WO2003027354A1 - Feuille metallique preenrobee possedant une excellente aptitude au formage a la presse et procede de production - Google Patents

Feuille metallique preenrobee possedant une excellente aptitude au formage a la presse et procede de production Download PDF

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Publication number
WO2003027354A1
WO2003027354A1 PCT/JP2002/009583 JP0209583W WO03027354A1 WO 2003027354 A1 WO2003027354 A1 WO 2003027354A1 JP 0209583 W JP0209583 W JP 0209583W WO 03027354 A1 WO03027354 A1 WO 03027354A1
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WIPO (PCT)
Prior art keywords
pigment
resin
coating layer
metal sheet
coating
Prior art date
Application number
PCT/JP2002/009583
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English (en)
Japanese (ja)
Inventor
Kouhei Ueda
Hiroshi Kanai
Yoshio Kimata
Original Assignee
Nippon Steel Corporation
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Publication date
Application filed by Nippon Steel Corporation filed Critical Nippon Steel Corporation
Priority to KR10-2004-7003948A priority Critical patent/KR20040044944A/ko
Publication of WO2003027354A1 publication Critical patent/WO2003027354A1/fr

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Classifications

    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • 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
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • 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
    • 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
    • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
    • B05D2701/10—Coatings being able to withstand changes in the shape of the substrate or to withstand welding withstanding draw and redraw process, punching
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a precoated metal sheet excellent in press formability and a method for producing the same.
  • the present invention relates to a surface-treated metal material excellent in press formability and corrosion resistance, and is used for home appliances, building materials, civil engineering, machinery, automobiles, and furniture.
  • Pre-painted metal coated with a colored resin coating has come to be used for home appliances, building materials, automobiles, etc., instead of the conventionally painted post-processed products.
  • This metal plate is obtained by coating a metal plate that has been subjected to a pretreatment for metal with a resin paint, and is generally used after being coated with the resin paint and cut and press-molded. For this reason, the corrosion resistance of the cut end surface where the metal not covered with the resin coating is exposed and the peeling of the resin coating during press working have been problems for the pre-coated metal plate. These problems have been solved by performing chromate treatment and including a hexavalent chromium-based anti-pigment pigment in the resin coating, and are now widely used.
  • the chemical conversion treatment technology disclosed in Japanese Patent Application Laid-Open No. 2001-899686 has excellent adhesion to a processed part in an Erichsen test or a T-bend test, but a press represented by deep drawing.
  • the moldability had a disadvantage that the coating film was easily bitten by a press die and peeled off compared to a precoated metal plate subjected to a chromate treatment.
  • a zinc phosphate treatment is used for the chemical conversion treatment.
  • An object of the present invention is to solve the above-mentioned problems in the prior art, to provide a pre-coated metal plate having excellent corrosion resistance even without containing hexavalent chromium, and further having excellent press formability, and a method for producing the same. Is the challenge
  • the present inventors formed a chemical conversion treatment coating layer containing at least one of tanyun or tannic acid, a silane coupling agent, and a fine silicic acid simultaneously, and further contained an aluminum phosphate-based pigment thereon.
  • a resin coating layer not only corrosion resistance, but also pressing We have found that a composite film with extremely good formability can be obtained.
  • the present invention has been completed based on such knowledge, and the gist thereof is as follows.
  • a precoated metal sheet excellent in press moldability further comprising a resin coating layer containing 1 to 140 parts by mass of an aluminum phosphate pigment based on 100 parts by mass of the resin solid content.
  • the resin coating layer further contains a water-proof pigment, and the total content of the water-proof pigment and the aluminum phosphate pigment is 140 parts by mass with respect to 100 parts by mass of the resin solid content.
  • At least one of tannin or tannic acid, silane coupling agent and fine silica are simultaneously contained on one or both sides of the metal plate
  • the coating solution is applied and dried to form a chemical conversion coating layer.
  • Excellent press moldability characterized by applying a resin paint containing 1 to 140 parts by mass of an aluminum phosphate pigment to 100 parts by mass of resin solid content, and drying and curing.
  • a method for manufacturing a pre-coated metal plate characterized by applying a resin paint containing 1 to 140 parts by mass of an aluminum phosphate pigment to 100 parts by mass of resin solid content, and drying and curing.
  • the resin coating further contains a water-proof pigment, and the total content of the water-proof pigment and the aluminum phosphate-based pigment is 140 parts by mass or less based on 100 parts by mass of the resin solid content.
