WO2011161968A1 - 亜鉛系めっき鋼板用の表面処理液ならびに亜鉛系めっき鋼板およびその製造方法 - Google Patents
亜鉛系めっき鋼板用の表面処理液ならびに亜鉛系めっき鋼板およびその製造方法 Download PDFInfo
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- WO2011161968A1 WO2011161968A1 PCT/JP2011/003596 JP2011003596W WO2011161968A1 WO 2011161968 A1 WO2011161968 A1 WO 2011161968A1 JP 2011003596 W JP2011003596 W JP 2011003596W WO 2011161968 A1 WO2011161968 A1 WO 2011161968A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/12—Wash primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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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
- 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
- C23C22/02—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 non-aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Definitions
- the present invention is a zinc suitable for use in applications that require oil retention in high temperature and high temperature and high humidity environments, such as motor cases of various motors (motor cases having a bearing holder portion for holding bearings).
- the present invention relates to a plated steel sheet and a manufacturing method thereof.
- the present invention also relates to a surface treatment solution useful for obtaining oil retention in a high temperature and high temperature and high humidity environment.
- motor case bearings of various motors used in automobiles, AV / OA equipment fields, etc. are widely used in which a rust-preventive film is formed on the surface of a zinc-based plated steel plate and plastic processing is performed. Yes. These bearings are roughly classified into rolling bearings and sliding bearings.
- various motor bearings used in electric motors used in automobiles, electronic recording equipment such as HDDs, and electronic equipment such as copying machines, etc. Many use plain bearings.
- Bearings for various motors used in automobiles, OA / AV devices, and the like generally have a structure that is held and fixed to a bearing holder portion formed in a motor case.
- the conventional research object has been focused on improving the bearing material, the bearing portion, and the structure around the bearing portion.
- Patent Documents 1 and 2 disclose a method for preventing the seepage of lubricating oil from the bearing portion by improving them.
- the improvement of the structure alone is not always sufficient to prevent the bleeding.
- Patent Document 3 and Patent Document 4 propose surface-treated galvanized steel sheets that are excellent in corrosion resistance, blackening resistance, appearance after press molding and corrosion resistance.
- Patent Document 5 proposes a film containing an organopolysiloxane compound as one of the silicon compounds and Patent Document 6 as an essential component of the silicon compound. It is not intended to improve.
- JP 7-238934 A Japanese Patent Laid-Open No. 9-210065 JP 2009-35758 A JP 2008-169470 A JP 2009-287049 A JP 2010-70786 A
- the present invention has been developed in view of the above-mentioned current situation, and it goes without saying that it has excellent appearance and corrosion resistance after press molding, as well as excellent oil retention in high temperature and high temperature and high humidity environments, particularly for motor cases and the like.
- a zinc-based plated steel sheet that can effectively prevent the seepage of lubricating oil that causes a shortage of lubricating oil in the bearing portion when applied to a component having a bearing holder portion for holding such a bearing. It aims at providing with the manufacturing method. It is another object of the present invention to provide a surface treatment solution suitable for obtaining a surface treatment film excellent in oil retention under high temperature and high temperature and high humidity environments.
- the inventors oozed the lubricating oil from the bearing portion on the inner surface of the motor case (surface treated steel plate surface) including the bearing holder portion. Because of this surface property, it was newly found out that one of the causes was that the lubricating oil in the bearing oozes out one after another on the inner surface of the surrounding case and spreads. And as a solution to this, by suppressing the wettability of the lubricating oil on the inner surface of the motor case (surface treated steel plate surface) including the bearing holder to a low level, the penetration of the lubricating oil from the bearing to the inner surface of the motor case is suppressed.
- the lubricating oil can be contained in the bearing, and as a result, it is possible to effectively suppress the seepage of the lubricating oil which causes a shortage of the lubricating oil in the bearing portion. Furthermore, a surface-treated steel sheet in which a surface treatment solution containing a predetermined amount of an organopolysiloxane compound in a solution based on a water-soluble zirconium compound is applied to the surface of a zinc-based plated steel sheet and dried is expected. It has been found that it is extremely useful for achieving the object, and the present invention has been completed.
- the gist configuration of the present invention is as follows. 1. Water-soluble zirconium compound (A), water-dispersible fine particle silica (B), silane coupling agent (C), vanadic acid compound (D), phosphoric acid compound (E), nickel compound (F), A surface treatment solution for a zinc-based plated steel sheet, characterized by containing the acrylic resin emulsion (G) and the organopolysiloxane compound (H) in a range satisfying the following conditions (1) to (8): .
- a surface treatment solution for a zinc-based plated steel sheet characterized by containing the acrylic resin emulsion (G) and the organopolysiloxane compound (H) in a range satisfying the following conditions (1) to (8): .
- Mass ratio (C) / (A Zr ) 0.6 to 2.5 between the silane coupling agent (C) and the Zr equivalent amount (A Zr ) of the water-soluble zirconium compound (A)
- Mass ratio (D V ) / (A Zr ) 0.04 of V converted amount (D V ) of vanadic acid compound (D) and Zr converted amount (A Zr ) of water-soluble zirconium compound (A) ⁇ 0.15
- Mass ratio (E P ) / (A Zr ) 0.11 between the P equivalent amount (E P ) of the phosphoric acid compound (E) and the Zr equivalent amount (A Zr ) of the water-soluble zir
- the content of the solid content (I s ) of the wax (I) in the total solid content of the surface treatment liquid is 2.5 to 10% by mass.
- the surface treatment solution described in 1 or 2 above is applied to the surface of a zinc-based plated steel sheet, and then dried by heating, so that the amount of Zr adhesion per side is 10 to 200 mg / m 2.
- the compound (f), the acrylic resin (g), and the organopolysiloxane compound-derived component (h) are contained within a range that satisfies the following conditions (11) to (15), and the Zr adhesion amount per one surface is A galvanized steel sheet having a coating of 10 to 200 mg / m 2 .
- Mass ratio (d V ) / (a Zr ) 0.04 to V converted amount (d V ) of vanadic acid compound (d) and Zr converted amount (a Zr ) of zirconium compound (a) 0.15
- Mass ratio (e P ) / (a Zr ) 0.11-0 of P equivalent amount (e P ) of phosphoric acid compound (e) and Zr equivalent amount (a Zr ) of zirconium compound (a) .55
- Mass ratio (f Ni ) / (a Zr ) 0.015-0.O between the Ni equivalent amount (f Ni ) of the nickel compound (f) and the Zr equivalent amount (a Zr ) of the zirconium compound (a).
- the content of acrylic resin (g) in the total amount of the solid content of the film is 0.5 to 10% by mass.
- Total amount (Si t ) of each of the fine particle silica (b), the silane coupling agent-derived component (c) and the organopolysiloxane compound-derived component (h) in terms of Si and the Zr equivalent amount of the zirconium compound (a) ( a Zr) and the mass ratio of (Si t) / (a Zr ) 0.23 ⁇ 1.0
- the appearance after press molding and the corrosion resistance are excellent, and it is possible to obtain a zinc-based plated steel sheet having excellent oil retention particularly in a high temperature and high temperature and high humidity environment.
