EP0155742A2 - Procédé et composition de revêtement pour le traitement de surfaces métalliques - Google Patents

Procédé et composition de revêtement pour le traitement de surfaces métalliques Download PDF

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Publication number
EP0155742A2
EP0155742A2 EP85200412A EP85200412A EP0155742A2 EP 0155742 A2 EP0155742 A2 EP 0155742A2 EP 85200412 A EP85200412 A EP 85200412A EP 85200412 A EP85200412 A EP 85200412A EP 0155742 A2 EP0155742 A2 EP 0155742A2
Authority
EP
European Patent Office
Prior art keywords
chromium
coating agent
total
weight ratio
coating
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.)
Granted
Application number
EP85200412A
Other languages
German (de)
English (en)
Other versions
EP0155742B1 (fr
EP0155742A3 (en
Inventor
Thomas J. Prescott
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
Parker Chemical Co
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, Parker Chemical Co filed Critical Henkel Corp
Publication of EP0155742A2 publication Critical patent/EP0155742A2/fr
Publication of EP0155742A3 publication Critical patent/EP0155742A3/de
Application granted granted Critical
Publication of EP0155742B1 publication Critical patent/EP0155742B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C22/24—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
    • C23C22/33—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 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
    • C23C22/74—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 for obtaining burned-in conversion coatings

