WO1996016205A1 - Korrosionsschutz und reibungsverminderung von metalloberflächen - Google Patents

Korrosionsschutz und reibungsverminderung von metalloberflächen Download PDF

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Publication number
WO1996016205A1
WO1996016205A1 PCT/EP1995/004466 EP9504466W WO9616205A1 WO 1996016205 A1 WO1996016205 A1 WO 1996016205A1 EP 9504466 W EP9504466 W EP 9504466W WO 9616205 A1 WO9616205 A1 WO 9616205A1
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WO
WIPO (PCT)
Prior art keywords
acid
aqueous solution
component
solution according
cans
Prior art date
Application number
PCT/EP1995/004466
Other languages
German (de)
English (en)
French (fr)
Inventor
Henry Rossmaier
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP95940171A priority Critical patent/EP0793738B1/de
Priority to AU41719/96A priority patent/AU698370B2/en
Priority to BR9509759A priority patent/BR9509759A/pt
Priority to DE59505673T priority patent/DE59505673D1/de
Priority to JP8516528A priority patent/JPH10509766A/ja
Publication of WO1996016205A1 publication Critical patent/WO1996016205A1/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
    • C23C22/05—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
    • C23C22/34—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 fluorides or complex fluorides

Definitions

  • the invention is in the field of surface treatment of shaped metal parts made of aluminum or aluminum alloys and of tinned steel (tinplate). It relates in particular to beverage and food containers made from these materials.
  • the aim of the invention is to provide the can surfaces with a paintable, anti-corrosion layer in the process of making the can, which facilitates the drainage of water and which, in particular, leads to a reduction in the coefficient of friction between cans in contact with one another and thus to transport the cans on conveyor belts is facilitated, while the porosity of a later coating is reduced.
  • Tins made of tinned steel (tinplate) and aluminum (or aluminum alloys, which are summarized below for simplicity under "aluminum”) are widely used for storing foods and beverages in particular.
  • these are usually washed after shaping, for which purpose, for example, acidic or alkaline cleaners are commercially available.
  • These cleaning solutions must have sufficient dissolving power for the metals in question in order to effectively remove metal debris from the cans.
  • the can surface itself can be roughened by the metal attack, which increases the friction between touching cans. As a result, the speed of the can transport on the conveyor belts is reduced, and particularly at locations where a can build-up of accumulation due to the individualization of the cans, the can transport can be completely blocked.
  • EP-B-8942 discloses treatment solutions, preferably for aluminum doses, containing a) 0.5 to 10 g / 1 polyacrylic acid or an ester here of and b) 0.2 to 8 g / 1 at least one of the compounds hexafluorozirconic acid , Hexafluorotitanic acid or hexafluorosilicic acid.
  • Conversion solutions for aluminum are known from US Pat. No. 4,470,853 which contain, inter alia, 10 to 150 ppm zirconium, 20 to 250 ppm fluoride, 15 to 100 ppm phosphate and 30 to 125 ppm tannin. Their pH is in the range of 2.3 to 2.95.
  • the use of tannin in the surface treatment of aluminum is also taught in DE-A-2446492, according to which aluminum is treated with an acidic, phosphate-containing solution which contains a metal salt of tannin in amounts between 0.1 and 10 g / l .
  • WO91 / 14014 describes an aqueous solution, the ions of Fe, Zr, Sn, Al or Ce, metal etching acids such as hydrofluoric acid, contains alkoxylated phosphoric acid esters and a combination of alkoxylated alcohols and alkoxylated alkylphenols.
  • WO94 / 01517 describes a process for the friction-reducing conversion treatment of metal cans, in which, in addition to inorganic metal compounds, alkoxylated or non-alkoxylated castor oil triglycerides, hydrogenated castor oil derivatives, alkoxylated or non-alkoxylated amine salts of fatty acids, alkoxylated or non-alkoxylated amino fatty acids or alkoxylated fatty acids or alkoxylated fatty acids -N-oxides, alkoxylated or non-alkoxylated quaternary ammonium salts or water-soluble organic polymers are used.
  • Amine oxides or quaternary ammonium salts in which at least one alkyl radical contains up to 20 carbon atoms are used. Amine compounds of this type are also used in the context of the present invention.
  • EP-A-612833 proposes a surface treatment with an ester between a polyglycerol and fatty acids to reduce friction.
