WO2003093533A1 - Plateau metallique thermostabilise presentant une resistance a la corrosion elevee, plateau metallique presentant un revetement organique et plateau metallique galvanise phosphate - Google Patents

Plateau metallique thermostabilise presentant une resistance a la corrosion elevee, plateau metallique presentant un revetement organique et plateau metallique galvanise phosphate Download PDF

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Publication number
WO2003093533A1
WO2003093533A1 PCT/JP2003/004688 JP0304688W WO03093533A1 WO 2003093533 A1 WO2003093533 A1 WO 2003093533A1 JP 0304688 W JP0304688 W JP 0304688W WO 03093533 A1 WO03093533 A1 WO 03093533A1
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Prior art keywords
mass
compound
titanium
zirconium
metal plate
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PCT/JP2003/004688
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English (en)
Japanese (ja)
Inventor
Kengo Yoshida
Toshikazu Amemiya
Atsushi Morishita
Akira Takahashi
Shigeyuki Meguro
Katsuyoshi Yamasoe
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Nippon Steel Corporation
Nippon Paint Co., Ltd.
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Application filed by Nippon Steel Corporation, Nippon Paint Co., Ltd. filed Critical Nippon Steel Corporation
Priority to AU2003236248A priority Critical patent/AU2003236248A1/en
Priority to JP2004501666A priority patent/JP4416645B2/ja
Publication of WO2003093533A1 publication Critical patent/WO2003093533A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating

Definitions

  • the present invention relates to a heat-treated metal sheet having excellent corrosion resistance, which can be suitably used for applications such as automobiles, home appliances, and building materials, and an organic-coated metal sheet having excellent flat plate corrosion resistance, processed part corrosion resistance, paint adhesion, and weldability. And a phosphate-treated zinc-based metal plate having excellent corrosion resistance and adhesion.
  • surface-treated steel sheets such as electro-zinc coated steel sheets and hot-dip zinc-coated steel sheets, have been developed and widely used in applications such as home appliances, building materials, and automotive parts. Many of these steel sheets have been treated with lip mouth treatment and phosphate for the purpose of improving corrosion resistance and paint adhesion.
  • the resin film used for such a steel sheet has only a heat resistance of about 150 to 250 ° C, and it cannot be said that it has a sufficient function for the heat resistance.
  • a heat treatment of about 600 ° C. is performed, and for a stove or the like, a heat treatment is performed at about 200 to 400 ° C. for a long time. used . Therefore, it is necessary to maintain sufficient performance such as corrosion resistance even under such heating.
  • Japanese Patent Publication No. Hei 6-23889 discloses an organic-inorganic composite having an organic-inorganic composite film on a chromate-coated steel sheet with excellent heat resistance, heat resistance, discoloration resistance and corrosion resistance.
  • a steel plate is disclosed.
  • Japanese Patent Application Laid-Open Publication No. 2000-15741 discloses that a zinc-based plated steel sheet has a straight silicone resin film formed on a surface thereof, which is resistant to discoloration upon heating, smoke generation upon heating, and corrosion resistance after heating. Further, a steel sheet having excellent scratch resistance is disclosed, and can be suitably used for applications such as a heat shrink band stove.
  • Japanese Unexamined Patent Publication (Kokai) No. 3-394855 discloses that after subjecting a zinc-based plated steel sheet to a close mate treatment, the aqueous resin has silica and a glass transition point (T g point) of 40 ° C. A coating material in which the above-mentioned paint is dispersed is coated with a dry mass of 0.3 to 3.0 g / m 2 . Also, Japanese Patent Application Laid-Open No. 3-28380 discloses that after a chromate treatment is applied to a galvanized steel sheet, a carboxylated polyethylene resin and a Teflon TM lubricant are used.
  • a lubricated steel sheet coated with 0.5 to 4.0 g / m 2 of paint as a dry mass is disclosed. Furthermore, in order to meet the demands of customers who require severe galling resistance, such as deep drawing workability, a solid lubricant has been added to the organic film to improve the lubricity. Steel plate was developed.
  • Japanese Patent Application Laid-Open No. Hei 6-173,037 discloses a steel sheet having a lubricating film in which silica and polyolefin are added to an ether-ester type urethane resin and an epoxy resin.
  • Japanese Patent Publication No. 41141/91 has excellent performance balance such as corrosion resistance, paint adhesion, fingerprint resistance and dew condensation resistance, and is currently one of the main products for home appliances. It is used as one. However, even surface-treated steel sheets coated with such an organic film may have scratches during handling, galling during press working, and abrasion during product transportation. .
  • any of the steel sheets disclosed in Japanese Patent Publication No. Hei 6-23989 and Japanese Patent Application Laid-Open No. 2000-15741 are required Need to be processed. Therefore, development of a heat-treated steel sheet that does not contain hexavalent chromium and has excellent corrosion resistance after heating has been desired.
  • the steel sheet disclosed in Japanese Patent Application Publication No. 2000-205,097 also requires a close mate treatment to obtain sufficient corrosion resistance. Therefore, development of an organic-coated steel sheet that does not contain hexavalent chromium and has excellent corrosion resistance has been desired.
