WO2010018763A1 - Composition de revêtement à base d’eau - Google Patents

Composition de revêtement à base d’eau Download PDF

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Publication number
WO2010018763A1
WO2010018763A1 PCT/JP2009/063751 JP2009063751W WO2010018763A1 WO 2010018763 A1 WO2010018763 A1 WO 2010018763A1 JP 2009063751 W JP2009063751 W JP 2009063751W WO 2010018763 A1 WO2010018763 A1 WO 2010018763A1
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parts
mass
coating film
calcium
coating composition
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PCT/JP2009/063751
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English (en)
Japanese (ja)
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英樹 松田
伶美 葛西
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関西ペイント株式会社
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Priority to CN2009801314003A priority Critical patent/CN102119196B/zh
Priority to JP2010524707A priority patent/JP5618830B2/ja
Publication of WO2010018763A1 publication Critical patent/WO2010018763A1/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
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

Definitions

  • the present invention relates to an aqueous coating composition capable of forming a coating film excellent in chemical resistance, corrosion resistance of a flat portion of a metal plate, corrosion resistance and adhesion of a processed portion or end surface portion of the metal plate, and the aqueous coating composition. It is related with the coating metal plate which has the coating film formed from.
  • pre-coated metal sheets such as pre-coated steel sheets painted by coil coating, etc.
  • building materials such as roofs, walls, shutters, garages, various household appliances, switchboards, refrigerated showcases, steel furniture, kitchen appliances, etc.
  • switchboards refrigerated showcases
  • steel furniture kitchen appliances, etc.
  • housing related product Widely used as a housing related product.
  • the precoated metal sheets are usually cut, press-molded and joined. Therefore, these house-related products often have a metal exposed portion that is a cut surface and a crack generating portion due to press working.
  • the exposed metal parts and cracked parts are more likely to have a lower corrosion resistance than other parts, so it is common to improve the corrosion resistance by including a chromium-based anticorrosive pigment in the undercoat of the pre-coated metal sheet. Has been done.
  • chromium-based rust preventive pigments contain hexavalent chromium excellent in rust prevention properties or generate hexavalent chromium. This hexavalent chromium is a problem from the viewpoint of health and environmental protection.
  • non-chromium anticorrosive pigments such as zinc phosphate, aluminum tripolyphosphate, and zinc molybdate have been put on the market, and various primers have been proposed as a combination of non-chromium pigments. ing. Furthermore, development of water-based paints has been required for the reduction of volatile organic compounds (VOC) due to environmental problems.
  • VOC volatile organic compounds
  • Patent Document 1 a vehicle component of an epoxy resin and a phenol resin, a rust preventive pigment of a combination of calcium silicate and phosphorus vanadate, or a combination of calcium carbonate, calcium silicate, aluminum phosphate, and phosphorus vanadate.
  • a paint containing an antirust pigment is described.
  • Patent Document 2 describes a paint in which polyester is mixed with a second magnesium phosphate and a burned manganese oxide / vanadium oxide as a rust preventive pigment, and a paint in which calcium phosphate and vanadium oxide are blended.
  • Patent Documents 1 and 2 when the rust preventive pigments described in Patent Documents 1 and 2 are applied to water-based paints, they are inferior in corrosion resistance compared to paints using chrome pigments, and in particular, the corrosion resistance in the processed parts and end face parts of metal plates is insufficient. is there. In addition, chemical resistance such as alkali resistance and acid resistance and water resistance may be inferior.
  • Patent Document 3 discloses that a vehicle component composed of an organic resin containing a hydroxyl group or an epoxy group and a curing agent has an oil absorption of 30 to 200 ml / 100 g and a pore volume of 0.05 to 1.2 ml / g.
  • a coating composition containing silica fine particles and having a glass transition temperature in a range of 40 to 125 ° C. of a cured coating film formed from the coating is described.
  • the coating film obtained by applying the silica fine particles described in Patent Document 3 to an aqueous paint is inferior in corrosion resistance and chemical resistance compared to a paint using a chromium-based pigment. Corrosion resistance at the end face was insufficient.
  • Patent Document 4 was blended with one or more non-chromium rust preventive pigments selected from magnesium phosphate, zinc phosphate, magnesium hydrogen phosphate, aluminum dihydrogen triphosphate, and calcium silicate.
  • a chromium-free coated steel sheet with excellent corrosion resistance characterized in that an undercoat film and a topcoat film containing a partially hydrolyzed condensate of tetraalkoxysilane as a hydrophilicity imparting agent are sequentially laminated on the surface of the plating layer It is disclosed.
  • Patent Document 5 discloses internal gelled hard polymer particles (a) having an average particle diameter of 0.4 to 0.6 ⁇ m, water-dispersible silica (b), glycidoxyalkyltrialkoxysilane (c), Painted zinc-based plated steel sheet treated with an aqueous rust-proof coating composition containing an organic vanadium compound (d), a water-dispersible urethane resin (e), a zirconium compound (f), and diammonium hydrogen phosphate (g) Is disclosed.
  • the coating film obtained by applying a paint containing a rust preventive pigment described in Patent Document 4 or Patent Document 5 is compared with a coating film obtained by applying a paint containing a chromium pigment.
  • the corrosion resistance and chemical resistance were inferior, and in particular, the corrosion resistance at the end face of the metal plate was insufficient.
  • An object of the present invention is to provide a non-chromium-based aqueous coating composition capable of forming a coating film excellent in chemical resistance, corrosion resistance of a flat portion of a metal plate, corrosion resistance and adhesion of a processed portion or end surface portion of the metal plate.
  • the object is to provide a coated metal sheet having a coating film having excellent coating film performance.
  • the present inventors have found that a specific vanadium compound (c1), a silicon compound, a cationic resin (A) and a polyisocyanate curing agent (B).
  • a water-based paint composition to which a rust-preventive pigment mixture (C) containing a predetermined amount of (c2) and a phosphate-based calcium salt (c3) is added, only chemical resistance and corrosion resistance of the flat portion of the coated metal plate can be obtained.
