes.
  • a comparative base coating (al) was obtained.
  • the properties and properties of the base paint (al) are shown in Table 11 below.
  • Coarse ground material was obtained with the same raw material composition as shown in Formulation 1, and this was used in the same composition ratio as in Formulation 2 above, and the circulation time for fine pulverization was extended to 120 minutes.
  • a comparative base paint (a2) was obtained in the same manner as in the above example, except for the above. The properties and characteristics of the comparative base paint (a2) are shown in Table 11 below.
  • the raw materials are blended in the ratio shown in the following Formulation 6, uniformly mixed by a high-speed mixer, heated and kneaded using a melt extruder, extruded into a sheet shape, and cooled and solidified to obtain a thickness of about lmm. Sea 1, get a thing. After the sheet material is crushed by a crusher, it is passed through a filter having a sieve of 1.0 mm to obtain a coarsely ground clear material having an average particle size of about 0.5 mm.
  • the reference black paint for color matching (b3) and the reference paint for color matching (b4) shown in Table 13 above were used as the paint base as described above.
  • Powder and color pigment are mixed in a powder state.Mikuguchi is a mixture of resin powder and pigment powder separately dispersed and mixed. The color pigment is melt-mixed with the resin, then finely pulverized, and mixed with the resin. This is different from the toning paint of the present invention in which the pigment is integrated.
  • pigment dispersions for aqueous paints shown in Table 14 below were used as toning paints (b5) and (b6). These pigment dispersions are obtained by dispersing an extremely fine pigment powder in an aqueous medium, and the color pigment is melt-mixed with a base resin and then finely pulverized to form the resin and pigment of the present invention. Is different from the toning paint. Table 14
  • the base paint and toning paint obtained above are used in various mixing ratios and combinations, and the toning is prepared by uniformly mixing with a disperser to prepare a toning paint.
  • the coating performance was examined. The results are shown in Table 15 and Tables 16 and 17.
  • Spray gun “W-100” (nozzle diameter: 1.3 mm) manufactured by Annest Iwata Co., Ltd. was used for spray painting, and the SPCC steel plate (same before) was spray-painted three times and then hot-air dried. The film was loaded into the machine and baked at 190 ° C for 20 minutes, and then the coating film performance was evaluated.
  • A1 B1 B2 B3 B4 B5 Control agent Particle size (m) Particle size () Stability Workability (jum) Blended Smoothness Ra (jum)
  • Table 15 above is an example that satisfies all of the preferable requirements defined in the present invention.
  • the coating workability is good and the coating film properties (color mixing and smoothness) are also extremely excellent.
  • the blending amount of the toning paint was specified to be 10 parts or 20 parts.However, when actually performing the toning, the toning was performed according to the target color tone of the base paint. It is natural that the blending amount of the toning paint is properly adjusted, and it is of course possible to perform delicate color matching using two or more kinds of toning paints.
  • reference numerals 7 and 8 shown in Tables 16 and 17 indicate that the particle size composition of the base paint and the toning paint is both appropriate, but the amount of the toning paint is too large. This is an example, and slight color mixing is observed.
  • Reference numerals 9, 10 are comparative examples in which the particle size composition of the base paint is appropriate but the particle size composition of the toning paint does not satisfy the specified requirements, and clear color mixing is observed.
  • Reference numeral 11 is a comparative example in which the average particle size of the base paint is too coarse
  • reference numeral 12 is a comparative example in which the average particle size of the base paint and the toning paint is too coarse. Are observed and the coating film performance (smoothness sagging) is poor.
  • Reference numerals 13 and 14 are comparative examples in which the average particle size of the base paint is too small, and the paint workability is poor irrespective of the toning paint, making it impossible to paint.
  • Reference numerals 15 and 16 and reference numerals 17 and 18 are examples in which a mixed dispersion of clear resin powder and fine pigment powder was used as a toning coating for a base coating with an appropriate particle size composition. Yes, the workability of coating and the smoothness of the coating film are good due to the appropriate particle size composition of the base paint, but the finished coating film surface is pigmented by the presence of ultrafine pigment powder alone. The color is floated by the powder, and the gloss is reduced. During storage, the pigment component and the base paint undergo phase separation.
  • the separation stability as a coating and coating using a spray gun It is possible to provide a water-dispersed powder coating material that has a fine surface, has little unevenness, and provides an excellent coating appearance without causing problems such as workability and waste liquid treatment.
  • the alkylene oxide adduct of the styrene / maleic acid copolymer preferably used in the present invention is composed of a saturated hydrocarbon bond.
  • the olepoxyl group derived from maleic acid has a high polarity, it has excellent adhesion to almost any object to be coated, including plastics, metals, and inorganic materials.
  • the alkylene oxide adduct is present in the molecule as a hydrophilic side chain away from the main chain of the styrene / maleic acid copolymer, so it has little steric hindrance to the main chain and functions as a hydrophilic group. Is fully demonstrated.
  • the surface of the coating particles is protected by the hydrophilic group, and rapid water evaporation does not occur on the particle surface even in the baking process. Less coating film defects such as pinholes.
  • the alkylene oxide adduct of a styrene / maleic acid copolymer preferably used in the present invention has a good balance between hydrophobicity and hydrophilicity, and thus exhibits excellent coating performance stably.
  • a coating resin or a pigment and a pigment are melt-mixed, preferably processed into a sheet, coarsely pulverized, and then finely pulverized using a circulation type bead mill.
  • a water-dispersed powder coating material satisfying the requirements of the above average particle size (D50) and particle size distribution can be easily produced.
  • the average particle size and the particle size distribution of the resin powder in the water-dispersed powder coating material, and further, the solid component concentration is used for the specified base coating material,
  • a water-dispersed toning powder coating with a specified particle size composition it is possible to adjust the delicate color matching of the base coating and toning with a paint sprayer, which is difficult with a water-dispersed powder coating. Easy to implement.