  • Phosphate treatment has attracted attention from an environmental point of view, but the phosphatized film itself does not have sufficient corrosion resistance and adhesion. Therefore, in general
  • Sealing treatment using an aqueous solution containing hexavalent chromium is performed to improve corrosion resistance and adhesion. Therefore, there is a need for the development of a sealing treatment technique that does not contain hexavalent chromium and can improve the corrosion resistance and adhesion of a phosphate treated film.
  • Japanese Patent Application Laid-Open No. 58-197284 describes that after treatment with phosphate, treatment with an aqueous solution containing polyacrylic acid and an aromatic polyhydric alcohol is carried out.
  • the corrosion resistance and the adhesion are inferior to those of the conventional sealing chromate treatment.
  • Japanese Patent Publication No. 59-141114 discloses a technique in which the surface of a chemical conversion treatment film is contacted with a post-treatment compound selected from poly (141-biphenol) or a derivative or a salt thereof.
  • a post-treatment compound selected from poly (141-biphenol) or a derivative or a salt thereof.
  • Japanese Patent Publication No. 60-34912 discloses that one or two or more of oxidized and precipitated inhibitors other than chromic acid may be used alone or on a phosphate film.
  • a technique is disclosed in which an aqueous solution containing 10 ppm to 20% in a complex is applied by means of spraying, coating, etc., and then dried.However, the corrosion resistance and adhesion are also higher when compared with conventional sealing chromate treatment. Poor nature. Disclosure of the invention
  • An object of the present invention is to solve the above problems and provide a heat-resistant metal plate excellent in corrosion resistance, an organic coated metal plate excellent in flat plate corrosion resistance, processed portion corrosion resistance, paint adhesion and weldability, and Excellent corrosion resistance and adhesion
  • An object of the present invention is to provide a metal plate coated with a phosphate-based zinc.
  • a titanium compound film containing a phosphoric acid compound and a guanidine compound as a pre-treatment film is formed on the surface of a metal or plated metal plate.
  • z or a zirconium compound film and further, by forming a silicate film on the zirconium compound film, a heat-treated metal sheet having excellent corrosion resistance can be obtained.
  • the first aspect of the present invention provides the following heat-resistant metal plate.
  • Magnesium, zinc, aluminum, and run One or more selected from the group consisting of tan, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and nickel compound, in an amount of 5 to 5 parts by mass per component (a) 100 parts by mass (in terms of titanium or zirconium).
  • the heat-resistant metal sheet having excellent corrosion resistance according to any one of (1) to (3), which contains 200 parts by mass.
  • One or more water-soluble resins should be contained in the pretreatment film in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium).
  • component (a) in terms of titanium or zirconium.
  • the heat-resistant metal sheet excellent in corrosion resistance according to any one of (1) to (4), which is characterized by the above-mentioned.
  • the silicate film is composed of an alkali metal silicate, colloidal silica, a silane coupling agent, and a polyolefin wax dispersion, and the content of alkali metal is 10%.
  • the heat-resistant metal sheet having excellent heat resistance according to any one of (1) to (5), wherein the heat-treated metal sheet has a content of up to 20% by mass.
  • the silicate film is composed of an alkali metal silicate, colloidal silica, a silane coupling agent, a phosphate, and a polyolefin wax dispersion, and (1) to (1) characterized in that the Si / P mass ratio in the coating is 30 to 150, and the alkali metal content is 10 to 2 ° mass%. 5) A heat-treated metal sheet having excellent corrosion resistance as described in 5).
  • the present inventors also provide a pretreatment film based on a titanium compound, a zirconium compound, or a mixture of a titanium compound and a zirconium compound, and a phosphoric acid compound and a guanidine compound.
  • a pretreatment film based on a titanium compound, a zirconium compound, or a mixture of a titanium compound and a zirconium compound, and a phosphoric acid compound and a guanidine compound.
  • the film-forming properties of the pretreatment film with titanium compound and zirconium compound, the barrier properties, adhesion, the inhibitory effect of phosphoric acid compounds and guanidine compounds, and the upper layer By adjusting the barrier effect of the formed organic-inorganic composite film, It has made it possible to dramatically improve the corrosion resistance of organic coated metal sheets. That is, in a second aspect, the present invention provides the following organically coated metal plate.
  • the pretreatment film comprises (b) a phosphoric acid compound and (c) a guanidine compound.
  • a phosphoric acid compound and (c) a guanidine compound.
  • organic-inorganic composite film is 0.1 to 3 containing from 5 to 35% weight% of colloidal silica mosquitoes in terms of solid content in the upper layer is et. 0 g / m 2 is formed An organically coated metal plate with excellent corrosion resistance.
  • One or more kinds selected from magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and a nickel compound are contained in the pretreatment film as a component (a) 1
  • One or more water-soluble resins are contained in the pretreatment film in an amount of 0.5 to 40 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium).
  • the present inventors have further developed a titanium compound film containing a phosphoric acid compound and a guanidine compound as a sealing treatment on the surface of a metal plate coated with zinc or a zinc-based alloy that has been treated with zinc phosphate.
  • a titanium compound film containing a phosphoric acid compound and a guanidine compound as a sealing treatment on the surface of a metal plate coated with zinc or a zinc-based alloy that has been treated with zinc phosphate.
  • a phosphate-treated zinc-coated steel sheet having excellent corrosion resistance and adhesion can be obtained.
  • the present invention provides the following zinc-coated zinc-coated steel sheet.
