WO2014196217A1 - Composition de revêtement - Google Patents

Composition de revêtement Download PDF

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Publication number
WO2014196217A1
WO2014196217A1 PCT/JP2014/051078 JP2014051078W WO2014196217A1 WO 2014196217 A1 WO2014196217 A1 WO 2014196217A1 JP 2014051078 W JP2014051078 W JP 2014051078W WO 2014196217 A1 WO2014196217 A1 WO 2014196217A1
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WIPO (PCT)
Prior art keywords
acid
parts
coating
coating composition
mass
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PCT/JP2014/051078
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English (en)
Japanese (ja)
Inventor
千里 松浦
児島　敬
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関西ペイント株式会社
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Application filed by 関西ペイント株式会社 filed Critical 関西ペイント株式会社
Priority to CN201480001869.6A priority Critical patent/CN104471004B/zh
Priority to JP2014534845A priority patent/JP5675005B1/ja
Publication of WO2014196217A1 publication Critical patent/WO2014196217A1/fr

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Classifications

    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09D5/002—Priming paints
    • 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
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a coating composition that has good storage stability, can maintain stain resistance over a long period of time when exposed outdoors, and can form a coating film with good coating film hardness and processability.
  • outdoor base materials for example, buildings, display objects, guard fences, appliances, machines, etc.
  • outdoor paints excellent in weather resistance for the purpose of decoration or protection.
  • paints used outdoors include polyurethane resin paints, fluororesin paints, silicone resin paints, acrylic resin paints, polyester paints, etc., but these paints are exposed outdoors.
  • soot, sand dust, iron powder, rain (acid rain), sunlight, etc. and the stain resistance is lowered.
  • a coating composition for a pre-coated steel sheet comprising (A) a polyol resin, (B) an amino resin, (C) an alkoxysilane compound, and (D) a curing catalyst and having excellent resistance to contamination against rainwater and workability is disclosed.
  • Patent Document 1 a coating composition for a pre-coated steel sheet comprising (A) a polyol resin, (B) an amino resin, (C) an alkoxysilane compound, and (D) a curing catalyst and having excellent resistance to contamination against rainwater and workability is disclosed.
  • the coating films obtained by applying the coating compositions described in Patent Document 1 and Patent Document 2 are insufficient in the durability of stain resistance, and are particularly semi-added with a matting agent such as silica. In the gloss coating, the contamination resistance was significantly reduced by outdoor exposure.
  • the problem to be solved by the present invention is a coating composition that has good storage stability, can maintain stain resistance over a long period of time when exposed outdoors, and can form a coating film with good coating film hardness and workability. Is to provide.
  • the amount of anionic surfactant (c) is 1 to 20 parts by mass relative to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). It has been found that the problem can be achieved by a coating composition containing 0.1 to 20 parts by mass of the cationic surfactant (d).
  • a coating composition comprising a hydroxyl group-containing resin (a), a crosslinking agent (b), an anionic surfactant (c) containing a sulfonic acid group or a sulfonate group, and a cationic surfactant (d), 1 to 20 parts by mass of an anionic surfactant (c) containing a sulfonic acid group or a sulfonate group with respect to 100 parts by mass in total of the solid content of the containing resin (a) and the crosslinking agent (b), and cationic A coating composition containing 0.1 to 20 parts by mass of a surfactant (d), 2.
  • the coating composition according to item 1 contained in 1.
  • the coating composition according to item 1 or 2 wherein the anionic surfactant (c) containing a sulfonic acid group or a sulfonic acid group is an alkylsulfosuccinic acid-based anionic surfactant, 4).
  • a primer coating film is formed on one or both surfaces of a metal plate, and a coating film is formed from the coating composition according to any one of items 1 to 5 on at least one surface of the primer coating film.
  • a method of forming a coating film It is related with the coating metal plate obtained by the coating-film formation method of 7.6.
  • the present invention is a coating composition having good storage stability, and the coating film obtained by applying the coating composition can maintain stain resistance over a long period of time when exposed outdoors, and further, the coating film hardness Excellent workability.
  • Coating composition of the present invention comprises a hydroxyl group-containing resin (a), a crosslinking agent (b), a sulfonic acid group or a sulfonic acid group base-containing anionic surfactant (c), and a cationic surfactant. It is a coating composition containing an agent (d) and, if necessary, urea resin particles (e). Details will be described below.
  • the hydroxyl group-containing resin (a) is a resin having two or more hydroxyl groups in one molecule, and may have a carboxyl group as necessary.
  • Specific examples of the hydroxyl group-containing resin (a) include acrylic resins, polyester resins, epoxy resins, polyurethane resins, and the like. From the viewpoint of improving stain resistance, coating film hardness, and processability, hydroxyl group-containing acrylic resins, hydroxyl groups -Containing polyester resins and the like are preferable, and hydroxyl group-containing polyester resins are particularly preferable.