  • An effective surface treatment of tinplate or aluminum nozzles should, on the one hand, meet the different requirements with regard to corrosion protection as well as freedom from pores and adhesion of a subsequent coating, which are checked according to different requirements according to different criteria, and on the other hand should ensure the most effective possible reduction in friction .
  • Systems known to date represent compromises between the different requirements and do not fully satisfy all points.
  • the object of the present invention is to provide a solution for the surface treatment of metal cans, which has an improved performance spectrum with regard to the different requirements.
  • an aqueous solution for treating surfaces made of aluminum or tin and also their alloys the one Has a pH in the range from 2.3 to 3.3 and contains at least the following components:
  • R 1 is a saturated or mono- or polyunsaturated alkyl radical with 8 to 22 C atoms
  • R 2 and R3 independently of one another an alkyl or hydroxyalkyl radical with 1 to 8 C atoms or an aryl or alkylaryl radical with 6 to 10 C- Atoms
  • R 4 is a radical of the type R 2 or R3 or a -0 ⁇ radical
  • the alkyl radicals R 1 can represent radicals with a certain chain length and a certain number of double bonds. From economic For reasons, however, it is preferable to use amine oxides or ammonium salts which are derived from oleochemical raw materials. In these cases, the R 1 radicals have a distribution of chain lengths and double bonds which are characteristic of the fatty acids in vegetable or animal fats and oils. Preference is given to using compounds of the general formula (I) in which R1 represents a mixture of alkyl groups, such as those fatty acid mixtures which can be obtained by hydrolysis of coconut oil, palm kernel oil or animal tallow.
  • Suitable amine oxides of the general formula (I) are: bis (2-hydroxyethyl) cocoalkylamine oxide (Aromox R C / 12), bis (2-hydroxyethyl) talkylkylamine oxide (Aromox R T / 12), dimethyl cocoalkylamine oxide (Aromox R DMC ), hydrogenated diethyl tallow alkyl amine oxide (Aromox R DMHT) and dimethyl hexadecyl amine oxide (Aromox R DM-16), all of which are available from Akzo Chemicals Inc.
  • quaternary ammonium salts of the general formula (I) are: dodecyl trimethyl ammonium chloride (Arquad 12-37W R) Octadecyltrime- methylammonium chloride (Arquad 18-50 R), dimethylbenzyl (Ci2-i8) - a lkylammoni- monium chloride (Arquad B-100) , Tris (2-hydroxyethyl) tallow alkyl ammonium acetate (Ethoquad R T / 13) and methyl bis (2-hydroxy-2-methylethyl) ammonium methyl sulfate (Propoquad R T / 12), all of which are also available from Akzo Chemicals Inc.
  • Preferred alkylamine oxides or quaternary ammonium salts of the general formula (I) are those which carry radicals R 2 , R 3 and, in the case of the quaternary ammonium salts, also R 4 which form when the alkyl amines are reacted with ethylene oxide, propylene oxide or butylene oxide. Examples include 2-hydroxyethyl groups and 2-hydroxy-2-methylethyl groups. As is customary in alkoxylation reactions, residues R2, R3 and R 4 can also arise in this case, in each of which several alkoxy groups are linked to one another via ether bonds. Such polyether residues with up to 8 carbon atoms are also within the scope of the invention.
  • the components of group a) are the active ingredients which reduce friction.
  • the effect of the components of group b) is mono-, di- or tri-basic hydroxycarboxylic acids having 4 to 7 carbon atoms in the molecule, the Sum of hydroxyl and carboxyl groups is at least 3, primarily in that a lacquer applied later has a reduced porosity and thus an increased corrosion resistance.
  • the porosity value referred to in the Anglo-Saxon literature as "Metal Exposure Value", MEV, can be determined by an electrochemical measurement and represents one of the quality requirements of the beverage industry for lacquered beverage cans ter MK "from Manfred Kunke, Berlin (Germany) or with an" Enamel Rater “from Wilkens-Anderson Co, Chicaco, Illinois.
  • the measurement is based on filling the inside of the beverage can with an electrolyte solution (50.6 g of table salt and 1.19 g of dioctyl sodium sulfosuccinate in 5 l of completely deionized water) and switching the can as an electrode.