  • Titanium compound is 1 to 20 Omg / m 2 or zirconium of compound 1 to zirconium terms 2 0 O mg / m 2, or titanium two ⁇ beam compound and a zirconium compound in total 1 ⁇ 2 0 O mg Zm 2 formed of titanium and zirconium two ⁇ beam converted respectively
  • At least one selected from the group consisting of magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and nickel compound is contained in the sealing film.
  • Metal plate with metal plating is included in an amount of 5 to 200 parts by mass with respect to 100 parts by mass (in terms of titanium or zirconium).
  • the sealing film contains 0.5 to 40 parts by mass of at least one water-soluble resin based on 100 parts by mass of component ('a) (in terms of titanium or zirconium).
  • component ('a) in terms of titanium or zirconium.
  • the heat-resistant metal sheet having excellent corrosion resistance according to the first aspect of the present invention will be described in detail.
  • a titanium compound or a zirconium compound, or a titanium compound and a zirconium Based on a mixture of compounds, use a mixture containing a phosphate compound and a guanidine compound.
  • the titanium compound and the zirconium compound form the pretreatment film, have a barrier property, adherence, inhibit the phosphoric acid compound and the guanidine compound, and form the silicate film formed on the upper layer.
  • the corrosion resistance of heat-treated metal sheets can be dramatically improved
  • the method for producing a heat-treated metal sheet having excellent corrosion resistance according to the present invention will be described in detail.
  • Examples of the metal or plated metal plate usable in the heat-resistant treated metal plate of the present invention include a steel plate and a zinc-plated metal plate plated with an upper layer thereof, a zinc-nickel plated metal plate, a zinc-iron plated metal plate, Zinc-chrome plated metal plate, zinc-aluminum plated metal plate, zinc-aluminum-magnesium plated metal plate, zinc-aluminum-magnesium-silicon plated metal plate, zinc-titanium-plated metal plate, zinc-magnesium-plated metal Sheet, zinc-based manganese-plated metal sheet, zinc-based electric plating, hot-dip plating, vapor-deposited steel plate, aluminum or aluminum alloy-plated metal plate, lead or lead alloy-plated metal plate, tin or tin alloy A small amount of dissimilar metal elements or impurities can be added to the plating metal plate and these plating layers.
  • Molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, antimony, tin, copper, cadmium, silicon, arsenic, and / or silica Includes those in which inorganic substances such as alumina and titania are dispersed.
  • the present invention can be used for multi-layer plating in combination with the above plating and other types of plating, for example, iron plating, iron monolith plating, and the like.
  • an alloy plating such as zinc-nickel having a high melting point.
  • the coating weight on the plated metal plate is preferably 1. ⁇ g Zm 2 or more on one side, and if it is less than this, the corrosion resistance decreases.
  • the component (a) is a titanium compound alone, a zirconium compound alone, or a mixture of a titanium compound and a zirconium compound, or a component (b).
  • Phosphoric acid compound, guanidine compound as component (c) Use
  • titanium compound as the component (a) examples include titanium hydrofluoric acid, titanium ammonium fluoride, titanium oxalate, titanium sulfate, titanium chloride, titanium isopropoxide, isopropyl titanate, titanium ethoxide, and the like. Titanium 2-ethyl-1-hexanolate, tetraisopropyl propyl titanate, tetra-n-butyl titanate, potassium titanium fluoride, sodium titanium fluoride and the like.
  • zirconium compounds include zirconium carbonate ammonium, dinolecon hydrofluoric acid, dinolecon fusidium ammonium, ginole konfujidani potassium, dinolecon fluoride sodium, zirconium acetyl acetate, Zirconium butoxide-1-butanol solution, dinoreconium-n-propoxide, dinoleconine nitrate, dinoleconium chloride, zirconium carboxylate, and the like.
  • the phosphoric acid compound as the component (b) includes, for example, orthophosphoric acid and orthophosphoric acid salts, polyphosphoric acid, metallic acid, pyrrolic acid, phenolic acid, etc. And the salts thereof.
  • the phosphoric acid compounds may be used alone or in combination of two or more.
  • the content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the phosphoric acid compound is less than 10 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is not economically desirable.
  • the guanidine compound as the component (c) includes, for example, guanidine hydrochloride, guanidine nitrate, guanidine carbonate, rodanguanidine, aminoguanidine bicarbonate, aminoguanidine hydrochloride, guanidine phosphate, and guanidine sulfamate. And the like.
  • the guanidine compound may be used alone or in combination of two or more.
  • As the content of guanidine compound The amount is 15 to 150 parts by mass based on 100 parts by mass of component (a) (converted value of titanium or zirconium). If the content of the guanidine compound is less than 15 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically unfavorable.
  • Metal compounds include magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, nickel oxides, hydroxides, complex fluorides, nitrates, and sulfuric acid. Salts and phosphates.
  • the metal compounds may be used alone or in combination of two or more.
  • the content of the metal compound is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the metal compound is less than 5 parts by mass, the effect of improving corrosion resistance cannot be obtained, and if it exceeds 200 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.
  • Corrosion resistance can be improved by adding a water-soluble resin to the pretreatment film.
  • the water-soluble resin include an acrylic resin, a urethane resin, an ethylene acryl copolymer, a phenol-based resin, a polyester-based resin, a polyolefin resin, an alkyd resin, and a polycarbonate-based resin.
  • the water-soluble resins may be used alone or in combination of two or more.