Definitions

  • the invention relates to a process for the treatment of metal surfaces by applying chromium-VI, silicate and / or silicic acid, phosphate and chromium-III-containing aqueous acidic coating agents and subsequent drying of the coating agent, its use for the treatment of cold-rolled steel and for the implementation of Appropriate coating agents.
  • the object of the invention is to provide a method and coating agent for treating metal surfaces which does not have the disadvantages of the known methods, is simple to carry out and leads to high-quality, in particular corrosion-protective coatings.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that a coating agent is applied in which the weight ratio of chromium-VI: chromium is in the range from (0.6 to 0.95): 1 lies.
  • Preferred refinements of the method according to the invention provide for a coating agent to be applied
  • the total PO 4 : chromium weight ratio is in the range from (0.1 to 5): 1, preferably from (0.1 to 1): 1, or
  • weight ratio chromium VI: SiO 2 : PO 4 : total chromium is in the range from (0.6 to 0.95): (0.5 to 5.0) : (0.1 to 5.0): 1 or in which the weight ratio of chromium-VI: SiO 2 : PO 4 : total chromium is in the range from (0.75 to 0.95): (1 to 3): (0.1 to 1.0): 1 .
  • the phosphate and chromate component can be introduced into the coating agent intended for carrying out the method according to the invention in any desired form, provided that the quality of the adhesion-promoting coating is not adversely affected thereby.
  • the addition as an alkali metal salt should be kept as low as possible and avoided as far as possible, since this can result in a loss of quality.
  • Phosphate and chromium VI are preferably used as relatively well soluble salts of di- or trivalent metals or of thermally stable ammonium or amine compounds (including the D ouble salts with the aforementioned metals), or as the acid introduced. Suitable divalent or trivalent metals are, for example, zinc, manganese, chromium, nickel, cobalt and iron.
  • the chromate component is preferably added as zinc dichromate or chromic acid and the phosphate component as zinc dihydrogen phosphate.
  • the silicate or the silica should be soluble in the coating agent or - homogeneously dispersible to form a colloidal dispersion. It is therefore preferably used in a finely divided form. Aerosols or precipitated silica are particularly suitable, but naturally occurring and finely ground quartz or diatomaceous earth can also be used if they can be dispersed homogeneously. Silicates such as montmorillonite or synthetic fluorosilicates such as e.g. Magnesium fluorosilicate with the trade name Laponit can be used. The use of soluble sodium or potassium silicates or fluorosilicates is less preferred, since these compounds tend to form glassy coatings with low adhesion. Therefore, preference is given to using water-insoluble silica or silicates that are colloidally distributable.
  • the chromium III content can be reduced by partial reduction aqueous chromic acid, for example with starch under heating, are produced in the customary manner (for example according to US Pat. No. 3,706,603), the resulting solution then containing chromium-VI and chromium-III compounds.
  • the coating agent used in the process according to the invention can also contain further additives. This is e.g. around divalent or trivalent metal cations, such as zinc, manganese, cobalt, nickel or iron, inert color pigments, in order to give the coating a specific color, silicone compounds, conductivity-producing materials, such as powdered metal (see, for example, US Pat. No. 3,671,331) or conductive carbon to increase weldability, and emulsifiers to keep the resin component in the dispersed state.
  • the emulsifier is usually already contained in the commercially available aqueous resin dispersion.
  • the coating agent can be used without pH adjustment. If the ingredients as salt are divalent or trivalent. Metals or added as acids, the pH will normally be below 2.5. When adding the components in the form of the ammonium or amine salts, the pH should be higher.
  • the coating agent can be produced by introducing the individual components in any order taking into account the weight ratios to be set.
  • the silica or the silicate is preferably added after the partial reduction of the hexavalent chromium, if the reduction is carried out with heating, since otherwise the dispersibility of the silica or silicate is impaired.
  • the aforementioned recommendation only applies in the event that the chromium III compound is obtained from chromium VI by reduction.
  • the components of the film on the metal surface are initially present in the same concentration as in the coating agent itself. Therefore, the concentrations of the active components in the supplement are essentially the same as in the working coating agent. This favors bathroom control and product uniformity.
  • the aqueous coating agent can be applied to the metal surface in any manner, as long as care is taken to ensure that the aqueous film has a reasonable and uniform thickness.
  • the film thickness can be checked in the simplest manner by rolling or squeezing rolls, the previous method of application being arbitrary and being able to be carried out, for example, electrostatically or by means of spray technology.
  • the layer thicknesses produced with the aid of the method according to the invention can be chosen within wide limits and can be, for example, 4.3 g / m 2 and higher.
  • the layer weight will normally be in the range of 54 to 1,076 mg / m 2 .
  • Typical coating weights for aluminum are tahlober inhabit surfaces 54 to 162 mg / m 2, for S 162 to 270 mg / m 2 and for zinc surfaces 108-216 mg / m 2.
  • the detailed process conditions are set depending on the desired layer weight.
  • a film of a certain thickness is applied to the metal surface and then dried. During the drying process, the concentration of the components of the coating agent and between it and the metal surface increases the reaction begins.
  • the process is particularly favorable can be carried out when applying a coating agent DES sen content of chromium from 0.8 to 12 wt .-%, preferably 0.8 to 8 wt .-%, is.
  • the coating agent can be applied at ambient temperature.
  • coating agents and / or metal surface can be heated.
  • the temperature of the metal can be brought to 93 ° C. or higher in the immersion or roll-up treatment, without the treatment bath being adversely affected.
  • the spraying technique even higher metal temperatures can be set.
  • the type of drying is not critical as long as the liquid film is not excessively interrupted or torn open, e.g. due to hot air currents or physical contact during drying.
  • the type of drying can influence the temperature required for drying. For example, drying takes place at a lower, maximum object temperature if it is carried out in the infrared oven instead of in the conventional oven.
  • the furnace temperature should be measured so that a metal temperature (maximum object temperature) of 52 to 163 ° C results.
  • Paint, varnish and the like can be applied to the dried layer in the usual way. Even though the paints or varnishes used in individual cases influence the corrosion resistance and the adhesion differently, it has been shown that with most of the commercially available paints and varnishes tested, the method according to the invention leads to results which are comparable to two- or three-stage conventional methods.
  • the method according to the invention is suitable for the treatment of aluminum, zinc, galvanized steel and iron-containing metal surfaces and alloys thereof.
  • a preferred application of the method according to the invention is in the treatment of cold-rolled steel, in particular because of the achievable high corrosion resistance and the achievable perfect deformability of the coated and temporarily stored strip or sheet.
  • Part of the invention is an aqueous coating agent for the treatment of metal surfaces containing chromium VI, silicate and / or silicic acid, phosphate and chromium III, which is characterized in that it contains chromium VI: chromium in total in the weight ratio of (0, 6 to 0.95): 1 contains ..
  • the absolute content of the active components of the coating agent essentially depends on the type of application. In general, the total chromium content is 0.8 to 12% by weight, preferably 0.8 to 8% by weight.
  • the advantage of the invention is, in particular, that coating agent is applied only once without rinsing, yet high corrosion protection - even with low layer weights - and good deformability are achieved as a result of good adhesion of paint or lacquer. A large number of metals can be treated.
  • the coating agent was applied to cold-rolled steel sheets with corrugated squeezing rollers, so that after drying in a conventional oven to a maximum temperature of the metal of 82 to 93 ° C., the layer weight was once 0.4 and once 0.183 g / m 2 . The sheets then rested for two weeks.
  • Example 1 After the procedure of Example 1, three coating compositions were prepared, which contained the components CrVI, PO 4 , Si0 2 and Cr total in the following weight ratios.
  • Coating agent 2a 0.6: 0.32: 2.0: 1.0
  • Coating agent 2b 0.6: 0.65: 2.0: 1.0
  • Coating agent 2c 0.6 0.97: 2.0: 1.0
  • coatings were applied using the aforementioned coating agents at a maximum object temperature of 82 to 93 ° C. in a conventional oven. Then the pre-treated sheets were painted.
  • a coating with 0.215 g / m 2 was applied to cold-rolled steel using a coating agent in which the weight ratio CrVI: PO 4 : SiO 2 : Cr was 0.93: 0.32: 2.0: 1.0 in total (after drying) applied.
  • the coating agent according to Example 3 was applied to the surface of hot-rolled steel sheet which had been preheated to approximately 93 ° C. After about 1 minute, the sheets were provided with a single-layer polyester lacquer or with a two-layer epoxy polyester topcoat. These sheets treated in this way were distinguished by excellent corrosion resistance, excellent paint adhesion and deformability.

