EP0391442B1 - Improved surface treatment for zinciferous surfaces - Google Patents

Improved surface treatment for zinciferous surfaces Download PDF

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Publication number
EP0391442B1
EP0391442B1 EP90106675A EP90106675A EP0391442B1 EP 0391442 B1 EP0391442 B1 EP 0391442B1 EP 90106675 A EP90106675 A EP 90106675A EP 90106675 A EP90106675 A EP 90106675A EP 0391442 B1 EP0391442 B1 EP 0391442B1
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European Patent Office
Prior art keywords
chromium
group
process according
chromate
silane coupling
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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.)
Expired - Lifetime
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EP90106675A
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German (de)
English (en)
French (fr)
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EP0391442A1 (en
Inventor
Noriaki Yoshitake
Kenshi Saeki
Takumi Nihon Parker Hiratsuka Dormitory Honda
Takao Ogino
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Henkel Corp
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Henkel Corp
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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
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
    • C23C22/38—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds containing also 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
    • C23C22/05—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
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
    • 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

  • This invention relates to a treatment method which is capable of developing a chromium containing film that provides an excellent base for paint, by having both good paint adherence and good corrosion resistance after painting, as well as excellent corrosion resistance, alkali resistance, and ease of welding, because of relatively low electrical resistance, when left unpainted.
  • Treatment according to the invention is applied to surfaces containing zinc as a predominant constituent, particularly to surfaces of electrogalvanized steel sheet, zinc-alloy electroplated steel sheet, and galvannealed steel sheet (collectively denoted as "zinc-plated steel sheet” below).
  • the invention of Japanese Patent Application Laid Open [Kokai] Number 50-158535 [158,535/75] concerns a method for the formation of solution resistant chromate films on the surface of zinc-plated steel sheet.
  • the chromate solution contains chromic anhydride, phosphoric acid, and water-soluble or water-dispersible polymer, and the Cr6+ in this treatment bath is at least 70 % reduced to Cr3+ by a reductant such as ethylene glycol.
  • a reductant such as ethylene glycol
  • the chromate bath taught in Japanese Patent Publication Number 61-58522 [58,522/86] contains specified amounts of chromic acid, reduced chromic acid, and silica sol components.
  • a surface-treated steel sheet carrying the chromate film formed by the method of this invention is processed for painting, most of the hexavalent chromium in the chromate film is easily eluted by the alkali rinse prior to painting.
  • the corrosion resistance of the film is then lowered due to its poor alkali resistance.
  • the film contains silica because the film contains silica, its weldability, for example, its spot weldability, is poor.
  • Japanese Patent Application Laid Open Numbers 58-22383 [22,383/83] and 62-83478 [83,478/87] are examples of the disclosure of the use of silane coupling agents as reductants for the hexavalent chromium in chromate treatment solutions. While the films formed by the methods of these references provide excellent paint bondability, the chromate film formed by the method of the former reference has a poor alkali resistance because it does not contain silica or organic polymer. In the latter reference, the spot weldability is unsatisfactory because colloidal silica is present.
  • GB-A- 2 180 263 teaches a surface treating solution comprising hexavalent and trivalent chromium, phosphate, and fluorozirconate ions, with certain specified ratios among the ions.
  • Silica is taught as a preferred optional component. With silica, the spot weldability of surfaces treated with such a solution is reduced, while without silica, the alkali resistance of the treated surface is often unsatisfactory.
  • One embodiment of the present invention is a process for treating objects with a zinciferous surface, preferably sheets of zinc-plated steel, by contact between the surface of the treated object and a liquid solution composition that comprises, or preferably consists essentially of, water and the following components:
  • composition of the aqueous solution used by the method of the present invention is discussed in more detail below.
  • This solution uses water as its solvent, and it contains 3.0 to 50 g/L of Cr6+ and 2.0 to 40 g/L of Cr3+ as essential components.
  • the formation of a satisfactorily corrosion-resistant chromium containing film becomes problematic when the Cr6+ falls below 3.0 g/L or the Cr3+ falls below 2.0 g/L.
  • the Cr6+ exceeds 50 g/L or the Cr3+ exceeds 40 g/L the chromate bath will have a high viscosity and a poor stability, and it becomes difficult to control the quantity of chromium deposited in the surface coating formed.
  • a crucial element of the composition is the ratio between Cr6+ and Cr3+. It is essential that the chromium ratio (Cr3+/Cr6+) fall within the range of 0.25 to 1.5. When the chromium ratio falls below 0.25, the oxidizing tendency of the Cr6+ content in the chromate bath is increased. As a result, when the silane coupling agent is added to such a bath, reduction of the Cr6+ in the chromate bath by the silane coupling agent tends to develop rather readily, and the chromate bath is heated by this. As a consequence, the rate of the Cr6+ reduction reaction by the solvent in the chromate bath and solvent volatilization are both increased, causing a decline in the quality of the chromate bath.
