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US3847663A - Cleaning of metals with compositions containing alkali metal silicate and chloride - Google Patents

Cleaning of metals with compositions containing alkali metal silicate and chloride Download PDF

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US3847663A
US3847663A US27325372A US3847663A US 3847663 A US3847663 A US 3847663A US 27325372 A US27325372 A US 27325372A US 3847663 A US3847663 A US 3847663A
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metal
parts
cleaning
sodium
water
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G Shumaker
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MAN-GILL CHEMICAL COMPANY AN OH CORP
Lubrizol Corp
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Lubrizol Corp
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • C23C22/80Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions

Abstract

Metal surfaces are cleaned, prior to phosphating or the like, with compositions containing alkali metal (especially sodium) silicates and chlorides, and preferably also containing surfactants and chelating agents. These compositions have cleaning power comparable to phosphate-containing cleaners and cause less water pollution upon discharge into natural waterways.

Description

UIllttEd States Patent 1191 3,847,663

Shumaker 9 1 Nov. 12, 1974 [54] CLEANING OF METALS WITH 2,490,062 12/1949 Jernstedt l48/6.15

O O O CONTAINING ALKALI 2,044,467 6/1936 Cleveland.. 252/135 2,440,837 5/1948 Webster 252/135 METAL SILICATE AND CHLORIDE 3,368,978 2/1968 ll'anl 252/527 [75] Inventor: Gary Allen Shumaker, Mentor, 2,956,026 10/1960 Lew 252/559 Ohm FOREIGN PATENTS OR APPLICATIONS [73] Assignee: The Lubrizol Corporation, 935,733 9/1963 Great Britain hffe OTHER PUBLIC TIONS [22] Fned: July 1972 Bennett, The Chemical Formulary, Vol. X1 1 l, 1967, 211 Appl. 190.; 273,253 P Related Application Data Primary Examiner-Herbert B. Guynn [63] Continuation-impart of Ser. No. 58,182, July 24, Attorney, Agent, ,-Fi w 1 Ad J 1970, abandoned- V William 11. Pittman [52] US. Cl 134/2, 134/29, 134/42,

148 615 R, 148 615 2, 252/135, 252/524, [57] ABSTRACT 252/526 Metal surfaces are cleaned, pr1or to phosphatmg or 51 Int. Cl C23g 1/14 the like, with Compositions containing alkali metal 5 Field f Search 5 5 7; 1311/2, 29 pecially sodium) silicates and chlorides, and prefera- 134/42, 40', l48/6.l5 R, 6.15 Z bly also containing surfactants and chelating agents. These compositions have cleaning power comparable 5 References Cited to phosphate-containing cleaners and cause less water UNITED STATES PATENTS pollution upon discharge into natural waterways. 2,322,349 6/1943 .lernstedt l48/6.l5 6 Claims, No Drawings 3,090,709 5/1963 Henricks l48/6.l5

CLEANING OF METALS WITIICOMPOSITIONS CONTAINING ALKALI METAL SILICATE AND CHLORIDE This application is a continuation-in-part of copending application Ser. No. 58,182, filed July 24, 1970, now abandoned.

This invention relates to methods for cleaning metal surfaces during processing thereof, especially prior to phosphating. More particularly, it relates toa method for cleaning a metal surface'which comprises contacting said surface with an aqueous cleaning composition wherein the active ingredientscomprise water-soluble alkali metal silicate and alkali metal chloride, the weight ratio of said silicate to said chloride being between about 4:1 and i021.

In the processing of metals, it is common practice to follow a drawing operation with a phosphating treatment to produce aphosphate coating on the metal which is resistant to corrosion and serves as a paint base. The metal emerging from the drawing operation almost always has foreign matter adhering to it, chiefly drawing oils and the like. Such foreign matter is extremely difficult to remove, but it must be removed before the metal'can be phosphated. It has been customarily removed by heavy-duty alkaline cleaners containing various combinations of ingredients such as phosphates, silicates and surfactants. Phosphate-containing cleaners are particularly effective. However, the recent emphasis'on avoidance of water pollution has aroused interest in cleaners whichdonot contain phosphate,

since phosphates apparently promote algae growth in natural waterways such as lakes and rivers into which the cleaners are discharged after use.

A principal object of the present invention, therefore, is to provide a new method for heavy-duty cleaning of metal surfaces.