  • the present inventors have found that a coating film excellent in corrosion resistance of a processed part and an end face part in a coated metal plate can be formed, and the present invention has been completed.
  • An aqueous coating composition containing a cationic resin (A), a polyisocyanate curing agent (B), and the following antirust pigment mixture (C).
  • Anticorrosive pigment mixture (C) consisting of at least one of vanadium pentoxide, calcium vanadate and ammonium metavanadate (c1), silicon compound (c2) and phosphate calcium salt (c3) And with respect to 100 parts by mass of the total solid content of the resin (A) and the curing agent (B),
  • the amount of the vanadium compound (c1) is 1 to 30 parts by mass
  • the amount of the silicic acid compound (c2) is 1 to 30 parts by mass
  • the amount of the phosphate calcium salt (c3) is 1 to 30 parts by mass
  • the amount of the rust preventive pigment mixture (C) is 3 to 90 parts by mass.
  • Item 2 The aqueous coating composition according to Item 1, wherein the cationic resin (A) is an amino group-containing epoxy resin. 3. Item 2. The aqueous coating composition according to Item 1, wherein the silicon compound (c2) is at least one selected from metal silicate salts, silica fine particles, and metal ion-exchanged silica fine particles. 4). Item 2. The aqueous coating composition according to Item 1, wherein the phosphate calcium salt (c3) is at least one of calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate and calcium tripolyphosphate. 5). Item 2.
  • the aqueous coating composition according to Item 1 comprising 0.1 to 10 parts by mass of a resol type phenolic resin based on the total solid content of the cationic resin (A) and the polyisocyanate curing agent (B). 6). Forming a coating film of the aqueous coating composition according to Item 1 on a metal plate, and forming a coating film of at least one or more types of top coating on the cured coating film Method. 7). 7. A coated metal plate having a coating film obtained by the coating film forming method according to item 6. 8). A coated article obtained by processing the coated metal sheet according to Item 7.
  • the aqueous paint composition containing the specific rust preventive pigment mixture of the present invention does not contain a chromium-based rust preventive pigment and is an aqueous paint, which is advantageous in terms of environmental hygiene.
  • the coating film obtained by coating the aqueous coating composition of the present invention is not only excellent in chemical resistance and corrosion resistance of the flat portion of the coated metal plate, but also has a conventional non-chromium rust preventive pigment. Demonstrates excellent effects in the corrosion resistance and adhesion of the processed parts and end face parts of the coated metal plate, which was difficult to achieve with the water-based paint contained.
  • a coated steel sheet coated with a cured coating film obtained by applying the aqueous coating composition of the present invention to a hot-dip galvanized steel sheet (GI steel sheet) that has not been subjected to chemical conversion treatment and then drying by heating is subjected to chemical conversion treatment.
  • the coated hot-dip galvanized steel sheet (GI steel sheet) can have corrosion resistance equal to or higher than that of a coated steel sheet coated with a cured coating film containing a chromate rust preventive pigment. For this reason, the chemical conversion treatment step (see FIG. 1) can be omitted, which is advantageous for process saving and resource saving of the coating line.
  • An example of a continuous coil coating line is shown.
  • An example of the coating-film structure of the coating film containing the water-based coating composition of this invention is shown.
  • the aqueous coating composition of the present invention relates to an aqueous coating composition comprising a specific amount of a cationic resin (A), a polyisocyanate curing agent (B), and a specific antirust pigment mixture (C). Details will be described below.
  • the metal plate to be coated is, for example, an electrogalvanized steel sheet, an electrogalvanized nickel plated steel sheet, a hot dip galvanized steel sheet, a zinc-aluminum hot dip plated steel sheet, a hot rolled steel sheet, a cold rolled steel sheet.
  • Examples include steel plates, stainless steel plates, copper-plated steel plates, aluminum plates, hot-dip zinc-zinc (Sn-10% Zn) -plated steel plates, hot-dip aluminum-plated steel plates, and Al-Mg alloys.
  • the cationic resin (A) is a resin having a cationizable group such as an amino group, an ammonium base, a sulfonium base, or a phosphonium base in the molecule.
  • the resin species include commonly used ones such as epoxy resins, acrylic resins, polybutadiene resins, alkyd resins, and polyester resins.
  • an amino group-containing epoxy resin obtained by addition reaction of an amino group-containing compound with an epoxy resin is not only excellent in chemical resistance, but also in the corrosion resistance of the flat part of the metal plate, and also improved in the corrosion resistance of the processed part and end face part. From the viewpoint of
  • amino group-containing epoxy resin for example, (1) Adducts of epoxy resins with primary mono- and polyamines, secondary mono- and polyamines or primary and secondary mixed polyamines (see, for example, US Pat. No. 3,984,299); (2) Adducts of epoxy resins with secondary mono- and polyamines having primary amino groups that are ketiminated (see, for example, US Pat. No. 4,017,438); (3) A reaction product obtained by etherification of an epoxy resin and a ketiminated hydroxy compound having a primary amino group (see, for example, JP-A-59-43013) Etc.
  • the epoxy resin used for the production of the amino group-containing epoxy resin is a compound having at least one, preferably two or more epoxy groups in one molecule.
  • the molecular weight of the epoxy resin is generally at least 300, preferably 400 to 4,000, more preferably “number average molecular weight” in the range of 800 to 2,500 and at least 160 g / eq, preferably 180 to 2,500 g / eq, More preferably, those having an epoxy equivalent weight within the range of 400 to 1,500 g / eq are suitable, and those obtained by reacting a polyphenol compound with an epihalohydrin are particularly preferred.
  • the “number average molecular weight” in the present specification is the same as that described in JIS K 0124-83, using the following four separation columns, using an eluent (tetrahydrofuran for GPC) at 40 ° C. and a flow rate of 1.0 ml. / Min was determined from a chromatogram obtained with an RI refractometer and a standard polystyrene calibration curve.
