US3625777A - Process for phosphate conversion coating - Google Patents

Process for phosphate conversion coating Download PDF

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Publication number
US3625777A
US3625777A US872022A US3625777DA US3625777A US 3625777 A US3625777 A US 3625777A US 872022 A US872022 A US 872022A US 3625777D A US3625777D A US 3625777DA US 3625777 A US3625777 A US 3625777A
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United States
Prior art keywords
starch
coating
zinc
paint
panels
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Expired - Lifetime
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US872022A
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English (en)
Inventor
Masanaga Okabe
Kakuro Muro
Masamichi Iizuka
Sumio Sakata
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Occidental Chemical Corp
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Hooker Chemical Corp
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Assigned to HOOKER CHEMICALS & PLASTICS CORP, A CORP OF NY reassignment HOOKER CHEMICALS & PLASTICS CORP, A CORP OF NY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OXY METAL INDUSTRIES CORPORATION reassignment OXY METAL INDUSTRIES CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). 4-09-74 Assignors: OXY METAL FINISHING CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS 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
    • C23C22/07—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
    • C23C22/12—Orthophosphates containing zinc cations

Definitions

  • This invention relates to improvements in process for phosphate conversion coating, that is, a method for forming coating films'of zinc phosphate on surfaces of metals, particularly iron, steel, zinc and its alloys (including electrogalvanized and hot dip galvanized steel,) and is aimed to attain fine and dense crystalline structure of zinc phosphate of the coating, along with considerable reduction in weight (or in thickness) of saidcoating and increasing in adherence of the same to base metals, thereby to improve paint bonding quality of the coating when the paint is applied to said coating and corrosion resistance of the coated metals.
  • a particular object of this invention is to provide a method for the fonnation of strong zinc phosphate coating which can withstand bending up to 180 or other severe mechanical forming operation without failing such as falling off, cracks or other ruptures.
  • This invention is available in very wide range as far as the acid zinc phosphate coating concerns, and is able to get similarly good results irrespective of kinds of metals to be coated, and in turn, irrespective of composition of ordinary treating solution to be used. Accordingly, with any of iron, steel, zinc or zinc alloys the above-mentioned objects are easily attained by the method of this invention, and these wide versatility constitutes an important special feature of this invention.
  • FIG. 1 is a diagram showing adhesiveness of zinc phosphate conversion coatings of the present invention which are applied on zinc galvanized steel sheets, and
  • FIG. 2 is a diagram showing the weights of said coatings.
  • FIG. 1 and 2 show respectively adhesiveness and weight of coatings both against change of added quantity of starch or like additives, when zinc phosphate conversion treatments upon zinc galvanized steel panel are processed in acid treating solution for zinc phosphate coating such as described later in our examples added by 0.0 l-l .0 percent by weight of soluble starch such as starch phosphate, dextrine according to this invention.
  • Starch or thelike materials which are available as additives according to the feature of this invention, are for example as follows: amylose, amylopectin, dextrin, starch, starch derivatives and, polysaccharides produced from acid decomposition of these, and as said starch derivatives, are included oxidized starch, starch phosphate, nitro-starch, starch sulfate carboxyl starch, hydroxyethyl starch, aminoethyl starch, alkyl starch and aryl starch.
  • This invention resides in adding one or more of starch or other polysaccharides such as described above by 0.0l-l.0 weight percent in total to a usual acid zinc phosphate coating solution.
  • Treating solution according to this invention is obtained only by adding a certain quantity of starch or other polysaccharides to the treating solution.
  • treating conditions including pH value, commonly employed conditions or values are available, and out of them appropriate ones may be selected depending upon the kind of metal to be treated. However, generally speaking, pH in the range of 2 to 3, a temperature in the range of 40 to C., and the treating time, in the case of spraying, from 3 to 10 seconds, while, in the case of dipping, from 5 seconds to 3 minutes, may be adequate.
  • Treating solution was prepared by diluting above described concentrated solution in 6 weight percent dilution and by adding 001-1 .0 weight percent of soluble starch or dextrin.
  • the prepared treating solution was heated to 40-70 C., and electrogalvanized or hot-dip-galvanized steel panels were subjected to spraying of the heated solution for 3-10 sec. or were dipped in a bath of the heated solution for 5-30 sec. By this treatment, zinc phosphate coating films firmly bound to the surfaces of said panels were obtained.
  • Treating solution was prepared by adding 0.2 g./l. of polyphosphate (such as sodium metaphosphate) and 0.l-1.0 weight percent of soluble starch or dextrin to 6 weight percent aqueous dilution of said concentrated solution shown in example l.
  • the treating solution was heated to 40-70 C., and electrogalvanized or hot-dip-galvanized panels were treated with this heated solution by spraying or dipping, and after the treatment, zinc phosphate coatings in the form of fine, dense and uniform crystalline structure, having coating weight of l .2-l .8 g./m. and uniform appearance were obtained.
  • EXAMPLE 3 Composition of treating solution: Zn 1.6 g./l. P0, 5.9 g./l. NO; 1.8 g./l. SiF 1.3 g./l. Ni 1.3 gJl. H 0 remainder
  • the above-indicated treating solution was added with 0.0 1-1 .0 weight percent of starch phosphate, and after heated to 40-70 C., was applied to electrogalvanized or hot-dip-galvanized steel panels by spraying or dipping. Obtained crystalline zinc phosphate coating were fine and uniform structure, having smooth appearance and film weight within a range of 1.2-1.8 g./m..
  • EXAMPLE 4 Composition of treating solution: Zn 5.5 g./l. Ni 0.3 g./l. P0, 16.4 g./l. N0 4.4 g./l. H O remainder Treating solution was heated to 40-70 C., and after added with 0.0l-l.0 weight percent of starch phosphate, was applied to elcctrogalvanized steel panels by spraying or dipping. The thus obtained zinc phosphate coating was uniform and had fine crystalline structure firmly bound to base metal, having film weight of 0.7-1 .5 g./m.
  • films obtained by prior method without an addition of starch phosphate were coarse in crystalline structure, lacking uniformity, and coating weight reached at 4.5 g./m.
  • EXAMPLE 5 Composition of treating solution: Zn 2.4 g./l. Ni 0.3 g./l. P0 6.8 g./l. N0 l.6 g./l. sis, 0.4 g./l. H 0 remainder Above solution were heated 40-50 C., and applied to surfaces of steel panels in two ways, that is, as itself (without addition) and after added with 2-3 g./l. of starch phosphate according to this invention.,The weights of coatings obtained in the former case were 2-3 g./m. while those of the latter case were decreased greatly down to 0.8-1.2 g./m., and moreover, the obtained coatings were far fine, dense and uniform, and firmly bound to the base metal.
  • a method for forming zinc-phosphate-conversion coatings on a metal surface comprising treating said metal surface with an aqueous zinc-phosphate-coating solution having incorporated therein at least one carbohydrate independently selected from the group consisting of starch, starch derivative, and polysaccharides produced by acid decomposition of starch or starch derivatives, wherein said carbohydrate is present in an amount from 0.01 to 1 percent by weight of the solution.
  • An aqueous composition useful for forming a zinc phosphate conversion coating on a metal surface comprising having incorporated into said composition from 0.01 to l percent by weight of the composition a carbohydrate independently selected from the group consisting of starch, starch derivative and polysaccharides produced by acid decomposition of starch or starch derivative.
  • composition of claim No. 5 wherein the carbohydrate is starch.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
US872022A 1968-10-31 1969-10-29 Process for phosphate conversion coating Expired - Lifetime US3625777A (en)

