EP0056675B1 - Vorbehandlungszusammensetzung für die Phosphatierung von Eisenmetallen und Verfahren zu deren Herstellung - Google Patents

Vorbehandlungszusammensetzung für die Phosphatierung von Eisenmetallen und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0056675B1
EP0056675B1 EP82200062A EP82200062A EP0056675B1 EP 0056675 B1 EP0056675 B1 EP 0056675B1 EP 82200062 A EP82200062 A EP 82200062A EP 82200062 A EP82200062 A EP 82200062A EP 0056675 B1 EP0056675 B1 EP 0056675B1
Authority
EP
European Patent Office
Prior art keywords
weight
measured
amount
composition
titanium
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
EP82200062A
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English (en)
French (fr)
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EP0056675A3 (en
EP0056675A2 (de
Inventor
Nobuo Nakatani
Tooru Tsuzuki
Hideo Shimizu
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
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Filing date
Publication date
Application filed by Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Priority to AT82200062T priority Critical patent/ATE10513T1/de
Publication of EP0056675A2 publication Critical patent/EP0056675A2/de
Publication of EP0056675A3 publication Critical patent/EP0056675A3/en
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Publication of EP0056675B1 publication Critical patent/EP0056675B1/de
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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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Definitions

  • This invention relates to an aqueous solution for the treatment of ferrous metal surfaces, to the treatment of ferrous metal surfaces with this aqueous solution, to a solid composition suitable for preparing the aqueous solution and to the production of the solid composition.
  • the usual treatment steps include the following in order: (1) degreasing; (2) washing with water; (3) surface preparation; (4) conversion coating; (5) washing with water; (6) drying; and (7) siccative coating.
  • surface preparation step various proposals have hitherto been made.
  • Japanese Patent Publication Number 7125/1964 discloses the use of a surface preparation composition which is produced by dissolving a titanium oxide with an excess quantity of sulphuric acid, adding thereto phosphoric acid or an alkali metal salt thereof, and/or pyrophosphoric acid or its alkali metal salt to form a slurry at pH of 1 or lower, followed by ageing the slurry at a pH of from 6.5 to 8.5.
  • This surface preparation composition is reported to contribute to the precipitation of the zinc phosphate coating in the conversion coating step which follows.
  • this composition does not provide the desired microcrystalline coating in the zinc phosphate conversion coating treatment.
  • the present invention relates to surface preparation compositions for the treatment of ferrous metal surfaces that do not suffer from the disadvantages of the prior art composition discussed above.
  • the surface preparation compositions of the present invention can be used for long periods of time and such use results in a uniform and dense zinc phosphate coating when a zinc phosphate conversion coating composition is applied to the surface so treated.
  • the surface preparation compositions of the invention can be used to pretreat any ferrous metal surface, such as steel or other alloys of iron where the alloy consists predominantly of iron.
  • composition for the treatment of ferrous metal surfaces which composition is an aqueous solution comprising:
  • a rust-inhibiting quantity of nitrite ion e.g. in the form of its alkali metal salt, such as the sodium or potassium salt, may be added to the solution, provided the quantity added is not so large as to interfere with the effectiveness of the compositions.
  • various compounds may be employed. Examples of such compounds include titanium sulphate or titanium oxide as a source of (a); phosphoric acid, a primary alkali metal salt (e.g. Na or K salt) or primary ammonium salt of phosphoric acid, a secondary alkali metal salt (e.g. Na or K salt) or secondary ammonium salt of phosphoric acid, or a tertiary alkali metal salt (e.g. Na or K salt) or tertiary ammonium salt of phosphoric acid as a source of (b); pyrophosphoric acid or an alkali metal salt (e.g.
  • Na or K salt or ammonium salt of pyrophosphoric acid as a source of (c); and carbonic acid, an alkali metal salt (e.g. Na or K salt) or ammonium salt of carbonic acid, alkali metal hydrogen carbonate (e.g. Na or K salt) or ammonium hydrogen carbonate as a source of (d).
  • an alkali metal salt e.g. Na or K salt
  • ammonium salt of carbonic acid e.g. Na or K salt
  • alkali metal hydrogen carbonate e.g. Na or K salt
  • ammonium hydrogen carbonate e.g. Na or K salt
  • the present invention also relates to solid compositions (conveniently in powder form) that can be added to water to form the aqueous pretreatment compositions of the invention.
  • solid compositions comprise:
  • a small quanity of nitrite ion can also be present to provide a rust-inhibiting quantity of nitrite ion when the solid compositions are diluted with a sufficient quantity of water to give the aqueous pretreatment compositions of the invention.