  • the content of the water-soluble resin is preferably in the range of 0.5 to 20 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the water-soluble resin is less than 0.5 part by mass, the effect of improving the corrosion resistance cannot be obtained.
  • the adhesion amount of the pre-treatment film may be 1 to 100 mg Zm 2 in titanium conversion, 1 to 100 mg / m 2 in zirconium compound in titanium conversion, or 1 to 100 mg / m 2 in zirconium conversion. A total of l-100 mg Zm 2 of the ruconium compound is deposited on titanium and zirconium respectively. If the amount of adhesion is less than 1 mg nom 2 in the above conversion value, sufficient corrosion resistance cannot be obtained, and if it exceeds 100 mg / m 2 , the effect of improving corrosion resistance saturates, which is economically undesirable.
  • a silicate film is formed to complete a heat-resistant metal plate.
  • the silicate compound used in the present invention is generally represented by M 20 ⁇ n SiO 2 (M is sodium, potassium, or an alkali metal of lithium, and n is an arbitrary number). Yes, at least one selected from sodium silicate, potassium silicate, and lithium silicate.
  • N which is the molar ratio of M 2 O to S i O 2 , is preferably in the range of 1 to 10. If the value of n is less than 1, the obtained film is likely to absorb moisture, and the water resistance and the adhesion of the film become insufficient, and the corrosion resistance deteriorates, which is not preferable. On the other hand, if it exceeds 10, the obtained film becomes brittle and the corrosion resistance of the processed portion deteriorates, which is not preferable.
  • the alkali metal contained in the silicate compound preferably has a content in the silicate film of 10 to 20% by mass in terms of solid content. If the amount is less than 10% by mass, the film-forming properties are poor and the corrosion resistance is poor.
  • any of spherical, linear, or beaded silica having a branched spherical colloidal force bonded thereto may be used.
  • the particle diameter is 5 to 50 nm
  • the diameter is 5 to 50 nm
  • the length / thickness ratio is 1 to 5 chemically bonded
  • branching Beaded silica It is preferable that the ratio of [the average particle diameter of the spherical force] to the length of the Z-bond is 4 or more and has one or more branches.
  • silane coupling agent used in the present invention examples include ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, and y- (2-aminoaminoethyl) amino.
  • the use of toxic silane or glycidoxypropyl triethoxysilane further improves the corrosion resistance of the silicate coating.
  • the mixing ratio of the silane coupling agent is preferably in the range of 1% by mass to 20% by mass in terms of solid content in the silicate film. If the amount is less than 1% by mass, the corrosion resistance is poor. If the amount exceeds 20% by mass, the stability and the corrosion resistance of the processing solution deteriorate, which is not preferable.
  • a polyethylene wax, a polypropylene wax, a polybutylene wax, or a modified polyolefin wax having a polar group added to these waxes may have an emulsifier concentration of 5% or less, preferably an emulsifier. Use a solution dispersed in water or an aqueous solution without using a solution.
  • the polar group is an oxidized polyolefin wax obtained by oxidizing a polyolefin with an oxidizing agent such as oxygen, ozone or nitric acid in the presence of a catalyst, or acrylic acid, methacrylinoleic acid, Tonic acid, maleic acid, Ethylene unsaturated carboxylic acid monomers such as fumaric acid and itaconic acid and polyolefin wax are dissolved with benzol, etc., and heated in a nitrogen stream with a polymerization initiator (peroxide, redox, heavy metal catalyst, etc.) to obtain a graph. .
  • an oxidizing agent such as oxygen, ozone or nitric acid in the presence of a catalyst, or acrylic acid, methacrylinoleic acid, Tonic acid, maleic acid, Ethylene unsaturated carboxylic acid monomers such as fumaric acid and itaconic acid and polyolefin wax are dissolved with benzol, etc., and heated in a
  • the mass average particle diameter of the polyolefin wax dispersion is preferably from 0.1 to 5. ⁇ ⁇ , more preferably from 0.3 to 1. ⁇ ⁇ . If the mass average particle size is less than 0.1 ⁇ , it is not preferable because the coagulation and the stability are poor. On the other hand, when the mass average particle size exceeds 5.0 ⁇ , the dispersion stability is poor, which is not preferable. Further, the ratio between the mass average particle diameter and the number average particle diameter is preferably in the range of mass average particle diameter / number average particle diameter, that is, approximately 3.
  • the mixing ratio of the polyolefin wax is preferably within a range of 35% by mass or less in terms of solid content in the silicate film. If it exceeds 35% by mass, the corrosion resistance after heating deteriorates, which is not preferable.
  • Is a as a-phosphate salt used in the present invention Seiri phosphate (H 3 P 0 4), TsugiAri phosphate (H 3 P 0 2), there phosphate (H 3 P 0 3), pyro-phosphate ( ⁇ 4 ⁇ 2 ⁇ 7) , Application Benefits poly-phosphate (H 5 P 3 O 1C) ) and chemical formula H X + 2 PXO 3X + 1 ( where X is an integer of three or more )), And all acids and salts thereof.
  • orthophosphate, phosphite, hypophosphite, and pyrophosphate are preferred because they are economical.
  • the Si / P mass ratio in the silicate film and the aqueous silicate aqueous solution is preferably in the range of 30 to 150. More preferably, the mass ratio of S i / P is 35 to 80. If the Si ZP mass ratio is less than 30, bath stability and corrosion resistance deteriorate. On the other hand, if the SiZP mass ratio exceeds 150, the effect of improving corrosion resistance and adhesion cannot be obtained.
