EP0742849A1 - Oberflächenbehandlungsmittel für eisen-zink-oberflächen - Google Patents

Oberflächenbehandlungsmittel für eisen-zink-oberflächen

Info

Publication number
EP0742849A1
EP0742849A1 EP95909324A EP95909324A EP0742849A1 EP 0742849 A1 EP0742849 A1 EP 0742849A1 EP 95909324 A EP95909324 A EP 95909324A EP 95909324 A EP95909324 A EP 95909324A EP 0742849 A1 EP0742849 A1 EP 0742849A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition according
zinciferous
plated steel
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95909324A
Other languages
English (en)
French (fr)
Other versions
EP0742849A4 (de
Inventor
Masayuki Aoyama
Takao Ogino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of EP0742849A1 publication Critical patent/EP0742849A1/de
Publication of EP0742849A4 publication Critical patent/EP0742849A4/de
Withdrawn legal-status Critical Current

Links

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
    • C23C22/48—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
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • B05D7/16—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 using synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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 invention relates to an optimized surface treatment agent that imparts both an excellent corrosion resistance and an excellent paint adherence to the surface of steel, especially steel sheet, plated with zinc or zinc-containing alloy (hereinafter abbreviated as zinciferous-plated steel).
  • zinciferous-plated steel The invention will be de ⁇ scribed below primarily with respect to use on steel sheet, but it is to be under ⁇ stood that any other shape of steel substrate may also be treated according to the invention.
  • Background Art Zinciferous-plated steel sheet utilizes the principle of sacrificial zinc corro ⁇ sion, which is a general method for preventing the corrosion of iron and steel. Zinciferous-plated steel sheet is used in a broad range of applications, extending over the automotive, building material, and household electrical appliance sect ⁇ ors.
  • One well-known non-chromate surface treatment method uses surface treatment agents based on tannic acid (tannic acid contains polyphenolic carbox ⁇ ylic acid).
  • tannic acid contains polyphenolic carbox ⁇ ylic acid.
  • zinc tannate produced by the reaction between tannic acid and zinc forms a protective coating. It is thought that the corrosion resistance of the zinciferous-plated steel sheet is improved through the action of this protective coating as a barrier to the infiltration of corrosive substances.
  • Japanese Patent Publication Number Sho 54-22781 [22,781/1979] teach- es a tannic acid-based surface treatment method comprising the treatment of zinciferous-plated steel sheet with an aqueous solution that contains at least tan ⁇ nic acid and silica sol. This method forms an ultrathin surface film that has a rust-inhibiting activity. The problem with this method is that this film still cannot deliver a satisfactory corrosion resistance. Otherwise, Japanese Patent Publication Number Sho 61 -33910 [33,910/
  • the present invention takes as its object the introduction of a chromium- free surface treatment agent that solves the problems described above for the prior art by simultaneously providing the excellent corrosion resistance and ex ⁇ cellent paint adherence required for zinciferous-plated steel sheet.
  • a coating having both a high corrosion resistance and a strong paint ad ⁇ herence can be produced by treating the surface of zinciferous-plated steel sheet with a surface treatment agent that contains a particular type of silane coupling agent and at least one selection from polyhydroxyaryl carboxylic acids and dep- sides of polyhydroxyaryl carboxylic acids.
  • the invention was achieved based on this finding.
  • the surface treatment agent according to the invention for zinciferous-plated steel sheet characteristically comprises, preferably consists essentially of, or more preferably consists of, water and the following essential components:
  • R denotes an alkyl group, which may be the same or different from one of the m YR and the n R moieties to another;
  • X denotes a meth- oxy or ethoxy moiety;
  • Y denotes a moiety selected from the group consist ⁇ ing of vinyl, amino, mercapto, glycidoxy, and methacryloxy moieties, which may be the same or different from one of the m YR moieties to an ⁇ other;
  • m is an integer with a value from 1 to 3; and
  • n is an integer with a value of 0 to (3-m); and optionally, one or more of: (C) water miscible monoalcohols;
  • (E) accelerator anions It is preferred, furthermore, that the total content of essential components (A) and (B) in the surface treatment agent according to the invention should be 1 to 50 weight %.