  • Examples of the polyphenol compound used for forming the epoxy resin include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], and bis (4 -Hydroxycyclohexyl) methane [hydrogenated bisphenol F], 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A], 4,4'-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) Ethane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxy-3-tert-butyl-phenyl) propane, bis (2-hydroxynaphthyl) methane, 1,1,2, 2-tetra (4-hydroxyphenyl) ethane, 4,4'-dihydride Carboxymethyl diphenyl sulfone, phenol novolak, and the like cresol novolak.
  • epoxy resin obtained by the reaction of the polyphenol compound and epichlorohydrin a resin represented by the following formula derived from bisphenol A is particularly preferable.
  • Examples of commercially available epoxy resins include jER828EL, jER1002, jER1004, jER1007 (Japan Epoxy Resin Co., Ltd., trade name), Araldite AER6099 (trade name, manufactured by Asahi Ciba Co., Ltd.), and Epomic R-309 (manufactured by Mitsui Chemicals, Product name).
  • the epoxy resin may be a modified epoxy resin reacted with a modifying component such as polyol, polyether polyol, polyester polyol, polyamidoamine, polybasic acid, polyisocyanate compound, or a lactone such as ⁇ -caprolactone.
  • a modified epoxy resin obtained by graft polymerization of an acrylic monomer or the like may be used.
  • the method for producing the modified epoxy resin by reacting the modified component with the epoxy resin is not particularly limited.
  • the reaction between the modified component and the epoxy resin is preferably carried out, for example, by reacting at 100 to 150 ° C. for 1 to 5 hours in a solvent capable of dissolving each of these components, if necessary, in the presence of a reaction catalyst. Can be done.
  • reaction catalyst examples include quaternary salt catalysts such as tetraethylammonium bromide, tetrabutylammonium bromide, triphenylbenzylphosphonium chloride, and amines such as triethylamine.
  • Examples of the primary mono- and polyamines, secondary mono- and polyamines, and primary and secondary mixed polyamines used in the production of the amino group-containing epoxy resin (1) include monomethylamine, dimethylamine, Mono- or di-alkylamines such as monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine; alkanolamines such as monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, monomethylaminoethanol; Examples include amine compounds such as alkylene polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
  • Examples of the secondary mono- and polyamine having a ketiminated primary amino group used in the production of the amino group-containing epoxy resin (2) include, for example, the production of the amine-added epoxy resin (1).
  • the primary and secondary mixed polyamines used in 1) for example, ketiminates of amine compounds produced by reacting ketone compounds with diethylenetriamine or the like can be mentioned.
  • Examples of the hydroxy compound having a ketiminated primary amino group used in the production of the amino group-containing epoxy resin of (3) above include, for example, those used in the production of the amine-added epoxy resin of (1) above.
  • primary mono- and polyamines secondary mono- and polyamines or primary and secondary mixed polyamines, compounds having primary amino groups and hydroxyl groups, such as monoethanolamine, mono (2-hydroxypropyl)
  • a hydroxyl group-containing ketimine product of an amine compound obtained by reacting a ketone compound with an amine or the like can be mentioned.
  • a modified epoxy resin obtained by reacting an aliphatic polybasic acid having 4 to 36 carbon atoms with an epoxy resin is used as an amine.
  • the aliphatic polybasic acid having 4 to 36 carbon atoms is preferably a saturated or unsaturated aliphatic polybasic acid having 6 to 36, such as hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrophthalic acid.
  • Acid methylhexahydrophthalic acid, methylhexahydroterephthalic acid, 1-tetrahydrophthalic acid, 2-tetrahydrophthalic acid, 3-tetrahydrophthalic acid, 4-tetrahydrophthalic acid, 1-tetrahydroisophthalic acid, 2-tetrahydroisophthalic acid, 3-tetrahydroisophthalic acid, 4-tetrahydroisophthalic acid, 1-tetrahydroterephthalic acid, 2-tetrahydroterephthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, hexachloroendomethylenetetra Alicyclic dicarboxylic acids such as drophthalic acid and their anhydrides; succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dodecanedicarbox
  • polyisocyanate compound examples include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,2′-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI [ Polymethylene polyphenyl isocyanate], bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate and the like; cyclization of these polyisocyanate compounds; A polymer or biuret body; or a combination thereof.
  • hexamethylene diisocyanate is preferable from the viewpoint of improving the corrosion resistance of the processed part and the end face part.
  • the addition reaction of the epoxy resin (modified epoxy resin) and the amino group-containing compound is usually performed in an appropriate solvent, preferably 80 to 170 ° C. (more preferably 90 to 150.degree. C.), preferably 1 to 6 hours (more preferably 1 to 5 hours).
  • the solvent include hydrocarbon solvents such as toluene, xylene, cyclohexane and n-hexane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone.
  • the use ratio of each reaction component in the above addition reaction is not strictly limited and can be changed as appropriate.
  • the epoxy resin is preferably 70 to 97% by mass, more preferably 70 to 95% by mass, still more preferably 80 to 95% by mass;
  • the amino group-containing compound is preferably 3 to 30% by mass, more preferably 5 to 30%. It is used within the range of mass%, more preferably 5 to 20 mass%.
  • the amount of the amino group-containing compound used is within the range where the amine value of the cationic resin as the final product of the present invention is 10 to 80 mgKOH / g, preferably 20 to 70 mgKOH / g. It is preferable from the viewpoint of improving the corrosion resistance of the coating film.
  • polyisocyanate curing agent (B) The aqueous coating composition of the present invention is a thermosetting coating obtained by blending a polyisocyanate curing agent (B) with a cationic resin (A).
  • polyisocyanate compound used in the polyisocyanate curing agent (B) known compounds can be used, such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,2′-diisocyanate, diphenylmethane.
  • aromatic polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI, and the like are used for the corrosion resistance of flat portions of metal plates. It is preferable from the viewpoint.