- the zinc-based plated steel sheet used as the base of the surface-treated steel sheet of the present invention is not particularly limited as long as it is a steel sheet containing zinc in the plating film, and is not limited, but is a hot dip galvanized steel sheet (GI) or alloyed with this.
- GI hot dip galvanized steel sheet
- Galvanized steel sheets such as alloyed hot-dip galvanized steel sheets (GA), Zn—Ni plated steel sheets, Zn—Al alloy plated steel sheets (for example, Zn-5 mass% Al alloy plated steel sheets, Zn-55 mass% Al alloy plated steel sheets) ) And Zn—Al—Mg plated steel sheet (for example, Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet, Zn-11 mass% Al-3 mass% Mg alloy plated steel sheet).
- GA alloyed hot-dip galvanized steel sheets
- Zn—Al alloy plated steel sheets for example, Zn-5 mass% Al alloy plated steel sheets, Zn-55 mass% Al alloy plated steel sheets
- Zn—Al—Mg plated steel sheet for example, Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet, Zn-11 mass% Al-3 mass% Mg alloy plated steel sheet.
- a small amount of dissimilar metal elements or impurities such as nickel, cobalt, manganese, iron, molybdenum, tungsten, titanium, chromium, aluminum, magnesium, lead, antimony, tin, copper are added to the plating layer of each zinc-based plated steel sheet.
- a plated steel sheet containing one type or two or more types can also be used as a zinc-based plated steel sheet as a base of the surface-treated steel sheet.
- a multi-layer plated steel sheet in which two or more layers of the same type or different types are plated can also be used.
- the surface treatment liquid of the present invention uses water as a solvent, and a water-soluble zirconium compound (A), water-dispersible fine particle silica (B), a silane coupling agent (C), and a vanadic acid compound (D) in the solvent. ), A phosphoric acid compound (E), a nickel compound (F), an acrylic resin emulsion (G), and an organopolysiloxane compound (H), and if necessary, a wax ( I) can also be included.
- a phosphoric acid compound (E), a nickel compound (F), an acrylic resin emulsion (G), and an organopolysiloxane compound (H) can also be included.
- the water-soluble zirconium compound is a component that forms the skeleton of the film, and has an effect of imparting improved corrosion resistance and good appearance after press molding to the obtained film.
- examples of the water-soluble zirconium compound (A) include zirconium nitrate, zirconium oxynitrate, zirconyl acetate, zirconyl sulfate, zirconyl ammonium carbonate, zirconyl potassium carbonate, and sodium zirconyl carbonate. More than seeds can be used. Further, it may contain an inorganic fluorine-containing compound such as zircon hydrofluoric acid or a salt thereof, and can be used as long as the solution is compatible.
- the water-dispersible fine particle silica has the effect of imparting, for example, improved corrosion resistance and a good appearance after press molding to the obtained film.
- the water-dispersible fine particle silica (B) is not particularly limited in particle size and type, but colloidal silica or dry silica can be used.
- colloidal silica include Snowtex O, C, N, 20, OS, OXS (registered trademark) manufactured by Nissan Chemical Co., Ltd., and AEROSIL50 manufactured by Nippon Aerosil Co., Ltd. as dry silica. , 130, 200, 300, 380 (registered trademark), etc., and one or more selected from these can be used.
- the mixing ratio of the water-dispersible fine particle silica (B) is the mass ratio (B s ) between the solid content (B s ) of the water-dispersible fine particle silica (B) and the Zr equivalent (A Zr ) of the water-soluble zirconium compound (A). ) / (A Zr ) in the range of 0.3 to 1.2. This is because when (B s ) / (A Zr ) is less than 0.3, the corrosion resistance and the appearance after pressing deteriorate, whereas when (B s ) / (A Zr ) exceeds 1.2, film formation is not achieved. This is because it becomes difficult and the corrosion resistance decreases.
- a preferred mass ratio (B s ) / (A Zr ) is in the range of 0.4 to 0.9.
- the silane coupling agent (C) causes a crosslinking reaction with the water-soluble zirconium compound (A) and the water-dispersible fine particle silica (B) to form a film having a three-dimensional crosslinking reaction structure. .
- the effect which improves the corrosion resistance of the film obtained, oil retention, etc. is provided to a film.
- silane coupling agent (C) examples include vinyl methoxy silane, vinyl ethoxy silane, vinyl trichloro silane, vinyl trimethoxy silane, vinyl triethoxy silane, ⁇ - (3,4 epoxy cyclohexyl) ethyl trimethoxy silane.
- the mixing ratio of the silane coupling agent (C) is 0.6 in terms of a mass ratio (C) / (A Zr ) between the silane coupling agent (C) and the Zr equivalent (A Zr ) of the water-soluble zirconium compound (A).
- the range is from ⁇ 2.5. This is because if the mass ratio (C) / (A Zr ) is less than 0.6, the appearance and oil retention after pressing are lowered, while if it exceeds 2.5, film formation becomes difficult and corrosion resistance is lowered. This is because the stability of the treatment liquid also decreases.
- a preferred mass ratio (C) / (A Zr ) is in the range of 0.8 to 1.8.
- the silane coupling agent (C) in this invention is 100% of solid content.
- the vanadic acid compound forms a sparingly soluble salt with the phosphoric acid compound described later, so that the phosphoric acid compound is fixed in the film and is effective in improving the corrosion resistance of the film.
- the vanadate compound (D) include ammonium metavanadate and sodium metavanadate, and one or more selected from these can be used.
- the compounding ratio of the vanadic acid compound (D) is the mass ratio (D V ) / ( V ) of the vanadate compound (D) in terms of V (D V ) and the Zr equivalent (A Zr ) of the water-soluble zirconium compound (A).
- a Zr ) is in the range of 0.04 to 0.15. This is because if the mass ratio (D V ) / (A Zr ) is less than 0.04, the corrosion resistance decreases, while if it exceeds 0.15, the appearance after pressing decreases.
- a preferred mass ratio (D V ) / (A Zr ) is in the range of 0.06 to 0.14.
- the phosphoric acid compound reacts with the plating film of the zinc-based plated steel sheet to form a hardly soluble salt, and is therefore an effective component for improving the corrosion resistance of the film.
- the phosphoric acid compound (E) is not particularly limited as long as it is compatible with the liquid.
- the water-soluble phosphoric acid compound include phosphoric acid, primary phosphate, and secondary phosphate. , Triphosphates, pyrophosphates, pyrophosphates, tripolyphosphates, tripolyphosphates, etc. condensed phosphates, phosphorous acid, phosphite, hypophosphorous acid, hypophosphite, and phosphones
- Examples include acids or phosphonates.
- examples of phosphonates include nitrilotrismethylenephosphonic acid, phosphonobutanetricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, methyldiphosphonic acid, methylenephosphonic acid, ethylidenediphosphonic acid, and 1-hydroxymethane-1.1.
- -Diphosphonic acid and ammonium salts and alkali metal salts thereof.