  • FIG. 1 is a schematic sectional view of a press-formed product of a pre-coated metal plate of the present invention.
  • a chemical conversion coating 2 containing at least one of tannin or tannic acid, a silane coupling agent, and fine silica at the same time 2
  • a resin coating 3 containing an aluminum phosphate pigment
  • an optional overcoat layer 4 are formed on both surfaces of the metal plate 1, a chemical conversion coating 2, a resin coating 3, and an optional top coating layer 4 may be formed.
  • the present invention relates to a method for producing a metal plate or a plated metal plate, wherein one or both of tannin and tannic acid as solids A chemical conversion treatment film layer containing both an encapsulating agent and fine-grained sily is formed, and a resin film layer containing 1 to 140 parts by mass of an aluminum phosphate pigment is formed thereon. Achieved by It is more preferable that the aluminum phosphate pigment is aluminum trihydrogen diphosphate because the coating film is less likely to be kinked during press molding. Further, if the chemical conversion coating layer applied to the prepreg metal sheet of the present invention further contains a polyester resin as a solid content, the adhesion of the coating film is improved, and the coating film is less likely to be galling during press molding. More suitable.
  • the resin coating layer formed on the prepreg metal plate of the present invention contains an anti-reflection pigment in addition to the phosphoric acid-based pigment, because the corrosion resistance of the prepreg metal plate is improved.
  • the amount of these pigments added is preferably such that the total content of the aluminum phosphate-based pigment and the water-proof pigment is 140 parts by mass or less based on 100 parts by mass of the resin solid content.
  • the anti-reflection pigment has calcium ion-exchangeable silicic acid, since the corrosion resistance is further improved.
  • the chemical conversion coating layer formed on the precoated metal sheet of the present invention may be a processing solution containing at least one of tannic acid and tannic acid, a silane coupling agent, and a fine-grained silicide force, or in addition to this. It is more preferable that the precoated metal sheet of the present invention can be manufactured more efficiently by applying and drying a treatment liquid containing a polyester resin. Further, the resin coating layer formed on the pre-coated metal plate of the present invention is formed by applying an aluminum phosphate-based pigment, or a resin paint containing an aluminum phosphate-based pigment and a water-proof pigment simultaneously, followed by drying and curing. It is more preferable to form the precoated metal sheet of the present invention because the precoated metal sheet of the present invention can be manufactured more efficiently.
  • the present inventors have conducted various studies on a non-chromate precoated metal sheet whose coating is difficult to be galled by a press mold when press-formed.
  • a chemical conversion coating layer containing tannic acid, a silane coupling agent, and fine silica at the same time is formed, and a resin coating layer containing an aluminum phosphate-based pigment is further formed thereon.
  • the phenomenon that the coating film is peeled off by the mold is dramatically improved.
  • the phenomenon in which the paint film is bitten by the press die during press molding and peels off is that the paint film on the prepote metal plate is rubbed with a high load by the press die and acts on the paint film at this time.
  • the first is to increase the adhesion between the coating and the metal.
  • tannin and / or tannic acid having excellent adhesion and the silane coupling agent and the fine-grained silica are used.
  • the adhesion of the coating is dramatically improved due to the synergistic effect, and the unique properties of the aluminum phosphate pigment This is presumed to be due to the fact that the shear stress generated in the coating film during press forming is less likely to be transmitted to the interface between the coating film and the metal plate due to the mechanical properties of the metal.
  • the metal sheet used for the pre-coated metal sheet of the present invention is a cold-rolled steel sheet, a hot-rolled steel sheet, a hot-dip galvanized steel sheet, an electro-zinc-plated steel sheet, a hot-dip galvanized steel sheet, an aluminum-plated steel sheet, an aluminum-zinc alloy
  • metal plates and plated plates such as plated steel plates, aluminum-magnesium-zinc plated steel plates, aluminum-magnesium-silicon-zinc plated steel plates, stainless steel plates, and aluminum plates can be applied. These metal plates may be used after being subjected to ordinary treatment such as hot water washing and alkali degreasing before the chemical conversion treatment.
  • the chemical conversion coating layer applied to the precoated metal plate of the present invention is a tandem coating. And tannic acid, silane coupling agent, and fine silica.
  • the tannin or tannic acid used may be a tannin which can be hydrolyzed or a condensed tannin, or a partially decomposed tannin may be used.
  • the tannins and tannic acids are not particularly limited, such as hamame tannins, quintuple tannins, gallic tannins, milanolan tannins, Jibijibi tannins, Anogaro villa tannins, Ronnie tannins, and catechins.
  • the use of “tanyunic acid: AL” (manufactured by Fuji Chemical Co., Ltd.) particularly improves the processing adhesion of the coating film.