  • hexamethylene diisocyanate as the isocyanate species, it is more preferable for improving the curability and improving the corrosion resistance of the processed part and the end face part of the precoated steel sheet because it can impart flexibility to the coating film.
  • polyisocyanate curing agent (B) a blocked polyisocyanate compound obtained by addition reaction of the polyisocyanate compound and the isocyanate blocking agent in an approximately chemical theoretical amount can be suitably used.
  • the isocyanate blocking agent is added to the isocyanate group of the polyisocyanate compound and blocked.
  • the blocked polyisocyanate compound produced by addition is stable at room temperature, but when heated to the baking temperature of the coating (usually 100 to 200 ° C), the isocyanate blocking agent can dissociate and regenerate free isocyanate groups It is desirable that
  • isocyanate blocking agent examples include oxime compounds such as methyl ethyl ketoxime, methyl amyl ketoxime, and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol, and cresol; n-butanol, 2-ethylhexanol, and the like.
  • the component (A) is preferably 60, based on the total solid mass of the component (A) and the component (B).
  • the coating stability and curability should be in the range of -95% by mass, more preferably 70-90% by mass, and component (B) preferably in the range of 5-40% by mass, more preferably 10-30% by mass. From the aspect, it is preferable.
  • cationic resin (A) and the polyisocyanate curing agent (B) various additives such as surfactants, surface conditioners and resol type phenol resins, organic solvents, etc. are used for the production of the aqueous coating composition of the present invention.
  • the prepared resin is water-soluble or water-dispersed with an organic carboxylic acid such as acetic acid, phosphoric acid, formic acid, propionic acid or lactic acid; an inorganic acid such as hydrochloric acid or sulfuric acid, etc. Can be obtained.
  • the above-mentioned resol type phenol resin is a phenol resin in which a methylol group is introduced by a condensation reaction of phenols such as phenol and bisphenol A and an aldehyde such as formaldehyde in the presence of a reaction catalyst, and an introduced methylol group. Also included are those obtained by alkyl etherification of a part of these with an alcohol having 6 or less carbon atoms.
  • the resol type phenolic resin has a number average molecular weight (Note 1) of preferably 200 to 1,000, more preferably 300 to 900, and an average number of methylol groups per benzene nucleus is 0.00. It is suitable to be in the range of 3 to 2.5, preferably 0.3 to 2.0. By using the above-mentioned resol type phenolic resin, it is possible to form a coating film having excellent coating performance such as adhesion. (Note 1) The number average molecular weight is as described in the aforementioned “cationic resin (A)”.
  • the blending amount of the resol type phenolic resin is preferably 1 to 20% by mass, more preferably 2 to 7% by mass, based on the total solid content of the component (A) and the component (B). It is preferable from the viewpoint of coating film adhesion and paint stability.
  • Antirust pigment mixture (C) The aqueous coating composition of the present invention contains a specific amount of a specific rust-preventive pigment mixture (C), thereby providing a coated metal having excellent chemical resistance, corrosion resistance of flat portions, corrosion resistance and adhesion of processed portions and end portions. A board can be obtained.
  • the rust preventive pigment mixture (C) comprises a vanadium compound (c1), a silicon compound (c2), and a phosphate calcium salt (c3).
  • the rust preventive pigment mixture (C) may contain compounds other than the vanadium compound (c1), the silicon compound (c2), and the phosphate calcium salt (c3).
  • Vanadium compound (c1) is at least one vanadium compound selected from vanadium pentoxide, calcium vanadate, and ammonium metavanadate. Vanadium pentoxide, calcium vanadate and ammonium metavanadate are excellent in elution of pentavalent vanadium ions into water, and the pentavalent vanadium ions released from the vanadium compound (c1) react with the material metal, It works effectively to improve corrosion resistance by reacting with ions from other antirust pigment mixtures. Among these, vanadium pentoxide is particularly effective in improving corrosion resistance.
  • Silicon compound (c2) contains at least one compound selected from metal silicate salts, silica fine particles, and metal ion exchanged silica fine particles.
  • the silicate metal salt is a salt composed of silicon dioxide and a metal oxide, and may be any of orthosilicate, polysilicate, and the like.
  • silicates include zinc silicate, aluminum silicate, aluminum orthosilicate, aluminum hydrated aluminum silicate, aluminum calcium silicate, sodium aluminum silicate, beryllium aluminum silicate, sodium silicate, calcium orthosilicate, calcium metasilicate, sodium calcium silicate, and silicic acid.
  • a metal silicate orthosilicate calcium, calcium metasilicate, magnesium metasilicate, and aluminum silicate are preferable, and orthosilicate calcium and calcium metasilicate are particularly preferable.
  • silica fine particles can be used without particular limitation as long as they are silica fine particles, such as silica fine powder with an untreated surface, silica fine powder with a surface treated with an organic material, calcium ion-exchanged silica fine particles, organic solvent-dispersed colloidal silica, etc. Can be mentioned.
  • silica fine particles whose surface is not treated or treated with an organic substance fine silica powder having an average particle diameter of 0.5 to 15 ⁇ m is preferable, and 1 to 10 ⁇ m is more preferable.
  • silica fine powder those having an oil absorption of 30 to 350 ml / 100 g, preferably 30 to 150 ml / 100 g can be suitably used.
  • the organic solvent-dispersible colloidal silica is also referred to as an organosilica sol, in which silica fine particles having a particle size of about 5 to 120 nm are stably dispersed in an organic solvent such as alcohols, glycols, and ethers.
  • organic solvent such as alcohols, glycols, and ethers.
  • examples of commercially available products include the OSCAL series (manufactured by Catalyst Kasei Co., Ltd.) and organosols (manufactured by Nissan Chemical Co., Ltd.).
  • the metal ion exchanged silica fine particles are silica fine particles in which metal ions are introduced into a fine porous silica carrier by ion exchange. Specifically, it is a silica fine particle into which calcium or magnesium is introduced.