  • the above-mentioned hydroxyl group-containing acrylic resin is a copolymer resin obtained by copolymerizing a hydroxyl group-containing acrylic monomer and other monomers.
  • hydroxyl group-containing monomer examples include glycols having 2 to 20 carbon atoms such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyicosyl (meth) acrylate, and (meth) acrylic.
  • examples include monoesterified products with acids.
  • monomers other than the hydroxyl group-containing monomer include, for example, (meth) acrylic acid alkyl ester having 1 to 22 carbon atoms, (meth) acrylic acid alkoxy alkyl ester having 2 to 18 carbon atoms, epoxy group-containing monomer, carboxyl A group-containing monomer, a monomer having an isocyanate group and a polymerizable unsaturated group in one molecule, styrene, ⁇ -methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, vinyl chloride and the like can be used.
  • alkyl ester having 1 to 22 carbon atoms of (meth) acrylic acid examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, Examples include octyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • Examples of the alkoxyalkyl ester having 2 to 18 carbon atoms of (meth) acrylic acid include methoxybutyl (meth) acrylate and methoxyethyl (meth) acrylate.
  • Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate.
  • Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, mesaconic acid, and anhydrides and half-esterified products thereof. Other monomers other than the hydroxyl group-containing monomer can be used alone or in combination of two or more.
  • the number average molecular weight of the above hydroxyl group-containing acrylic resin is preferably about 1,000 to 50,000, more preferably about 2,000 to 20,000.
  • the hydroxyl value of the resin is preferably about 20 to 200 mg KOH / g, more preferably about 50 to 150 mg KOH / g.
  • the hydroxyl group-containing polyester resin can be usually produced by an esterification reaction or a transesterification reaction with the polybasic acid component (a1) and the alcohol component (a2).
  • the said polybasic acid component (a1) can use the compound normally used as a polybasic acid component at the time of manufacture of a polyester resin.
  • a polybasic acid component (a1) an alicyclic polybasic acid, an aliphatic polybasic acid, an aromatic polybasic acid etc. can be used, for example.
  • an alicyclic polybasic acid is a compound having one or more alicyclic structures (mainly 4- to 6-membered rings) and two or more carboxyl groups in one molecule, an acid anhydride of the compound, and the compound The esterified product.
  • Examples of the alicyclic polybasic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl Alicyclic polycarboxylic acids such as -1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid; Examples thereof include anhydrides of these alicyclic polyvalent carboxylic acids; lower alkyl esterified products of these alicyclic polyvalent carboxylic acids.
  • An alicyclic polybasic acid can be used individually or in combination of 2 or more types.
  • Examples of the alicyclic polybasic acid include 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1 , 2-dicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic anhydride can be preferably used.
  • 1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid anhydride can be particularly preferably used from the viewpoint of hydrolysis resistance.
  • the aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an esterified product of the aliphatic compound, for example, succinic acid, Aliphatic polycarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, octadecanedioic acid, citric acid; Acid anhydrides; and lower alkyl esterified products of these aliphatic polyvalent carboxylic acids.
  • An aliphatic polybasic acid can be used individually or in combination of 2 or more types.
  • a dicarboxylic acid having an alkyl chain having 4 to 18 carbon atoms examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, and octadecanedioic acid.
  • adipic acid can be preferably used.
  • the aromatic polybasic acid is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound and an esterified product of the aromatic compound, for example, phthalic acid, Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid; anhydrides of these aromatic polycarboxylic acids; And lower alkyl esterified products of monovalent carboxylic acids. Aromatic polybasic acids can be used alone or in combination of two or more.
  • a polyhydric alcohol having two or more hydroxyl groups in one molecule can be suitably used.
  • a polyhydric alcohol an alicyclic diol, an aliphatic diol, an aromatic diol etc. can be mentioned, for example.
  • the alicyclic diol is generally a compound having one or more alicyclic structures (mainly 4- to 6-membered rings) and two hydroxyl groups in one molecule.
  • Examples of the alicyclic diol include dihydric alcohols such as 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F; these dihydric alcohols include ⁇ -caprolactone and the like.
  • Examples include polylactone diol to which a lactone compound is added, and these can be used alone or in combination of two or more.
  • the aliphatic diol is generally an aliphatic compound having two hydroxyl groups in one molecule.
  • Examples of the aliphatic diol include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3 -Butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3 -Pent
  • the aromatic diol is generally an aromatic compound having two hydroxyl groups in one molecule.
  • Examples of the aromatic diol include ester diol compounds such as bis (hydroxyethyl) terephthalate; alkylene oxide adducts of bisphenol A and the like, and these can be used alone or in combination of two or more.
  • polyhydric alcohol other than the alicyclic diol, aliphatic diol and aromatic diol examples include polyether diol compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol; glycerin, trimethylol ethane, trimethylol propane, Trivalent or higher alcohols such as glycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol; these trivalent or higher alcohols And a polylactone polyol compound in which a lactone compound such as ⁇ -caprolactone is added.