  • the solid compositions can be prepared by (A) mixing the sources of titanium compound, phosphate and/or acid phosphate, and pyrophosphate together with water in the above proportions; (B) heating the resulting mixture, e.g. at a temperature in the range of from 100° to 120°C until the water content is substantially removed, e.g. to a level of 1.5% by weight or less; and (C) mixing, which should be even mixing, the resulting solid residue with the source of carbonate and/or acid carbonate added in the above proportion.
  • a titanium phosphate colloid adheres thereto, which serves to accelerate the formation of a zinc phosphate conversion coating by providing crystal nuclei around which the zinc phosphate coating can form.
  • the resulting zinc phosphate coating has excellent characteristics as a base for siccative coatings such as paint.
  • the titanium compound concentration is lower than the amount specified, the colloid which becomes the crystal nuclei for the zinc phosphate coating is formed in too small a quantity.
  • the titanium compound concentration is higher than the amount specified, no enhanced effect is obtained.
  • the phosphate and/or acid phosphate concentration specified is also present for the same purpose, i.e. to provide an adequate quantity of titanium phosphate colloid on the ferrous metal surface.
  • the pyrophosphate has the beneficial effect of micronizing the zinc phosphate conversion coating.
  • concentration of pyrophosphate is below the range specified, adequate micronizing is not achieved.
  • concentration is above the range specified, the pyrophosphate tends to react with the iron in the ferrous metal surface, resulting in the inhibition of formation of a zinc phosphate conversion coating.
  • the pH buffer effect is not obtained, i.e. when the pH of the present aqueous pretreatment composition is lower than the required values, the pyrophosphate ion tends to react with the ferrous metal surface, resulting in the inhibition of the subsequent zinc phosphate conversion coating formation.
  • too high a pH value does not give a preferred conversion coating for pretreatments of electro coating.
  • aqueous surface preparation compositions When the present aqueous surface preparation compositions are used in the pretreatment of ferrous metal surfaces, such compositions can be used for long periods of time, and provide a base for uniform, dense zinc phosphate conversion coatings.
  • the surface preparation compositions of the present invention are especially effective for preparing ferrous metal surfaces for zinc phosphate treatment for electro coating.
  • the long-term stability of the instant surface preparation compositions is particularly advantageous in the dipping type treatment of metals in which a large quantity of surface preparation composition is employed.
  • An aqueous surface treatment composition was prepared using the following quantities of ingredients:
  • An aqueous surface treatment composition was prepared using the following quantities of ingredients:
  • a solid mixture was formed in accordance with the process of Example I, and the mixture was added to sufficient water to give a solution of 0.1% concentration.
  • aqueous surface treatment composition was prepared from the following ingredients using the procedure of Example I, except that the solid mixture formed was diluted with water to form a 0.05% aqueous solution:
  • Each of three degreased commercial cold rolled steel plates was treated with one of the new aqueous compositions of Examples I, II and III, i.e. one plate was treated with the composition of Example I, a second plate with the composition of Example II, etc.
  • the plates were treated by dipping them for 1 minute in the aqueous composition, allowing excess liquid to drip off, and immediately dipping them into a zinc phosphate conversion coating bath (Nippon Paint Co. "GRANODINE SD 2000”) for 2 minutes at a bath temperature of 50°C.
  • the plates were then washed with water, dried, and evaluated; in addition, the above procedure was repeated with an additional three steel plates after the aqueous compositions of Examples I, II and III had stood for 10 days.
  • the results obtained are given in the Table below Example VIII, together with the pH values of the pretreatment compositions.
  • An aqueous surface treatment composition was prepared from the following ingredients:
  • Example II A solid mixture was formed from the above ingredients in accordance with the procedure of Example I (except that all of the above ingredients were mixed together and heated to form the solid mixture). A 0.05% aqueous solution was formed according to the procedure of Example I.
  • An aqueous surface treatment composition was prepared from the following ingredients in accordance with the procedure of Example V except that the solid mixture was diluted with water to form a 0.1% aqueous solution.
  • An aqueous surface treatment composition was prepared from the following ingredients in accordance with the procedure of Example V except that the solid mixture was diluted with water to form a 0.07% aqueous solution.
  • Example IV Six degreased commercial cold rolled steel plates of the type used in Example IV were treated according to the procedure of Example IV. The results obtained are given in the Table below for comparison purposes.