- One or more selected from these phosphoric acid compounds can be used.
- the blending ratio of the phosphoric acid compound (E) is the mass ratio (E P ) / P conversion amount (E P ) of the phosphoric acid compound (E) and the Zr conversion amount (A Zr ) of the water-soluble zirconium compound (A).
- (A Zr ) is in the range of 0.11 to 0.55. The reason is that if the mass ratio (E P ) / (A Zr ) is less than 0.11, the corrosion resistance decreases, while if it exceeds 0.55, the appearance after pressing decreases.
- a preferred mass ratio (E P ) / (A Zr ) is in the range of 0.20 to 0.37.
- the nickel compound is an effective component for improving the corrosion resistance of the coating because it is deposited on the plated coating of the zinc-based plated steel sheet to form a hardly soluble salt.
- the nickel compound (F) is not particularly limited as long as it is compatible with the liquid, and examples thereof include nickel nitrate, nickel sulfate, nickel carbonate, nickel chloride, and nickel phosphate. One or more selected from among them can be mixed and used.
- the mixing ratio of the nickel compound (F) is the mass ratio (F Ni ) / (A of the Ni equivalent amount (F Ni ) of the nickel compound (F) and the Zr equivalent amount (A Zr ) of the water-soluble zirconium compound (A).
- Zr ) is in the range of 0.015 to 0.065. This is because if the mass ratio (F Ni ) / (A Zr ) is less than 0.015, the corrosion resistance decreases, and if it exceeds 0.065, the corrosion resistance decreases.
- a preferred mass ratio (F Ni ) / (A Zr ) is in the range of 0.023 to 0.049.
- the acrylic resin emulsion is a component that forms the skeleton of the film, and is an effective component for improving the corrosion resistance of the resulting film.
- the acrylic resin emulsion (G) is an aqueous emulsion resin obtained by emulsion polymerization of vinyl monomers such as acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, and styrene, and if compatible,
- vinyl monomers such as acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, and styrene
- Especially a nonionic emulsifier can be used conveniently.
- nonionic emulsifiers those having polyethylene oxide or polypropylene oxide in their structure can be particularly preferably used.
- the blending ratio of the solid content (G s ) of the acrylic resin emulsion (G) is in the range of 0.5 to 10% by mass with respect to the total solid content of the surface treatment liquid. This is because if the amount is less than 0.5% by mass, the corrosion resistance decreases, while if it exceeds 10% by mass, the appearance after press molding may be decreased due to an increase in organic components.
- a preferable blending ratio is in the range of 1 to 9% by mass, and more preferably in the range of 2 to 8% by mass.
- Tg glass transition temperature
- FOX glass transition temperature
- Wi is a mass fraction of component i
- Tgi Tg (K) of component i.
- the organopolysiloxane compound is an important substance for exhibiting oil retention in a high temperature and high temperature and high humidity environment, which is the object of the invention.
- the organopolysiloxane compound (H) is not particularly limited as long as it can be blended in the liquid, and it is possible to use a product obtained by mechanical emulsification or emulsion polymerization using an appropriate emulsifier.
- organopolysiloxanes having a viscosity at 25 ° C. of 1 to 100,000 mm 2 / s are particularly suitable. This is because if the viscosity at 25 ° C. is 1 mm 2 / s or more, the oil retention is sufficient, while if it is 100,000 mm 2 / s or less, it is compatible with the liquid.
- the blending ratio of the solid content (H s ) of the organopolysiloxane compound (H) is in the range of 0.55 to 6.5 mass% with respect to the total solid content of the surface treatment liquid. The reason is that if the amount is less than 0.55% by mass, the oil retention is lowered, whereas if it exceeds 6.5% by mass, not only the effect is saturated, but also the corrosion resistance is lowered.
- a preferable blending ratio is in the range of 0.7 to 4.6% by mass.
- the total amount (Si T ) of the water-dispersible fine particle silica (B), the silane coupling agent (C) and the organopolysiloxane compound (H) in terms of Si is the Zr equivalent amount (A Zr ) of the water-soluble zirconium compound (A).
- a mass ratio (Si T ) / (A Zr ) of 0.23 to 1.0 This is because if the mass ratio (Si T ) / (A Zr ) is less than 0.23, the corrosion resistance and the appearance after press molding are lowered, while if it exceeds 1.0, the corrosion resistance is lowered.
- a preferred mass ratio (Si T ) / (A Zr ) is in the range of 0.30 to 0.67.
- the surface treatment liquid may further contain wax (I).
- the wax (I) is not particularly limited as long as it is compatible with the liquid. Examples thereof include polyolefin waxes such as polyethylene, montan wax, paraffin wax, microcrystalline wax, carnauba wax, lanolin wax, and fluorine wax, and one or more selected from these can be used.
- the blending ratio of the solid content (I s ) is desirably in the range of 2.5 to 10% by mass with respect to the total solid content of the surface treatment liquid. This is because the appearance after press molding does not deteriorate if the amount is 2.5% by mass or more, whereas the corrosion resistance does not decrease if the amount is 10% by mass or less.
- a preferred blending ratio is in the range of 3.4 to 7.1% by mass.
- the pH of the surface treatment solution of the present invention is not particularly limited, but is preferably about pH 6 to 11 in terms of the stability of the treatment agent. This is because if the pH of the treatment agent is 6 or more, the stability of the treatment agent is not lowered and the corrosion resistance is not lowered. On the other hand, if the pH is 11 or less, the etching of zinc in the plating film is appropriate and the corrosion resistance is low. It is because it does not fall. More preferably, the pH is 8-10. In addition, as an alkali used for adjusting to this pH, ammonia and an amine are preferable, and a phosphoric acid compound is preferable as an acid.
- the surface treatment film is formed by applying the surface treatment liquid described above to the surface of the zinc-based plated steel sheet and drying it by heating. It is important that the adhesion amount of the surface treatment film after heat drying is in the range of 10 to 200 mg / m 2 in terms of Zr of the zirconium compound in the film. This is because when the adhesion amount is less than 10 mg / m 2 , sufficient corrosion resistance and oil retention at high temperatures cannot be obtained, while when it exceeds 200 mg / m 2 , the film is thick, so that the appearance and corrosion resistance after press molding are increased. This is because of a decrease. A preferable adhesion amount is in the range of 30 to 150 mg / m 2 . Moreover, this surface treatment liquid can be applied not only once but also a plurality of times to the zinc-based plated steel sheet.
- a generally known method can be used.
- a coating method any method such as a roll coater (3-roll method, 2-roll method) or a squeeze coater may be used.
- coating treatment with a squeeze coater or the like, immersion treatment, spray treatment may be used, and then the coating amount may be adjusted, the appearance may be made uniform, and the film thickness may be made uniform by an air knife method or a roll drawing method. .
- the drying temperature of the heat treatment is preferably 50 to 250 ° C. as the ultimate plate temperature. This is because if it is 250 ° C. or lower, the coating does not crack and does not lower the corrosion resistance. On the other hand, if it is 50 degreeC or more, there is not much moisture remaining in a film
- Such a steel sheet can be obtained by the above-described method for producing a zinc-based plated steel sheet using the surface treatment liquid described above.