  • polyether diol compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol
  • glycerin trimethylol ethane, trimethylol propane
  • Trivalent or higher alcohols such as gly
  • trivalent or higher alcohols can be suitably used from the viewpoint of increasing the molecular weight and improving the reactivity of the modification reaction with the fatty acid when using the fatty acid.
  • the trihydric or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol and the like.
  • trimethylolpropane is particularly preferable.
  • Examples of the alcohol component (a2) other than the polyhydric alcohol include monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, and 2-phenoxyethanol; propylene oxide, butylene oxide, and synthetic highly branched saturated fatty acids.
  • An alcohol compound obtained by reacting a monoepoxy compound with an acid such as glycidyl ester (trade name “Cardura E10” manufactured by HEXION Specialty Chemicals) and the like can be used as necessary.
  • the production of the hydroxyl group-containing polyester resin is not particularly limited, and can be performed according to a usual method.
  • it is produced by reacting an acid component having the polybasic acid component as an essential component with an alcohol component in a nitrogen stream at 150 to 250 ° C. for 5 to 10 hours to perform an esterification reaction or a transesterification reaction. Can do.
  • the acid component and alcohol component may be added at once, or may be added in several portions. Moreover, after synthesize
  • a catalyst may be used to promote the reaction.
  • known catalysts such as dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, and tetraisopropyl titanate can be used.
  • the hydroxyl group-containing polyester resin can be modified with a fatty acid, an oil or fat, a monoepoxy compound, a polyisocyanate compound or the like during the preparation of the resin, or after the esterification reaction or the transesterification reaction.
  • a hydroxyl group-containing polyester resin modified with a fatty acid or oil is referred to as an alkyd resin.
  • fatty acid examples include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil
  • fatty acids such as fatty acids and safflower oil fatty acids; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and the like.
  • Examples of the fat include coconut oil, cottonseed oil, hemp seed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, safflower oil and the like.
  • polyisocyanate compound used for the modification examples include aliphatic diisocyanate compounds such as lysine diisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane.
  • -Aliphatic diisocyanate compounds such as -2,6-diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; aromatics such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate Diisocyanate compounds; organics such as polyisocyanates such as lysine triisocyanate and more Reisocyanate itself, or an adduct of each of these organic polyisocyanates and polyhydric alcohol, low molecular weight polyester resin or water, or a cyclized polymer of each of the above organic diisocyanates (for example, isocyanurate), biuret type Additives can be mentioned. These can be used alone or in combination of two or more.
  • the number average molecular weight of the hydroxyl group-containing polyester resin is preferably 2,000 to 30,000, particularly within the range of 3,000 to 25,000, from the viewpoints of coating film hardness, processability, and finish of the resulting coating film. It is preferred to have a number average molecular weight.
  • the number average molecular weight and the weight average molecular weight are values obtained by converting the number average molecular weight and the weight average molecular weight measured using a gel permeation chromatograph (GPC) based on the molecular weight of standard polystyrene. is there.
  • GPC gel permeation chromatograph
  • the hydroxyl value of the hydroxyl group-containing polyester resin is preferably from 5 to 250 mgKOH / g, particularly preferably from 10 to 200 mgKOH / g, from the viewpoint of curability of the resulting coating film.
  • the acid value of the hydroxyl group-containing polyester resin is preferably in the range of 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, from the viewpoint of processability and water resistance.
  • Crosslinking agent (b) The crosslinking agent (b) in the coating composition of the present invention can be used without particular limitation as long as it can react with the hydroxyl group of the hydroxyl group-containing resin (a) by heating and can be cured.
  • Examples include benzoguanamine resin, urea resin, and blocked polyisocyanate.
  • the melamine resin examples include a monohydric alcohol having 1 to 8 carbon atoms, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, in which a part or all of the methylol group of methylolated melamine is used. And partially etherified or fully etherified melamine resins etherified with i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
  • Examples of commercially available melamine resins include Cymel 202, Cymel 232, Cymel 235, Cymel 238, Cymel 254, Cymel 266, Cymel 267, Cymel 272, Cymel 285, Cymel 301, Cymel 303, Cymel 325, Cymel 327, and Cymel 350. , Cymel 370, Cymel 701, Cymel 703, Cymel 1141 (manufactured by Nippon Cytec Industries, Inc.), Uban 20SE60 (manufactured by Mitsui Cytec Co., Ltd.), and the like.
  • benzoguanamine resin examples include a methylolated benzoguanamine resin obtained by a reaction between benzoguanamine and an aldehyde.
  • aldehyde examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
  • those obtained by etherifying this methylolated benzoguanamine resin with one or more alcohols are also included in the benzoguanamine resin.
  • Examples of the alcohol used for etherification include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, and 2-ethylhexanol. .
  • monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, and 2-ethylhexanol.