  • Zinciferous-plated steel which can be treated with the surface treatment agent of the invention encompasses steel coated with zinc or a zinc alloy, for ex ⁇ ample, Zn/Fe alloy, Zn/Ni alloy, Zn/AI alloy, and the like.
  • Polyhydroxyaryl carboxylic acids usable by the present invention must have at least two hydroxyl substituents and at least one carboxyl substituent on a single aromatic nucleus.
  • Such acids are exemplified by gallic acid, protocate- chuic acid, gallocarboxylic acid, and the like.
  • Suitable as the depsides of polyhy ⁇ droxyaryl carboxylic acids are, for example, meta-digallic acid, trigallic acid, diplo- schistesic acid, tannin, tannic acid, and so forth.
  • the tannin used in the present invention is a general term for substances extractable by hot water from the seeds, fruits, shells, leaves, roots, wood, and bark of plants and able to convert raw animal hides into leather.
  • Tannic acid is the tannin obtained from Chinese or Turkish nutgall, etc. The type and quantity of addition of these substances is not critical.
  • silane coupling agent that has a chemical structure with general form- ula (I) may be used in the present invention.
  • compounds from the following groups (a) - (c) can be used and are generally preferred.
  • amino-functional silane coupling agents e.g., N-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane N-(2-aminoethyl)-3-aminopropyl trimethoxy silane 3-aminopropyl triethoxy silane
  • mercapto-functional silane coupling agents e.g., 3-mercaptopropyl trimethoxy silane.
  • the surface treatment agent of the invention may in general be prepared by dissolving or dispersing the aforementioned essential components in water. While the total concentration of the essential components is not specifically re ⁇ stricted, the sum of the concentrations of the essential components, i.e., silane coupling agent + polyhydroxyaryl carboxylic acid(s) and/or depside(s) of polyhy ⁇ droxyaryl carboxylic acid(s) is preferably 1 to 50 weight %. When the total amount of these essential components falls below 1 weight %, the treated zincif- erous-plated steel sheet will not always exhibit the good corrosion resistance that is the goal of the present invention.
  • the surface treatment agent according to the invention may contain addi ⁇ tives in addition to the essential components already discussed above.
  • Metal ions may be added in order to improve the insolubility of the treated zinciferous- plated steel sheet.
  • Metal ions usable for this purpose are exemplified by iron, nickel, manganese, cobalt, zinc, aluminum, calcium, and magnesium ions, with zinc and magnesium ions being particularly preferred.
  • a reaction ac ⁇ celerator may be added in order to accelerate the reaction with the surface of the zinciferous-plated steel sheet.
  • Preferred for use as this reaction accelerator are, for example, phosphate ions, nitrate ions, fluoride ions, and organic acids other than those that are part of component (A). Fluoride ions are particularly preferred as the reaction accelerator.
  • optional component (C) is optional component (C) as de- scribed above, of which methanol is the most preferred embodiment. Independ ⁇ ently, a concentration of optional component (C) in the range from 1 to 30, more preferably 5 to 15, or still more preferably 9 to 11 , weight % is preferred in the treatment compositions according to the invention.
  • the treatment temperature or treatment time crucial, but in general the treatment temperature is preferably 10° C to 40° C and the treatment time is preferably 0.1 to 10 seconds.
  • Zinciferous-plated steel sheet treated with the surface treatment agent of the invention exhibits both an excellent corrosion resistance and an excellent paint adherence.
  • the polyhydrox ⁇ yaryl carboxylic acid or depside thereof in the treatment agent is believed to react with the zinc to form a protective coating on the surface of the zinciferous-plated steel sheet.
  • This protective coating then would prevent the infiltration of corros- ive substances, thus yielding the improved corrosion resistance.
  • the improved paint adherence is believed to occur as the result of adsorption of the functional groups in the silane coupling agent to the surface of the zinciferous-plated steel sheet.
  • a moderately alkaline degreaser (FINECLEANERTM 4336, commercially available from Nihon Parkerizing Company, Limited, Tokyo) was used a concen ⁇ tration of 20 g/L.
  • the dirt and oil adhering on the surface were removed by spraying the zinciferous-plated steel sheet with the aqueous degreaser solution using a treatment temperature of 60° C and a treatment time of 20 seconds.