A further object is to provide a metal cleaning method in which the use of phosphates is avoided or substantially avoided, thereby decreasing the tendency of such compositions to pollute water.

Other objects will in part be obvious and will in part appear hereinafter.

The essential ingredients in the compositions used in the method of this invention are a water-soluble alkali metal silicate and an alkali metal chloride. By alkali metal" is meant the metals in Group [A of the Periodic Table; that is, lithium, sodium, potassium, rubidium and cesium. Sodium and potassium are preferred, and because of their ready availability and low cost, the sodium salts are most often used.

Any water-soluble alkali metal silicate may be used in the method of this invention. Thus, suitable sodium silicates include sodium disilicate, Na Si O sodium metalsilicate, Na SiO and its hydrates; sodium orthosilicate, Na SiO and so-called water glass, which is a liquid mixture of various sodium silicates. Sodium metasilicate is, however, preferred.

The alkali metal chloride may likewise be from any suitable source, but the preferred chlorides consist of crystals with high absorbent power. Particularly useful is a form of common salt sold by the Morton Salt Company and identified as North Star Fine."

The weight ratio of silicate to chloride in the compositions used in the method of this invention should be between about 4:1 and Weight ratios on the order of 7:1 or 8:1 are preferred.

boxylic acids derived from long-chain alkyl-substituted imidazolines, of long-chain polycarboxylic acids, of betaine sulfonates derived from long-chain fatty acids,

and of sulfonates of oxyethylated amines. Surfactants are particularly desirable in the compositions used in the method of this invention because they. are ordinarily instrumental in starting the cleaning process which is continued by the alkaline ingredients.

The presence of chelating agents is preferred partly because of the absence of phosphates, which ordinarily serve that purpose when they are present. Suitable chelating agents include the various amainopolycarboxylic acids andtheir water-soluble salts, such as ethylenediaminetetraacetic acid, trimethylenediaminetetraacetic acid, nitrilotriacetic acid and the like. Particularly useful is the tetrasodium salt of ethylenediaminetetraacetic acid, sold under the trade name Versene.

The proportions of surfactants and chelating agents used are usually about 3-10 parts by weight per parts of active ingredients (excluding water).

Suitable for use as fillers and pH control agents are such materials as sodium carbonate (soda ash) and similar alkaline materials which are water-soluble and inexpensive.

For certain purposes, especially when the material to be removed from the surface is very stubborn and persistent, the compositions may also contain conditioners or activators of the type used to prepare metal surfaces for phosphating. Exemplary of such conditioners or activators are the titanium phosphate compositions described in US. Pat. No. 2,322,349.

The preferred cleaning compositions contain about 65-80 parts by weight of sodium metasilicate, about 5-15 parts of sodium chloride, about 5-15 parts of sodium carbonate, about 0-10 parts of ethylenediaminetetraacetic acid or a water-soluble salt thereof (an optional ingredient), about 4-l0 parts of at least one non-ionic or amphotenc surfactant, and optionally about 4-10 parts of colloidal titanium phosphate.

Exemplary concentrates for preparing the cleaning compositions used in the method of this invention are listed in the following table.

Parts by weight -Continued Parts by weight 1 2 3 Tergitol Min'Foam 1X" (modified linear alcohol ethoxylate) Triton QS-lS" (sulfonate of polyethoxylated C, tertiary alk primary amine) Colloidal titanium phosphate For use, concentrates such as those listed in the table are dissolved in water to a concentration of about 5-2O grams per liter, preferably about 5-10 grams per liter. The aqueous cleaner thus prepared is contacted with the metal surface by spraying, dipping or the like, preferably at a temperature of about 50l0OC. Contact between the metal and the cleaner is continued for a period of time sufficient to remove drawing oils and other foreign matters from the metal surface, usually about 30 seconds to 1 minute. The surface is then rinsed with water and a phosphate coating is applied thereto by conventional methods.

- The effectiveness of the method of this invention is shown in a series of tests in which various drawing oils are applied by brush to 4 inches X 8 inches cold-rolled steel panels which are then sprayed with cleaning compositions prepared from the concentrates of Examples 1.-3 by dilution with water to 7.5 grams per liter, the temperature of the cleaning composition during spraying being 71C. The cleaning compositions are used both pure and contaminated with 5, 10, and grams per liter of the drawing oil. The cleaning operation is continued for seconds, after which the steel panels are rinsed with water, phosphated with a phosphating solution of the type disclosed in U.S. Pat. No. 3,090,709 containing zinc, calcium and ammonium ions, and rinsed with ,a conventional chromiumcontaining rinse solution. The appearance of the phosphate coating is then evaluated to determine the effectiveness of the cleaner.