Abstract

La présente invention concerne un revêtement en poudre dispersée dans l'eau comprenant une résine de revêtement en poudre se caractérisant par un diamètre particulaire médian (D50) de 1 à 30 µm, de préférence de 5 à 15 µm, et encore plus préférentiellement par une distribution des calibres particulaires telle que la proportion en particules d'au moins 50 µm de diamètre, et la proportion en particules de 0,5 µm de diamètre maximum font chacune au maximum 10 % de la masse. Pour élaborer ce revêtement, on disperse dans l'eau la résine de revêtement en poudre, de préférence en présence, d'une part d'un additif fait d'un copolymère d'acide maléique du styrène avec un oxyde d'alkylène, et d'autre part d'un tensioactif. Ce revêtement qui est très maniable à l'application, se distingue par sa bonne stabilité au stockage. Il permet la réalisation de films de revêtement lisses dont la surface présente de bonnes propriétés et un bel aspect. L'invention concerne également un procédé de production de ce revêtement en poudre dispersée dans l'eau. L'invention concerne enfin un procédé d'échantillonnage des couleurs avec ce revêtement en poudre.
PCT/JP2003/004677 2002-04-15 2003-04-14 Revetement en poudre dispersee dans l'eau, procede de production correspondant, et procede d'echantillonnage de la couleur WO2003087248A1 (fr)

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JP2002-112562 2002-04-15
JP2002112562 2002-04-15
JP2002-208603 2002-07-17
JP2002208603 2002-07-17
JP2003011333A JP2004224833A (ja) 2003-01-20 2003-01-20 水分散型粉体塗料組成物
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3067398A1 (fr) * 2015-02-24 2016-09-14 J Colors S.p.A. Produit decoratif
WO2018018399A1 (fr) * 2016-07-26 2018-02-01 江门骅弘科技股份有限公司 Feuille de couleur universelle à base d'eau de type dispersion