  • the addition amount of at least one of tannin and tannic acid is not particularly specified, but the content in the chemical conversion solution applied to a metal plate to form this is 2 to 80 g / l. If so, it is more suitable. If at least one of tannin or tannic acid is less than 2 g / 1, the protective effect and coating adhesion may not be ensured, while the protective effect may exceed 80 g / l. Or the adhesion of the coating film may be reduced, or it may not be dissolved in the aqueous solution.
  • silane coupling agent to be used examples include ⁇ - (2-aminoethyl) aminoprovirtrimethoxysilane, y- (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoaminoethyl) amine Minopropyl triethoxysilane, y- (2-aminoethyl) aminopropylmethyl ethoxysilane, y- (2 -aminonoethyl) aminopropylmethyldimethoxysilane, ⁇ -methacryloxypropyl trimethoxysilane, ⁇ —Methacryloxypropylmethyl dimethoxysilane, -methacryloxypropyl built-triethoxysilane, y —Methacryloxypropylmethylmethylethoxysilane, N-i3
  • the amount of the silane coupling agent to be added is not particularly specified, but it is more preferable that the content in the chemical conversion solution applied to the metal plate to form the chemical conversion coating layer is 2 to 80 g / 1. It is. If it is less than 2 g Zl, sufficient coating film adhesion may not be obtained during processing, and the corrosion resistance may not be sufficient. If it exceeds 80 g / l, the adhesion of the coating film may be reduced.
  • the fine silica used in the present invention is a generic term for silica capable of stably maintaining a water-dispersed state when dispersed in water to have a fine particle size.
  • Examples of the finely divided silica include “Snowtex N”, “Snowtex C”, “Snowtex UP”, ⁇ Snowtex PS ”(all manufactured by Nissan Chemical Industries), and“ Adelate AT-120Q ”.
  • Commercially available silica gel such as “Asahi Denka Kogyo” or powdered silica such as Aerosil # 300 (Nippon Aerosil) can be used.
  • the fine silica may be appropriately selected depending on the required performance.
  • fine-grained silica such as “Snowtex C” that can stably disperse even at a pH of 4 or more can improve the storage stability of the base treating agent. This is because the pH of the chemical solution can be adjusted to 4 or more, and the pH is low and the reactivity is high. This is probably because the reaction of the coupling agent can be suppressed.
  • the addition amount of the fine silicic acid is not particularly specified, but the content in the chemical conversion treatment liquid applied to the metal plate to form the chemical conversion coating layer is limited.
  • It is preferably from 1 to 40 g / 1. If it is less than 1 g / 1, the coating adhesiveness of the coating film may be poor, and if it exceeds 40 g / 1, the effects of processing adhesion and corrosion resistance are saturated, which is uneconomical.
  • the chemical conversion coating layer further contains a polyester resin as a solid content because the processing adhesion is further improved.
  • a polyester resin There is no particular restriction on the content of the polyester resin.However, if the content in the chemical conversion solution applied to the metal plate to form the chemical conversion coating layer is l to 60 g Zl, Processing adhesion is improved. If the amount is less than 1 g / l, the effect of the addition of the resin is not observed. If the amount exceeds 60 gZl, the adhesion to the coating film may be rather deteriorated.
  • the polyester resin include “Finetex ES-650”, “Finetex ES-611J”, “Finetex ES-670J”,
  • Finetex ES 675 (all manufactured by Dainippon Ink and Chemicals), Byronal MD—1200, Pai-Narual MD—122, and Byronal MD— 1250 ",” Bi-Naru MD-1-1100 “,” Bi-Naru MD-133 “,” Bi-Ronal MD-193 “(all manufactured by Toyobo Co., Ltd.), etc. Can be used.
  • An acid, an alkali, or the like may be added to the chemical conversion treatment solution applied to form the chemical conversion treatment film layer of the present invention for pH adjustment within a range where performance is not impaired.
  • the baking temperature is preferably 50 to 250 ° C. At temperatures below 50 ° C, water Since the evaporation rate of the minute is slow and sufficient film-forming property cannot be obtained, the protection is insufficient. On the other hand, when the temperature exceeds 250 ° C., the alkyl portion of tannin, a tannic acid-silane coupling agent, which is an organic substance, undergoes denaturation such as thermal decomposition, and the adhesion and corrosion resistance decrease. 70 to 160 ° C is more preferable. In hot air drying, drying for 1 second to 5 minutes improves the production efficiency, and is more preferable.
  • the coating method of the chemical conversion treatment liquid is not particularly limited, and a generally known coating method, for example, a roll coating, a Ringer's Nore coat, an air spray, an airless spray, an immersion, or the like can be adopted. Further, it is more preferable to apply the coating on a continuous coating line called a general coil coating line or sheet coating line, which is complete with these coating devices, because the coating work efficiency is high and mass production is possible.
  • the amount of the chemical conversion coating layer to be deposited is preferably 10 to 500 mg / m 2 as a solid content. If it is less than 100 mg / m 2 , sufficient working adhesion will not be ensured, and if it exceeds 500 mg / m 2 , the working adhesion will rather decrease.
  • the resin of the resin coating layer formed on the chemical conversion coating layer may be of any type such as an aqueous type, a solvent type and a powder type.