When tested by this method, the cleaners of Examples 1 and 2 gave results equal to those of comparable phosphate-containing cleaners at all levels of contamination, when used to remove ordinary drawing oils. Rust-preventive drawing oils were resistant to the cleaners of Examples 1 and -2 but were removed by the cleaner of Example 3, to a degree comparable to that of known heavy-duty phosphate cleaners.

' What is claimed is:

l. A method for cleaning the surface of metals during processing thereof which comprises contacting said surface at a temperature of about 50-100C. with an aqueous cleaning composition in the liquid state wherein the active ingredients comprise water-soluble alkali metal silicate and alkali metal chloride, the weight ratio of said silicate to said chloride being between about 4:1 and 10:1.

2. A method according to claim I wherein the alkali metal is sodium.

3. A method according to claim 2 wherein the cleaning composition additionally contains at least one nonionic or amphoteric surfactant and a chelating agent, each being present in the amount of about 3l0 parts by weight per parts of active ingredients.

4. A method according to claim 3 wherein the chelating agent is ethylenediaminetetraacetic acid or a watersoluble salt thereof.

5. A method according to claim 2 wherein the active ingredients in said cleaning composition consist essentially of about 65-80 parts by weight of sodium metasilicate, about 51 5 parts of sodium chloride, about 5-15 parts of sodium carbonate, about 0-10 parts of ethylenediaminetetraacetic acid or a water-soluble salt thereof, and about 4-10 parts of at least one non-ionic or amphoteric surfactant, said ingredients being dissolved in water to a concentration of about 5-20 grams per liter.

6. A method according to claim 5 wherein the composition additionally contains about 4-10 parts by weight of colloidal titanium phosphate.

Claims (6)

1. A METHOD FOR CLEANING THE SURFACE OF METALS DURING PROCESSING THEREOF WHICH COMPRISES CONTACTING SAID SURFACE AT A TEMPERATURE OF ABOUT 50*-100*C WITH AN AQUEOUS CLEANING COMPOSITION IN THE LIQUID STATE WHEREIN THE ACTIVE INGREDIENTS COMPRISE WATER-SOLUBLE ALKALI METAL SILICATE AND ALKALI METAL CHLORIDE, THE WEIGHT RATIO OF SAID SILICATE TO SAID CHLORIDE BEING BETWEEN ABOUT 4:1 AND 10:1.
2. A method according to claim 1 wherein the alkali metal is sodium.
3. A method according to claim 2 wherein the cleaning composition additionally contains at least one non-ionic or amphoteric surfactant and a chelating agent, each being present in the amount of about 3-10 parts by weight per 100 parts of active ingredients.
4. A method according to claim 3 wherein the chelating agent is ethylenediaminetetraacetic acid or a water-soluble salt thereof.
5. A method according to claim 2 wherein the active ingredients in said cleaning composition consist essentially of about 65-80 parts by weight of sodium metasilicate, about 5-15 parts of sodium chloride, about 5-15 parts of sodium carbonate, about 0-10 parts of ethylenediaminetetraacetic acid or a water-soluble salt thereof, and about 4-10 parts of at least one non-ionic or amphoteric surfactant, said ingredients being dissolved in water to a concentration of about 5-20 grams per liter.
6. A method accordIng to claim 5 wherein the composition additionally contains about 4-10 parts by weight of colloidal titanium phosphate.
US3847663A 1970-07-24 1972-07-19 Cleaning of metals with compositions containing alkali metal silicate and chloride Expired - Lifetime US3847663A (en)