Landscapes

  • 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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
EP85200412A 1984-03-23 1985-03-19 Procédé et composition de revêtement pour le traitement de surfaces métalliques Expired - Lifetime EP0155742B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59259184A 1984-03-23 1984-03-23
US592591 1984-03-23

Publications (3)

Publication Number Publication Date
EP0155742A2 true EP0155742A2 (fr) 1985-09-25
EP0155742A3 EP0155742A3 (en) 1987-04-29
EP0155742B1 EP0155742B1 (fr) 1991-07-24

Family

ID=24371303

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85200412A Expired - Lifetime EP0155742B1 (fr) 1984-03-23 1985-03-19 Procédé et composition de revêtement pour le traitement de surfaces métalliques

Country Status (11)

Country Link
EP (1) EP0155742B1 (fr)
JP (1) JPS60218483A (fr)
AR (1) AR242247A1 (fr)
AU (1) AU580041B2 (fr)
BR (1) BR8501308A (fr)
CA (1) CA1256003A (fr)
DE (2) DE3509556A1 (fr)
GB (1) GB2155962B (fr)
MX (1) MX166776B (fr)
NZ (1) NZ211485A (fr)
ZA (1) ZA852128B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992009721A1 (fr) * 1990-11-28 1992-06-11 Henkel Corporation Composition et procede pour chromer des surfaces metalliques
DE102015104887B4 (de) 2015-03-30 2022-05-19 Benteler Steel/Tube Gmbh Rohrprodukt und Verfahren zu dessen Herstellung

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0222282A3 (fr) * 1985-11-04 1987-08-19 HENKEL CORPORATION (a Delaware corp.) Procédé de dépôt de couches organiques sur des surfaces métalliques
JPH07116615B2 (ja) * 1986-05-20 1995-12-13 日本パ−カライジング株式会社 亜鉛又は亜鉛合金メツキ鋼板、冷延鋼板及びステンレス鋼板用クロメ−ト処理液及びクロメ−ト処理方法
JPS6313741A (ja) * 1986-07-04 1988-01-21 大同鋼板株式会社 塗装チタン板
JPS6313740A (ja) * 1986-07-04 1988-01-21 大同鋼板株式会社 塗装鋼板
US4881975A (en) * 1986-12-23 1989-11-21 Albright & Wilson Limited Products for treating surfaces
GB2201157B (en) * 1986-12-23 1991-07-17 Albright & Wilson Processes and products for surface treatment
JPS63171685A (ja) * 1986-12-30 1988-07-15 Nippon Steel Corp 耐食性白色クロメ−ト処理方法
EP0305560B1 (fr) * 1987-08-31 1991-06-26 Nippon Paint Co., Ltd. Particule métallique
JPH0637706B2 (ja) * 1987-09-04 1994-05-18 日新製鋼株式会社 亜鉛めっき鋼板の高耐食クロメート処理方法
EP0310103A1 (fr) * 1987-10-01 1989-04-05 HENKEL CORPORATION (a Delaware corp.) Procédé de prétraitement pour aluminium
JPH01123673A (ja) * 1987-11-06 1989-05-16 Nippon Parkerizing Co Ltd アルミニウムの防黴菌性・親水性表面処理方法
JPH01240673A (ja) * 1988-03-22 1989-09-26 Nippon Steel Corp 耐食性に優れたゴールド色クロメート処理メッキ鋼板の製造方法
JPH03146676A (ja) * 1989-10-31 1991-06-21 Kobe Steel Ltd 耐吸湿汚れ性にすぐれるクロメート処理鋼板の製造方法
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
JP2668474B2 (ja) * 1991-10-29 1997-10-27 黒野 朔 アルミニウムの表面保護塗装材
JPH0693464A (ja) * 1992-09-10 1994-04-05 Nippon Steel Corp 塗装鋼板用下地塗布クロメート組成物および処理方法
JPH0693466A (ja) * 1992-09-10 1994-04-05 Nippon Steel Corp 塗装鋼板用下地塗布クロメート組成物および処理方法
JPH06108265A (ja) * 1992-09-29 1994-04-19 Nippon Steel Corp 塗装鋼板用下地塗布クロメート処理方法