  • a counter electrode is immersed in the electrolyte solution and the flowing current is read off in mA after the voltage has been switched on and a waiting time of 4 seconds has elapsed. If the can is perfectly coated, no current flow is expected. Increasing current flow in mA, which represents the "metal exposure value", indicates an increasing permeability of the coating for ions, which can be interpreted as porosity. For a later filling with soft drinks, for example, it is required that the average MEV should be below 5 mA at a test voltage of 6.3 V.
  • the essence of the present invention is that components b) in the treatment solution significantly lower the MEV, without the other properties such as friction reduction and corrosion protection, which are essentially due to components a), c) and d) of the treatment solution ⁇ are to be influenced negatively.
  • Suitable hydroxycarboxylic acids are malic acid, tartaric acid, citric acid and in particular those carboxylic acids which can be obtained by oxidation of sugars of the pentose and hexose type.
  • carboxylic acids are gluconic acid, sugar acid, mannosugar acid, Mucic acid and glucuronic acid. Gluconic acid is particularly preferred.
  • These acids can be used as such or in the form of their water-soluble salts, in particular their sodium salts.
  • the pH of the inventive treatment solutions in the range 2.3 to 3.3 are the Hy ⁇ droxycarbon Acid depending on their pK partially as such, and teilwei ⁇ se in the form of their anions.
  • Suitable complex fluorides of group c) are, for example, hexafluorotitanate, hexafluorozirconate, hexafluorohafnate, hexafluorosilicate or tetrafluoroborate.
  • hexafluorozirconate is preferred. It is immaterial whether the complex fluorides are used as water-soluble salts, for example as sodium or ammonium salts, or as free acids.
  • the treatment solution according to the invention has a pH in the effective range from 2.3 to 3.3. At pH values outside this range, the formation of the desired corrosion-protective and friction-reducing layer becomes all the more unsatisfactory the further one moves away from the specified range.
  • component d) comprises 10 to 100% by weight of phosphoric acid or whose anions exist. If phosphoric acid is not used as the only acid in group d), the use of nitric acid or its anions is advantageous.
  • the effect of the combination of substances described above can be enhanced by adding further active substances from the prior art:
  • tannin in the concentration range 50 to 500 mg / l increases the effect of the hydroxycarboxylic acids of group b) with regard to the reduction of the "metal exposure value" of a coating subsequently applied. Accordingly, it is preferred that the treatment solution according to the invention additionally contains tannin. Tannins (compare, for example, Römpp Chemie Lexikon 9th edition 1992, keyword “Tannin”) stands as a group name for a number of natural polyphenols of very diverse compositions that can be derived from gallic acid. The gallic acid derivatives are often esterified with glucose. In the form of vegetable extracts of different origins, the tannins represent a known active ingredient group for leather tanning.
  • the treatment solution contains surface-active components that tend to foam due to the components of group a), it can Ker bath movement such as for spray systems may be necessary to add defoamers to the treatment baths. Amounts in the range of 50 to 500 mg / 1 should generally be sufficient.
  • Alkyl polyalkoxy esters for example, are suitable as defoamers. A suitable polyalkoxy ester of this type is available under the trade name Foamaster R C14 from Henkel KGaA, Düsseldorf (Germany).
  • a further improvement of the coating in particular with regard to its paintability, can be achieved by additionally adding water-soluble or water-dispersible organic polymers to the treatment solution in concentrations of about 100 to about 1000 mg / l.
  • These polymers can be selected from h) homopolymers or heteropolymers of ethylene oxide, propylene oxide and / or butylene oxide, i) homopolymers or heteropolymers of acrylic acid, maleic acid and / or derivatives thereof, k) homopolymers or heteropolymers of vinylphenol and / or vinylphenol derivatives, 1) homopolymers or heteropolymers of vinyl alcohol and / or vinyl alcohol derivatives.
  • Polymers of the type mentioned are commercially available.
  • the group k) polyvinylphenol derivatives are obtainable by a Mannich reaction of polyvinylphenol with aldehydes with alkylamines.
  • a reaction product of poly (4-vinylphenol) with formaldehyde and 2-alkylamino-1-ethanol may be mentioned.
  • Further information on this polymer and its use in the surface treatment of aluminum can be found in WO92 / 07973.
  • Compositions of ready-to-use treatment solutions according to the invention have been described above. It is of course possible to prepare these baths directly by mixing the individual components in the specified concentration ranges on site.