  • the type of resin generally known ones such as polyacrylic resin, polyolefin resin, polyurethane resin, epoxy resin, polyester resin, polybutylal resin, and melamine resin can be used. It can be used as it is or in combination.
  • the resin coating layer of the precoated metal plate of the present invention needs to contain 1 to 140 parts by mass of an aluminum phosphate pigment based on 100 parts by mass of the resin solids.
  • the addition amount of the aluminum phosphate-based pigment is less than 1 part by mass, there is no effect on the galling of the coating film by the die during press molding, and this is unsuitable.
  • the greater the amount of aluminum phosphate pigment added the more the coating will seize during press molding. It is more effective and more suitable for steel, but if it exceeds 140 parts by mass, it is not suitable because the workability as a pre-coated metal plate is significantly poor.
  • aluminum phosphate-based pigment generally known ones, for example, aluminum trihydrogen phosphate, aluminum metal methacrylate, and the like can be used, and aluminum trihydrogen phosphate is used. Are more readily available and more suitable.
  • Aluminum trihydrogen diphosphate can be used, for example, “K—WHITE” manufactured by Tika.
  • the total content of the aluminum phosphate pigment and the water-proof pigment is preferably 140 to 100 parts by mass of the resin solid content. Less than parts by weight is preferred. If the total added amount of the aluminum phosphate pigment and the anti-reflective pigment exceeds 140 parts by mass, problems such as greatly deteriorated workability when the precoated metal plate is bent may occur, which is preferable. Not good.
  • anti-pigment pigments As the anti-pigment added to the resin coating layer of the precoated metal sheet of the present invention, generally known anti-pigment pigments can be used.
  • phosphoric acid-based pigments such as zinc phosphate and iron phosphate
  • molybdenum acid such as calcium molybdate, aluminum molybdate, and barrier molybdate.
  • vanadium-based pigments such as vanadium oxide
  • Chromate-based anti-pigment pigments Fine particles such as water-dispersible silica, fumed silica, and calcium ion-exchangeable silica can be used.
  • the chromate prevention described in (4) ⁇ It is desirable not to use pigments due to environmental concerns.
  • the chromate prevention described in (4) ⁇ It is desirable not to use pigments due to environmental concerns.
  • the chromate prevention described in (4) ⁇ It
  • calcium ion-exchangeable silica is harmless to the environment and has a large protective effect. Therefore, if this is added as a protective pigment, the protective effect is more exhibited. It is suitable.
  • the calcium ion-exchangeable silica “Shieldex” manufactured by Gracce can be used. Further, these anti-sun pigments may be added in combination of two or more kinds.
  • a known pigment generally called an extender or a coloring pigment for coloring is used in combination.
  • the extender pigment is a general term for pigments added to improve various properties required for resin coatings, such as the brittleness of the resin coating layer and the concealability after coating.
  • Talc which plays a role in the above, titanium white (titanium oxide) for improving the concealing property of the resin coating, and silica for improving the scratch resistance of the glossy resin coating of the resin coating.
  • the total amount of the total addition of the aluminum phosphate pigment, the anti-reflection pigment, and the extender coloring pigment is based on 100 parts by mass of the resin solid content in the resin paint. It is preferable that the amount be 140 parts by mass or less. If the amount of all pigments exceeds 140 parts by mass, In some cases, problems such as poor workability when bending a metal plate may occur.
  • the thickness of the resin coating containing the aluminum phosphate pigment of the precoated metal plate of the present invention is not particularly limited, but various properties of the resin coating vary depending on the film thickness. There is a need to.
  • a resin paint containing the amount of the face specified in the present invention with respect to the resin solid content in advance is used. It is more preferable to produce and apply it, and then to dry and cure it, because the production efficiency is improved.
  • These resin coatings can be used in any form such as solvent-based coatings, water-based coatings, melt-type coatings, powder coatings, electrodeposition coatings, ultraviolet-curing coatings, and electron beam-curing coatings.
  • These resin coating methods can be applied by generally known coating methods such as roll coating, curtain flow coating, roller curtain coating, die coating, air spray, airless spraying, electrodeposition coating, powder coating, and the like.
  • a continuous coating line called a general coil coating line or sheet coating line equipped with a roll coat, curtain flow coat, and roller curtain coat
  • coating work efficiency is high and mass production is possible. It is suitable.
  • a generally known drying and curing method such as a hot air oven, a direct fire oven, a far-infrared opening, and an induction heating oven can be used.
  • a generally known ultraviolet irradiation device can be used.
  • an electron beam-curable resin coating a generally known electron beam irradiation device can be used. .
  • an overcoating resin coating layer may be further provided on the resin coating layer containing the aluminum phosphate-based pigment. This is more preferable because the color tone appearance, the design appearance, and other resin film performance of the painted metal plate are improved.