- the zinc-based plated steel sheet thus obtained has on its surface a zirconium compound (a), fine-particle silica (b), a silane coupling agent-derived component (c), a vanadate compound (d), and a phosphate compound.
- a nickel compound (f), an acrylic resin (g), and an organopolysiloxane compound-derived component (h) are contained within the following range, and the Zr adhesion amount per side is 10 to 200 mg. / M 2 . If necessary, the solid content of the wax (i) the (i s) can be contained within the following range.
- Mass ratio (d V ) / (a Zr ) 0.04 to V converted amount (d V ) of vanadic acid compound (d) and Zr converted amount (a Zr ) of zirconium compound (a) 0.15
- Mass ratio (e P ) / (a Zr ) 0.11-0 of P equivalent amount (e P ) of phosphoric acid compound (e) and Zr equivalent amount (a Zr ) of zirconium compound (a) .55
- Mass ratio (f Ni ) / (a Zr ) 0.015-0.O between the Ni equivalent amount (f Ni ) of the nickel compound (f) and the Zr equivalent amount (a Zr ) of the zirconium compound (a).
- the content of acrylic resin (g) in the total amount of the solid content of the film is 0.5 to 10% by mass.
- Total amount (Si t ) of each of the fine particle silica (b), the silane coupling agent-derived component (c) and the organopolysiloxane compound-derived component (h) in terms of Si and the Zr equivalent amount of the zirconium compound (a) ( a Zr) and the mass ratio of (Si t) / (a Zr ) 0.23 ⁇ 1.0 (16) relative to the total weight of coating solids, the solid content (i s) of the wax (i) 2.5 to 10 mass%
- the inventors consider as follows. First, it is considered that the oil retention is improved by increasing the affinity between the surface treatment film and the lubricating oil. In particular, when an organopolysiloxane compound is blended, it is considered that the oil retention is improved because the alkyl group of the organopolysiloxane compound exhibits a high affinity with the lubricating oil. In addition, the effect of the organopolysiloxane compound in a high temperature and high temperature and high humidity environment is also expected to be improved when the silane coupling agent forms a siloxane bond in the organopolysiloxane compound.
- water-soluble zirconium is considered to bind to fine particle silica or a silane coupling agent and serve as a film binder.
- the inorganic film formed in this way is less likely to adhere to or accumulate on a processed product or a mold like an organic polymer. Further, when the wax is contained, the stress applied to the film is relieved, so that the appearance after press molding and the corrosion resistance can be improved.
- the amount of the surface-treated film adhered is in the range of 10 to 200 mg / m 2 in terms of Zr of the zirconium compound in the film because the reason for limiting the amount of the surface-treated film described above is limited. It is as follows.
- Test plate preparation method (1) Test material (material) The following commercially available materials were used as test materials.
- a zinc basis weight 20/20 (g / m 2), which means that the both surfaces of the steel sheet having a plating of 20 (g / m 2).
- Pretreatment (cleaning) As a method for preparing a test piece, first, the surface of the above-mentioned test material was treated with Palclean N364S manufactured by Nihon Parkerizing to remove oil and dirt on the surface. Next, after washing with tap water and confirming that the surface of the metal material was wet with 100% water, a method of pouring pure water and drying the moisture in an oven heated to 100 ° C. was used.
- G ⁇ Acrylic resin emulsion (G)>
- G1 Styrene-ethyl methacrylate-n-butyl acrylate-acrylic acid (Tg: 18 ° C)
- G2 Methyl methacrylate-2-ethylhexyl acrylate-acrylic acid (Tg: 14 ° C.)
- G3 Styrene-ethyl methacrylate-n-butyl acrylate-acrylic acid (Tg: 5 ° C.)
- G4 Styrene-ethyl methacrylate-n-butyl acrylate-acrylic acid (Tg: 40 ° C.)
- H1 Methylphenyl silicone oil (viscosity 100mm 2 / s)
- H2 Dimethyl silicone oil (viscosity 0.65mm 2 / s)
- H3 Methyl phenyl silicone oil (viscosity 500,000 mm 2 / s)
- the above surface treatment solution was coated on each test plate using a bar coater, and then placed in an oven without being washed with water.
- the drying temperatures shown in Tables 2-1 and 2-2 were used.
- the adhesion amount of the surface treatment film is adjusted by the concentration of the surface treatment solution, and the adhesion amount of the film is quantified by using a calibration curve obtained from a standard plate with a known Zr adhesion amount using a fluorescent X-ray analyzer. .
- the drying conditions were adjusted by the oven temperature and the time in the oven. The drying temperature indicates the temperature reached on the test plate surface.
- the specific method of bar coating is as follows.
- the treatment agent was dropped on the test plate and painted with a # 3-5 bar coater. In that case, it adjusted so that it might become the predetermined
- Tables 2-1 and 2-2 show the types of test plates (test materials) for each test level, the coating method, and the drying temperature during film formation. The compositions and Zr adhesion amounts of the obtained galvanized steel sheet films are shown in Tables 3-1 and 3-2.
- ⁇ Bleeding spread height less than 0.5 cm ⁇ : Bleeding spread height of 0.5 cm or more and less than 1.0 cm ⁇ -: Bleeding spread height of 1.0 cm or more and less than 1.5 cm ⁇ : Bleeding spread height of 1.5 cm Or more, less than 3.0 cm x: spreading spread height of 3.0 cm or more
- the test plate described above has a kinematic viscosity at 40 ° C. of 51 to 69 mm 2 / s and a kinematic viscosity at 100 ° C. of 11.1 to 14.9 mm 2 / s.
- s lubricating oil (“ALL TIME J 652” manufactured by NOK Cluber Co., Ltd.) is placed in a container, and the lower end of a vertically placed test material is immersed in the lubricating oil in the container at 60 ° C. and a relative humidity of 90 % And left for 3 days to measure the spreading spread of the lubricant.
- the evaluation criteria are as follows.
- ⁇ Bleeding spread height less than 0.5 cm ⁇ : Bleeding spread height of 0.5 cm or more and less than 1.0 cm ⁇ -: Bleeding spread height of 1.0 cm or more and less than 1.5 cm ⁇ : Bleeding spread height of 1.5 cm Or more, less than 3.0 cm x: spreading spread height of 3.0 cm or more
- Thickness of galvanized steel sheet 0.8mm, forming speed: 450mm / sec, blank diameter ⁇ 90mm (First stage) Punch diameter ⁇ 49mm, punch and die clearance 1.0mm (Second stage) Punch diameter ⁇ 39mm, punch-to-die clearance 0.8mm (3rd stage) Punch diameter ⁇ 32mm, punch-to-die clearance 0.8mm (4th stage) Punch diameter ⁇ 27.5mm, punch and die clearance 0.8mm (5th stage) Punch diameter ⁇ 24.4mm, punch and die clearance 0.8mm
- the determination method was as follows. A: Peeling debris accumulated in the lubricating oil hardly adheres to the surface of the molding material, and blackening of the molding material surface is not confirmed. ⁇ : Exfoliation residue accumulated in the lubricating oil is slightly attached to the surface of the molding material, but no blackening is observed on the surface of the molding material. ⁇ -: Peeling debris accumulated in the lubricating oil is slightly adhered to the surface of the molding material, and slight darkening is observed on the surface of the molding material. ⁇ : A small amount of debris accumulated in the lubricating oil adheres to the surface of the molding material, and a little darkening is observed on the surface of the molding material. X: A large amount of peeling residue accumulated in the lubricating oil adheres to the surface of the molding material, and darkening is remarkably observed on the surface of the molding material.