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JPS51123239A (en) * 1975-04-21 1976-10-27 Mitsubishi Electric Corp A process for preparing an aqueous powdered resin dispersion varnish f or use in electrodeposition
JPS5277133A (en) * 1975-12-24 1977-06-29 Dainippon Toryo Co Ltd Color matching of slurry paint
JPS52107033A (en) * 1976-03-05 1977-09-08 Nippon Paint Co Ltd Method of manufacturing slurry-type water dispersed paint
JPS52132036A (en) * 1976-04-28 1977-11-05 Nippon Paint Co Ltd Water-dispersed coating composition
JPS52146440A (en) * 1976-06-01 1977-12-06 Nippon Paint Co Ltd Color mixing for slurry aqueous dispersion coating
JPS54158437A (en) * 1978-06-05 1979-12-14 Dainippon Toryo Co Ltd Water-dispersed thermosetting resin coating composition
JPS5734165A (en) * 1980-08-11 1982-02-24 Kansai Paint Co Ltd Aqueous dispersion type slurry resin paint
JPS5759959A (en) * 1980-09-26 1982-04-10 Dainippon Toryo Co Ltd Color matching of slurry paint
JPH1180647A (ja) * 1997-07-17 1999-03-26 Nippon Paint Co Ltd 貴金属又は銅のコロイド溶液及びその製造方法並びに塗料組成物及び樹脂成型物
JP2001220544A (ja) * 2000-02-08 2001-08-14 Kansai Paint Co Ltd 水分散塗料組成物
EP1167478A1 (fr) * 2000-06-30 2002-01-02 Kansai Paint Co., Ltd. Résine comme agent de dispersion de pigments
JP2002275427A (ja) * 2001-03-22 2002-09-25 Kansai Paint Co Ltd 粉体スラリー樹脂組成物
JP2002285097A (ja) * 2001-03-26 2002-10-03 Kansai Paint Co Ltd 水分散性艶消し塗料組成物

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Publication number Priority date Publication date Assignee Title
JPS51123239A (en) * 1975-04-21 1976-10-27 Mitsubishi Electric Corp A process for preparing an aqueous powdered resin dispersion varnish f or use in electrodeposition
JPS5277133A (en) * 1975-12-24 1977-06-29 Dainippon Toryo Co Ltd Color matching of slurry paint
JPS52107033A (en) * 1976-03-05 1977-09-08 Nippon Paint Co Ltd Method of manufacturing slurry-type water dispersed paint
JPS52132036A (en) * 1976-04-28 1977-11-05 Nippon Paint Co Ltd Water-dispersed coating composition
JPS52146440A (en) * 1976-06-01 1977-12-06 Nippon Paint Co Ltd Color mixing for slurry aqueous dispersion coating
JPS54158437A (en) * 1978-06-05 1979-12-14 Dainippon Toryo Co Ltd Water-dispersed thermosetting resin coating composition
JPS5734165A (en) * 1980-08-11 1982-02-24 Kansai Paint Co Ltd Aqueous dispersion type slurry resin paint
JPS5759959A (en) * 1980-09-26 1982-04-10 Dainippon Toryo Co Ltd Color matching of slurry paint
JPH1180647A (ja) * 1997-07-17 1999-03-26 Nippon Paint Co Ltd 貴金属又は銅のコロイド溶液及びその製造方法並びに塗料組成物及び樹脂成型物
JP2001220544A (ja) * 2000-02-08 2001-08-14 Kansai Paint Co Ltd 水分散塗料組成物
EP1167478A1 (fr) * 2000-06-30 2002-01-02 Kansai Paint Co., Ltd. Résine comme agent de dispersion de pigments
JP2002275427A (ja) * 2001-03-22 2002-09-25 Kansai Paint Co Ltd 粉体スラリー樹脂組成物
JP2002285097A (ja) * 2001-03-26 2002-10-03 Kansai Paint Co Ltd 水分散性艶消し塗料組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3067398A1 (fr) * 2015-02-24 2016-09-14 J Colors S.p.A. Produit decoratif
WO2018018399A1 (fr) * 2016-07-26 2018-02-01 江门骅弘科技股份有限公司 Feuille de couleur universelle à base d'eau de type dispersion

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