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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)

Claims (13)

1. Wässrige Lösung für die Behandlung von eisenhaltigen Metallflächen, wobei die Lösung enthält: . "
a) eine Titanverbindung in einer Menge von 1 bis 100 Gew.-ppm, berechnet als Titan;
b) ein Phosphat und/oder saures Phosphat in einer Menge von insgesamt 50 bis 1500 Gew.-ppm, gemessen als PO4;
c) Pyrophosphat in einer Menge von 10 bis 300 Gew.-ppm gemessen als P207 und
d) Carbonat und/oder saures Carbonat in einer Menge von insgesamt 20 bis 1500 Gew.-ppm, gemessen als C03;

und wobei die Lösung einen pH-Wert von 8,5 bis 9,5 aufweist.
2. Lösung gemäß Anspruch 1, worin die Titanverbindung entweder Titansulfat oder Titanoxid ist.
3. Lösung gemäß Anspruch 1 oder 2, worin (b), (c) und (d) jeweils in Form eines Ammonium- oder eines Alkalimetallsalzes vorliegen.
4. Lösung gemäß einem der vorgehenden Ansprüche, die eine Rost-inhibierende Menge von Nitritionen enthält.
5. Verfahren zur Behandlung einer reinen eisenhaltigen Metalloberfläche, wobei auf die Oberfläche eine Lösung gemäß einem der vorgehenden Ansprüche aufgebracht wird.
6. Verfahren gemäß Anspruch 5, worin die eisenhaltige Metalloberfläche in die wässrige Zusammensetzung eingetaucht wird.
7. Verfahren gemäß Anspruch 5 oder 6, worin die eisenhaltige Metalloberfläche anschließend mit einer Zinkphosphat-Umwandlungs-Überzugszusammensetzung behandelt wird.
8. Feste Zusammensetzung enthaltend:
(a) eine Titanverbindung in einer Menge von 1 bis 100 Gewichtsteilen, gemessen als Titan;
(b) ein Phosphat und/oder saures Phosphat in einer Menge von insgesamt 50 bis 1500 Gewichtsteilen, gemessen als P04;
(c) Pyrophosphat in einer Menge von 10 bis 300 Gewichtsteilen, gemessen als P2O7; und
(d) Carbonat und/oder saures Carbonat in einer Menge von insgesamt 20 bis 1500 Gewichtsteilen, gemessen als C03.
9. Zusammensetzung gemäß Anspruch 8, worin die Titanverbindung entweder Titansulfat oder Titanoxid ist.
10. Zusammensetzung gemäß Anspruch 8 oder 9, worin (b), (c) und (d) jeweils anwesend sind in Form eines Ammonium oder eines Alkalimetallsalzes.
11. Zusammensetzung gemäß einem der Ansprüche 8 bis 10, die eine Rost-inhibierende Menge an Nitritionen enthält.
12. Verfahren zur Herstellung einer Zusammensetzung gemäß einem der Ansprüche 8 bis 11 wobei:
(A) (a), (b) und (c) wie in Anspruch 8 definiert in Wasser zusammengemischt werden;
(B) die wässrige Mischung erhitzt wird zur Entfernung von im wesentlichen des gesamten Wassers darin und
(C) Mischen des sich ergebenden festen Rückstandes mit (d) wie in Anspruch 8 definiert.
13. Verfahren gemäß Anspruch 12, worin die Stufe (B) bei einer Temperatur von 100 bis 120°C durchgeführt wird.
EP82200062A 1981-01-19 1982-01-19 Vorbehandlungszusammensetzung für die Phosphatierung von Eisenmetallen und Verfahren zu deren Herstellung Expired EP0056675B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82200062T ATE10513T1 (de) 1981-01-19 1982-01-19 Vorbehandlungszusammensetzung fuer die phosphatierung von eisenmetallen und verfahren zu deren herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP56007028A JPS5855229B2 (ja) 1981-01-19 1981-01-19 リン酸亜鉛処理用表面調整剤
JP7028/81 1981-01-19