- Table 4-1 and Table 4-2 show the survey results on the quality (corrosion resistance, oil retention and appearance after pressing) of the surface-treated zinc-plated steel sheet obtained.
- both zinc-based plated steel sheets having a Zr-containing coating using a surface treatment solution that is a component according to the present invention have good corrosion resistance and appearance after press molding.
- the oil retention in a high temperature and high temperature and high humidity environment is excellent.
- all of the comparative examples were inferior in one or more of corrosion resistance, appearance after press molding, and oil retention.
- the present invention it is possible to provide a galvanized steel sheet that is excellent in oil retention in a high temperature and high temperature and high humidity environment. As a result, smooth sliding of the rotating shaft with respect to the bearing can be ensured for a long time, thereby reducing vibration and noise and extending the life of various motors used in automobiles, AV / OA equipment fields, etc. Can do.
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Abstract
Description
これら軸受は、転がり軸受とすべり軸受とに大別されるが、近年、自動車に用いられる電装モーター、HDDなどの電子記録機器、およびコピー機などの電子機器に用いられる各種モーターの軸受等は、その多くがすべり軸受を用いている。
自動車、OA・AV機器などで使用される各種モーターの軸受(軸受部材)は、モーターケースに形成された軸受ホルダ部に保持・固定される構造が一般的である。このようなモーターの軸受部における潤滑油の滲み出しを防止するために、従来の研究対象は、専ら軸受材料や軸受部および軸受部周辺の構造などの改善に向けられてきた。
例えば、特許文献1および2では、それらを改善することにより、軸受部からの潤滑油の滲み出しを防止する方法が開示されている。しかし、それら構造の改善だけでは、滲み出し防止効果は必ずしも十分なものとはいえなかった。
ここに、特許文献3および特許文献4には、耐食性、耐黒変性、プレス成形後の外観や耐食性に優れた表面処理亜鉛系めっき鋼板が提案されている。しかしながら、これらの鋼板は、油保持性の効果はほとんど期待できないか、常温では一定の効果があったとしても、高温あるいは高温多湿といった過酷な環境下では、常温の場合と比べるとその効果は限定的なものでしかなかった。
特許文献5には、ケイ素化合物の1つとして、また特許文献6には、ケイ素化合物の必須成分として、オルガノポリシロキサン化合物を含有する皮膜がそれぞれ提案されているが、これらは鋼板の油保持性の改善を目的としたものではない。
また、本発明は、高温および高温高湿環境下での油保持性に優れた表面処理皮膜を得るのに好適な表面処理液を提供することを目的とする。
そして、この解決策として、軸受ホルダ部を含めたモーターケース内面(表面処理鋼板表面)の潤滑油ぬれ性を低いレベルに抑えることにより、軸受からモーターケース内面への潤滑油の浸透を抑えることで、潤滑油を軸受内に封じ込めることができ、その結果、軸受部の潤滑油不足を生じるような潤滑油の滲み出しを効果的に抑制できることを併せて見出した。
そしてさらに、水溶性ジルコニウム化合物をベースとする溶液中に、所定量のオルガノポリシロキサン化合物を含有させた表面処理液を、亜鉛系めっき鋼板の表面に塗布・乾燥した表面処理鋼板が、所期した目的の達成のためには極めて有用であることを知見し、本発明を完成するに至った。
1.水溶性ジルコニウム化合物(A)と、水分散性微粒子シリカ(B)と、シランカップリング剤(C)と、バナジン酸化合物(D)と、リン酸化合物(E)と、ニッケル化合物(F)と、アクリル樹脂エマルション(G)と、オルガノポリシロキサン化合物(H)とを、下記(1)~(8)の条件を満足する範囲で含有することを特徴とする亜鉛系めっき鋼板用の表面処理液。
記
(1)水分散性微粒子シリカ(B)の固形分(Bs)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(Bs)/(AZr)=0.3~1.2
(2)シランカップリング剤(C)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(C)/(AZr)=0.6~2.5
(3)バナジン酸化合物(D)のV換算量(DV)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(DV)/(AZr)=0.04~0.15
(4)リン酸化合物(E)のP換算量(EP)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(EP)/(AZr)=0.11~0.55
(5)ニッケル化合物(F)のNi換算量(FNi)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(FNi)/(AZr)=0.015~0.065
(6)表面処理液の全固形分における、アクリル樹脂エマルション(G)の固形分(Gs)の含有量が0.5~10質量%
(7)表面処理液の全固形分における、オルガノポリシロキサン化合物(H)の固形分(Hs)の含有量が0.55~6.5質量%
(8)水分散性微粒子シリカ(B)、シランカップリング剤(C)およびオルガノポリシロキサン化合物(H)の各Si換算の合計量(SiT)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(SiT)/(AZr)=0.23~1.0
記
(9)表面処理液の全固形分における、ワックス(I)の固形分(Is)の含有量が2.5~10質量%
記
(11)バナジン酸化合物(d)のV換算量(dV)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(dV)/(aZr)=0.04~0.15
(12)リン酸化合物(e)のP換算量(eP)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(eP)/(aZr)=0.11~0.55
(13)ニッケル化合物(f)のNi換算量(fNi)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(fNi)/(aZr)=0.015~0.065
(14)皮膜固形分の合計量における、アクリル樹脂(g)の含有量が0.5~10質量%
