WO2002036854A1 - Feuille d'acier galvanisee a base de zinc, traitee au phosphate et presentant une remarquable aptitude a la deformation et procede de production associe - Google Patents
Feuille d'acier galvanisee a base de zinc, traitee au phosphate et presentant une remarquable aptitude a la deformation et procede de production associe Download PDFInfo
- Publication number
- WO2002036854A1 WO2002036854A1 PCT/JP2000/007774 JP0007774W WO0236854A1 WO 2002036854 A1 WO2002036854 A1 WO 2002036854A1 JP 0007774 W JP0007774 W JP 0007774W WO 0236854 A1 WO0236854 A1 WO 0236854A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- steel sheet
- phosphate
- zinc
- wax
- treated
- Prior art date
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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
- C23C22/05—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
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
-
- 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
- C23C22/73—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 characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
- C10M101/025—Petroleum fractions waxes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- 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
- B05D7/14—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 to metal, e.g. car bodies
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/14—Synthetic waxes, e.g. polythene waxes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/14—Synthetic waxes, e.g. polythene waxes
- C10M2205/143—Synthetic waxes, e.g. polythene waxes used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
Definitions
- the present invention relates to a phosphate-treated zinc-based steel sheet having excellent workability and used for applications such as automobiles, home appliances, and building materials. Background technology
- Zinc-based steel sheets used for applications such as automobiles, home appliances, and building materials have been conventionally treated with phosphate, chromate, and even organic coatings to improve their added value such as corrosion resistance and workability. Often. In recent years, due to environmental problems, in particular, chromated steel sheets have tended to be disliked because they may contain hexavalent chromium, and there has been an increasing demand for phosphate treatment. From the viewpoint of workability, Zn-Ni alloy-plated steel sheets are widely used because they show good characteristics, but are widely used because of the Ni-containing alloy plating. There is a problem when it becomes expensive. For this reason, attempts have been made to increase the added value by applying phosphate treatment to electric zinc plated steel sheets, molten zinc plated steel sheets, or alloyed molten zinc plated steel sheets, which are inexpensive to manufacture.
- JP-A-7-138764 discloses a zinc phosphate treated zinc-based steel sheet containing at least one of Fe, Co, Ni, Ca, Mg, Mn, etc., and having excellent pressability. However, even in this technique, sufficient performance cannot be obtained in the above-described bead press drawing. Disclosure of the invention
- An object of the present invention is to solve the above-mentioned drawbacks and to provide a phosphate-treated zinc-based steel plate having excellent workability.
- the present inventors have studied the addition of wax to a phosphate-treated film in order to improve the workability of a phosphate-treated zinc-based steel sheet.
- the known phosphating treatment involves spraying an acidic aqueous solution containing phosphate ions and metal cations, or immersing a zinc-based plated steel sheet in the aqueous solution, and treating the phosphating solution on the surface of the plating layer with p. Since crystals are formed by the increase of H, it is difficult to contain the box in the film. Further, when a wax film was further formed on the phosphate film, the wax was not sufficiently fixed to the film, so that there was a problem in workability and, in addition, adhesion of the coating.
- a phosphate film containing a polyolefin wax or a modified polyolefin wax can be obtained by applying an aqueous solution containing the solution and drying the solution, and it has been found that extremely good workability can be achieved.
- the gist of the present invention is a zinc-based plated steel sheet having a phosphate film on its surface, wherein the phosphate film contains polyolefin wax or modified polyolefin wax. It is a phosphate-treated galvanized steel sheet with excellent workability, and a method for producing such a phosphate-treated galvanized steel sheet includes phosphoric acid on the surface of a zinc-based plated steel sheet. After the salt treatment, an aqueous solution containing polyolefin wax or modified polyolefin wax, phosphate ions and polyvalent metal ions is applied and dried.
- the zinc-based plating steel sheet used in the present invention is not particularly limited, and any of pure zinc plating and alloy plating can be used, and the good workability improvement effect can be enjoyed. Plating, molten zinc plating, alloyed molten zinc plating Tsuke is preferred.
- phosphate film formed on the zinc plating there is no particular limitation on the phosphate film formed on the zinc plating, but in general, a zinc phosphate film that forms so-called whipite crystals, or? 6, ⁇ , (0, 3 ⁇ 4111, 1 ⁇ , &,
- Examples include a zinc phosphate coating modified with an element such as Cu.
- the aqueous solution applied to the upper layer of the phosphate film formed on the zinc plating must contain a polyolefin wax or a modified polyolefin wax, and phosphate ions and polyvalent metal ions.
- a phosphate film containing wax can be formed.