  • SHIELDEX registered trademark
  • SHIELDEXAC-3 SHIELDEXAC-3
  • SHIELDEXC-5 all of which are manufactured by WR Grace & Co.
  • Alkaline earth metal ions released from metal ion-exchanged silica are involved in electrochemical action and various salt forming actions, and effectively work to improve corrosion resistance. Moreover, the silica fixed in the coating film effectively works to suppress peeling of the coating film in a corrosive atmosphere.
  • the phosphate calcium salt (c3) is a phosphate containing calcium as a metal element.
  • the phosphate calcium salt (c3) is a phosphate containing calcium as a metal element.
  • calcium phosphate, calcium ammonium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate phosphate, tripoly A calcium phosphate etc. can be mentioned.
  • Phosphate ions and calcium ions released from the phosphate calcium salt (c3) effectively work to improve corrosion resistance.
  • the antirust pigment mixture (C) is the vanadium compound (c1) with respect to 100 parts by mass of the total solid content of the cationic resin (A) and the polyisocyanate curing agent (B).
  • silicon compound (c2) and phosphate calcium salt (c3) are within the following ranges.
  • Vanadium compound (c1) 1 to 30 parts by mass, preferably 1 to 20 parts by mass
  • Silicon compound (c2) 1 to 30 parts by mass, preferably 1 to 20 parts by mass
  • Phosphate-based calcium salt (c3) 1 to 30 parts by mass, preferably 1 to 20 parts by mass.
  • the mixing ratio (mass basis) of the vanadium compound (c1), the silicon compound (c2), and the phosphate calcium salt (c3) is preferably 3 to 20/3 to 20/5 to 20 More preferably, it is 15/5 to 15/10 to 20. It exists in the said range, since it can obtain the coating film excellent not only in chemical resistance and the corrosion resistance of the flat part of a metal plate but the corrosion resistance and adhesion of the processed part and end surface part of a metal plate.
  • the addition amount of the vanadium compound (c1), the silicon compound (c2), and the phosphate calcium salt (c3) is within the above range, so that not only chemical resistance, corrosion resistance of the flat portion of the metal plate, but also metal Since the coating film excellent in the corrosion resistance and adhesion of the processed part and end face part of the plate can be obtained, it is preferable.
  • the amount of the rust preventive pigment mixture (C) is 3 to 100 parts by mass based on 100 parts by mass of the total solid content of the cationic resin (A) and the polyisocyanate curing agent (B). 90 parts by mass, preferably 9 to 60 parts by mass.
  • the amount of the rust preventive pigment mixture (C) is within the above range, a coating film having excellent chemical resistance, corrosion resistance of the flat portion of the metal plate, corrosion resistance and adhesion of the processed portion and end surface portion of the metal plate is obtained. This is preferable.
  • the aqueous coating composition of the present invention synergistically combines the vanadium compound (c1), the silicon compound (c2) and the phosphate calcium salt (c3) in a predetermined amount as the antirust pigment mixture (C). Corrosion resistance can be improved.
  • the rust preventive pigment mixture (C) is not particularly limited, but is preferably a mixture containing vanadium pentoxide, calcium metasilicate and calcium phosphate, and the combination of vanadium pentoxide, calcium metasilicate and calcium phosphate is Particularly preferred from the viewpoint of corrosion resistance.
  • (C2) and a mixture of the phosphoric acid calcium salt (c3) are mixed with 10,000 parts by mass of a 5% by mass sodium chloride aqueous solution at 25 ° C.
  • the pH of the filtrate obtained by filtering the supernatant liquid which has been added to the above and stirred for 6 hours and allowed to stand at 25 ° C. for 48 hours is preferably 3 to 8, more preferably 4 to 6.
  • the solubility of the vanadium compound (c1), the silicate compound (c2), and the phosphate calcium salt (c3) in water and the solution of the antirust pigment and the metal plate It is preferable from the viewpoint of reactivity and corrosion resistance.
  • the amount of the vanadium compound (c1) in the range of 1 to 30 parts by mass with respect to 10,000 parts by mass of a 5% by mass sodium chloride aqueous solution at 25 ° C. (C2) is added in any amount within the range of 1 to 30 parts by mass, and any amount within the range of 1 to 30 parts by mass of the acid-based calcium salt (c3) is added to dissolve the dissolved solution.
  • the filtrate is, in the filtrate for measuring pH, the amount of the vanadium compound (c1) in the range of 1 to 30 parts by mass with respect to 10,000 parts by mass of a 5% by mass sodium chloride aqueous solution at 25 ° C. (C2) is added in any amount within the range of 1 to 30 parts by mass, and any amount within the range of 1 to 30 parts by mass of the acid-based calcium salt (c3) is added to dissolve the dissolved solution.
  • the antirust pigment mixture (C) and, if necessary, a pigment dispersing resin, a coloring pigment, an extender pigment, an organic tin compound, an ultraviolet absorber, and an ultraviolet stabilizer are mixed, and dispersion mixing such as ball mill, sand mill, pebble mill, etc. It is blended as a pigment dispersion paste obtained by dispersion treatment in the machine.
  • antirust agents other than a vanadium compound (c1), a silicon compound (c2), and a phosphoric acid type calcium salt (c3) it is the quantity which does not inhibit the addition effect of an antirust pigment mixture (C). Can be added.
  • the pigment dispersion resin known resins can be used, for example, a base resin having a hydroxyl group and a cationic group, a tertiary amine type epoxy resin, a quaternary ammonium salt type epoxy resin, a tertiary sulfonium salt type epoxy resin, or the like. Can be used.
  • the amount of the pigment dispersing resin used is preferably in the range of 1 to 150 parts by weight, particularly 10 to 100 parts by weight per 100 parts by weight of the pigment component.
  • coloring pigment examples include organic coloring pigments such as cyanine blue, cyanine green, organic red pigments such as azo and quinacridone; and inorganic coloring pigments such as titanium white, titanium yellow, bengara, carbon black, and various fired pigments. Among them, titanium white can be preferably used.