  • Adhesion amount range Kei acid coating to 0. 1 ⁇ 3. 0 g / m 2 as a dry weight. Preferably 0. 3 ⁇ 1. O g Zm 2 to al of. Adhesion amount The but 0. Lg Z in m less than 2 poor scratch resistance and corrosion resistance of interest, or 3. 0 g / m 2 and more than a pre undesirable because weldability becomes difficult treatment film and Kei salt coating
  • any method such as spraying, curtain, flow coater, Rhono recorder, Nor coater, brush coating, dipping, and air knife drawing may be used.
  • the baking temperature of the pretreatment film is not particularly specified, but is preferably in the range of 40 to 200 ° C.
  • the baking temperature of the silicate film is preferably in the range of 100 to 200 ° C.
  • drying equipment a method using hot air blowing, a method using indirect heating using a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be adopted.
  • a titanium compound, a zirconium compound, or a mixture of a titanium compound and a zirconium compound is used as a base and contains a phosphoric acid compound and a guanidine compound.
  • the titanium compound and the zirconium compound impart the film-forming properties, barrier properties, and adhesion of the pre-treated film, the inhibitory effect of the phosphate compound and the guanidine compound, and the organic-inorganic composite film formed thereover. The interaction can dramatically improve the corrosion resistance of the organically coated metal sheet.
  • Metal or plating that can be used in the organic coated metal plate of the present invention may be the same as that used for the heat-resistant metal plate on the first side.
  • the titanium compound of component (a) is the same as that used in the first aspect.
  • the zirconium compound is the same as that used in the first aspect.
  • the phosphoric acid compound as the component (b) is the same as that used in the first aspect.
  • the phosphoric acid compounds may be used alone or in combination of two or more.
  • the content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium- or zirconium). If the content of the phosphoric acid compound is less than 10 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.
  • the guanidine compound as the component (c) is the same as that used in the first aspect.
  • the guanidine compound may be used alone or in combination of two or more.
  • the content of the guanidine compound is 15 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the guanidine compound is less than 15 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.
  • the corrosion resistance can be further improved by adding a metal compound to the pretreatment film.
  • metal compounds the first The same ones used on the sides can be used.
  • the metal compounds may be used alone or in combination of two or more.
  • the content of the metal compound is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the metal compound is less than 5 parts by mass, the effect of improving the corrosion resistance cannot be obtained.
  • the corrosion resistance can be improved by adding a water-soluble resin to the pretreatment film.
  • the same water-soluble resin as used in the first aspect can be used.
  • the water-soluble resins may be used alone or in combination of two or more.
  • the content of the water-soluble resin is preferably in the range of 0.5 to 40 parts by mass relative to 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the water-soluble resin is less than 0.5 parts by mass, the effect of improving corrosion resistance cannot be obtained.
  • the adhesion amount of the pretreatment film is as follows: titanium compound: 1 to 100 mg Zm 2 in titanium conversion; zirconium compound: 1 to 100 mg / m 2 in zirconium conversion; or titanium compound And zirconium compounds in total in terms of titanium and zirconium, respectively.
  • an organic-inorganic composite film is formed after forming a pretreatment film on a metal or plated metal plate to complete an organic-coated metal plate. Next, the organic-inorganic composite film will be described.
  • Aqueous resins for the organic-inorganic composite film used in the present invention include acryl ester / acrylic acid copolymer, epoxy'acrylic acid, olefin acrylic acid copolymer, olefin ionomer, and styrene.
  • Acrylic acid copolymers, urethane acrylic acid copolymers, urethane epoxy resins, ethylene imide acrylic resins and the like can be used. It is preferable to use an emulsion dispersed in an aqueous solvent as a coating for forming a film. If necessary, a bridging agent such as various melamine resins and amino resins may be added.
  • an acrylic resin such as a copolymer of acrylic acid and the like.
  • a urethane epoxy resin having both hardness and elongation.
  • any of spherical, linear, or branched colloidal silica having a branched colloidal silica force may be used.
  • the particle diameter is 5 to 50 nm
  • the diameter is 5 to 50 nm and the length-to-thickness ratio is chemically bonded to 1 to 5;
  • the ratio of [average particle diameter of spherical die force / length of the binder] is 4 or more and has one or more branches.
  • the colloidal force is incorporated in the aqueous organic / inorganic composite film in an amount of 5 to 35% by mass in terms of solid content. If it is less than 5% by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 35% by mass, paint adhesion deteriorates, which is not preferable.
  • the scratch resistance can be further improved by adding a predetermined amount of polyolefin wax dispersion to the organic-inorganic composite coating.
  • polyethylene wax, polypropylene wax, polybutylene wax or a modified polyolefin wax having a polar group added to these waxes has an emulsifier concentration of 5% or less, preferably without using an emulsifier.
  • emulsifier concentration 5% or less, preferably without using an emulsifier.
  • Polar groups convert polyolefin waxes to oxygen, ozone or nitric acid in the presence of a catalyst.
  • an acid monomer and a polyolefin wax are dissolved with benzol or the like, and are heated and graphed together with a polymerization initiator (peroxide, redox, heavy metal catalyst, etc.) in a nitrogen stream.
