EP0135622B1 - Phosphatation de surfaces métalliques - Google Patents

Phosphatation de surfaces métalliques Download PDF

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Publication number
EP0135622B1
EP0135622B1 EP83304846A EP83304846A EP0135622B1 EP 0135622 B1 EP0135622 B1 EP 0135622B1 EP 83304846 A EP83304846 A EP 83304846A EP 83304846 A EP83304846 A EP 83304846A EP 0135622 B1 EP0135622 B1 EP 0135622B1
Authority
EP
European Patent Office
Prior art keywords
ion
zinc
seconds
coating
phosphate
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.)
Expired
Application number
EP83304846A
Other languages
German (de)
English (en)
Other versions
EP0135622A1 (fr
Inventor
Yasutake Mino
Ryoichi Murakami
Koichi Saito
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
Nippon Paint Co Ltd
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 Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Priority to EP83304846A priority Critical patent/EP0135622B1/fr
Priority to DE8383304846T priority patent/DE3378641D1/de
Priority to AT83304846T priority patent/ATE39134T1/de
Priority to MX200034A priority patent/MX161907A/es
Priority to BR8400392A priority patent/BR8400392A/pt
Priority to CA000446700A priority patent/CA1218284A/fr
Priority to ES535314A priority patent/ES8607423A1/es
Publication of EP0135622A1 publication Critical patent/EP0135622A1/fr
Priority to US06/783,059 priority patent/US4673444A/en
Application granted granted Critical
Publication of EP0135622B1 publication Critical patent/EP0135622B1/fr
Expired 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
    • C23C22/07—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
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • 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
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations

Definitions

  • This invention relates to phosphating metal surfaces.
  • Japanese Patent Publications (unexamined) No. 107784/1980 and No. 152183/1980 (both in the name Nippon Paint Co. Ltd.) disclose phosphating methods for treating iron-based metal surfaces which are particularly suitable for treating manufactured products having complicated surfaces, such as automobile bodies.
  • the phosphating methods are in use commercially in the automotive industry for pre-treating automobile bodies prior to cationic electrocoating, which is a coating process now used extensively in this industry.
  • 107784/1980 is carried out by first subjecting the metal surface to a dipping treatment with an acidic aqueous solution containing 0.5 to 1.5 g/I of zinc ion, 5 to 30 g/I of phosphate ion, and 0.01 to 0.2 g/I of nitrite ion and/or 0.05 to 2 g/I of m-nitrobenzenesulfonate ion at a bath temperature of 40° to 70°C for 15 seconds or more, followed by spraying with the above-mentioned solution for 2 seconds or more.
  • 152183/1980 comprises spraying onto the metal surface an acidic aqueous solution containing 0.4 to 1.0 g/I of zinc ion, 5 to 40 g/I of phosphate ion, 0.01 to 0.2 g/I of nitrite ion and 2.0 to 5.0 g/I of chlorate ion at 40° to 70°C for 40 seconds or more.
  • U.S. Patent 3,338,755 discloses a process for phosphating metal surfaces with a phosphating solution containing zinc, manganese, phosphate, nitrate, and nitrite, as essential ingredients, in stated proportions.
  • German Patent 29 31 693 discloses a phosphating process using a solution containing zinc, manganese, phosphate, nitrate, and chlorate ions in stated gram-atom relationships.
  • Japanese Patent J50139-039 discloses a conversion coating solution containing manganese ions for the treatment of zinc surfaces.
  • this prior art solution contains from 3 to 20 g/I of zinc ions, which results in a conversion coating having leaf-like crystals on iron-based surfaces. Such leaf-like crystals are unsuitable as a substrate for cationic electrocoating.
  • the solutions of this patent are unsuitable for treating both zinc-based and iron-based surfaces.
  • EP-A-0 018 841 discloses a coating composition for forming a zinc phosphate coating on a metal surface, which composition comprises an acidic, aqueous solution containing about 0.4 to about 1 g/I of zinc, about 5 to about 40 g/I of phosphate, and about 0.01 to about 0.2 g/I of nitrite.
  • the specification states that there are applications where advantages can be realized by applying the composition utilizing intermittent spraying, and that for these applications, the composition includes also about 2 to about 5 g/I of chlorate.
  • the aqueous coating solution may contain, in addition to the aforementioned ingredients, one or more of: nickel, cobalt, calcium and manganese ions, and one or more of nitrate, chloride and complex fluoride ions.
  • EP-A-0 060 716 discloses a process for phosphating an iron- or zinc-based metal surface comprising subjecting the metal surface to a dipping treatment in an acidic aqueous solution characterized in that the solution contains:
  • the conversion coating accelerator is preferably at least one of the following:
  • the acidic aqueous solution may also contain one or more of the following:
  • the present inventors have surprisingly found that by the inclusion of defined quantities of manganese ion in certain acidic aqueous phosphating solutions, very satisfactory results can be attained when the resulting solutions are applied by spraying more than once.
  • the inventors have further found that the amounts of chlorate ion can be markedly lower than those of known compositions.
  • the present invention provides an improved phosphating method for metal surfaces, which is particularly suitable for treating metal surfaces, such as those of car bodies, which have both iron-based surfaces and zinc-based surfaces.
  • the method is especially advantageous for forming phosphate coating films suitable for electrocoating, particularly cationic electrocoating.
  • the invention provides a process for phosphating an iron- or zinc-based metal surface comprising contacting the metal surface with an acidic aqueous solution containing:
  • the solution can be formed by a method comprising diluting with water a concentrate which comprises:
  • a metal substrate having an iron- or zinc-based surface, which surface is coated with a zinc phosphate conversion coating which contains from 1 to 20%, preferably 2 to 15%, especially 2 to 7%, by weight of manganese, and which coating has a non-leaf-like crystal structure on iron-based surfaces.
  • the solution contains 0.1 to 0.4 g/I of zinc ion. In another particular, preferred, embodiment, the solution contains 1.6 to 2.0 g/I of zinc ion. In another particular, preferred, embodiment, the solution contains 0.2 to 0.5 g/I of manganese ion.
  • the present acidic aqueous solution may also contain one or more of the following:
  • the chlorate concentration in the present solution is preferably 0.2 to 1.5 g/I.
  • the present process is carried out preferably at a temperature of from 40° to 70°C, especially 45° to 60°C, and preferably for a contact time of at least 5 seconds, more preferably at least 15 seconds, especially 30 to 180 seconds, and most preferably 30 to 120 seconds, as hereinafter discussed.
  • the period of spray treatment is generally at least 5 seconds. It should be noted that at temperatures below about 40°C coatings can be formed, but the coating is sparse, coating formation is relatively slow and longer times are required to form satisfactory coatings. At temperatures above 70°C, the conversion coating accelerators begin to decompose at an unacceptable rate, changing the composition of the solution and resulting in an unacceptable conversion coating; also, precipitates begin to form in the bath.
  • the phosphated metal surface(s) are then usually coated with a siccative coating by a known electrocoating process, preferably by the cationic electrocoating process.
  • iron- or zinc-based metal surface means iron-based surfaces, iron alloy-based surfaces, zinc-based surfaces, and zinc alloy-based surfaces.
  • Zinc-based and zinc alloy-based surfaces include, for example, zinc plated steel plate formed by hot dipping, alloyed zinc plated steel plate formed by hot dipping, zinc plated steel plate formed by electroplating, and alloyed zinc plated steel plate formed by electroplating.