  • the top-coating resin coating layer can be formed by applying a generally known top-coat paint, drying and baking to cure.
  • Generally known topcoats include, for example, polyester-based topcoats, epoxy-based topcoats, urethane-based topcoats, acrylic-based topcoats, and melamine-based topcoats.
  • any form such as a solvent-based coating, a water-based coating, a powder coating, an electrodeposition coating, an ultraviolet curing coating, and an electron beam curing coating can be used.
  • coloring pigments and extenders such as titanium oxide (TiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), calcium carbonate (Ca) CO 3), sulfuric Paris um (B a S 0 4), alumina (A 1 2 O 3), Kaori Nkure, carbon black, iron oxide (F e 2 O 3
  • the top coat paint may be a well-known design paint, for example, a fuse skin paint, a fine paint, a hammer tone paint, a mat paint, a metallic paint, a pearl paint, a texture paint, etc. Can be used.
  • the coating method of the top coat paint is a commonly known coating method, for example, Lono record, curtain flow coat, roller curtain coat, die coat, air spray, airless spray, electrodeposition coating, powder coating, It can be carried out by dipping, painting, brushing, etc.
  • the method of drying and baking of the top coat paint is a commonly known drying and baking method such as a hot air oven, a direct fire oven, a far infrared oven, and an induction heating oven. Can be.
  • a hot air oven a direct fire oven
  • a far infrared oven a far infrared oven
  • an induction heating oven can be.
  • the top coat is an ultraviolet-curable resin coating
  • a generally known ultraviolet irradiation device can be used.
  • the top coating is an electron beam-curable resin coating
  • a generally known electron beam irradiation device can be used.
  • the following chemical conversion pretreatment liquids were prepared as the chemical conversion pretreatment liquids used for the test materials in the experiment (A): An aqueous solution containing 20 g of tannic acid, 40 g / l of a silane coupling agent, and 20 g of fine silica was prepared and used as a metal pretreatment agent.
  • tannic acid use “Tannic acid AL” manufactured by Fuji Chemical Co., Ltd .
  • silane coupling agents ⁇ -glycidoxypropyltrimethoxysilane
  • fine silica use “Snowtec Ichigo” manufactured by Nissan Chemical Co., Ltd.
  • aqueous solution containing 20 g of tannic acid, 40 g of a silane coupling agent, 20 g / l of fine silica, and 20 g / 1 of a polyester resin was prepared as a metal pretreatment agent.
  • tannic acid ALj manufactured by Fuji Chemical Industry Co., Ltd. ⁇ -daricidoxyprobuilt remethoxysilane manufactured by Fuji Chemical Industry Co., Ltd., and Nissan Chemical Co., Ltd.
  • "Finetex ES-650 J" manufactured by Dainippon Ink Co., Ltd. was used as the polyester resin.
  • ZM-130AN manufactured by Nippon Parti Rising Co., Ltd., which is a commercially available coating mate treatment, was used.
  • a resin paint is added to a commercially available polyester-, urethane-, or epoxy-based clear paint that does not contain any pigment, by adding an aluminum phosphate-based pigment and, if necessary, an anti-reflective paint, followed by stirring. It was created.
  • "K-I-G 105" manufactured by Tiriki Co., Ltd. was used as the aluminum phosphate pigment.
  • anti-pigment "NP-530" manufactured by Toho Pigment Co., Ltd. (described as "phosphoric acid Zn” in the table) is used as a zinc phosphate-based anti-pigment, and G is used as calcium ion exchange silica.
  • Race company "S hieldex—C303” Was described as “C a — S i”), and commercially available stoichiometric chromate (described as “S r — C r” in the table) was used as the chromium-based anti-pigment pigment.
  • Table 1 shows the amount of each pigment added.
  • “Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.
  • Silica in the table
  • an oxidized white pigment “CR-95” manufactured by Ishihara Sangyo Co., Ltd. (described as “Titanium White” in the table) was added as titanium.
  • the amount of each pigment added is described in the table.
  • the chemical conversion treatment liquid (C) it was applied so that the amount of adhesion would be 50 mg / 2 in terms of metal powder.
  • a degreased metal plate was immersed in the chemical conversion treatment liquid (E) for 2 minutes, and dried in a hot-air drying oven to obtain a chemical conversion treatment coating layer.
  • the chemical conversion treatment (E) was coated so that the amount of zinc phosphate attached was 2 g / m 2 .
  • the plate temperature reached during chemical conversion drying was 60 ° C.
  • the coating was applied to a thickness of 5 ⁇ m, and the coating was dried and cured in an induction heating furnace blown with hot air under conditions where the ultimate plate temperature of the metal plate was 210 ° C to obtain a resin coating layer.
  • the painted metal plate was sprayed with water using a spray and cooled with water.
  • a top coat is applied on the resin coating layer containing the aluminum phosphate pigment so that the film thickness after drying is 15 // m using a mouth coater, and the coating is applied to an induction heating furnace blown with hot air.
  • Dry baking was performed at 230 ° C. After drying and baking, the painted metal plate was sprayed with water by spraying and cooled with water to obtain a pre-coated metal plate as a test material.
  • the prepared precoated metal plate was bent at 180 °, and the coating film of the processed portion was observed with a 20-power loupe to check for any cracks in the coating film.