  • the mass average particle diameter of the polyolefin wax purge ion is preferably from 0.1 to 5.1 ⁇ , more preferably from 0.3 to: 1.1 ⁇ .
  • the mass average particle size is less than 0.1 ⁇ , it is not preferable because the aggregation and the stability are poor.
  • the mass average particle size exceeds 5.0 ⁇ , the dispersion stability is poor, which is not preferable.
  • the ratio of the mass average particle diameter to the number average particle diameter is preferably in the range of mass average particle diameter / number average particle diameter, that is, approximately 3.
  • the polyolefin wax is preferably blended in the organic-inorganic composite film in a range of 35% by mass or less in terms of solid content. If it exceeds 35% by mass, paint adhesion is deteriorated, which is not preferable.
  • Adhesion amount range of organic-inorganic composite coating film is a dry weight and 0. 1 ⁇ 3. 0 g / m 2 . More preferably, it is 0.3 to 1.5 g / m 2 . If the adhesion amount is less than 0.1 g / m 2 , the intended corrosion resistance is inferior, and if it exceeds 3.0 g / m 2 , the weldability becomes difficult.
  • Coating methods for forming the pretreatment film and the organic-inorganic composite film in the second aspect include spray, curtain, flow coater, roll coater, per coater, brush coating, immersion, and analytic drawing. Either method may be used.
  • the baking temperature of the pretreatment film is preferably in the range of 40 to 200 ° C.
  • the baking temperature of the organic-inorganic composite film is preferably in the range of 80 to 250 ° C. If the temperature is lower than 80 ° C, water in the organic-inorganic composite paint However, it is difficult to completely volatilize, so that the corrosion resistance is lowered. If the temperature exceeds 250 ° C., the skin is hardened too much and the workability is lowered, which is not preferable.
  • drying equipment a method using hot air blowing, a method using indirect heating using a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be adopted.
  • the sealing treatment film in the phosphate-treated zinc-coated metal sheet of the present invention is based on a titanium compound, a zirconium compound, or a mixture of a titanium compound and a zirconium compound, It contains a compound and a guanidine compound. Titanium compound and zirconium compound provide film-forming properties, barrier properties and adhesion of sealing film, and sealing film by inhibitor effect of phosphoric acid compound and guanidine compound The corrosion resistance can be dramatically improved.
  • the plating metal plate usable in the phosphate-treated zinc plating metal plate of the present invention includes a zinc plating metal plate, a zinc-nickel plating metal plate, a zinc-iron plating metal plate, and a zinc plating metal plate.
  • Chrome plated metal plate, zinc-aluminum plated metal plate, zinc-aluminum-magnesium plated metal plate, zinc-aluminum-magnesium-silicon plated metal plate, zinc-titanium plated metal plate, zinc-magnesium plated metal Includes zinc-based electric plating, hot-dip plating, and vapor-deposited steel sheets, such as sheets and zinc-manganese-plated metal sheets.
  • the coating weight on one side of the plated metal plate is 0.2 g Zm 2 or more, and if it is less than this, the corrosion resistance decreases.
  • the zinc-coated steel sheet is first subjected to a zinc phosphate treatment, and then subjected to a sealing treatment.
  • the zinc phosphate treatment method is not particularly limited as long as it can be used industrially.
  • the coating amount of the zinc phosphate treated film is preferably in the range of 1.0 to 3.0 gm 2 . If it is less than 1.0 g Zm 2 , the corrosion resistance deteriorates, and if it exceeds 3.0 g Zm 2 , the weldability deteriorates.
  • the titanium compounds of component (a) are the same as those used in the first aspect.
  • the zirconium compound is the same as that used in the first aspect.
  • the phosphoric acid compound as the component (b) is the same as that used in the first aspect.
  • the phosphoric acid compounds may be used alone or in combination of two or more.
  • the content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass of the component (a) (in terms of titanium or zirconium). If the content of the phosphoric acid compound is less than 10 parts by mass, sufficient corrosion resistance cannot be obtained, and if it exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.
  • the guanidine compound as the component (c) is the same as that used in the first aspect.
  • the guanidine compound may be used alone or in combination of two or more.
  • the content of the guanidine compound is 15 to 150 parts by mass with respect to 100 parts by mass of component (a) (in terms of titanium or zirconium).
  • the guanidine compound content is less than 15 parts by mass. When the amount exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.
  • the corrosion resistance can be further improved.
  • the same metal compound as that used in the first aspect can be used.
  • the metal compounds may be used alone or in combination of two or more.
  • the content of the metal compound is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the metal compound is less than 5 parts by mass, the effect of improving corrosion resistance cannot be obtained, and if it exceeds 200 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.
  • Corrosion resistance can also be improved by adding a water-soluble resin to the sealing film.
  • the same water-soluble resin as that used in the first aspect can be used.
  • the water-soluble resins may be used alone or in combination of two or more.
  • the content of the water-soluble resin is preferably in the range of 0.5 to 40 parts by mass based on 100 parts by mass of component (a) (in terms of titanium or zirconium). If the content of the water-soluble resin is less than 0.5 part by mass, the effect of improving corrosion resistance cannot be obtained, and if it exceeds 40 parts by mass, the effect of improving corrosion resistance is saturated, which is economically undesirable.