Applications Claiming Priority (1)

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JP7891868 1968-10-31

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US3625777A true US3625777A (en) 1971-12-07

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DE (1) DE1955002C3 (https=)
FR (1) FR2022052A1 (https=)
GB (1) GB1257947A (https=)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3776782A (en) * 1971-03-15 1973-12-04 Amchem Prod Polyester and polyamide adhesion improvers
US4497668A (en) * 1982-12-08 1985-02-05 Gerhard Collardin Gmbh Phosphating process for zinc-plated metals
US4762572A (en) * 1985-10-18 1988-08-09 Gerhard Collardin Gmbh Process for phosphating electrolytically zinc-coated metals
US5378292A (en) * 1993-12-15 1995-01-03 Henkel Corporation Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator
WO2000005066A1 (en) * 1998-07-21 2000-02-03 Henkel Corporation Conditioning metal surfaces before phosphating them
US6478860B1 (en) * 1998-07-21 2002-11-12 Henkel Corporation Conditioning metal surfaces before phosphating them
US20040011428A1 (en) * 2000-10-06 2004-01-22 Mitsuru Nakamura Surface-treating agent for metallic material with excellent suitability for press forming and chemical treatment and method of treatment
US20060228481A1 (en) * 2003-01-11 2006-10-12 Georg Gros Method for coating metallic surfaces, coating composition, and coatings produced in said manner
US20130306185A1 (en) * 2012-05-18 2013-11-21 Tube-Mac Industries, Ltd. Method of Making Hydralic Tubing
US9255332B2 (en) 2013-09-05 2016-02-09 Ppg Industries Ohio, Inc. Activating rinse and method for treating a substrate
CN114427089A (zh) * 2020-09-21 2022-05-03 中国石油化工股份有限公司 无磷预膜剂和循环水系统预膜处理的方法及其应用
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5811515B2 (ja) * 1979-05-11 1983-03-03 日本ペイント株式会社 金属表面にリン酸亜鉛皮膜を形成するための組成物
DE19523919A1 (de) * 1995-06-30 1997-01-02 Metallgesellschaft Ag Verfahren zur Ergänzung von Phosphatierungslösung
JPH10204649A (ja) * 1997-01-24 1998-08-04 Nippon Parkerizing Co Ltd 金属表面のりん酸塩処理水溶液及び処理方法
US6179934B1 (en) 1997-01-24 2001-01-30 Henkel Corporation Aqueous phosphating composition and process for metal surfaces