  • a benzoguanamine resin obtained by etherifying at least a part of the methylol group of the methylolated benzoguanamine resin with a monohydric alcohol having 1 to 4 carbon atoms is preferable.
  • benzoguanamine resin examples include, for example, My Coat 102, My Coat 105, My Coat 106 [all of which are manufactured by Mitsui Cytec Co., Ltd.], Nicarak SB-201, Nicarac SB-203, Nicarac SB-301, Nicarac SB -303, Nicalac SB-401 [above, both are manufactured by Sanwa Chemical Co., Ltd.] and other methyl etherified benzoguanamine resins; Cymel 1123 [above, manufactured by Mitsui Cytec Co., Ltd.], etc.
  • Mixed etherified benzoguanamine resins such as methyl ether and ethyl ether Methyl ether and butyl ether such as My Coat 136 [above, manufactured by Mitsui Cytec Co., Ltd.], Nikalac SB-255, Nikalac SB-355, Nikalac BX-37, Nikalac BX-4000 [above, both manufactured by Sanwa Chemical Co., Ltd.]
  • the urea resin is obtained by a condensation reaction between urea and formaldehyde, and can be dissolved or dispersed in a solvent or water.
  • the polyisocyanate compound is a compound having two or more isocyanate groups in one molecule.
  • aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, Aliphatic diisocyanates such as dimer acid diisocyanate and lysine diisocyanate; alicyclic diisocyanates such as methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexane diisocyanate and cyclopentane diisocyanate; a biuret type adduct of the polyisocyanate, isocyanuric Ring type addition ; These polyisocyanates and low molecular weight or high molecular weight
  • the free isocyanate groups of these polyisocyanate compounds are converted into phenolic compounds, oxime compounds, active methylene compounds, lactam compounds, alcohol compounds, mercaptan compounds, acid amide compounds, imide compounds, amine compounds, imidazole compounds, urea systems.
  • a blocked polyisocyanate blocked with a blocking agent such as a compound, a carbamic acid compound, and an imine compound can also be used.
  • the mixing ratio of the hydroxyl group-containing resin (a) and the crosslinking agent (b) is 60 to 95 parts by weight, preferably 70 to 90 parts by weight, based on the total solid content of both.
  • the mass part and the crosslinking agent (b) are 5 to 40 parts by mass, preferably 10 to 30 parts by mass, from the viewpoint of adhesion to the base material and curability.
  • the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b) is usually 20 to 95% by mass, more preferably 35 to 85%, based on the total solid content of the coating composition of the present invention. % By mass.
  • Anionic surfactant (c) containing a sulfonic acid group or a sulfonic acid group contains an anionic surfactant (c) containing a sulfonic acid group or a sulfonic acid group.
  • the presence of an anionic surfactant (c) containing a sulfonic acid group or a sulfonic acid group in the coating film of the coating composition of the present invention enhances the detergency of contaminants adhered to the coating film surface. Can do.
  • anionic surfactant (c) containing a sulfonic acid group or a sulfonic acid group examples include monoalkyl sulfosuccinic acid ester salts, dialkyl sulfosuccinic acid ester salts, sulfosuccinic acid alkyl disalts, and polyoxyethylene alkyl sulfosuccinic acid disalts.
  • alkylbenzene sulfonic acid type anionic surfactants such as sodium dodecylbenzene sulfonate
  • alkyl diphenyl ether disulfonic acid type anionic surfactants such as sodium dodecyl diphenyl ether disulfonate
  • poly Anionic surfactants based on ammonium sulfate ester having a polyoxyalkylene group such as ammonium oxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene polycyclic phenyl ether ammonium sulfate; mono- or didodecyl diphenyl Sodium oxide disulfonate, sodium diisopropylnaphthalenesulfonate, sodium naphthalenesulfonate formalin condensate, Examples thereof include alkyl sulfoacetates and
  • anionic surfactants (c) containing these sulfonic acid groups or sulfonate groups may be used alone or in combination of two or more.
  • anionic surfactants (c) containing the sulfonic acid group or sulfonate group sulfosuccinic acid-based anionic surfactants, particularly dialkylsulfosuccinic acids having the structural formula represented by the following general formula (1) Sodium salts are particularly preferred for improving stain resistance.
  • R 1 and R 2 are the same or different and each represents an alkyl group having 1 to 15 carbon atoms
  • sulfosuccinic acid-based anionic surfactants include “Perex OT-P”, “Perex TR”, “Perex CS” and “Perex TA” manufactured by Kao Corporation; “Call 290-A”, “New Call 290-M”, “New Call 291-M”, “New Call 291-PG”, “New Call 291-GL”, “New Call 292-PG”, “New Call 293 "Neocoal SW-C”, “Neocoal YSK”, and “Neocoal P” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. may be mentioned.
  • the compounding quantity of the anionic surfactant (c) containing a sulfonic acid group or a sulfonate group is sulfone with respect to 100 mass parts of total solid content of a hydroxyl-containing resin (a) and a crosslinking agent (b).