  • bending was performed so that the surface coated with the resin coating containing the aluminum phosphate-based pigment was on the outside. Further, an adhesive tape was stuck to the applied portion, and the remaining state of the coating film when the adhesive tape was vigorously peeled off was visually observed. In this test, the tape was peeled twice. The bending was performed at 20 ° C. in an atmosphere of 0 T.
  • the evaluation of coating film cracking is ⁇ when there is no coating film cracking, ⁇ when there is about 1 to 3 small cracks in the coating film, ⁇ when there is very small cracking in the coating film, ⁇ In addition, X was evaluated when there was a clearly large crack visually observed on the entire processed part.
  • the evaluation of the remaining state of the coating film after peeling off with a tape was evaluated as ⁇ when the coating film was not peeled off and remained on the plated steel sheet, ⁇ when the coating film was partially peeled slightly, and Was evaluated as “ ⁇ ” when the part was severely peeled off, and as “X” when peeling was observed over almost the entire bent portion.
  • the precoated metal plate was subjected to 0 T processing (ECCA-T 7), immersed in boiling water for 1 hour, taken out and left for 24 hours, and then the coating film was subjected to tape peeling.
  • the evaluation of the remaining state of the coating film was as follows: ⁇ : when the coating film remained on the steel plate without peeling at all; ⁇ : when the coating film partially peeled slightly; Peeling was evaluated as ⁇ , and peeling was evaluated as X when peeling was observed over almost the entire bent part.
  • test method that reproduces the peeling of the coating film caused by the coating film of the pre-coated metal plate being pressed by the press mold when the pre-coated metal plate is press-formed.
  • Test method (public technique 95-10778).
  • the prepared precoated metal plate was cut into a test piece of 30 mm (width) x 300 mm (length), and this test piece was cut into a flat die and a die provided with a 3 mm radius bead. And sandwich it. At this time, the test piece was sandwiched between the surface coated with the resin paint containing aluminum phosphate pigment (evaluation surface) so that the bead of the die was pressed, and a 1 t load was applied to apply additional force to the die bead.
  • the metal part was pressed against the evaluation surface of the pre-coated metal plate.
  • the precoated metal plate was pulled out at a speed of 200 mm Z min, and the state of peeling of the coating film on the evaluation surface of the precoated metal plate rubbed with a bead was visually observed and evaluated.
  • the evaluation was ⁇ when the coating film was not peeled at all, ⁇ when the coating film was partially peeled, and about 20% as the area ratio of the part rubbed with the bead.
  • the case where the above was peeled was marked as ⁇ , and the case where the entire surface was peeled was marked as X.
  • the salt spray test was carried out according to the method described in 4.0-9.1.
  • the salt water was sprayed on the surface coated with the resin paint containing the aluminum phosphate pigment so as to wipe it.
  • the test time was 120 h when the precoated metal sheet was a cold-rolled steel sheet, 240 h when it was an electro-galvanized steel sheet, hot-dip galvanized steel sheet, 55% alloyed aluminum.
  • Zn-l 1% aluminum-1 3% magnesium-1 0.2% silicon-plated steel sheet the time was set at 360 h.
  • the evaluation method for the coating film at the cut part is as follows: ⁇ when the maximum blister width on one side of the cut is less than 1 mm, ⁇ when it is 2 mm or more and less than 3 mm, ⁇ when it is 3 mm or more and less than 5 mm, X was evaluated when it was 5 mm or more.
  • the evaluation method of the cut end face part is ⁇ when the swollen width from the end face is less than 2 mm, ⁇ when it is 2 mm or more and less than 3 mm, ⁇ when it is 3 mm or more and less than 5 mm, 5 mm. In the above cases, it was evaluated as X.
  • Example 13 G1 B e. Lyester 20 Ca- ⁇ 100 Silica 40 160
  • the coating film is suitable because it is less likely to peel off in the coating film galling test using beads.
  • the precoated metal sheet of the present invention contains a polyester resin in the chemical conversion coating layer, thereby improving the processing adhesion of the coating film, and peeling off the coating film in a galling test of the coating film using a bead. This is more preferable because it is difficult to carry out (Example of the present invention—comparison between No. 1 and N 0.10).
  • the resin coating was prepared by adding a water-proof pigment in addition to the aluminum phosphate-based pigment (Example 1 of the present invention, No. 8 to 22), the one not added (Example of the present invention—No.
  • Corrosion resistance is improved as compared to 7).
  • the pigment is a calcium ion-exchangeable silica (Example of the present invention—No. 1, 8 to: 14, 17 to 22)
  • the corrosion resistance is further improved, and the conventional chromate. It is suitable because it has the same corrosion resistance as the one to which a systemic pigment is added (Example of the present invention—No. 16 and Comparative example 1 No. 26).
  • the present invention it is possible to provide a pre-coated metal sheet that is excellent in workability and corrosion resistance of a coating film and is very suitable for press molding without using hexavalent chromium, which is likely to affect the environment. It has become possible. Therefore, it can be said that the present invention is an invention having extremely high industrial value.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