  • the alkali remaining on the surface of the treated steel sheet was then washed off using tap water to yield the clean zinciferous-plated steel sheet surface.
  • Example 1 The EG material, cleaned as described above, was immersed at room temperature for 20 seconds in a surface treatment bath prepared by dissolving 0.5 weight % of gallic acid, 0.5 weight % of 3-glycidoxypropyl trimethoxy silane, and 10 weight % of methanol in deionized water. This was followed by draining and drying to a sheet temperature of 100° C.
  • a surface treatment bath prepared by dissolving 0.5 weight % of gallic acid, 0.5 weight % of 3-glycidoxypropyl trimethoxy silane, and 10 weight % of methanol in deionized water. This was followed by draining and drying to a sheet temperature of 100° C.
  • Example 2 The EG material, cleaned as described above, was immersed at room temperature for 20 seconds in a surface treatment bath prepared by dissolving 0.5 weight % of gallic acid, 0.5 weight % of 3-glycidoxypropyl trimethoxy silane, and 10 weight % of methanol in deionized water
  • Example 3 The treatment procedure of Example 1 was executed on the HDG material instead of the EG material used in Example 1.
  • Example 4 The treatment procedure of Example 3 was executed on the HDG material instead of the EG material used in Example 3.
  • Example 5
  • a surface treatment bath prepared by dissolving 10 weight % of pro- tocatechuic acid, 2.5 weight % of 3-aminopropyl triethoxy silane, and 10 weight % of methanol in deionized water. This was followed by drying to a sheet tem ⁇ perature of 100° C.
  • Example 7 The treatment procedure of Example 5 was executed on the HDG material instead of the EG material used in Example 5.
  • Example 7 The EG material, cleaned as described above, was immersed at room temperature for 20 seconds in a surface treatment bath prepared by dissolving 18.0 weight % of quebracho tannin, 32.0 weight % of 3-mercaptopropyl trime ⁇ thoxy silane, and 10 weight % of methanol in deionized water. This was followed by draining with a wringer roll and drying to a sheet temperature of 100° C. o
  • a surface treatment bath prepared by dissolving 18.0 weight % of quebracho tannin, 32.0 weight % of 3-mercaptopropyl trime ⁇ thoxy silane, and 10 weight % of methanol in deionized water. This was followed by draining with a wringer roll and drying to a sheet temperature of 100° C.
  • Example 7 The treatment procedure of Example 7 was executed on the HDG material instead of the EG material used in Example 7. Comparative Example 1
  • Comparative Example 3 The treatment procedure of Comparative Example 1 was executed on the 0 HDG material instead of the EG material used in Comparative Example 1. Comparative Example 3
  • the zinciferous-plated steel sheet was coated with paint (Delicon #700 from Dainip- pon Toryo Kabushiki Kaisha) and baked at 140° C for 20 minutes to yield a 25 micrometer-thick paint film. (0 Primary paint adherence
  • Crosscut test a Crosshatch pattern of 1 mm x 1 mm squares was cut in the paint film on the product's surface using an NT cutter, and the number of squares re- maining after peeling with adhesive tape was counted.
  • Crosscut/Erichsen test the specimen was extruded 5 mm after the crosscut evaluation, and the number of squares remaining after peeling with adhesive tape was counted. (in Secondary paint adherence The painted sheet was immersed in boiling pure water for 2 hours and was then evaluated by the crosscut test and crosscut/Erichsen test as described above for primary paint adherence.
  • results reported for the crosscut and crosscut/Erichsen tests are the number of squares remaining unpeeled after tape peeling before the virgule ("/") out of the number of total squares after the virgule.
  • Zinciferous-plated steel treated with the surface treatment agent according to the invention exhibits an excellent performance in both critical areas of corro ⁇ sion resistance and paint adherence.
  • the surface treatment agent of the inven ⁇ tion is also very safe and highly advantageous in terms of environmental protec- tion and recyclability.
  • the treatment agent of the invention will be particularly effective in those sectors in which environmental problems might occur due to chromium elution from the surface of chromated zinciferous-plated steel sheet.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP95909324A 1994-02-03 1995-02-01 Oberflächenbehandlungsmittel für eisen-zink-oberflächen Withdrawn EP0742849A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP1169594A JPH07216268A (ja) 1994-02-03 1994-02-03 耐食性、塗装密着性に優れた亜鉛含有金属めっき鋼板用表面処理剤
JP11695/94 1994-02-03
PCT/US1995/000977 WO1995021277A1 (en) 1994-02-03 1995-02-01 Surface treatment agent for zinciferous-plated steel