  • An anionic surfactant (c) containing an acid group or a sulfonate group is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, to provide a coating excellent in stain resistance, coating film hardness, and processability. This is preferable because a film can be obtained.
  • Cationic surfactant (d) By containing the cationic surfactant (d) in the coating composition of the present invention, the effect of retaining the anionic surfactant (c) in the obtained coating film can be obtained, and the anion can be obtained by rainwater or the like. The surfactant (c) can be prevented from flowing out of the coating film, and the durability of the stain resistance can be ensured.
  • a cationic surfactant (d) there is no restriction
  • alkylamine cationic surfactants such as coconut amine acetate and stearylamine acetate; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, And quaternary ammonium salt cationic surfactants such as alkylbenzyldimethylammonium chloride.
  • cationic surfactant (d) examples include acetamine 24, acetamine 86 (above, alkylamine cationic surfactant manufactured by Kao Corporation), DISPER BYK-108, DISPER BYK-109, DISPER BYK.
  • DISPER BYK-161 (above, manufactured by Big Chemie Japan, alkylamine-based cationic surfactant), coatamine 24P, coatamine 86P conch, coatamine 60W, coatamine 86W, coatamine D86P, sanizole C, sanisol B-50 ( As described above, quaternary ammonium salt cationic surfactant manufactured by Kao Corporation), Cathogen TML, Cathogen TMP, Cathogen TMS, Cathogen ES-O, Cathogen ES-L, Cathogen ES-P, Cathogen Emissions DDM-PG, Kachiogen S, Kachiogen BC-50, Kachiogen D2, Kachiogen TBB (manufactured by Dai-ichi Kogyo Seiyaku Co., quaternary ammonium salt type cationic surfactant), and the like.
  • Cathogen TML Cathogen TMP
  • Cathogen TMS Cathogen TMS
  • Cathogen ES-O Cathogen
  • Such a cationic surfactant (d) is blended in an amount of 0.1 to 20 parts by weight, preferably 100 parts by weight of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b).
  • the amount of 2 to 16 parts by mass, more preferably 3 to 10 parts by mass is preferable because a coating film excellent in stain resistance, coating film hardness, and processability can be obtained.
  • the paint composition of the present invention can reduce the gloss of the coating film by blending the urea resin particles (e).
  • the 60-degree specular gloss is 1 to 65, preferably the 60-degree specular gloss.
  • a matte coating film of 5 to 55 can be obtained.
  • the urea resin particles (e) are in the form of a powder obtained by pulverizing a resin obtained by a condensation reaction between urea and an aldehyde component, and those having an average particle diameter of 1 to 10 ⁇ m, preferably 2 to 8 ⁇ m are suitable. .
  • the average particle diameter is a median diameter (d50) value of a volume-based particle size distribution measured by a laser diffraction scattering method using a Microtrac particle size distribution measuring device (trade name “MT3300”, manufactured by Nikkiso Co., Ltd.).
  • aldehyde component formaldehyde, acetaldehyde, crotonaldehyde, benzaldehyde or the like can be used.
  • formaldehyde when formaldehyde is used, the condensation reaction is easy to proceed, which is convenient.
  • Examples of commercially available products of urea resin particles include Pergo Pack M3, Pergo Pack M4, Pergo Pack M5 (trade name, manufactured by Lonza Japan), SOOFINE JJ POWDER (trade name, manufactured by Hangzhou Seika Kogyo Co., Ltd.), and the like.
  • the urea resin particles (e) to be blended in the coating composition of the present invention as necessary are blended according to the degree of the desired matting coating film, when the matting coating film is formed,
  • the amount of urea resin particles (e) is usually 1 to 50 parts by weight, preferably 2 to 30 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the total solid content of a) and the crosslinking agent (b). It is desirable from the viewpoint of obtaining coating stability and a matte coating film.
  • the coating composition of the present invention includes, as necessary, pigments such as a lubricity imparting agent, coloring pigments and extender pigments, curing catalysts, pigment dispersants, ultraviolet absorbers, ultraviolet stabilizers, antifoaming agents, surface Adjustment agents, paint additives such as surfactants different from the anionic surfactant (c) and the cationic surfactant (d), other matting agents such as silica fine powder, organic solvents, etc.
  • pigments such as a lubricity imparting agent, coloring pigments and extender pigments, curing catalysts, pigment dispersants, ultraviolet absorbers, ultraviolet stabilizers, antifoaming agents, surface Adjustment agents, paint additives such as surfactants different from the anionic surfactant (c) and the cationic surfactant (d), other matting agents such as silica fine powder, organic solvents, etc.
  • pigments such as a lubricity imparting agent, coloring pigments and extender pigments, curing catalysts, pigment dispersants, ultraviolet
  • lubricity-imparting agent conventionally known lubricants in the paint field can be used as long as they can impart slipperiness to the coating surface without deteriorating the appearance of the coating surface.