  • extender pigment examples include talc, clay, silica, mica, alumina, calcium carbonate, and barium sulfate.
  • the addition amount of the color pigment and extender pigment is not particularly limited. For example, for the total solid content of 100 parts by mass of the cationic resin (A) and the polyisocyanate curing agent (B), respectively. About 1 to 100 parts by mass.
  • organic tin compound dibutyltin dibenzoate, dioctyltin oxide, dibutyltin oxide and the like can be suitably used.
  • the organic solvent is blended as necessary for improving the paintability of the aqueous coating composition of the present invention, and can dissolve or disperse the cationic resin (A) and the polyisocyanate curing agent (B). Things can be used. Specifically, for example, hydrocarbon solvents such as toluene, xylene, high-boiling petroleum hydrocarbons, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether List ester solvents such as acetate and diethylene glycol monoethyl ether acetate, alcohol solvents such as methanol, ethanol, isopropanol, and butanol, ether alcohol solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether.
  • silane coupling agent examples include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycid.
  • An aqueous coating composition can be prepared by adding a pigment dispersion paste containing the antirust pigment mixture (C) as described above to the above emulsion and adjusting the mixture with water.
  • the aqueous coating composition of the present invention can obtain a coated metal sheet by coating and curing on a metal sheet.
  • the metal plate to be painted include the metal plates described above.
  • the surface of these metal plates may be subjected to chemical conversion treatment (pretreatment).
  • FIG. 1 is a model diagram of a coating line when the aqueous coating composition of the present invention is used as an undercoat.
  • the coating film obtained by coating the hot-dip galvanized steel sheet with the aqueous coating composition of the present invention can provide a coating film having excellent corrosion resistance without being subjected to chemical conversion treatment (pretreatment).
  • the chemical conversion treatment (pretreatment) process can be omitted in the line, which can contribute to saving processes and resources.
  • the chemical conversion treatment (pretreatment) that can be performed as necessary includes, for example, phosphate treatment such as zinc phosphate treatment and iron phosphate treatment, composite oxide film treatment, chromium phosphate treatment, and chromate treatment. Can be mentioned.
  • the coating using the aqueous coating composition of the present invention can be performed on the metal plate by a known method such as a roll coating method, a curtain flow coating method, a spray method, a brush coating method, or a dipping method.
  • the cured film thickness of the coating film obtained from the aqueous coating composition is not particularly limited, but is usually 0.5 to 10 ⁇ m, preferably 2 to 7 ⁇ m.
  • Curing of the coating film may be appropriately set according to the type of resin used and the like, and the maximum temperature reached by the material is preferably 100 to 250 ° C. Is baked for 15 to 60 seconds under conditions of 180 to 230 ° C. In the case of baking in a batch method, it can also be carried out by baking at 80 to 200 ° C. for 10 to 30 minutes.
  • the coating film formed by coating the water-based coating composition of the present invention on a metal plate exhibits excellent corrosion resistance not only on the flat portion of the metal plate but also on the processed portion and end surface portion of the metal plate.
  • the corrosion progressing site and its periphery are adjusted to a pH range suitable for the oxidation-reduction reaction between the pentavalent vanadium ion and the material metal by the phosphate ions eluting at the same time.
  • each of the (c1), (c2) and (c3) can effectively counteract the weak acid resistance, alkali resistance and water resistance. Furthermore, since calcium ions have an action of suppressing the dissolution of the material metal in a strong alkali atmosphere in which the material metal having a pH exceeding 10 is easily dissolved, excellent chemical resistance and water resistance can be achieved at the same time. The fact that the synergistic effect of the action based on these rust preventive pigment mixtures worked greatly also contributed greatly to the excellent corrosion resistance of the water-based paint.
  • the glass transition temperature of the cured coating film obtained from the aqueous coating composition of the present invention is 40 to 115 ° C., preferably 50 to 105 ° C., from the viewpoint of the corrosion resistance, acid resistance and workability of the coating film. Is preferred.
  • the glass transition temperature of the coating film is measured by temperature dispersion at a frequency of 110 Hz using DINAMIC VISCOELASTOMETER MODEL VIBRON (dynamic viscoelastometer model vibron) DDV-IIEA (manufactured by Toyo Baldwin, automatic dynamic viscoelasticity measuring machine). Is the maximum temperature obtained from the change in tan ⁇ .
  • a top coating film can be provided on the resulting coating film obtained by baking and drying the aqueous coating composition (see FIG. 2).
  • the film thickness of the top coat film is 5 to 100 ⁇ m, preferably 10 to 50 ⁇ m.
  • top coating material examples include, for example, known top coating materials such as polyester resin-based, alkyd resin-based, silicon-modified polyester resin-based, silicon-modified acrylic resin-based, and fluorine resin-based coatings for precoated steel sheets.
  • known top coating materials such as polyester resin-based, alkyd resin-based, silicon-modified polyester resin-based, silicon-modified acrylic resin-based, and fluorine resin-based coatings for precoated steel sheets.
  • the type of top coat is not limited to the above.
  • a coated metal plate with particularly excellent workability can be obtained by using a polyester-based topcoat for advanced processing.
  • the corrosion resistance of the flat portion of the metal plate has been considerably improved. In the processed part, the corrosion resistance was insufficient.
  • the aqueous paint composition of the present invention it is possible to obtain a coating film that has chemical resistance and can exhibit excellent corrosion resistance in any of the flat surface portion, end surface portion, and processed portion of the metal plate. Can do.
  • Example 3 Cationic Epoxy Resin No.
  • Example 3 (2 basic acid modified system)
  • jER1004 bisphenol A type epoxy resin, epoxy value 0.108 mol / 100 g, number average molecular weight 1,650, manufactured by Japan Epoxy Resins Co., Ltd.
  • 25 parts of 3-methoxybutyl acetate was heated and mixed at 100 ° C.