  • the chromium ratio can be controlled by the addition as necessary of a reductant such as ethanol, methanol, oxalic acid, starch, sucrose, and the like.
  • PO43 ⁇ is preferably added as orthophosphoric acid (H3PO4).
  • H3PO4 orthophosphoric acid
  • the corrosion resistance and alkali resistance of the surface coating formed on the zinciferous surfaces treated are reduced.
  • exceeding 100 g/L promotes the rapid reduction of the Cr6+ in the solution by the silane coupling agent, and the quality of the solution is degraded as a result.
  • a particularly important aspect of the PO43 ⁇ content is its ratio relative to the quantity of total chromium (Cr6+ + Cr3+) in the solution, and a PO43 ⁇ /total Cr ratio within the range of 0.1 to 1.2 is preferred.
  • this ratio falls below 0.1, the alkali resistance and corrosion resistance of the surface film formed during a process according to the invention tend to decline.
  • reduction of the Cr6+ in the chromate bath by the silane coupling agent proceeds very easily, with the result that the Cr6+ in the chromate bath is substantially or almost completely reduced to Cr3+ prior to application. As a consequence, the quality of the chromate bath is reduced, and it becomes difficult to form a coating which satisfies the object of the present invention.
  • the solution used contains 3 to 50 g/L of another component which functions as a wettability improver: one compound or, if desired, a mixture of compounds selected from C4 - C8 tertiary alcohols and acetonitrile.
  • a wettability improver one compound or, if desired, a mixture of compounds selected from C4 - C8 tertiary alcohols and acetonitrile.
  • Each of these compounds has a relatively high stability with regard to the Cr+6 present in the chromate bath at bath temperatures below approximately 35 degrees Centigrade, while none adversely affects the quality of the treatment film formed to any significant degree.
  • each can function to increase the wettability of the chromate bath on the plated surface. Accordingly, each can contribute to increasing the uniformity of chromium coating weight on the treated surface during high-speed operations.
  • this organic component is added in greater amounts, the greater the total chromium concentration in the treatment solution, and the greater the application speed.
  • the organic component is preferably selected from tert-butyl alcohol and/or tert-amyl alcohol.
  • the alkali resistance of the treated surface can be increased by the optional addition of 0.2 to 10 g/L of zinc ions to the aqueous treatment bath.
  • the improvement is vanishingly small at a zinc ion quantity below 0.2 g/L, while exceeding 10 g/L tends to precipitate the Cr3+ in the treatment bath.
  • the Zn2+ ions are preferably added to the treatment bath in the form of zinc oxide, zinc carbonate, zinc phosphate, or zinc hydroxide.
  • complex fluoride may optionally be added to the treatment bath, either by itself or together with zinc. It is preferably added in the range of 0.2 to 8 g/L based on F.
  • Preferred examples of the complex fluoride are fluozirconic acid (H2ZrF6), fluotitanic acid (H2TiF6), fluosilicic acid (H2SiF6), and fluoboric acid (H2BF6).
  • H2ZrF6 fluozirconic acid
  • H2TiF6 fluotitanic acid
  • H2SiF6 fluosilicic acid
  • fluoboric acid H2BF6
  • This zinc or other metal complex becomes a constituent component of the chromium containing film formed, and contributes to improving the film's uniformity and corrosion resistance.
  • the effects of addition are difficult to note at fluoride quantities below 0.2 g/L, while exceeding 8 g/L lowers the corrosion resistance of the chromium containing film formed.
  • silane coupling agent is preferably first mixed with the chromate bath at a molar ratio referred to the gram-atomic concentration of Cr6+ in the chromate bath within the range of 0.05 to 0.30.
  • the silane coupling agent component is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, and mixtures of any two or more of these.
  • Silane coupling agents with the above general formula are preferred because they have good solubilities in the aqueous solution used to contact zinc surfaces in a process according to this invention and make a relatively large contribution to improving the corrosion resistance of the protective film formed on the zinc surface.
  • the treatment bath mixed with silane coupling agent as explained above, may be coated on the zinc-plated steel sheet or other zinciferous surface by, for example, a roll coater, curtain coater, or any other convenient method that establishes contact between the solution and the surface to be treated and results in a satisfactorily uniform coating of the solution over the surface before drying.
  • a film with a chromium content of 10 to 200 mg/m2 be formed by drying for 5 to 10 seconds at a temperature on the drying surface of 60 to 150 degrees Centigrade.
  • the liquid treating solution itself should be maintained at no greater than 35 degrees Centigrade and preferably at no greater than 25 degrees Centigrade after addition of the silane coupling agent to the bath.
  • Treatment solution according to this invention is satisfactorily stable for approximately 1 month at relatively low chromium concentrations, but use within 1 week after the addition of the silane component is strongly preferred for such solutions with high chromium concentrations.
  • the corrosion resistance of the treated object with a film as formed and the corrosion resistance after painting are both unsatisfactory with less than 10 mg/m2 of chromium uptake during a treatment according to this invention.
  • uptakes exceeding 200 mg/m2
  • it becomes difficult to control the quantity of chromium adherence in the chromate film the improvement in corrosion resistance reaches an upper limit and further benefits cannot be expected; and paint adherence is reduced because portions of the chromate film are easily removed by external forces when it is so thick.