Publications (3)

Publication Number Publication Date
EP0056675A2 EP0056675A2 (de) 1982-07-28
EP0056675A3 EP0056675A3 (en) 1982-08-04
EP0056675B1 true EP0056675B1 (de) 1984-11-28

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EP82200062A Expired EP0056675B1 (de) 1981-01-19 1982-01-19 Vorbehandlungszusammensetzung für die Phosphatierung von Eisenmetallen und Verfahren zu deren Herstellung

Country Status (4)

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EP (1) EP0056675B1 (de)
JP (1) JPS5855229B2 (de)
AT (1) ATE10513T1 (de)
DE (1) DE3261311D1 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61257481A (ja) * 1985-05-10 1986-11-14 Nippon Parkerizing Co Ltd りん酸塩皮膜化成処理用水性表面調整液
JPS6343039U (de) * 1986-09-06 1988-03-22
CA1309315C (en) * 1987-07-14 1992-10-27 Toan Manh Ngo Compositions and process for metal treatment
DE3814363A1 (de) * 1988-04-28 1989-11-09 Henkel Kgaa Titanfreie aktivierungsmittel, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung
US5026423A (en) * 1989-02-22 1991-06-25 Monsanto Chemical Company Compositions and process for metal treatment
US5112395A (en) * 1989-02-22 1992-05-12 Monsanto Company Compositions and process for metal treatment
JPH0394075A (ja) * 1989-09-04 1991-04-18 Nippon Parkerizing Co Ltd 表面調整処理方法
JP4295216B2 (ja) * 2002-07-31 2009-07-15 新日本製鐵株式会社 樹脂ライニング鋼管およびその製造方法
CN108463577B (zh) * 2015-11-04 2021-11-19 伊利诺斯工具制品有限公司 缓蚀剂和水调理剂
KR20190043155A (ko) 2016-08-24 2019-04-25 피피지 인더스트리즈 오하이오 인코포레이티드 금속 기판을 처리하기 위한 알칼리성 조성물

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE885638C (de) * 1945-02-27 1953-08-06 Metallgesellschaft Ag Verfahren zur Herstellung einer Vorspuelloesung fuer die Phosphatierung
US2490062A (en) * 1949-01-21 1949-12-06 Westinghouse Electric Corp Cleaning and activating compositions and use thereof in producing protective phosphate coatings on metal surfaces
GB774667A (en) * 1955-12-01 1957-05-15 John Arthur Kemp Improvements in or relating to the phosphate coating of metal surfaces
FR1291347A (fr) * 1961-06-06 1962-04-20 Parker Ste Continentale Procédé de phosphatation par pulvérisation du fer et de l'acier
US3728163A (en) * 1970-05-25 1973-04-17 Balm Paints Ltd Alkaline liquids for cleaning metals
BE789347A (fr) * 1971-09-30 1973-01-15 Amchem Prod Procédés et compositions pour le traitement de surface ferreuses et de zinc

Also Published As

Publication number Publication date
JPS5855229B2 (ja) 1983-12-08
ATE10513T1 (de) 1984-12-15
JPS57120678A (en) 1982-07-27
EP0056675A3 (en) 1982-08-04
DE3261311D1 (en) 1985-01-10
EP0056675A2 (de) 1982-07-28

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