  • a titanium compound is 1 ⁇ 2 0 0 mg / m 2 or zirconium compound is 1 ⁇ 2 0 0 mg / m or titanium of compound in terms of zirconium, in Chita Niumu terms
  • the zirconium compound is deposited on titanium and zirconium in a total amount of 1 to 20 mg / m 2, respectively . If the amount of adhesion is less than 1 mg / m 2 in the above conversion value, sufficient corrosion resistance cannot be obtained, and if it exceeds 200 mg / m 2 , the effect of improving corrosion resistance is saturated, which is not economically preferable.
  • the coating method for forming the sealing film is ' ⁇ , power' ⁇ ten, flow 1 ⁇ co 1 ⁇ ta 1 ⁇ ⁇ , mouth 1 ⁇ noreko 1 ⁇ ⁇ ta 1 ⁇ , no 1 ⁇ 1 ⁇ 1 ⁇ , brush coating, dipping and air knife drawing etc.
  • the above method may be used.
  • the baking temperature is not particularly specified, but is preferably
  • the temperature be 40 to 200 ° C.
  • drying equipment a method using hot air blowing, a method using indirect heating using a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be adopted.
  • the present invention is not limited by these Examples, the power S for specifically explaining the present invention by Examples and Comparative Examples.
  • Table 1 shows a list of pretreatment chemicals used in the examples.
  • Titanium compound A 1 Titanium hydrofluoric acid (reagent)
  • Phosphoric acid compound B 1 Orthophosphoric acid (reagent)
  • Guanidine phosphate manufactured by Sanwa Chemical Co.
  • Guanidine compound C 2 Guanidine nitrate (reagent)
  • Table 3 The metal plates shown in Table 3 were used. Table 3 Types of metal plates and coating weight (plate thickness: 1.2 mm)
  • the titanium compound, zirconium compound, phosphoric acid compound, guanidine compound, metal compound, and water-soluble resin shown in Table 1 were distributed in the ratio shown in Table 5. Then, a pretreatment liquid was prepared.
  • An aqueous silicate coating was prepared by mixing the silicate, colloidal silica, silane coupling agent, phosphate and polyolefin as shown in Table 2 in the proportions shown in Table 6.
  • the pretreatment liquid prepared in (3) was applied so as to have the values shown in Tables 7 to 9 in terms of dry weight, and dried at a final plate temperature of 80 ° C.
  • the silicate treatment solution prepared in (4) was applied so that the values shown in Tables 7 to 9 were obtained, dried at a plate temperature of 120 ° C, and cooled with water to obtain a sample for evaluation. Produced.
  • the amounts of the pretreatment film and the silicate film were calculated by measuring the amount of the liquid film at the time of application by a gravimetric method.
  • the sample for evaluation prepared in (5) was sprayed with a 5% aqueous NaCl solution on the coated steel sheet at an ambient temperature of 35 ° C in accordance with the salt water fog test method described in JIS Z 2371.
  • the whitening occurrence rate after the time was measured and evaluated.
  • ⁇ and ⁇ were determined to be good.
  • test piece of the evaluation sample prepared in (5) was subjected to 6 mm Elixen processing, and was subjected to a salt water spray test method described in JIS Z 2371, at an ambient temperature of 35 ° C and 5% NaCl.
  • the aqueous solution was sprayed on the coated steel sheet sample, and the occurrence of white spots in the processed portion after 48 hours was measured.
  • the following reviews ⁇ and ⁇ were determined to be good.
  • the sample prepared in (5) is subjected to a heat treatment up to 600 ° C by an induction heating method, and is subjected to 5% at an ambient temperature of 35 ° C according to the salt spray test method described in JIS Z 2371. NaCl aqueous solution was sprayed on the coated steel sheet sample, and after 48 hours, the reddish emission rate in the processed part was measured and evaluated. In the following evaluations, ⁇ and ⁇ were determined to be good.
  • a rectangular cylinder crank press test was performed on the sample prepared in (5).
  • the conditions of the square cylinder crank press test were as follows: a sample (0.8 x 220 x 180 mm) was molded to 65 x 115 mm and a height of 5 Omm with a blank pressure of 6 tons. The sliding surface after molding was visually evaluated. In the following evaluations, ⁇ and ⁇ were judged to be good.
  • the continuous spot A welding test was performed to determine the number of hit points at which a nugget diameter of 3 mm or more could be formed stably.
  • Table 79 shows the above evaluation results. From Table 79, it is clear that the heat-treated metal sheet of the present invention is excellent not only in flat plate corrosion resistance, corrosion resistance in a processed portion, and corrosion resistance after heating but also in scratch resistance and weldability. o. Ti / Zr-f ligated compound Phosphorus ligated compound Anisin's compound Metallic ligated compound Water-soluble tree
  • Table 11 lists the chemicals for organic-inorganic composite coatings used in the examples.Table 11 Chemicals for organic-inorganic composite coatings
  • Table 12 The metal plates shown in Table 12 were used.
  • Table 1 2 Types of metal plates and coating weight (plate thickness 2 mm)
  • a titanium compound, a zirconium compound, a phosphoric acid compound, a guanidine compound, a metal compound, and a water-soluble resin shown in Table 10 were blended in the ratio shown in Table 13 to prepare a pretreatment liquid.
  • organic resin, colloidal silica, and polyolefin wax shown in Table 11 were blended in the ratio shown in Table 14 to prepare an organic-inorganic composite paint.