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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951681A (en) * 1973-11-01 1976-04-20 Kolene Corporation Method for descaling ferrous metals
US3973998A (en) * 1975-05-05 1976-08-10 Celanese Coatings & Specialties Company Rinsing solutions for acid cleaned iron and steel surfaces
US4065324A (en) * 1976-12-16 1977-12-27 Burton, Parsons And Company, Inc. Contact lens cleaning solution
US4127423A (en) * 1977-09-13 1978-11-28 Burton, Parsons And Company, Inc. Contact lens cleaning solution
US4379834A (en) * 1978-11-17 1983-04-12 Hoechst Aktiengesellschaft Process for cleaning copper-containing metal surfaces
US4539133A (en) * 1983-03-02 1985-09-03 Lever Brothers Company Process for preparation of an anti-corrosive aqueous liquid detergent composition
US4592785A (en) * 1983-12-15 1986-06-03 General Electric Company Proteinaceous soil removal process
EP0310587A1 (en) * 1987-09-30 1989-04-05 Monsanto Company Compositions and process for metal treatment
US4957568A (en) * 1988-04-28 1990-09-18 Henkel Kommanditgesellschaft Auf Aktien Composition and process for activating metal surfaces prior to zinc phosphating and process for making said composition
US5064556A (en) * 1991-02-13 1991-11-12 Provision, Inc. Golf club cleaning composition and method
US5096609A (en) * 1990-02-15 1992-03-17 Hoechst Aktiengesellschaft Detergent containing sodium disilicate having a water content of 0.3 to 6% by weight
US5234506A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and method
US5234505A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5261967A (en) * 1991-07-17 1993-11-16 Church & Dwight Co, Inc. Powdered electric circuit assembly cleaner
US5264046A (en) * 1991-07-17 1993-11-23 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and cleaning method
US5264047A (en) * 1991-07-17 1993-11-23 Church & Dwight Co., Inc. Low foaming effective hydrotrope
US5282992A (en) * 1992-04-07 1994-02-01 Betz Laboratories, Inc. Lubricating metal cleaner additive
US5431847A (en) * 1991-07-17 1995-07-11 Charles B. Barris Aqueous cleaning concentrates
US5433885A (en) * 1991-07-17 1995-07-18 Church & Dwight Co., Inc. Stabilization of silicate solutions
USRE35017E (en) * 1991-07-17 1995-08-15 Church & Dwight Co., Inc. Method for removing soldering flux with alkaline salts, an alkali metal silicate and anionic polymer
US5443651A (en) * 1990-02-06 1995-08-22 Monsanto Company Process for metal cleaning
USRE35045E (en) * 1991-07-17 1995-10-03 Church & Dwight Co., Inc. Method for removing soldering flux with alkaline metal carbonate salts and an alkali metal silicate
USRE35115E (en) * 1991-07-17 1995-12-12 Church & Dwight Co. Inc. Low foaming effective hydrotrope
WO1998039498A1 (en) * 1997-03-07 1998-09-11 Henkel Corporation Conditioning metal surfaces prior to phosphate conversion coating
US6214132B1 (en) * 1997-03-07 2001-04-10 Henkel Corporation Conditioning metal surfaces prior to phosphate conversion coating
CN101608314B (en) 2008-06-16 2011-02-23 南京科润工业介质有限公司 Anti-emulsification water-soluble metal washing agent
CN105274547A (en) * 2015-11-10 2016-01-27 荆门市拓达科技有限公司 Efficient water-based cleaning agent

Citations (8)

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US2044467A (en) * 1931-05-27 1936-06-16 Philadelphia Quartz Co Cleansing preparation
US2322349A (en) * 1941-10-25 1943-06-22 Westinghouse Electric & Mfg Co Corrosion resistant coating for metal surfaces
US2440837A (en) * 1943-07-28 1948-05-04 J H Shoemaker Metal cleaning composition
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
US2956026A (en) * 1955-03-22 1960-10-11 California Research Corp Sulfonate detergent compositions
US3090709A (en) * 1953-08-10 1963-05-21 Lubrizol Corp Phosphate coating of metals
GB935733A (en) * 1961-03-16 1963-09-04 Basf Ag Detergents and cleaning products
US3368978A (en) * 1964-12-28 1968-02-13 Monsanto Co Builder compositions and detergent compositions using same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2044467A (en) * 1931-05-27 1936-06-16 Philadelphia Quartz Co Cleansing preparation
US2322349A (en) * 1941-10-25 1943-06-22 Westinghouse Electric & Mfg Co Corrosion resistant coating for metal surfaces
US2440837A (en) * 1943-07-28 1948-05-04 J H Shoemaker Metal cleaning composition
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
US3090709A (en) * 1953-08-10 1963-05-21 Lubrizol Corp Phosphate coating of metals
US2956026A (en) * 1955-03-22 1960-10-11 California Research Corp Sulfonate detergent compositions
GB935733A (en) * 1961-03-16 1963-09-04 Basf Ag Detergents and cleaning products
US3368978A (en) * 1964-12-28 1968-02-13 Monsanto Co Builder compositions and detergent compositions using same