  • Tsunodim 205 (dimer acid, manufactured by Tsukino Food Industry Co., Ltd.) was added, and the reaction was allowed to proceed for 2 hours. After confirming that the acid value was 0.5 mgKOH / g or less, 2.36 parts of monoethanolamine was added, and the reaction was further continued for 2 hours. After confirming that the epoxy value was 0.018 mol / 100 g, 1.89 parts of diethanolamine was added, and the reaction was further continued for 1 hour.
  • Production Example 11 Production Example of Resin for Pigment Dispersion jER828EL (Note 4) 1010 parts, 390 parts of bisphenol A, Plaxel 212 (polycaprolactone diol, Daicel Chemical Industries, Ltd., trade name, weight average molecular weight of about 1,250) 240 parts and 0.2 parts of dimethylbenzylamine were added and reacted at 130 ° C. until the epoxy equivalent reached about 1,090 g / eq.
  • Resin for Pigment Dispersion jER828EL (Note 4) 1010 parts, 390 parts of bisphenol A, Plaxel 212 (polycaprolactone diol, Daicel Chemical Industries, Ltd., trade name, weight average molecular weight of about 1,250) 240 parts and 0.2 parts of dimethylbenzylamine were added and reacted at 130 ° C. until the epoxy equivalent reached about 1,090 g / eq.
  • Production Example 12 Pigment Dispersion Paste No. 1.
  • Production Example 1 Pigment-dispersing resin with a solid content of 60% obtained in Production Example 11 (solid part 5 parts), vanadium pentoxide 2 parts, calcium metasilicate 1 part, calcium phosphate 2 parts, titanium white 20 parts , 20 parts of barita (barium sulfate) and 37.6 parts of deionized water were added and dispersed in a ball mill for 20 hours, and the pigment was dispersed until the tube (particle diameter of the coarse pigment particles) was 20 ⁇ m or less. 55% pigment dispersion paste no. 1 was obtained.
  • Silicia 710 and “Shieldex C303” in Table 2 are as follows. Silicia 710: fine silica powder, average particle size 2.8 ⁇ m, oil absorption 190 ml / 100 g, BET specific surface area 700 m 2 / g, Shieldex C303 manufactured by Fuji Silysia Chemical Co., Ltd. R. Grace & Co. Made by company
  • Production Example 22 Production of resol type phenolic resin crosslinking agent solution
  • a reaction vessel 100 parts of bisphenol A, 178 parts of 37% formaldehyde aqueous solution and 1 part of sodium hydroxide were blended, reacted at 60 ° C. for 3 hours, and dehydrated at 50 ° C. for 1 hour under reduced pressure.
  • 100 parts of n-butanol and 3 parts of phosphoric acid were added, and the reaction was carried out at 110 to 120 ° C. for 2 hours.
  • the resulting solution was filtered to remove the sodium phosphate produced to obtain a resol type phenolic resin crosslinking agent solution having a solid content of about 50%.
  • the obtained resin had a number average molecular weight of 880, an average number of methylol groups per benzene nucleus of 0.4, and an average number of alkoxymethyl groups of 1.0.
  • Example 1 Water-based paint composition No. Production of emulsion No. 1 obtained in Production Example 4 1 333.3 parts (solid content 100 parts), 55% pigment dispersion paste No. 1 obtained in Production Example 12. No. 1 was mixed with 90.9 parts (solid content 50 parts) and deionized water 75.8 parts to obtain an aqueous coating composition No. 1 having a solid content of 30%. 1 was obtained.
  • Examples 2 to 18 Water-based paint composition No. 2 to No. Production of No. 18 Aqueous coating composition No. 1 was prepared in the same manner as in Example 1 except that the formulations shown in Tables 4 and 5 below were used. 2 to No. 18 was obtained.
  • Paint specification 1 It is obtained by Examples and Comparative Examples on a Galvalume steel plate (plate thickness 0.35 mm, plating basis weight 150 g / m 2 , indicated as “GL steel plate” in the table) that has been subjected to a non-chromium chemical conversion treatment (pretreatment).
  • aqueous coating composition was applied with a bar coater so as to have a dry film thickness of 3 ⁇ m, and dried by heating in a conveyor oven at 140 ° C. (maximum material arrival temperature) for 20 seconds.
  • each primer coating plate was obtained by heating and drying in a conveyor oven for 40 seconds.
  • Paint specification 2 Each water-based paint obtained by Examples and Comparative Examples on a hot-dip galvanized steel sheet (sheet thickness 0.35 mm, galvanized basis weight 250 g / m 2 , abbreviated as “GI steel sheet” in the table) not subjected to chemical conversion treatment
  • the composition was coated with a bar coater so that the dry film thickness was 3 ⁇ m, and dried in a conveyor oven at 140 ° C. (maximum material reaching temperature) for 15 seconds.
  • the same water-based paint composition as the front surface was coated with a bar coater to a dry film thickness of 3 ⁇ m, and 140 ° C (the highest material) (Primary temperature) for 15 seconds in a conveyor oven to obtain a primer coated plate.
  • KP Color 1510 Korean Paint Co., Ltd., trade name, polymer polyester-based top coat, brown, glass transition temperature of cured coating is about 40 ° C
  • the coated film was coated with a coater so that the dry film thickness was about 15 ⁇ m, baked in a conveyor oven at 220 ° C. (maximum material arrival temperature) for 40 seconds, and each test plate GI-1 to GI-28 (front surface) To be subjected to the test.
  • Paint specification 3 Each water-based coating composition obtained by Examples and Comparative Examples was applied to a cold-rolled steel sheet (having a thickness of 0.8 mm, indicated as “SPC steel sheet” in the table) subjected to zinc phosphate conversion treatment with a bar coater. The coating was applied so that the dry film thickness was 8 ⁇ m, and dried in a conveyor oven at 180 ° C. (the highest material reached temperature) for 30 seconds.