  • examples include polyolefin waxes such as polyethylene wax; polyether-modified silicone oil, higher fatty acid ester-modified silicone oil, modified silicone oil such as higher alkoxy-modified silicone oil; paraffin wax such as microcrystalline wax; montan wax, lanolin wax, carna
  • fatty acid ester waxes such as uba wax, beeswax and whale wax, and fluorine waxes such as ethylene tetrafluoride.
  • the pigment examples include white pigments such as titanium white and zinc white; blue pigments such as cyanine blue and indanthrene blue; green pigments such as cyanine green and patina; organic red pigments such as azo and quinacridone.
  • Red pigments such as Bengala, Bengala
  • organic yellow pigments such as benzimidazolone, isoindolinone, isoindoline, and quinophthalone
  • yellow pigments such as titanium yellow, yellow lead, and yellow iron oxide
  • carbon black, graphite Examples thereof include coloring pigments such as black pigments such as pine smoke; extender pigments such as clay, talc, barita and calcium carbonate; rust preventive pigments such as aluminum tripolyphosphate, zinc molybdate and vanadium pentoxide;
  • the pigment is usually 10 to 300 parts by weight, preferably 20 to 150 parts by weight (total amount of coating composition solids), based on 100 parts by weight of the total solids of the hydroxyl group-containing resin (a) and the
  • the curing catalyst is blended as necessary to promote the reaction between the hydroxyl group-containing resin (a) and the crosslinking agent (b), and when the crosslinking agent (b) is an amino resin.
  • a sulfonic acid compound or an amine neutralized product of a sulfonic acid compound is preferably used.
  • the sulfonic acid compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like.
  • the amine in the amine neutralized product of the sulfonic acid compound may be any of primary amine, secondary amine, and tertiary amine. Of these, an amine neutralized product of p-toluenesulfonic acid and / or an amine neutralized product of dodecylbenzenesulfonic acid is preferable from the viewpoints of coating stability, reaction promoting effect, and physical properties of the obtained coating film.
  • examples of the curing catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanote), Mention may be made of organometallic compounds such as dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, monobutyltin trioctate, lead 2-ethylhexinate and zinc octylate.
  • the curing catalyst is 0.1 to 5.0 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). Is suitable.
  • the coating composition of the present invention comprises a hydroxyl group-containing resin (a), a crosslinking agent (b), an anionic surfactant (c) containing a sulfonic acid group or a sulfonate group, a cationic surfactant (d), necessary
  • a hydroxyl group-containing resin a
  • a crosslinking agent b
  • an anionic surfactant c
  • a sulfonic acid group or a sulfonate group a cationic surfactant (d)
  • Coating method of the present invention For coating the coating composition of the present invention, Ford Cup No. It is preferable to adjust the solid content concentration within the range of 20 to 60% by mass so that a viscosity in the range of 10 to 100 seconds can be obtained at 4 (20 ° C.).
  • the coating film forming method using the coating composition of the present invention forms a primer coating film on one or both surfaces of a metal plate, and forms a top coating film by the coating composition on at least one surface of the primer coating film. It is characterized by doing.
  • the metal plate to be coated is a cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, alloy galvanized steel plate (galvanized steel plate such as iron-zinc, aluminum-zinc, nickel-zinc). , Aluminum plate, stainless steel plate, copper plate, copper plated steel plate, tin plated steel plate and the like.
  • the metal surface which is the material to be coated, may be painted as long as it is not contaminated with oil or other pollutants, but it is well known to improve adhesion and corrosion resistance with the coating film. It is desirable to apply a metal surface treatment.
  • These known surface treatment methods include phosphate surface treatment, chromate surface treatment, zirconium surface treatment and the like.
  • a primer for forming a primer coating film on a metal plate As a primer for forming a primer coating film on a metal plate, a known primer used in the colored color steel sheet coating field, the industrial machine coating field, the metal part coating field, or the like can be applied. From the viewpoint of environmental protection, it is preferable to use a chromium-free primer coating that does not contain a chromium-based rust preventive component.
  • the chrome-free primer coating is appropriately selected depending on the type of material to be coated and the type of metal surface treatment. Epoxy-based and polyester-based primer coatings and their modified primer coatings are particularly suitable, and workability is particularly required. In this case, a polyester primer paint is suitable.
  • the primer coating is applied by a known coating method such as roll coating or spray coating so that the thickness of the primer coating film is 1 to 30 ⁇ m, preferably 2 to 20 ⁇ m. Usually, it is at an ambient temperature of 80 to 300 ° C. for 5 seconds. When coil coating is applied for about ⁇ 1 hour, it is preferably cured by heating for 15 seconds to 120 seconds under the condition that the maximum material reaching temperature is 140 to 250 ° C.
  • the primer coating film may be a single layer or two layers in which a second primer coating film (intermediate coating film) is formed on the first primer coating film.