  • the pretreatment liquid prepared in (3) was applied so as to have the values shown in Tables 15 to 17 as a dry weight, and dried at a final plate temperature of 80 ° C.
  • the organic-inorganic composite treatment solution prepared in (4) was applied so that the values shown in Tables 15 to 17 were applied, dried at a final plate temperature of 120 ° C, and then cooled with water to obtain a sample for evaluation.
  • the amounts of the pretreatment film and the organic-inorganic composite film were calculated by measuring the amount of the liquid film at the time of application by a gravimetric method.
  • the evaluation sample prepared in (5) was evaluated in the same manner as in the example of the first aspect, except that the whitening rate after 48 hours was measured and evaluated.
  • the evaluation sample prepared in (5) was evaluated in the same manner as in the example of the first aspect, except that the evaluation was performed by measuring the whitening rate in the processed portion after 24 hours.
  • a percoater Using a percoater, apply a melamine-alkyd resin paint (Amilac # 1000, manufactured by Kansai Paint Co., Ltd.) on the surface-treated metal plate so that the dry film thickness becomes 25 ⁇ . Bake at ° C for 20 minutes. Next, a 7 mn ⁇ Erichsen process was applied, and an adhesive tape (Nichipan Co., Ltd .: Cellotape) was attached to the Eriksen portion of the test piece. The adhesive tape was immediately pulled obliquely at an angle of 45 °, and the appearance of the Erichsen-processed portion was visually evaluated. In the following evaluations, ⁇ and ⁇ were judged to be good.
  • the sample prepared in (5) was evaluated as described in the example for the first aspect.
  • Tables 15 to 17 show the above evaluation results. From Tables 15 to 17, it is clear that the organically coated metal sheet of the present invention is excellent in flat plate corrosion resistance, corrosion resistance in processed parts, paint adhesion and weldability.
  • the organic-coated metal sheet of the present invention is a metal sheet having good flat plate corrosion resistance, corrosion resistance in a processed portion, paint adhesion and weldability, and is therefore suitable as a material in the fields of home appliances, building materials and automobiles. It is.
  • Table 18 shows a list of drugs used in the examples.
  • a titanium compound, a zirconium compound, a phosphoric acid compound, a guanidine compound, a metal compound, and a water-soluble resin shown in Table 18 were blended at the ratios shown in Tables 20 and 21 to prepare a sealing treatment solution.
  • the evaluation sample prepared in (5) was evaluated for the whitening rate after 48 hours.
  • the evaluation sample prepared in (5) was evaluated in the same manner as in the example of the first aspect, except that the evaluation of the white spots in the processed portion after 24 hours was performed.
  • the paint adhesion of the surface-treated metal sheet sample was evaluated as described in the example for the second aspect.
  • the sample prepared in (5) was evaluated as described in the example for the first aspect.
  • Tables 20 and 21 show the above evaluation results. From Tables 20 and 21, it is clear that the phosphate-treated zinc-coated metal sheet of the present invention is excellent in flat plate corrosion resistance, processed part corrosion resistance, adhesion and weldability.
  • the heat-resistant metal sheet of the present invention is a heat-resistant metal sheet having good corrosion resistance, it is suitable as a heat-resistant material in the fields of home appliances, building materials and automobiles.
  • the organic coated metal plate of the present invention is also a metal plate having good flat plate corrosion resistance, corrosion resistance in a processed portion, paint adhesion and weldability, and is therefore suitable as a material in the fields of home appliances, building materials and automobiles.
  • the phosphate-treated zinc-coated metal sheet of the present invention is also a metal sheet having good corrosion resistance and adhesion, and is therefore suitable as a material for use in home appliances, building materials, and automobiles.

Abstract

L'invention concerne un plateau métallique thermostabilisé, présentant une résistance élevée à la corrosion ; un plateau métallique présentant un revêtement organique ; et un plateau métallique galvanisé phosphaté. Ce plateau métallique thermostabilisé comprend un plateau métallique ou un plateau métallique plaqué et, superposé sur une surface de celui-ci, une précouche constituée d'un composé de titane et/ou d'un composé de zirconium (a), d'un composé de phosphate (b) et d'une composé de guanidine (c), la précouche étant recouverte d'un revêtement de silicate. Dans le plateau métallique présentant un revêtement organique, la précouche est recouverte d'un revêtement composite organique/inorganique contenant de la silice colloïdale. Le plateau métallique galvanisé phosphaté comprend un plateau métallique en zinc ou un plateau métallique plaqué avec un alliage de zinc, présentant un revêtement de phosphate de zinc sur sa surface, le revêtement de phosphate de zinc étant recouvert d'un revêtement d'étanchéité constitué d'un composé de titane et/ou d'un composé de zirconium (a), d'un composé de phosphate (b) et d'un composé de guanidine (c).
PCT/JP2003/004688 2002-04-16 2003-04-14 Plateau metallique thermostabilise presentant une resistance a la corrosion elevee, plateau metallique presentant un revetement organique et plateau metallique galvanise phosphate WO2003093533A1 (fr)

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WO2010041428A1 (fr) * 2008-10-08 2010-04-15 新日本製鐵株式会社 Matériau métallique ayant une excellente résistance à la corrosion
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US7029522B2 (en) * 2003-02-17 2006-04-18 Nippon Paint Co., Ltd. Rust prevention coating agent and method of rust-proofing
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