- the polyvalent metal ion is preferably Mg z + , Mn 2t , Ca 2+ , Zn 2+ , Ni 2t , Co 2+ , Al 3+ , and may be used alone or in combination of two or more. it can. Of these, Mg ”or Mn 2+ is the most preferable in consideration of corrosion resistance.
- the easiest to manufacture is to use a mixed aqueous solution of polyolefin wax or modified polyolefin wax (hereinafter referred to as wax) and polyphosphate.
- Mg biphosphate As the biphosphate, Mg biphosphate, AI biphosphate, Mn biphosphate, Ca biphosphate and the like can be used. Among them, Mg biphosphate is most preferable in consideration of corrosion resistance.
- the wax is preferably a cationic or nonionic wax from the viewpoint of stable miscibility with phosphate ion and polyvalent metal ion.
- the amount of the wax added is not particularly limited, but is generally preferably about 10% or less with respect to the total weight of the phosphate film in consideration of the adhesion of the coating.
- FIGS. 1 and 2 show SEM photographs (15 Kv, X500) of the wax-containing phosphate film produced by the methods of Examples 1 and 2 described later, and FIG. A S ⁇ photo (15 ⁇ , X500) of a wax-free phosphate film produced by the method is shown.
- Fig. 4 shows the FT-IR (PER IN-ELMER, high sensitivity reflection method) chart for each sample. These were observed after ultrasonic cleaning (5 minutes) of the steel sheet in n-hexane solvent.
- the wax-containing phosphate film of the present invention is the same as a normal wax-free phosphate film. Such a uniform and dense crystalline state is exhibited, and the presence or absence of wax cannot be determined from the surface properties.
- FIG. 4 it can be seen that the wax-containing phosphate film of the present invention has an absorption peak attributable to the C—H bond of the wax at 2800 to 3000 cm 1 . Can be confirmed.
- the OO SOOOcm- 1 peak in FT-IR is also detected when a thin film is formed by applying only wax on a phosphate coating containing no wax.
- the peak intensity decreases significantly, and the peak disappears before long. Therefore, the difference from the wax-containing phosphate film of the present invention can be confirmed (simplified method).
- the surface can be rubbed with a solvent to determine whether or not the surface is visible after rubbing.
- the wax-containing phosphate film of the present invention hardly shows any traces).
- a film formed by applying only wax on a phosphate film containing no wax is easily removed by the solvent component in the cleaning oil. ) Does not provide good workability. Also, the adhesion of the coating tends to be inferior, which is not preferable.
- the FT-IR may absorb OO SOOOciir 1 even with a phosphate film that does not contain a box. Therefore, before measurement, degreasing must be performed with a solvent such as n-hexane.
- FIG. 1 is a diagram based on a surface SEM photograph (X500) of the wax-containing phosphate-treated zinc plating steel sheet in Example 1.
- FIG. 2 is a diagram based on a surface SEM photograph (X500) of the wax-containing phosphate-treated galvanized steel sheet in Example 2.
- FIG. 3 is a diagram based on the surface SEM photograph (X500) of the zinc-free phosphate-treated zinc-coated steel sheet in Comparative Example 2.
- FIG. 4 is an FT-1R chart of a phosphate-treated zinc plated steel sheet of Example 1, Example 2, and Comparative Example 2.
- the mixture was mixed so that the ratio became 0: 5, and the mixture was applied to the zinc phosphate-treated steel plate with a roll coater overnight, and dried so that the reached plate temperature reached 100 ° C.
- the weight to be applied was calculated from the weight difference between the steel sheet before application and the steel sheet after application and drying, and the value was set to 0.7 g / m 2 .
- Example 6 The adjustment was performed in the same manner as in Example 1 except that Ca biphosphate (manufactured by Yoneyama Chemical Industry Co., Ltd.) was used instead of the aqueous solution of Mg biphosphate.
- Ca biphosphate manufactured by Yoneyama Chemical Industry Co., Ltd.
- a magnesium phosphate aqueous solution (manufactured by Yoneyama Chemical Industry Co., Ltd.) was applied to the zinc phosphate-treated steel sheet of Comparative Example 1 with a roll coater, and dried so that the reached sheet temperature reached 100 ° C.
- the weight to be applied was calculated from the weight difference between the steel sheet before application and the steel sheet after application, and the value was set to 0.7 g / m 2 .
- Comparative Example 3 (Comparative Example 3) '-Nonionic modified polyethylene polyethylene glycol (Semichemical SH5200 manufactured by Sanyo Kasei Kogyo Co., Ltd.) was applied to the zinc phosphate-treated plated steel sheet of Comparative Example 1 with a roll coater, and the reached plate temperature was 100. It was dried to be ° C. The weight to be applied was calculated from the weight difference between the steel sheet before application and the steel sheet after application and drying, and the value was set to O.lg / m 2 .