(15)微粒子シリカ(b)、シランカップリング剤由来成分(c)およびオルガノポリシロキサン化合物由来成分(h)の各Si換算の合計量(Sit)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(Sit)/(aZr)=0.23~1.0
記
(16)皮膜固形分の合計量に対し、ワックス(i)の固形分(is)の含有量が2.5~10質量%
本発明の表面処理鋼板のベースとなる亜鉛系めっき鋼板としては、そのめっき皮膜中に亜鉛を含有する鋼板であればよく、特に制限はないが、溶融亜鉛めっき鋼板(GI)又はこれを合金化した合金化溶融亜鉛めっき鋼板(GA)等の亜鉛めっき鋼板、Zn-Niめっき鋼板、Zn-Al合金めっき鋼板(例えば、Zn-5質量%Al合金めっき鋼板、Zn-55質量%Al合金めっき鋼板)、およびZn-Al-Mgめっき鋼板(例えばZn-6質量%Al-3質量%Mg合金めっき鋼板、Zn-11質量%Al-3質量%Mg合金めっき鋼板)などを挙げることができる。
本発明の表面処理液は、水を溶媒とし、この溶媒中に水溶性ジルコニウム化合物(A)と、水分散性微粒子シリカ(B)と、シランカップリング剤(C)と、バナジン酸化合物(D)と、リン酸化合物(E)と、ニッケル化合物(F)と、アクリル樹脂エマルション(G)と、オルガノポリシロキサン化合物(H)とを含有させたものであり、さらに必要に応じて、ワックス(I)を含有させることもできる。
ここに、水溶性ジルコニウム化合物(A)としては、硝酸ジルコニウム、オキシ硝酸ジルコニウム、酢酸ジルコニル、硫酸ジルコニル、炭酸ジルコニルアンモニウム、炭酸ジルコニルカリウム、および炭酸ジルコニルナトリウムなどが挙げられ、これらのうちから選んだ1種以上を用いることができる。
また、ジルコンフッ化水素酸やその塩などのような無機フッ素含有化合物を含んだものでも良く、液が相溶する限り使用可能である。
ここに、水分散性微粒子シリカ(B)としては、粒径や種類などに特に制限はないが、コロイダルシリカや乾式シリカを用いることができる。コロイダルシリカとしては、例えば、日産化学(株)製のスノーテックスO、C、N、20、OS、OXS(登録商標)などが挙げられ、また、乾式シリカとしては日本アエロジル(株)製のAEROSIL50、130、200、300、380(登録商標)などが挙げられ、これらのうちから選んだ1種以上を用いることができる。
ここに、シランカップリング剤(C)としては、例えば、ビニルメトキシシラン、ビニルエトキシシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、β-(3,4エポキシシクロヘキシル)エチルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、N-β(アミノエチル)γ-アミノプロピルメチルジメトキシシラン、N-β(アミノエチル)γ-アミノプロピルメチルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-メタクリロキシプロピルメチルトリメトキシシラン、γ-メタクリロキシプロピルメチルジエトキシシラン、γ-メタクリロキシプロピルメチルトリエトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン、γ-メルカプトプロピルメチルトリメトキシシラン、p-スチリルトリメトキシシラン、γ-アクリロキシプロピルトリメトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、γ-ウレイドプロピルトリエトキシシラン、γ-クロロプロピルトリメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、γ-イソシアネートプロピルトリエトキシシラン、γ-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、およびN-(ビニルベンジルアミン)-β-アミノエチル-γ-アミノプロピルトリメトキシシランなどが挙げられ、これらのうちから選んだ1種以上を用いることができる。
ここに、バナジン酸化合物(D)としては、例えば、メタバナジン酸アンモニウム、およびメタバナジン酸ナトリウムが挙げられ、これらのうちから選んだ1種以上を用いることができる。
ここに、リン酸化合物(E)は、液に相溶するものであれば特に制限はなく、この水溶性リン酸化合物としては、例えば、リン酸、第一リン酸塩、第二リン酸塩、第三リン酸塩、ピロリン酸、ピロリン酸塩、トリポリリン酸、トリポリリン酸塩、などの縮合リン酸塩、亜リン酸、亜リン酸塩、次亜リン酸、次亜リン酸塩、およびホスホン酸またはホスホン酸塩等が挙げられる。さらに、ホスホン酸塩としては、例えばニトリロトリスメチレンホスホン酸、ホスフォノブタントリカルボン酸、エチレンジアミンテトラメリレンホスホン酸、メチルジホスホン酸、メチレンホスホン酸、エチリデンジホスホン酸、1-ヒドロキシメタン-1.1-ジホスホン酸、およびこれらのアンモニウム塩、アルカリ金属塩などが挙げられる。これらリン酸化合物のうちから選んだ1種以上を用いることができる。
ここに、ニッケル化合物(F)としては、液に相溶するものであれば特に制限はなく、例えば、硝酸ニッケル、硫酸ニッケル、炭酸ニッケル、塩化ニッケル、およびリン酸ニッケルなどが挙げられ、これらのうちから選んだ1種以上を混合して用いることができる。
ここに、アクリル樹脂エマルション(G)としては、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、およびスチレン等のビニル系モノマーを乳化重合した水系エマルション樹脂であって、相溶性があれば、乳化剤の有無や乳化剤の種類に特に制限はないが、なかでもノニオン系乳化剤は好適に使用できる。また、ノニオン系乳化剤の中でも、ポリエチレンオキサイドやポリプロピレンオキサイドをその構造に持つものは、特に好適に使用できる。
1/Tg=Σ(Wi/Tgi)・・・式(1)
ここで、Wiは、成分iの質量分率であり、また、Tgiは、成分iのTg(K)である。
というのは、ノニオン系アクリル樹脂エマルションのTgが10℃以上であれば、プレス後の外観が低下することなく、一方、Tgが30℃以下であれば、耐食性が低下することがないからである。
ここに、オルガノポリシロキサン化合物(H)としては、液に配合可能であれば特に制限はなく、適当な乳化剤を用いて機械乳化や乳化重合したものを使用することが可能である。
例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ブチルトリメトキシシラン、ペンチルトリメトキシシラン、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、デシルトリメトキシシラン、ドデシルトリメトキシシラン、テトラデシルトリメトキシシラン、オクタデシルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、3,3,3-トリフロロプロピルトリメトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のアルコキシシランや、
メチルハイドロジェンシリコーンオイル、ジメチルシリコーンオイル、ジエチルシリコーンオイル、ジイソプロピルシリコーンオイル、ジブチルシリコーンオイル、ジアミルシリコーンオイル、ジヘキシルシリコーンオイル、ジラウリルシリコーンオイル、ジステアリルシリコーンオイル、
メチルフェニルシリコーンオイル、ジフェニルシリコーンオイル、エチルフェニルシリコーンオイル、イソプロピルフェニルシリコーンオイル、ブチルフェニルシリコーンオイル、アミルフェニルシリコーンオイル、ヘキシルフェニルシリコーンオイル、ラウリルフェニルシリコーンオイル、ステアリルフェニルシリコーンオイル等が挙げられる。
本発明では、これらのうちから選んだ1種以上を用いることができる。
このワックス(I)としては、液に相溶するものであれば特に制限はない。