  • a second primer coating film intermediate coating film
  • the first primer film has an anticorrosion function
  • the second primer film intermediate film
  • the primer coating can also have different functions.
  • the present coating composition in the coating film forming method of the present invention is applied on at least one surface of the primer coating film.
  • the coating method include curtain coating, roll coater coating, dip coating and spray coating.
  • the coating thickness after drying is 5 to 50 ⁇ m, preferably 8 to 25 ⁇ m. Is done.
  • the coating method is not limited, but curtain coating and roll coater coating are recommended because of the economics of coil coating.
  • roll coater coating the bottom feed method (so-called reverse coating or natural coating) using a normal two-roll system is practically performed, but the uniformity of the coating surface is best. Therefore, a top feed or bottom feed method using three rolls can be performed.
  • the method for forming a coating film according to the present invention may include a step of curing the coating film of the coating composition of the present invention obtained in the above step.
  • the condition for curing the coating film with the coating composition of the present invention is usually about 15 seconds to 30 minutes at a material maximum temperature of 120 to 260 ° C. In the field of pre-coating, which is applied by coil coating or the like, it is usually performed at a material reaching maximum temperature of 160 to 260 ° C. for a baking time of 15 to 90 seconds.
  • the coating film formed from the composition of the present invention contains an anionic surfactant (c) containing a sulfonic acid group or a sulfonate group and a cationic surfactant (d) in the coating film. This improves hydrophilicity and improves the detergency of the contaminant adhered to the coating surface, and an anionic surfactant (c) containing a sulfonic acid group or a sulfonate group by the cationic surfactant (d). ) Is retained in the coating film, and the anionic surfactant (c) containing a sulfonic acid group or a sulfonate group is prevented from flowing out of the coating film by rainwater or the like, and is resistant to contamination. It was possible to secure sustainability. Furthermore, the matte coating film by the coating composition in which the urea resin particles (e) are added to the composition of the present invention makes it difficult for the contaminants to adhere, and the matte coating film can also improve the stain resistance. It was made.
  • Production and production example 1 of hydroxyl group-containing polyester resin (a) Production of polyester resin solution (a1 component) A reactor equipped with a thermometer, a stirrer, a heating device and a rectifying tower was charged with 1079 parts of isophthalic acid, 407 parts of adipic acid, 466 parts of neopentyl glycol and 802 parts of trimethylolpropane, and the temperature was raised to 160 ° C. The temperature was gradually raised from 160 ° C. to 230 ° C. over 3 hours.
  • the rectifying column was replaced with a water separator, and 124 parts of xylene was added to the contents, and xylene was also added to the water separator to azeotrope water and xylene.
  • the condensed water was removed, the reaction was continued until the acid value reached 10 mgKOH / g, the mixture was cooled, and 855 parts of cyclohexanone was added to the reaction product to obtain a polyester resin solution having a solid content of 55%.
  • the obtained resin had a hydroxyl value of 184 mgKOH / g and a number average molecular weight of 3,400.
  • Production Example 2 Production of acrylic resin solution (a2 component) Into a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, 480 parts of butyl acetate was charged and heated to 130 ° C. while blowing nitrogen gas, and then the styrene was removed from the dropping device while maintaining the temperature. A mixed solution of 200 parts, methyl methacrylate 290 parts, cyclohexyl methacrylate 250 parts, 2-hydroxyethyl methacrylate 260 parts and 2,2′-azobis (2-methylbutyronitrile 50 parts) was added dropwise over 3 hours.
  • the reaction product was aged at 130 ° C. for 1 hour, and the solid content was adjusted with cyclohexanone to obtain an acrylic resin solution having a resin solid content of 55%.
  • the obtained resin had a hydroxyl value of 107 mgKOH / g and a number average molecular weight of 8,000.
  • the coating composition No. having a viscosity of 80 seconds (Ford Cup # 4, 25 ° C.) was diluted. 1 was obtained.
  • Comparative Example 1 Paint composition No. 22 Polyester resin solution 80 parts (solid content) obtained in Production Example 1, Cymel 303 (Note 2) 20 parts (solid content), and Taipei CR-95 (Note 13) 120 parts, dodecylbenzenesulfonic acid 0. To 5 parts, an organic solvent (a mixed solvent of cyclohexanone / swazol 1500, 40/60) was added for dilution, and the coating composition No. with a viscosity of 80 seconds (Ford Cup # 4, 25 ° C.) was used. 22 was obtained.
  • an organic solvent a mixed solvent of cyclohexanone / swazol 1500, 40/60
  • Comparative Examples 2 to 8 Coating composition No. 23-No. 29 production A coating composition No. 1 was prepared in the same manner as in Comparative Example 1 except that the contents shown in Table 3 were used. 23-No. 29 was obtained.