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Title
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Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951681A (en) * 1973-11-01 1976-04-20 Kolene Corporation Method for descaling ferrous metals
US3973998A (en) * 1975-05-05 1976-08-10 Celanese Coatings & Specialties Company Rinsing solutions for acid cleaned iron and steel surfaces
US4065324A (en) * 1976-12-16 1977-12-27 Burton, Parsons And Company, Inc. Contact lens cleaning solution
US4127423A (en) * 1977-09-13 1978-11-28 Burton, Parsons And Company, Inc. Contact lens cleaning solution
US4379834A (en) * 1978-11-17 1983-04-12 Hoechst Aktiengesellschaft Process for cleaning copper-containing metal surfaces
US4539133A (en) * 1983-03-02 1985-09-03 Lever Brothers Company Process for preparation of an anti-corrosive aqueous liquid detergent composition
US4592785A (en) * 1983-12-15 1986-06-03 General Electric Company Proteinaceous soil removal process
EP0310587A1 (en) * 1987-09-30 1989-04-05 Monsanto Company Compositions and process for metal treatment
US4957568A (en) * 1988-04-28 1990-09-18 Henkel Kommanditgesellschaft Auf Aktien Composition and process for activating metal surfaces prior to zinc phosphating and process for making said composition
US5443651A (en) * 1990-02-06 1995-08-22 Monsanto Company Process for metal cleaning
US5096609A (en) * 1990-02-15 1992-03-17 Hoechst Aktiengesellschaft Detergent containing sodium disilicate having a water content of 0.3 to 6% by weight
US5064556A (en) * 1991-02-13 1991-11-12 Provision, Inc. Golf club cleaning composition and method
US5234506A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and method
US5261967A (en) * 1991-07-17 1993-11-16 Church & Dwight Co, Inc. Powdered electric circuit assembly cleaner
US5264046A (en) * 1991-07-17 1993-11-23 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and cleaning method
US5234505A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5549761A (en) * 1991-07-17 1996-08-27 Church & Dwight Co., Inc. Method for removing rosin soldering flux from a printed wiring board
USRE35115E (en) * 1991-07-17 1995-12-12 Church & Dwight Co. Inc. Low foaming effective hydrotrope
US5393448A (en) * 1991-07-17 1995-02-28 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and method
US5397495A (en) * 1991-07-17 1995-03-14 Church & Dwight Co. Inc. Stabilization of silicate solutions
US5431847A (en) * 1991-07-17 1995-07-11 Charles B. Barris Aqueous cleaning concentrates
US5433885A (en) * 1991-07-17 1995-07-18 Church & Dwight Co., Inc. Stabilization of silicate solutions
USRE35017E (en) * 1991-07-17 1995-08-15 Church & Dwight Co., Inc. Method for removing soldering flux with alkaline salts, an alkali metal silicate and anionic polymer
US5264047A (en) * 1991-07-17 1993-11-23 Church & Dwight Co., Inc. Low foaming effective hydrotrope
USRE35045E (en) * 1991-07-17 1995-10-03 Church & Dwight Co., Inc. Method for removing soldering flux with alkaline metal carbonate salts and an alkali metal silicate
US5282992A (en) * 1992-04-07 1994-02-01 Betz Laboratories, Inc. Lubricating metal cleaner additive
WO1993025727A1 (en) * 1992-06-10 1993-12-23 Church & Dwight Company, Inc. Low foaming effective hydrotrope
WO1998039498A1 (en) * 1997-03-07 1998-09-11 Henkel Corporation Conditioning metal surfaces prior to phosphate conversion coating
US6214132B1 (en) * 1997-03-07 2001-04-10 Henkel Corporation Conditioning metal surfaces prior to phosphate conversion coating
CN101608314B (en) 2008-06-16 2011-02-23 南京科润工业介质有限公司 Anti-emulsification water-soluble metal washing agent
CN105274547A (en) * 2015-11-10 2016-01-27 荆门市拓达科技有限公司 Efficient water-based cleaning agent

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Owner name: MAN-GILL CHEMICAL COMPANY, 23000 ST. CLAIR AVE., C

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. EFFECTIVE JUNE 30, 1981.;ASSIGNOR:ROHCO, INC., AN OH CORP.;REEL/FRAME:003928/0049

Effective date: 19810630