La présente invention concerne une feuille métallique préenrobée possédant une excellente aptitude au formage à la presse qui est munie, sur l'une de ses faces ou sur ses deux faces, d'une couche de revêtement de traitement chimique comprenant comme composants solides du tannin et/ou de l'acide tannique, un agent de couplage silane et de la silice particulaire, et d'une couche de revêtement en résine qui est formée sur la couche de revêtement de traitement chimique et qui comprend 100 parties en poids de résine sur une base solide et de 1 à 140 parties en poids d'un pigment phosphate d'aluminium. La couche de revêtement de traitement chimique contient en outre de préférence une résine polyester, et la couche de revêtement en résine contient en outre de préférence un pigment anticorrosion. Le tripolyphosphate de dihydrogène d'aluminium représente le pigment phosphate d'aluminium optimal. La silice échangeuse d'ions calcium représente le pigment anticorrosion optimal.
PCT/JP2002/009583 2001-09-19 2002-09-18 Feuille metallique preenrobee possedant une excellente aptitude au formage a la presse et procede de production WO2003027354A1 (fr)

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KR10-2004-7003948A KR20040044944A (ko) 2001-09-19 2002-09-18 우수한 프레스 성형성을 갖는 전코팅 금속 시트 및 그제조 방법

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JP2001285378 2001-09-19
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JP2002170098A JP3950370B2 (ja) 2001-09-19 2002-06-11 プレス成形性に優れるプレコート金属板及びその製造方法

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Cited By (2)

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EP1643009A1 (fr) * 2002-07-02 2006-04-05 Nippon Steel Corporation Plaque métallique prérevêtue ayant une excellente formabilité à la presse et son procédé de fabrication
CN102168264A (zh) * 2011-03-28 2011-08-31 佛山市南海华豪铝型材有限公司 铝材喷涂前复合纳米陶瓷硅烷复合膜的方法