  • pH of the aqueous chromate bath used in the present invention is not critical, values around 1.0 to 3.0 are preferable.
  • the Cr6+, Cr3+, and PO43 ⁇ components in the aqueous chromate bath are believed to react with one another and/or the treated surface, at a rate speeded by the thermal energy supplied by drying.
  • the constituent components of the resulting chromate film are believed to be the colorless materials respectively specified in (a) and (b) below, the green material specified in (c), and the gold colored material specified in (d) and (e).
  • the aforementioned chromic chromate (e) can undergo condensation reactions as depicted by Figure 1, while at the same time, the chromic chromate is cross linked as depicted in Figure 2 by the hydrolyzate ⁇ f ⁇ deriving from the silane coupling agent. Moreover, the hexavalent chromium in the chromic chromate is reduced by the methanol. Therefore, it is thought that a companion macromolecular network structure is formed by the development of complex cross linkages between the chromic chromate and silane coupling agent hydrolyzate.
  • each of the aforementioned components (a), (b), (c), and (d) may be present within the structure of the macromolecular, chromium containing coating represented by Figures 1 and 2, either in a chain-stopping position or bonded with said macromolecular chromium compound.
  • the chromate film having this network molecular structure exhibits a strong alkali resistance, i.e., the chromium in the film strongly resists elution due to alkali rinsing. Moreover, it is thought that this network molecular structure contributes to increasing both the corrosion resistance and uniformity.
  • this film does not contain silica or an organic macromolecular compound, the electrical resistance of the film is relatively low, so that it is relatively easy to weld surfaces treated according to this invention.
  • Chromate coating bath No. A as reported in Table 1 was prepared as follows: 200 grams ("g") of chromic anhydride (Cr2O6) was first dissolved in 500 g of water, 86 g of phosphoric acid (75% aqueous solution) and 18 g of methanol were added to the aqueous solution thus obtained, and this was then heated for 1 hour at 80 to 90 degrees Centigrade to cause reduction to a Cr3+/Cr6+ weight ratio of 1.0. After cooling, 26 g of tert-butanol and sufficient water to make a total weight of 1 kg were added. This solution is denoted in the following as the aqueous base solution.
  • aqueous base solution was then diluted with water to give a total chromium concentration (Cr6+ + Cr3+) of 40 g/L, along with 10 g/L tert-butanol.
  • Silane coupling agent gamma-glycidoxypropyltrimethoxysilane from Toshiba Silicone Company, Limited
  • Silane coupling agent was then added with stirring, in an amount to yield a concentration of 9 g/L, to give final treating bath No. A.
  • the treated zinc coated steel was painted with a bakeable melamine alkyd paint (DeliconTM 700 White from Dainippon Paint Company, Limited) and then baked for 20 minutes at 140 degrees Centigrade to give a painted sheet carrying a 25 micrometer thick coating.
  • a bakeable melamine alkyd paint (DeliconTM 700 White from Dainippon Paint Company, Limited) and then baked for 20 minutes at 140 degrees Centigrade to give a painted sheet carrying a 25 micrometer thick coating.
  • the treated sheet was alkali rinsed using the conditions specified below, and the quantity of adhering chromium in mg/m2 was measured by X-ray fluorescence both before and after this rinse.
  • the "alkali resistance" as reported in Table 2 is defined as the percentage of the chromium originally present that is removed by this rinsing. Thus, the alkali resistance increases as the percent value declines, and a zero value indicates absolutely no loss from alkali in this test, or complete resistance.
  • the alkali rinse conditions were as follows: 2 minute spray at 60 degrees Centigrade using a 2% aqueous solution of a sodium silicate-based alkaline degreaser (Par-Clean® N364S from Nihon Parkerizing Company, Limited).
  • test specimen 70 x 150 mm
  • salt-spray test specified in Japanese Industrial Standard ("JIS") Z-2371 for 150 hours.
  • JIS Japanese Industrial Standard
  • the corrosion resistance was evaluated on the basis of the development of white rust by surveying the entire area of the test specimen and reported using the following symbols:
  • test specimen was subjected to a composite corrosion test (50 cycles) both before and after alkali rinsing. Each cycle consisted of salt spray for 4 hours, drying at 60 degrees Centigrade for 2 hours, and wetting at 50 degrees Centigrade and a relative humidity of ⁇ 95 % for 2 hours.
  • the corrosion resistance was evaluated on the basis of the development of red rust by surveying the entire area of the test specimen and reported according to the symbols below.
  • the painted test specimen (with no alkali rinse) was extruded 6 mm.
  • Conventional transparent adhesive tape was then applied and rapidly peeled off, and the degree of paint film peeling was inspected and reported with the same symbols as for the crosscut test.
  • practice of the present invention forms a surface film which is very uniformly distributed over the surface of zinc objects, especially zinc-plated steel sheet.
  • the treated sheet is well suited to welding, resistant to alkali treatment and corrosion, and very well adapted for painting, because paint adheres very well and the painted surface is corrosion resistant.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
EP90106675A 1989-04-07 1990-04-06 Improved surface treatment for zinciferous surfaces Expired - Lifetime EP0391442B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP89415/89 1989-04-07
JP1089415A JPH0753911B2 (ja) 1989-04-07 1989-04-07 亜鉛系めっき鋼板のクロメート処理方法