- Wax presence / absence Ultrasonic degreasing (5 minutes) in each of the samples of Examples 1 to 6 and Comparative Examples 1 to 3 in a solvent (n-hexane), followed by FT_IR measurement, and the peak of OO SOOOciir 1 Judgment from the presence or absence
- the steel sheet of the present invention does not use harmful substances such as hexavalent chromium, has a simple production method, is excellent in cost, and is suitable for various uses such as automatic, home appliances, and building materials.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Treatment Of Metals (AREA)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001210565A AU2001210565B2 (en) | 2000-11-06 | 2000-11-06 | Zinc-based metal plated steel sheet treated with phosphate excellent in formability and method for producing the same |
CA002427492A CA2427492A1 (en) | 2000-11-06 | 2000-11-06 | Phosphate-treated galvanized steel sheet with improved workability and production method thereof |
EP00971790A EP1338676A1 (en) | 2000-11-06 | 2000-11-06 | Zinc-based metal plated steel sheet treated with phosphate excellent in formability and method for producing the same |
KR10-2003-7005547A KR20030045127A (ko) | 2000-11-06 | 2000-11-06 | 가공성이 우수한 인산염 처리 아연계 도금 강판 및 그제조 방법 |
PCT/JP2000/007774 WO2002036854A1 (fr) | 2000-11-06 | 2000-11-06 | Feuille d'acier galvanisee a base de zinc, traitee au phosphate et presentant une remarquable aptitude a la deformation et procede de production associe |
AU1056501A AU1056501A (en) | 2000-11-06 | 2000-11-06 | Zinc-based metal plated steel sheet treated with phosphate excellent in formability and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2000/007774 WO2002036854A1 (fr) | 2000-11-06 | 2000-11-06 | Feuille d'acier galvanisee a base de zinc, traitee au phosphate et presentant une remarquable aptitude a la deformation et procede de production associe |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002036854A1 true WO2002036854A1 (fr) | 2002-05-10 |
Family
ID=11736654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/007774 WO2002036854A1 (fr) | 2000-11-06 | 2000-11-06 | Feuille d'acier galvanisee a base de zinc, traitee au phosphate et presentant une remarquable aptitude a la deformation et procede de production associe |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1338676A1 (xx) |
KR (1) | KR20030045127A (xx) |
AU (2) | AU2001210565B2 (xx) |
CA (1) | CA2427492A1 (xx) |
WO (1) | WO2002036854A1 (xx) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06299367A (ja) * | 1993-04-15 | 1994-10-25 | Nippon Steel Corp | プレス油省略可能非脱膜型潤滑めっき鋼板の製造方法 |
EP0653502A2 (en) * | 1993-11-11 | 1995-05-17 | Nihon Parkerizing Co., Ltd. | Zinc-containing metal-plated composite steel article and method of producing the same |
JPH08252520A (ja) * | 1995-03-20 | 1996-10-01 | Nippon Steel Corp | プレス加工特性の優れた表面処理鋼板及びその製造方法 |
-
2000
- 2000-11-06 WO PCT/JP2000/007774 patent/WO2002036854A1/ja not_active Application Discontinuation
- 2000-11-06 AU AU2001210565A patent/AU2001210565B2/en not_active Ceased
- 2000-11-06 KR KR10-2003-7005547A patent/KR20030045127A/ko not_active Application Discontinuation
- 2000-11-06 EP EP00971790A patent/EP1338676A1/en not_active Withdrawn
- 2000-11-06 CA CA002427492A patent/CA2427492A1/en not_active Abandoned
- 2000-11-06 AU AU1056501A patent/AU1056501A/xx active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06299367A (ja) * | 1993-04-15 | 1994-10-25 | Nippon Steel Corp | プレス油省略可能非脱膜型潤滑めっき鋼板の製造方法 |
EP0653502A2 (en) * | 1993-11-11 | 1995-05-17 | Nihon Parkerizing Co., Ltd. | Zinc-containing metal-plated composite steel article and method of producing the same |
JPH08252520A (ja) * | 1995-03-20 | 1996-10-01 | Nippon Steel Corp | プレス加工特性の優れた表面処理鋼板及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1338676A1 (en) | 2003-08-27 |
KR20030045127A (ko) | 2003-06-09 |
AU2001210565B2 (en) | 2005-04-21 |
AU1056501A (en) | 2002-05-15 |
CA2427492A1 (en) | 2003-04-30 |
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