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1329573A (en) * 1919-09-25 1920-02-03 William H Allen Rust preventing and arresting solution
US1514494A (en) * 1922-05-29 1924-11-04 Randall Williams Company Rust remover and preventative
US2137370A (en) * 1935-12-11 1938-11-22 Unger Theodor Broch Method of coating iron and steel surfaces
FR865727A (fr) * 1940-02-08 1941-05-31 Procédé de phosphatation permettant la préparation et la phosphatation des surfaces métalliques
CA478620A (en) * 1951-11-13 Thome-Johannesen Ole Methods of and materials for production of protecting coatings on iron and steel surfaces and iron objects of any kind or shape
US2854369A (en) * 1957-10-04 1958-09-30 Oakite Prod Inc Increasing the solubility of metal accelerators in phosphatizing solutions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA478620A (en) * 1951-11-13 Thome-Johannesen Ole Methods of and materials for production of protecting coatings on iron and steel surfaces and iron objects of any kind or shape
US1329573A (en) * 1919-09-25 1920-02-03 William H Allen Rust preventing and arresting solution
US1514494A (en) * 1922-05-29 1924-11-04 Randall Williams Company Rust remover and preventative
US2137370A (en) * 1935-12-11 1938-11-22 Unger Theodor Broch Method of coating iron and steel surfaces
FR865727A (fr) * 1940-02-08 1941-05-31 Procédé de phosphatation permettant la préparation et la phosphatation des surfaces métalliques
US2854369A (en) * 1957-10-04 1958-09-30 Oakite Prod Inc Increasing the solubility of metal accelerators in phosphatizing solutions

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3776782A (en) * 1971-03-15 1973-12-04 Amchem Prod Polyester and polyamide adhesion improvers
US4497668A (en) * 1982-12-08 1985-02-05 Gerhard Collardin Gmbh Phosphating process for zinc-plated metals
US4762572A (en) * 1985-10-18 1988-08-09 Gerhard Collardin Gmbh Process for phosphating electrolytically zinc-coated metals
US5378292A (en) * 1993-12-15 1995-01-03 Henkel Corporation Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator
WO1995016805A1 (en) * 1993-12-15 1995-06-22 Henkel Corporation Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator
US6478860B1 (en) * 1998-07-21 2002-11-12 Henkel Corporation Conditioning metal surfaces before phosphating them
WO2000005066A1 (en) * 1998-07-21 2000-02-03 Henkel Corporation Conditioning metal surfaces before phosphating them
US20040011428A1 (en) * 2000-10-06 2004-01-22 Mitsuru Nakamura Surface-treating agent for metallic material with excellent suitability for press forming and chemical treatment and method of treatment
US20060228481A1 (en) * 2003-01-11 2006-10-12 Georg Gros Method for coating metallic surfaces, coating composition, and coatings produced in said manner
US20130306185A1 (en) * 2012-05-18 2013-11-21 Tube-Mac Industries, Ltd. Method of Making Hydralic Tubing
US9365944B2 (en) * 2012-05-18 2016-06-14 Tube-Mac Piping Technologies Ltd. Method of making hydralic tubing
US9255332B2 (en) 2013-09-05 2016-02-09 Ppg Industries Ohio, Inc. Activating rinse and method for treating a substrate
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
CN114427089A (zh) * 2020-09-21 2022-05-03 中国石油化工股份有限公司 无磷预膜剂和循环水系统预膜处理的方法及其应用
CN114427089B (zh) * 2020-09-21 2024-05-07 中国石油化工股份有限公司 无磷预膜剂和循环水系统预膜处理的方法及其应用

Also Published As

Publication number Publication date
GB1257947A (https=) 1971-12-22
DE1955002C3 (de) 1978-08-24
DE1955002B2 (de) 1977-12-15
DE1955002A1 (de) 1970-09-10
FR2022052A1 (https=) 1970-07-24

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AS Assignment

Owner name: HOOKER CHEMICALS & PLASTICS CORP 32100 STEPHENSON

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:003942/0016

Effective date: 19810317

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Owner name: OXY METAL INDUSTRIES CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084

Effective date: 19741220

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Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054

Effective date: 19820330