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US2529206A (en) * 1948-02-18 1950-11-07 Gen Electric Process for increasing the corrosion resistance of ferrous articles
BE667113A (fr) * 1964-08-12 1965-11-16
FR1568655A (fr) * 1967-06-14 1969-05-23
US3798074A (en) * 1972-03-23 1974-03-19 Allegheny Ludlum Ind Inc Surface finishing
US4227946A (en) * 1979-02-09 1980-10-14 Oakite Products, Inc. No-rinse pre-paint coating composition and method
JPS58177475A (ja) * 1982-04-12 1983-10-18 Nisshin Steel Co Ltd 防食性のすぐれた高加工性、耐汚染性プレコ−ト金属板の製造方法
FR2550551A1 (fr) * 1983-08-12 1985-02-15 Nippon Light Metal Co Procede de traitement de surface hydrophile d'objets en aluminium et produits ainsi obtenus

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US4032366A (en) * 1975-05-23 1977-06-28 Allegheny Ludlum Industries, Inc. Grain-oriented silicon steel and processing therefor
JPS5917521B2 (ja) * 1975-08-22 1984-04-21 川崎製鉄株式会社 方向性けい素鋼板に耐熱性のよい上塗り絶縁被膜を形成する方法
CA1089155A (fr) * 1975-08-29 1980-11-11 Wilbur S. Hall Traitement de revetements electrolytiques dans une solution au chrome
DE2711431C2 (de) * 1977-03-16 1986-12-11 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Oberflächenbehandlung von Metallen
US4183772A (en) * 1978-01-30 1980-01-15 Union Carbide Corporation Composition and method for coating metal surfaces
DE2907093A1 (de) * 1979-02-23 1980-08-28 Metallgesellschaft Ag Mittel und verfahren zur erzeugung nichtmetallischer ueberzuege auf eisen und stahl
US4347085A (en) * 1981-04-23 1982-08-31 Armco Inc. Insulative coatings for electrical steels
US4548646A (en) * 1982-11-15 1985-10-22 Sermatech International Incorporated Thixotropic coating compositions and methods
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Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2529206A (en) * 1948-02-18 1950-11-07 Gen Electric Process for increasing the corrosion resistance of ferrous articles
BE667113A (fr) * 1964-08-12 1965-11-16
FR1568655A (fr) * 1967-06-14 1969-05-23
US3798074A (en) * 1972-03-23 1974-03-19 Allegheny Ludlum Ind Inc Surface finishing
US4227946A (en) * 1979-02-09 1980-10-14 Oakite Products, Inc. No-rinse pre-paint coating composition and method
JPS58177475A (ja) * 1982-04-12 1983-10-18 Nisshin Steel Co Ltd 防食性のすぐれた高加工性、耐汚染性プレコ−ト金属板の製造方法
FR2550551A1 (fr) * 1983-08-12 1985-02-15 Nippon Light Metal Co Procede de traitement de surface hydrophile d'objets en aluminium et produits ainsi obtenus

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PATENTS ABSTRACTS OF JAPAN, Band 8, nr. 11 (G-205)[1448], 18. Januar 1984; & JP-A-58 177 475 (NITSUSHIN SEIKOU K.K.) 1-10-1983 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992009721A1 (fr) * 1990-11-28 1992-06-11 Henkel Corporation Composition et procede pour chromer des surfaces metalliques
US5395655A (en) * 1990-11-28 1995-03-07 Henkel Corporation Composition and process for chromating metal surfaces
DE102015104887B4 (de) 2015-03-30 2022-05-19 Benteler Steel/Tube Gmbh Rohrprodukt und Verfahren zu dessen Herstellung

Also Published As

Publication number Publication date
JPH0422986B2 (fr) 1992-04-21
AU4028085A (en) 1985-09-26
GB8507516D0 (en) 1985-05-01
GB2155962B (en) 1987-12-31
ZA852128B (en) 1985-11-27
CA1256003A (fr) 1989-06-20
MX166776B (es) 1993-02-03
JPS60218483A (ja) 1985-11-01
DE3583512D1 (de) 1991-08-29
DE3509556A1 (de) 1985-10-24
AU580041B2 (en) 1988-12-22
NZ211485A (en) 1988-07-28
BR8501308A (pt) 1985-11-19
EP0155742B1 (fr) 1991-07-24
AR242247A1 (es) 1993-03-31
GB2155962A (en) 1985-10-02
EP0155742A3 (en) 1987-04-29

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