Publications (2)

Publication Number Publication Date
EP0742849A1 true EP0742849A1 (de) 1996-11-20
EP0742849A4 EP0742849A4 (de) 1997-02-26

Family

ID=11785176

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95909324A Withdrawn EP0742849A4 (de) 1994-02-03 1995-02-01 Oberflächenbehandlungsmittel für eisen-zink-oberflächen

Country Status (6)

Country Link
EP (1) EP0742849A4 (de)
JP (1) JPH07216268A (de)
BR (1) BR9506685A (de)
CA (1) CA2182395A1 (de)
MX (1) MX9603096A (de)
WO (1) WO1995021277A1 (de)

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Publication number Priority date Publication date Assignee Title
US5868819A (en) * 1996-05-20 1999-02-09 Metal Coatings International Inc. Water-reducible coating composition for providing corrosion protection
US6488805B1 (en) 1996-07-23 2002-12-03 Vantico, Inc. Metal surface treatment
DE19642725A1 (de) * 1996-10-17 1998-04-30 Suratech Gmbh Verfahren zur haftfesten Verbindung von Lack oder Klebstoff mit einem Oberflächenbereich eines Werkstücks aus verzinktem Stahl oder verzinkten Eisen-Legierungen und dessen Verwendung
CN1203209C (zh) * 1997-09-17 2005-05-25 舍米塔尔公开有限公司 金属底材的防腐蚀方法和组合物
DE19814605A1 (de) * 1998-04-01 1999-10-07 Kunz Gmbh Mittel zur Versiegelung von metallischen, insbesondere aus Zink oder Zinklegierungen bestehenden Untergründen
JP4165943B2 (ja) * 1998-11-18 2008-10-15 日本ペイント株式会社 亜鉛被覆鋼および無被覆鋼の防錆コーティング剤
FR2796655B1 (fr) * 1999-07-22 2001-10-19 Dacral Sa Procede et composition de traitement anti-corrosion d'un substrat metallique prealablement protege par une couche de revetement a base de zinc
US6270884B1 (en) 1999-08-02 2001-08-07 Metal Coatings International Inc. Water-reducible coating composition for providing corrosion protection
FR2799211B1 (fr) * 1999-09-30 2002-05-10 Dacral Sa Revetement et procede de traitement anticorrosion de pieces metalliques
US7291402B2 (en) 2002-07-23 2007-11-06 Jfe Steel Corporation Surface-treated steel sheets of good white rust resistance, and method for producing them
ES2316706T3 (es) * 2002-12-24 2009-04-16 Chemetall Gmbh Metodo de pre-tratamiento para revestir.
JP4500113B2 (ja) 2003-06-16 2010-07-14 Ｊｆｅスチール株式会社 高耐食性表面処理鋼板及びその製造方法
US7524535B2 (en) * 2004-02-25 2009-04-28 Posco Method of protecting metals from corrosion using thiol compounds
WO2006082951A1 (ja) * 2005-02-02 2006-08-10 Nihon Parkerizing Co., Ltd. 水系金属材料表面処理剤、表面処理方法及び表面処理金属材料
JP5688522B2 (ja) * 2010-01-21 2015-03-25 日本ペイント株式会社 銅の表面処理剤
KR102692287B1 (ko) * 2019-05-07 2024-08-05 현대자동차주식회사 금속 및 수지의 이종 재질간의 접착력 향상 방법
CN110129784B (zh) * 2019-05-30 2021-03-12 廊坊师范学院 涂装前钢铁表面处理剂的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4247344A (en) * 1975-10-15 1981-01-27 Nippon Steel Corporation Rust preventing treatment of metal-plated steel materials
JPS5337150A (en) * 1976-09-02 1978-04-06 Nippon Packaging Kk Surface treatment of zinc or zinc alloy
JPS6056226B2 (ja) * 1978-07-31 1985-12-09 東亞合成株式会社 亜鉛系基材の表面処理方法
JPS6022067B2 (ja) * 1982-09-30 1985-05-30 日本パ−カライジング株式会社 金属表面の皮膜形成方法
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
KR970004371B1 (ko) * 1991-12-12 1997-03-27 엔 케이 케이 코오포레이숀 프레스 성형성과 내식성이 우수한 아연계 도금강판
US5389405A (en) * 1993-11-16 1995-02-14 Betz Laboratories, Inc. Composition and process for treating metal surfaces

Also Published As

Publication number Publication date
WO1995021277A1 (en) 1995-08-10
EP0742849A4 (de) 1997-02-26
BR9506685A (pt) 1997-11-18
CA2182395A1 (en) 1995-08-10
MX9603096A (es) 1997-05-31
JPH07216268A (ja) 1995-08-15

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