  • An important advantage of the present invention is that surfaces of metal components, such as car bodies, that contain both iron-based surfaces and zinc-based surfaces can be treated by the process of the invention with excellent results.
  • the process of the invention produces better conversion coatings than are obtainable with conventional dip or spray treating processes, and the amount of etching of the metal surfaces during the present process is only 2/3 to 4/5 that of conventional processes, so that both the quantity of chemicals used in the process as well as sludge formation is only from 2/3 to 4/5 that of conventional processes.
  • the present process is equally applicable to the treatment of a single metal surface of a type described above.
  • the metal surface to be phosphated is preferably first degreased by dipping in and/or spraying with a known alkaline degreasing agent at 50° to 60°C for a few minutes; washed with tap water; dipped in and/or sprayed with a known surface conditioner at room temperature for 10 to 30 seconds; and the thus treated metal surface then contacted with the acidic aqueous solution of the invention at 40° to 70°C for at least 5 seconds. Finally, the thus treated metal surface is preferably washed with tap water and then with deionized water. An acidic final chromate rinse can be employed before the rinse with deionized water.
  • the acidic aqueous solution contains
  • the ranges can be adjusted depending on the intended objects, materials and conditions used. However, when the amount of zinc ion is less than 0.1 g/l, an even phosphate film will seldom form on an iron-based surface, and a partially blue-coloured film is formed. On the other hand, when the amount of zinc ion is in excess of 2.0 g/I, then the film tends to be in the form of leaf-like crystals and deficient in secondary adhesion, which renders it unsuitable as a substrate for cationic electrocoating.
  • the amount of phosphate ion in the solution is less than about 5 g/l, an uneven film results, whereas when the amount of phosphate ion exceeds 30 g/I, no further improvement in the phosphate film is realized and hence, the use of greater quantities of phosphate is uneconomical.
  • the amount of manganese ion is less than about 0.2 g/l, the manganese content in the film formed on the zinc-based surface is insufficient, resulting in inadequate adhesivity of the siccative coating film to the phosphate conversion coating after cationic electrocoating.
  • the amount of manganese ion exceeds 3 g/l, no further improvement in the phosphate coating is realized and hence, use of a greater quantity is uneconomical.
  • the present contact of the metal surface with the coating solution a plurality of times can be by intermittent spraying of the metal surface.
  • the coating solution can be applied by intermittent spray where the metal substrate is sprayed for about 5 to about 30 seconds, then allowed to stand without any coating application for about 5 to about 30 seconds, and then sprayed for at least 5 seconds, with a total spray time of at least 40 seconds. This cycle can be carried out once, twice or three times.
  • treating times and treating sequences can be changed according to the composition of the metal substrate to be treated and the treating solution and conditions to be used.
  • the coating solution is conveniently applied at a spraying pressure of from about 0.5 to about 2 kg/cm 2.
  • the resulting phosphate film present on the zinc-based surface should preferably contain from about 1.0 to about 20% by weight, more preferably from about 2 to about 18% by weight, and most preferably from about 5 to about 18% by weight of manganese ion, which is very important for the subsequent cationic electrocoating.
  • the zinc ion is usually present in from about 28 to about 45% by weight, preferably about 28 to about 40% by weight.
  • nickel ion is used in the solution, then from about 0.3 to about 4% by weight, preferably about 0.5 to about 4% by weight of nickel is usually present in the coating.
  • the remainder of the coating is usually phosphate and water, except for quantities of other ions such as sodium, calcium and magnesium, which usually total less than 1% by weight. It has also been found that as the content of manganese in the bath increases, increased manganese coating results. However, increasing the manganese level of the coating above the ranges given above does not improve coating quality.
  • sources of zinc ions for use in the invention one or more of the following can be employed: zinc oxide, zinc carbonate, and zinc nitrate.
  • sources of phosphate ions one or more of the following can be used: sodium phosphate, zinc phosphate, and manganese phosphate.
  • sources of manganese ions one or more of the following can be employed: manganese carbonate, manganese nitrate, manganese chloride, and manganese phosphate.
  • sources of nitrite conversion coating accelerator sodium nitrite or ammonium nitrite can be employed.
  • sources of chlorate ions chloric acid, sodium chlorate or ammonium chlorate can be employed.
  • the addition of nickel ion to the manganese-containing composition results in further improvement in the performance of the phosphate conversion coating, so that the adhesion and the corrosion-resistance of the film produced by cationic electrocoating are also further improved.
  • nickel carbonate, nickel nitrate, nickel chloride, nickel phosphate, etc. can be used for nickel ions; sodium nitrate, ammonium nitrate, zinc nitrate, manganese nitrate, nickel nitrate, etc. for nitrate ions; and sodium m-nitrobenzene-sulfonate or hydrogen peroxide for additional conversion coating accelerators.
  • the acidic aqueous treating solutions are conveniently prepared by diluting an aqueous concentrate which contains a number of the solution ingredients in proper weight ratios, and then adding other ingredients as needed to prepare the treating solutions.
  • the concentrates are advantageously formulated to contain zinc ion, phosphate ion and manganese ion, and optionally nickel ion, in a weight proportion of
  • the concentrates are preferably formulated to contain at least about 25 g/I, and more preferably from about 50 g/I to 130 g/l, of zinc ion.
  • the phosphated metal surface is preferably rinsed and electrocoated.
  • Example XXV The invention is illustrated by the following Example XXV. Comparative Examples I-XXIV and XXVI-XXXI are presented for purposes of comparison.