  • the same water-based paint composition as the front surface was coated with a bar coater to a dry film thickness of 20 ⁇ m, and 180 ° C. (the best material)
  • the coating plate for test SP-1 to SP-28 was obtained by heating and drying in a conveyor oven for 30 minutes at the final temperature.
  • Coating film adhesion In accordance with JIS K-5600-5-6 (1999) cross-cut tape method, the gap between the cuts is set to 1 mm, and 100 cross-cuts are made. The number of grids remaining on the coated surface after the tape was brought into close contact and peeled off rapidly was examined.
  • A There is no abnormality such as blistering or whitening in the coating film, and there are 100 remaining grids
  • ⁇ There is no abnormality such as blistering or whitening in the coating film, and there are 91 to 99 residual grids.
  • ⁇ Slightly abnormalities such as blistering or whitening were observed in the coating film and the residual grid number was 91 to 99, or there was no abnormality such as blistering or whitening in the coating film, but the remaining grid pattern was 71 to 99 90 pieces
  • X The occurrence of blistering on the coating film is considerably or remarkably observed, or the number of remaining grids is 70 or less.
  • A There is no abnormality such as blistering or whitening in the coating film, and there are 100 remaining grids
  • ⁇ There is no abnormality such as blistering or whitening in the coating film, and there are 91 to 99 residual grids.
  • ⁇ Slightly abnormalities such as blistering or whitening were observed in the coating film and the residual grid number was 91 to 99, or there was no abnormality such as blistering or whitening in the coating film, but the remaining grid pattern was 71 to 99 90 pieces
  • X Generation
  • A There is no occurrence of swelling, and the tape peeling width from the cut part is 1.5 mm or less.
  • ⁇ There is no occurrence of blisters, and the tape peeling width from the cut part exceeds 1.5 mm, 3 mm or less,
  • ⁇ Slight occurrence of swelling is observed, but tape peeling width from the cut portion is 3 mm or less, or occurrence of swelling is not recognized, but the tape peeling width from the cut portion exceeds 3 mm,
  • X Generation
  • A There is no occurrence of swelling, and the tape peeling width from the cut part is 1.5 mm or less.
  • ⁇ There is no occurrence of swelling, and the tape peeling width from the cut part exceeds 1.5 mm and is 3 mm or less.
  • ⁇ Slight occurrence of swelling is observed, but tape peeling width from the cut portion is 3 mm or less, or occurrence of swelling is not recognized, but the tape peeling width from the cut portion exceeds 3 mm,
  • X Generation
  • the 4T bending section is a process in which the surface of the coating plate is bent outward, four plates having the same thickness as the coating plate are sandwiched inside, and the coating plate is bent 180 degrees in a vise. That's it.
  • the test was performed for 300 cycles (1800 hours in total) with 1 cycle of (drying 2 hours) ⁇ (drying 2 hours at 30 ° C.).
  • the state of the edge part, cross cut part, and 4T bending process part of the coating board after this test was evaluated.
  • Salt spray test The back and cut surfaces of each test coating plate cut to a size of 5 cm ⁇ 10 cm were sealed with a rust-proof paint, and a cross cut reaching the substrate was put in the center of the surface of the coating plate. .
  • the coated plate is subjected to a salt spray test (JIS Z-2371) with 5% saline at 35 ° C. for 500 hours to evaluate the occurrence of red rust on the coated surface after the test, and the cellophane adhesive tape is adhered to the crosscut part.
  • the tape peeling width (one side) from the cut part in the coating film after abrupt peeling was evaluated.
  • A There is little or no red rust, and the tape peeling width from the cut part is less than 5 mm.
  • ⁇ The occurrence of red rust is considerably recognized, and the tape peeling width from the cut portion is less than 5 mm, or the occurrence of red rust is not or slight, but the tape peeling width from the cut portion is 5 mm or more and less than 10 mm
  • ⁇ generation of red rust is observed in the entire cut portion, but the tape peeling width from the cut portion is 5 mm or more and less than 10 mm, or the occurrence of red rust is not recognized in the entire cut portion but is considerably recognized, and the tape peeling width from the cut portion Is 10 mm or more
  • X The occurrence of red rust was observed in the entire cut part, and the tape peeling width from the cut part was 10 mm or more.
  • the present invention can provide a coated metal plate and a coated article excellent in chemical resistance, corrosion resistance of a flat surface portion, corrosion resistance of a processed portion and an end surface portion, and adhesion.
  • the undercoat coating film (the aqueous coating composition of the present invention) is shown.

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Abstract

La présente invention concerne une composition de revêtement à base d’eau sans chrome qui peut former un film de revêtement excellent en terme de résistance chimique, de résistance à la corrosion de zones plates de feuilles métalliques, de résistance à la corrosion de zones usinées ou de surfaces d’extrémité de feuilles métalliques, et d’adhérence ; et des feuilles métalliques revêtues munies de films de revêtement excellents en terme desdites propriétés. L’invention concerne une composition de revêtement à base d’eau comprenant une résine cationique (A), un durcisseur à base de polyisocyanate (B), et un mélange de pigments antirouille (C), caractérisée en ce que le mélange de pigments antirouille (C) a la composition suivante : au moins un composé de vanadium (c1) choisi parmi le pentoxyde de divanadium, le vanadate de calcium et le métavanadate d’ammonium, un composé de silicium (c2), et un sel de calcium (c3) d’un acide phosphorique, les quantités du composé de vanadium (c1), du composé de silicium (c2), du sel de calcium (c3), et du mélange de pigments antirouille (C) étant respectivement de 1 à 30 parties en poids, 1 à 30 parties en poids, 1 à 30 parties en poids, et 3 à 90 parties en poids, pour 100 parties en poids de la matière solide totale de la résine (A) et du durcisseur (B).
PCT/JP2009/063751 2008-08-11 2009-08-03 Composition de revêtement à base d’eau WO2010018763A1 (fr)

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JP2019107586A (ja) * 2017-12-15 2019-07-04 日鉄日新製鋼株式会社 塗装金属板の製造方法
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