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JP4654089B2 (ja) * 2004-12-03 2011-03-16 新日本製鐵株式会社 耐久密着性に優れたクロメートフリー樹脂複合型制振材料
JP4895535B2 (ja) * 2005-06-27 2012-03-14 新日本製鐵株式会社 非クロメート系リン酸塩処理亜鉛めっき鋼板
CN101232994B (zh) * 2005-07-28 2012-10-03 新日本制铁株式会社 预涂金属板及其制造方法
DE102007038215A1 (de) * 2007-08-13 2009-02-19 Nano-X Gmbh Verfahren zur Herstellung einer aktiven Korrosionsschutzbeschichtung auf Bauteilen aus Stahl
JP4433334B2 (ja) * 2008-01-24 2010-03-17 ユケン工業株式会社 防錆塗膜を有する部材
JP5677337B2 (ja) * 2011-02-09 2015-02-25 新日鐵住金株式会社 プレコート金属板用下地処理剤、それを塗布した塗装下地処理金属板、及びそれを使用したプレコート金属板
JP5800668B2 (ja) * 2011-10-18 2015-10-28 日新製鋼株式会社 塗装ステンレス鋼板とポリカーボネート樹脂組成物の成形体とが接合された複合体およびその製造方法
CN103360833B (zh) * 2012-03-31 2015-11-18 攀钢集团攀枝花钢铁研究院有限公司 一种金属防护涂料及其用途和热镀金属材料
JP6703803B2 (ja) * 2013-10-31 2020-06-03 株式会社神戸製鋼所 表面処理金属板および金属板複合樹脂成形品
CN104594773B (zh) * 2014-12-08 2016-05-04 苏州福特美福电梯有限公司 轿壁门板及其涂装方法
CN113956760B (zh) * 2016-05-16 2023-09-08 蓝野钢铁有限公司 涂覆方法
CN106883738A (zh) * 2017-03-27 2017-06-23 德施普科技发展温州有限公司 一种具有防腐蚀性能的球墨铸铁管及其制备方法
JP6760196B2 (ja) * 2017-05-08 2020-09-23 日本軽金属株式会社 アルミニウム塗装材及びその製造方法

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JPS55148773A (en) * 1979-05-07 1980-11-19 Mitsui Mining & Smelting Co Ltd Surface treatment of zinc or zinc alloy product
JPS5719381A (en) * 1980-07-07 1982-02-01 Showa Alum Corp Formation of heating surface on aluminum material
JPS59116381A (ja) * 1982-12-24 1984-07-05 Mitsui Mining & Smelting Co Ltd 亜鉛および亜鉛合金面の表面処理法
JP2001089868A (ja) * 1999-07-16 2001-04-03 Nippon Steel Corp プレコート金属板用下地処理剤、それを塗布した塗装下地処理金属板、及びそれを使用した塗膜の加工密着性に優れるプレコート金属板

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JPH0912931A (ja) * 1995-07-04 1997-01-14 Teika Corp プレコート鋼板用塗料組成物

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JPS55148773A (en) * 1979-05-07 1980-11-19 Mitsui Mining & Smelting Co Ltd Surface treatment of zinc or zinc alloy product
JPS5719381A (en) * 1980-07-07 1982-02-01 Showa Alum Corp Formation of heating surface on aluminum material
JPS59116381A (ja) * 1982-12-24 1984-07-05 Mitsui Mining & Smelting Co Ltd 亜鉛および亜鉛合金面の表面処理法
JP2001089868A (ja) * 1999-07-16 2001-04-03 Nippon Steel Corp プレコート金属板用下地処理剤、それを塗布した塗装下地処理金属板、及びそれを使用した塗膜の加工密着性に優れるプレコート金属板

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1643009A1 (fr) * 2002-07-02 2006-04-05 Nippon Steel Corporation Plaque métallique prérevêtue ayant une excellente formabilité à la presse et son procédé de fabrication
EP1643009A4 (fr) * 2002-07-02 2009-12-09 Nippon Steel Corp Plaque métallique prérevêtue ayant une excellente formabilité à la presse et son procédé de fabrication
CN102168264A (zh) * 2011-03-28 2011-08-31 佛山市南海华豪铝型材有限公司 铝材喷涂前复合纳米陶瓷硅烷复合膜的方法

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MY144027A (en) 2011-07-29
CN1304639C (zh) 2007-03-14
TW591118B (en) 2004-06-11
CN1556873A (zh) 2004-12-22
JP3950370B2 (ja) 2007-08-01
KR20040044944A (ko) 2004-05-31

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