  • test plate On a zinc-aluminum alloy-plated steel plate (GL material, plate thickness 0.35 mm) on which a primer coating film having a dry film thickness of 3 ⁇ m was formed, using the roll coater, in the above examples and comparative examples.
  • the obtained coating composition No. 1-No. No. 29 was coated to a dry film thickness of 18 ⁇ m and baked for 40 seconds under the condition that the maximum material arrival temperature was 220 ° C. to obtain a test plate.
  • Tables 1 to 3 below show the results of testing using each test plate according to the test conditions described below.
  • R 3 represents an alkyl group having 1 to 15 carbon atoms
  • Catiogen ES-L Daiichi Kogyo Seiyaku Co., Ltd., trade name, quaternary ammonium salt cationic surfactant
  • Acetamine 86 Kao Corporation, trade name, alkylamine cationic surfactant Agent
  • Sanizol C Kao Corporation, trade name, quaternary ammonium salt-based cationic surfactant (Note 10)
  • DISPER BYK-161 Big Chemie Japan, alkylamine-based cationic surfactant (Note 11) SOOFINE JJ POWDER: manufactured by Hangzhou Seika Kogyo Co., Ltd., trade name, urea resin particles, average particle size 2.5 ⁇ m
  • Silicia 445 manufactured by Fuji Silysia Chemical Co., Ltd., trade name, silica fine powder, matting agent
  • test conditions of the tests in Tables 1 to 3 are as follows.
  • Pencil hardness The paint film on the test plate was subjected to a pencil scratch test specified in JIS K 5600-5-4 (1999) and evaluated by tearing the paint film. Higher hardness is preferred.
  • Outdoor exposure test An outdoor exposure test specimen (100 ⁇ 300 mm) is attached to an installation table that models the eaves at an angle of 4 degrees from the vertical so that the coating faces the north side. An exposure test was conducted on the rooftop of Kansai Paint Co., Ltd. in Ota-ku, Tokyo. The color difference ( ⁇ E) from the initial coating plate was changed to JIS Z8370 for “2 months after the start of exposure” and “12 months after the start of exposure”. Based on this, measurement was performed using a multi-light source spectrocolorimeter MSC-5N manufactured by Suga Test Instruments Co., Ltd., and evaluation was performed according to the following criteria. S is ⁇ E is less than 1 A is ⁇ E is 1 or more and less than 2 B is ⁇ E is 2 or more and less than 5, For C, ⁇ E is 5 or more.
  • 60 degree specular gloss The 60-degree specular reflectance was measured according to the 60-degree specular gloss specified in JIS Z 8741 (1997).
  • B Storage stability Outdoor exposure test (2 months after the start of exposure), outdoor exposure test (12 months after the start of exposure) and processability are all S, A or B, and at least one of these 4 items is B Yes, pencil hardness is 3H or more C Storage stability, outdoor exposure test (2 months after the start of exposure), outdoor exposure test (12 months after the start of exposure), and workability are all S, A, B or C Yes, and at least one of these four items is C, or the pencil hardness is 2H or less

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Abstract

L'invention concerne une composition de revêtement qui présente une bonne stabilité en stockage, qui permet de maintenir une résistance aux taches lors d'une exposition en extérieur et qui permet de former un film de revêtement présentant une bonne dureté de revêtement et une bonne aptitude au façonnage. La présente invention concerne une composition de revêtement qui comprend une résine contenant des groupes hydroxyle (a), un agent de réticulation (b), un tensioactif anionique (c) qui comprend un groupe acide sulfonique ou une base d'acide sulfonique et un tensioactif cationique (d), et qui contient 1-20 parties en masse du tensioactif anionique (c) qui comprend un groupe acide sulfonique ou une base d'acide sulfonique et 0,1-20 parties en masse du tensioactif cationique (d) rapporté à 100 parties en masse de la teneur totale en solides de la résine contenant des groupes hydroxyle (a) et de l'agent de réticulation (b).
PCT/JP2014/051078 2013-06-03 2014-01-21 Composition de revêtement WO2014196217A1 (fr)

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JP2018076438A (ja) * 2016-11-10 2018-05-17 関西ペイント株式会社 アルミニウム部材用艶消しクリヤ塗料組成物

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JP7074984B2 (ja) * 2017-11-29 2022-05-25 関西ペイント株式会社 水性２液型１コート塗料組成物
CN108756889B (zh) * 2018-06-08 2019-08-30 北京中煤矿山工程有限公司 反井钻机扩孔施工破碎地层临时支护方法
JP2021143312A (ja) * 2020-03-13 2021-09-24 株式会社Lixil 親水処理塗料組成物
CN111575414A (zh) * 2020-06-16 2020-08-25 遂昌润德皮饰有限公司 一种抗拉皮革表层水处理工艺

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JPH1069024A (ja) * 1996-08-28 1998-03-10 Fuji Photo Film Co Ltd 写真用塗布液組成物およびそれを用いたハロゲン化銀写真感光材料
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