例えば、ポリエチレンなどのポリオレフィンワックス、モンタンワックス、パラフィンワックス、マイクロクリスタリンワックス、カルナバワックス、ラノリン系ワックス、およびフッ素系ワックスなどが挙げられ、これらのうちから選んだ1種以上を用いることができる。
なお、このpHに調整するのに用いられるアルカリとしてはアンモニア、アミンが好ましく、一方、酸としてはリン酸化合物が好ましい。
また、この表面処理液は、亜鉛系めっき鋼板に対して、1度の塗布だけでなく、複数回の塗布をすることもできる。
塗布法としては、ロールコーター(3ロール方式、2ロール方式)、スクイズコーターなどいずれの方法でも良い。また、スクイズコーターなどによる塗布処理や、浸漬処理、スプレー処理でも良く、さらにその後に、エアーナイフ法やロール絞り法により塗布量の調整、外観の均一化、膜厚の均一化を行ってもよい。
かくして得られた亜鉛系めっき鋼板は、その表面に、ジルコニウム化合物(a)と、微粒子シリカ(b)と、シランカップリング剤由来成分(c)と、バナジン酸化合物(d)と、リン酸化合物(e)と、ニッケル化合物(f)と、アクリル樹脂(g)と、オルガノポリシロキサン化合物由来成分(h)とを下記の範囲で含有するものであり、片面当たりのZr付着量は10~200mg/m2とする。さらに必要に応じて、ワックス(i)の固形分(is)を下記の範囲で含有させることもできる。
(11)バナジン酸化合物(d)のV換算量(dV)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(dV)/(aZr)=0.04~0.15
(12)リン酸化合物(e)のP換算量(eP)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(eP)/(aZr)=0.11~0.55
(13)ニッケル化合物(f)のNi換算量(fNi)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(fNi)/(aZr)=0.015~0.065
(14)皮膜固形分の合計量における、アクリル樹脂(g)の含有量が0.5~10質量%
(15)微粒子シリカ(b)、シランカップリング剤由来成分(c)およびオルガノポリシロキサン化合物由来成分(h)の各Si換算の合計量(Sit)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(Sit)/(aZr)=0.23~1.0
(16)皮膜固形分の合計量に対し、ワックス(i)の固形分(is)の含有量が2.5~10質量%
まず、表面処理皮膜と潤滑油の親和力が大きくなることで、油保持性が向上すると考えられる。
特に、オルガノポリシロキサン化合物を配合した場合、オルガノポリシロキサン化合物のアルキル基が潤滑油と高い親和力を呈するため、油保持性が良好になると考えられる。また、オルガノポリシロキサン化合物はシランカップリング剤がシロキサン結合を形成することによっても、高温および高温高湿環境下でのオルガノポリシロキサン化合物の効果が向上するものと思われる。
さらに、ワックスを含有させた場合、皮膜が受ける応力が緩和されるため、プレス成形後の外観、および耐食性を向上させることができる。
(1)供試材(素材)
以下の市販の材料を供試材として使用した。
(i)電気亜鉛めっき鋼板(EG):板厚=0.8mm、亜鉛目付量=20/20(g/m2)
(ii)溶融亜鉛めっき鋼板(GI):板厚=0.8mm、亜鉛目付量=60/60(g/m2)
なお、例えば、電気亜鉛めっき鋼板において、亜鉛目付量=20/20(g/m2)とは、鋼板の両面のそれぞれに20(g/m2)のめっきを有することを意味する。
試験片の作製方法としては、まず上記の供試材の表面を、日本パーカライジング製パルクリーンN364Sを用いて処理し、表面上の油分や汚れを取り除いた。次に、水道水で水洗して金属材料表面が100%水で濡れることを確認したあと、更に純水を流しかけ、100℃に熱したオーブンで水分を乾燥する方法を用いた。
表1-1、表1-2および表1-3に示す組成(質量比)になる種々の亜鉛系めっき鋼板用の表面処理液を作製した。なお、表面処理液中における固形分濃度は、5質量%とした。
<水溶性ジルコニウム化合物(A)>
A1:炭酸ジルコニルナトリウム
A2:炭酸ジルコニルアンモニウム
B1:スノーテックスN(登録商標)
B2:スノーテックスO(登録商標)
C1:γ-アミノプロピルトリエトキシシラン
C2:γ-グリシドキシプロピルトリメトキシシラン
D1:メタバナジン酸ナトリウム
D2:メタバナジン酸アンモニウム
E1:1-ヒドロキシメタン-1.1-ジホスホン酸
E2:リン酸
F1:硝酸ニッケル六水和物
F2:硫酸ニッケル六水和物
G1:スチレン-エチルメタアクリレート-n-ブチルアクリレート-アクリル酸
(Tg:18℃)
G2:メチルメタクリレート-2-エチルヘキシルアクリレート-アクリル酸
(Tg:14℃)
G3:スチレン-エチルメタアクリレート-n-ブチルアクリレート-アクリル酸
(Tg:5℃)
G4:スチレン-エチルメタアクリレート-n-ブチルアクリレート-アクリル酸
(Tg:40℃)
H1:メチルフェニルシリコーンオイル(粘度100mm2/s)
H2:ジメチルシリコーンオイル(粘度0.65mm2/s)
H3:メチルフェニルシリコーンオイル(粘度500,000mm2/s)
I1:ポリエチレンワックス(ケミパールW900(登録商標))
上記の表面処理液を、バーコーターを用いて各試験板上に塗装し、その後、水洗することなく、そのままオーブンに入れ、表2-1および表2-2に示す乾燥温度で乾燥し、表2-1および表2-2に併記した量の皮膜を形成した。
この表面処理皮膜の付着量は表面処理液の濃度により調整し、皮膜の付着量はZrを蛍光X線分析装置により、Zr付着量が既知の標準板より得られた検量線を用いて定量した。
乾燥条件は、オーブンの温度とオーブンに入れている時間とで調節した。なお、乾燥温度は試験板表面の到達温度を示す。バーコート塗装の具体的な方法は、以下のとおりである。
試験水準毎の試験板(供試材)の種類、塗装方法、皮膜形成時の乾燥温度を表2-1および表2-2に示す。また、得られた亜鉛めっき鋼板皮膜の組成およびZr付着量を表3-1および表3-2に示す。
(5-1)耐食性評価
上記の方法で作製した試験板を70×150mmに切り出し、裏面と端部をビニールテープでシールして以下の試験を行った。評価は、錆び発生面積率を目視にて判定した。
塩水噴霧試験(SST:JIS-Z-2371に準ずる):
SST72時間後の白錆び発生面積率を目視にて、下記判定基準で評価した。
判定基準:
◎ :錆び発生面積率5%未満
○ :錆び発生面積率5%以上20%未満
○-:錆び発生面積率20%以上30%未満
△ :錆び発生面積率30%以上40%未満
× :錆び発生面積率40%以上
上記した試験板を、40℃での動粘度が51~69mm2/s、100℃での動粘度が11.1~14.9mm2/sの潤滑油(NOKクリューバー(株)製「ALL TIME J 652」)を容器に入れ、鉛直に立てた試験材の下端部を容器内の潤滑油に浸した状態で85℃で3日間放置し、潤滑剤の滲み拡がり高さを測定した。その判定基準は、以下のとおりである。
◎ :滲み拡がり高さ0.5cm未満
○ :滲み拡がり高さ0.5cm以上、1.0cm未満
○-:滲み拡がり高さ1.0cm以上、1.5cm未満
△ :滲み拡がり高さ1.5cm以上、3.0cm未満
× :滲み拡がり高さ3.0cm以上
上記した試験板を、40℃での動粘度が51~69mm2/s、100℃での動粘度が11.1~14.9mm2/sの潤滑油(NOKクリューバー(株)製「ALL TIME J 652」)を容器に入れ、鉛直に立てた試験材の下端部を容器内の潤滑油に浸した状態で60℃、相対湿度90%の環境下で3日間放置し、潤滑剤の滲み拡がり高さを測定した。その評価基準は、以下のとおりである。
◎ :滲み拡がり高さ0.5cm未満
○ :滲み拡がり高さ0.5cm以上、1.0cm未満