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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)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)
  • Chemically Coating (AREA)

Claims (9)

1. Un procédé de phosphatation de surface métallique à base de fer ou de zinc, par mise en contact de cette dernière avec une solution acide aqueuse contenant:
a) de 0,1 à 2,0 g/I d'ion zinc
b) de 5 à 30 g/I d'ion phosphate
c) de 0,2 à 3 g/I d'ion manganèse,
d) de 0,01 à 0,2 g/I d'ion nitrate à titre d'accélérateur de revêtement de conversion; et
e) de 0,05 à 1,9 g/l d'ion chlorate,
lequel procédé est caractérisé par le fait que la mise en contact s'effectue par plusieurs pulvérisations de la solution sur la surface métalliques.
2. Un procédé conforme à la revendication 1, caractérisé par le fait que le traitement est constitué d'un à trois cycles de pulvérisation intermittents, chacun comprenant une première pulvérisation d'une durée de 5 à 30 seconds, suivie de pulvérisations discontinues d'une durée de 5 à 30 secondes, suivi d'un cycle de pulvérisation final de 5 secondes au moins, la durée total de traitement pour chacun des cycles étant au moins de 40 secondes.
3. Un procédé conforme à la revendication 1 ou 2, caractérisé par le fait que le traitement a lieu par pulvérisation, sur la surface métallique, d'une solution contenant:
a) de 0,5 à 2 g/I d'ion zinc
b) de 10 à 20 g/I d'ion phosphate
c) de 0,6 à 3 g/I d'ion manganèse
d) de 0,01 à 0,2 g/I d'ion nitrate à titre d'accélérateur de revêtement de conversion; et
e) de 0,05 à 1,9 g/I d'ion chlorate.
4. Un procédé conforme à la revendication 3, caractérisé par le fait que la solution contient de 0,5 à 1,5 g/I d'ion zinc.
5. Un procédé conforme à l'une des revendications précédentes, caractérisé par le fait que la solution contient également de 0,1 à 4 g/I d'ion nickel.
6. Un procédé conforme à l'une des revendications précédentes, caractérisé par le fait que la solution contient également de 0,1 à 10 g/I d'ion nitrate.
7. Un procédé conforme à l'une des revendications précédentes, caractérisé par le fait que la température est comprise entre 40 et 70°C.
8. Un procédé conforme à l'une des revendications précédentes, caractérisé par le fait que la surface métallique traitée inclut à la fois une surface à base de fer et une surface à base de zinc.
9. Un procédé conforme à l'une des revendications précédentes, caractérisé par le fait que la surface métallique phosphatée est rincée et électroplaquée.
EP83304846A 1981-03-16 1983-08-22 Phosphatation de surfaces métalliques Expired EP0135622B1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP83304846A EP0135622B1 (fr) 1983-08-22 1983-08-22 Phosphatation de surfaces métalliques
DE8383304846T DE3378641D1 (en) 1983-08-22 1983-08-22 Phosphating metal surfaces
AT83304846T ATE39134T1 (de) 1983-08-22 1983-08-22 Phosphatierung von metalloberflaechen.
MX200034A MX161907A (es) 1983-08-22 1984-01-13 Procedimiento para fosfatar un substrato de metal a base de hierro o zinc
BR8400392A BR8400392A (pt) 1983-08-22 1984-01-31 Processo para fosfatizacao de uma superficie de metal a base de ferro ou zinco,composicao aquosa acida,concentrado aquoso e substrato de metal
CA000446700A CA1218284A (fr) 1983-08-22 1984-02-03 Phosphatation de surfaces metalliques
ES535314A ES8607423A1 (es) 1983-08-22 1984-08-21 Procedimiento para fosfatar una superficie metalica basada en hierro o zinc
US06/783,059 US4673444A (en) 1981-03-16 1985-10-01 Process for phosphating metal surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP83304846A EP0135622B1 (fr) 1983-08-22 1983-08-22 Phosphatation de surfaces métalliques

Publications (2)

Publication Number Publication Date
EP0135622A1 EP0135622A1 (fr) 1985-04-03
EP0135622B1 true EP0135622B1 (fr) 1988-12-07

Family

ID=8191259

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83304846A Expired EP0135622B1 (fr) 1981-03-16 1983-08-22 Phosphatation de surfaces métalliques

Country Status (7)

Country Link
EP (1) EP0135622B1 (fr)
AT (1) ATE39134T1 (fr)
BR (1) BR8400392A (fr)
CA (1) CA1218284A (fr)
DE (1) DE3378641D1 (fr)
ES (1) ES8607423A1 (fr)
MX (1) MX161907A (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3537108A1 (de) * 1985-10-18 1987-04-23 Collardin Gmbh Gerhard Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
US4793867A (en) * 1986-09-26 1988-12-27 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
US5238506A (en) * 1986-09-26 1993-08-24 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating
DE3918136A1 (de) * 1989-06-03 1990-12-06 Henkel Kgaa Verfahren zur erzeugung von manganhaltigen phosphatueberzuegen auf metalloberflaechen
JPH0525652A (ja) * 1990-01-26 1993-02-02 Ppg Ind Inc リン酸塩被膜組成物および亜鉛・ニツケル・マンガンホスフエート塗料の適用方法
DE4443882A1 (de) * 1994-12-09 1996-06-13 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen
US5900073A (en) * 1996-12-04 1999-05-04 Henkel Corporation Sludge reducing zinc phosphating process and composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5811514B2 (ja) * 1979-05-02 1983-03-03 日本ペイント株式会社 金属表面の保護方法
GB2072225B (en) * 1980-03-21 1983-11-02 Pyrene Chemical Services Ltd Process and composition for coating metal surfaces
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting

Also Published As

Publication number Publication date
DE3378641D1 (en) 1989-01-12
CA1218284A (fr) 1987-02-24
ES8607423A1 (es) 1986-06-01
MX161907A (es) 1991-03-01
BR8400392A (pt) 1985-06-11
ES535314A0 (es) 1986-06-01
EP0135622A1 (fr) 1985-04-03
ATE39134T1 (de) 1988-12-15

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