Publications (2)

Publication Number Publication Date
EP0391442A1 EP0391442A1 (en) 1990-10-10
EP0391442B1 true EP0391442B1 (en) 1993-10-06

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EP90106675A Expired - Lifetime EP0391442B1 (en) 1989-04-07 1990-04-06 Improved surface treatment for zinciferous surfaces

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EP (1) EP0391442B1 (da)
JP (1) JPH0753911B2 (da)
KR (1) KR930007389B1 (da)
AT (1) ATE95575T1 (da)
DE (1) DE69003716T2 (da)
DK (1) DK0391442T3 (da)
ES (1) ES2045616T3 (da)
NZ (1) NZ233236A (da)
ZA (1) ZA902660B (da)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07100873B2 (ja) * 1989-09-27 1995-11-01 日本パーカライジング株式会社 亜鉛系メッキ鋼板のクロメート塗布液
JPH0696778B2 (ja) * 1990-10-05 1994-11-30 新日本製鐵株式会社 亜鉛系めっき鋼板のクロメート処理方法
JPH0753913B2 (ja) * 1990-11-14 1995-06-07 新日本製鐵株式会社 有機複合めっき鋼板の製造方法
JP2743220B2 (ja) * 1991-04-22 1998-04-22 新日本製鐵株式会社 ポリウレタン重防食被覆鋼材
WO1999008806A1 (en) * 1997-08-21 1999-02-25 Henkel Corporation Process for coating and/or touching up coatings on metal surfaces
DE19740248A1 (de) * 1997-09-12 1999-03-18 Henkel Kgaa Chromatierung oder Nachpassivierung mit stabilisierten Cr(III)/Cr(VI)-haltigen Lösungen
ES2175778T3 (es) * 1997-09-17 2002-11-16 Chemetall Plc Procedimiento y composciones para prevenir la corrosion de sustratos de metal.
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
US6663700B1 (en) * 2000-10-31 2003-12-16 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
US6669764B1 (en) * 2000-10-31 2003-12-30 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys
JP3873642B2 (ja) * 2001-03-21 2007-01-24 Ｊｆｅスチール株式会社 錫めっき鋼板
DE10162756A1 (de) * 2001-12-20 2003-07-10 Walter Hillebrand Gmbh & Co Schwarzpassivierungsverfahren
RU2547374C1 (ru) * 2014-01-31 2015-04-10 Закрытое акционерное общество "ФК" Хроматирующий состав для обработки оцинкованной стали

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6256580A (ja) * 1985-09-05 1987-03-12 Nippon Parkerizing Co Ltd 亜鉛系メツキ鋼板のクロメ−ト塗布液

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Publication number Publication date
JPH0753911B2 (ja) 1995-06-07
DE69003716D1 (de) 1993-11-11
ATE95575T1 (de) 1993-10-15
NZ233236A (en) 1992-05-26
KR930007389B1 (ko) 1993-08-09
JPH02267277A (ja) 1990-11-01
ES2045616T3 (es) 1994-01-16
DK0391442T3 (da) 1993-12-20
DE69003716T2 (de) 1994-02-17
ZA902660B (en) 1991-01-30
KR900016497A (ko) 1990-11-13
EP0391442A1 (en) 1990-10-10

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