○-:滲み拡がり高さ1.0cm以上、1.5cm未満
△ :滲み拡がり高さ1.5cm以上、3.0cm未満
× :滲み拡がり高さ3.0cm以上
各試験板に潤滑油を塗油した状態で、下記プレス条件の多段絞り成形を行い、金型に付着する汚れを拭き取ることなく10回連続で成形した後、10個目の成形材表面に付着した剥離カスの程度と、成形材表面の黒ずみ(黒化)の程度を目視で観察し、評価した。
〔プレス条件〕
亜鉛系めっき鋼板の板厚:0.8mm、成形速度:450mm/秒、ブランク径Φ90mm
(1段目)ポンチ径Φ49mm、ポンチとダイスのクリアランス1.0mm
(2段目)ポンチ径Φ39mm、ポンチとダイスのクリアランス0.8mm
(3段目)ポンチ径Φ32mm、ポンチとダイスのクリアランス0.8mm
(4段目)ポンチ径Φ27.5mm、ポンチとダイスのクリアランス0.8mm
(5段目)ポンチ径Φ24.4mm、ポンチとダイスのクリアランス0.8mm
◎ :潤滑油に蓄積された剥離カスが成形材表面にほとんど付着しておらず、成形材表面の黒ずみも確認されない。
○ :潤滑油に蓄積された剥離カスが成形材表面に極わずかに付着しているが、成形材表面の黒ずみは確認されない。
○-:潤滑油に蓄積された剥離カスが成形材表面にわずかに付着しており、成形材表面に軽微な黒ずみが観察される。
△ :潤滑油に蓄積された剥離カスが成形材表面に少量付着しており、成形材表面に黒ずみがやや多く観察される。
× :潤滑油に蓄積された剥離カスが成形材表面に多量に付着しており、成形材表面に黒ずみが顕著に観察される。
これに対し、比較例は、いずれも、耐食性、プレス成形後の外観および油保持性のいずれか一つまたは一つ以上で劣っていた。
Claims (5)
- 水溶性ジルコニウム化合物(A)と、水分散性微粒子シリカ(B)と、シランカップリング剤(C)と、バナジン酸化合物(D)と、リン酸化合物(E)と、ニッケル化合物(F)と、アクリル樹脂エマルション(G)と、オルガノポリシロキサン化合物(H)とを、下記(1)~(8)の条件を満足する範囲で含有することを特徴とする亜鉛系めっき鋼板用の表面処理液。
記
(1)水分散性微粒子シリカ(B)の固形分(Bs)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(Bs)/(AZr)=0.3~1.2
(2)シランカップリング剤(C)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(C)/(AZr)=0.6~2.5
(3)バナジン酸化合物(D)のV換算量(DV)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(DV)/(AZr)=0.04~0.15
(4)リン酸化合物(E)のP換算量(EP)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(EP)/(AZr)=0.11~0.55
(5)ニッケル化合物(F)のNi換算量(FNi)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(FNi)/(AZr)=0.015~0.065
(6)表面処理液の全固形分における、アクリル樹脂エマルション(G)の固形分(Gs)の含有量が0.5~10質量%
(7)表面処理液の全固形分における、オルガノポリシロキサン化合物(H)の固形分(Hs)の含有量が0.55~6.5質量%
(8)水分散性微粒子シリカ(B)、シランカップリング剤(C)およびオルガノポリシロキサン化合物(H)の各Si換算の合計量(SiT)と水溶性ジルコニウム化合物(A)のZr換算量(AZr)との質量比(SiT)/(AZr)=0.23~1.0 - 前記表面処理液がさらにワックス(I)を、下記(9)の条件を満足する範囲で含有することを特徴とする請求項1に記載の亜鉛系めっき鋼板用の表面処理液。
記
(9)表面処理液の全固形分における、ワックス(I)の固形分(Is)の含有量が2.5~10質量% - 請求項1または2に記載の表面処理液を、亜鉛系めっき鋼板の表面に塗布し、ついで加熱乾燥し、片面当たりのZr付着量を10~200mg/m2とすることを特徴とする亜鉛系めっき鋼板の製造方法。
- 亜鉛系めっき鋼板の表面に、ジルコニウム化合物(a)と、微粒子シリカ(b)と、シランカップリング剤由来成分(c)と、バナジン酸化合物(d)と、リン酸化合物(e)と、ニッケル化合物(f)と、アクリル樹脂(g)と、オルガノポリシロキサン化合物由来成分(h)とを、下記(11)~(15)の条件を満足する範囲で含有し、片面当たりのZr付着量が10~200mg/m2である皮膜を有することを特徴とする亜鉛系めっき鋼板。
記
(11)バナジン酸化合物(d)のV換算量(dV)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(dV)/(aZr)=0.04~0.15
(12)リン酸化合物(e)のP換算量(eP)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(eP)/(aZr)=0.11~0.55
(13)ニッケル化合物(f)のNi換算量(fNi)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(fNi)/(aZr)=0.015~0.065
(14)皮膜固形分の合計量における、アクリル樹脂(g)の含有量が0.5~10質量%
(15)微粒子シリカ(b)、シランカップリング剤由来成分(c)およびオルガノポリシロキサン化合物由来成分(h)の各Si換算の合計量(Sit)とジルコニウム化合物(a)のZr換算量(aZr)との質量比(Sit)/(aZr)=0.23~1.0 - 前記皮膜がさらにワックス(i)を、下記(16)の条件を満足する範囲で含有することを特徴とする請求項4に記載の亜鉛系めっき鋼板。
記
(16)皮膜固形分の合計量に対し、ワックス(i)の固形分(is)の含有量が2.5~10質量%
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CN104250743A (zh) * | 2014-09-16 | 2014-12-31 | 朱忠良 | 一种镀锌板复合钝化工艺 |
TWI586835B (zh) * | 2016-05-27 | 2017-06-11 | 中國鋼鐵股份有限公司 | 用於金屬表面處理之水性組成物、表面處理方法、保護膜及表面處理鍍鋅鋼板 |
JP2018087755A (ja) * | 2016-11-29 | 2018-06-07 | 中西金属工業株式会社 | 磁気エンコーダ及びその製造方法 |
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 |
JP7232640B2 (ja) * | 2018-12-21 | 2023-03-03 | 株式会社放電精密加工研究所 | 水性防錆表面処理組成物および表面被覆金属部材 |
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MY179468A (en) | 2020-11-06 |
TWI449806B (zh) | 2014-08-21 |
JP5927787B2 (ja) | 2016-06-01 |
KR20130041090A (ko) | 2013-04-24 |
CN102947487A (zh) | 2013-02-27 |
JP2012026033A (ja) | 2012-02-09 |
KR101468651B1 (ko) | 2014-12-04 |
CN102947487B (zh) | 2015-04-01 |
SG186231A1 (en) | 2013-01-30 |
TW201204871A (en) | 2012-02-01 |
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