  • the invention also includes aqueous concentrates of the treatment solutions which, by dilution with water, give the treatment solutions according to the invention. It is technically and economically most attractive to adjust the concentrates so that the ready-to-use treatment solutions can be obtained from them by dilution with water in a volume ratio between 1:50 and 1:200. For example, the concentrate can be adjusted so that it has to be diluted 1: 100 with water to prepare the ready-to-use treatment solution.
  • the treatment solution according to the invention is preferably used in a process for the production of cans, in particular beverage cans made of aluminum alloys.
  • the preformed cans are generally subjected to a one- or two-stage acidic or alkaline cleaning, which is usually followed by rinsing with tap water.
  • the cans are then brought into contact with the treatment solution according to the invention, which can be done, for example, by immersing the cans in the solution or by spraying the cans with the solution.
  • the temperature of the treatment solution should be in the range between 30 to 60 ° C. and in particular 40 to 45 ° C.
  • the duration of the treatment should not be less than 10 seconds. A treatment duration of more than 120 seconds does not bring any technical advantage.
  • the invention also encompasses a method for producing a protective layer on aluminum or tin surfaces and alloys thereof which protect against corrosion, reduce friction and improve paintability, characterized in that the surfaces are coated with an aqueous solution according to a method or more of claims 1 to 8, which has a temperature in the range of 30 to 60 ° C, for a period between 10 and 120 seconds in contact, which is preferably used for the treatment of cans made of aluminum or aluminum alloys.
  • the invention was tested on aluminum beverage cans with a volume between 330 and 350 ml, as are customary for soft drinks.
  • the preformed cans were first cleaned (acidic cleaner Ridoline R 124, Henkel KGaA, Düsseldorf; 54 to 60 ° C, 1 minute) and then rinsed with tap water at room temperature. Thereafter, the surface treatment was carried out with treatment solutions according to the invention and with comparison solutions according to the table with pH values in the range between 2.45 and 2.93 at temperatures between 40 and 45 ° C. for a treatment period of 30 seconds in spraying. This was followed by rinsing with tap water, followed by rinsing with demineralized water, in each case at room temperature, after which the cans were dried at 150 ° C. for 5 minutes.
  • the well water resistance was determined by immersing the unpainted cans for 30 minutes in a 66 ° C solution of 0.2 g / 1 sodium tetraborate decahydrate, then rinsing them with demineralized water and drying them at 105 ° C in a drying oven. The can bottoms were then assessed visually according to the degree of their discoloration. No discoloration or slight discoloration is considered acceptable, dark or irregular discoloration is unacceptable. Both the cans treated with the process variants according to the invention and with comparison processes according to the prior art passed this test for corrosion resistance. The surface friction of the unpainted beverage cans was determined on a tilting table. For this, 3 tins treated in the same way are used.
  • Two cans are arranged parallel to one another on the tilting table so that their longitudinal axis is perpendicular to the tilting axis.
  • a third can is placed with its longitudinal axis perpendicular to the tilting axis so that it is shifted by about 0.5 cm in the direction of the tilting axis relative to the lower cans, being placed opposite to the lower cans with the open side in the direction of the tilting axis becomes.
  • the tilting table is then automatically tilted at a constant speed and the angle of inclination oc is determined, at which the upper box slips and thereby touches an off switch.
  • the tangent of the inclination angle ⁇ at which the slipping takes place, is referred to as the coefficient of friction.
  • the cans connected as electrodes were filled with an electrolyte solution (50.6 g of sodium chloride and 1.19 g of dioctyl sodium sulfosuccinate in 5 l of completely deionized water), into which a metal bracket was immersed as a counter electrode. After applying the voltage, the current was measured in mA after 4 seconds and set as the MEV value. An upper MEV value of 5 mA is specified as the test criterion for beverage cans for soft drinks. The results obtained are entered in the table. The table also contains the number of doses that were measured per treatment solution, the mean MEV value, the maximum observed MEV value and the number of doses at which the specification was exceeded by a maximum MEV value of 5 mA. The composition of the sample solutions is shown in the table.

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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)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
PCT/EP1995/004466 1994-11-23 1995-11-14 Korrosionsschutz und reibungsverminderung von metalloberflächen WO1996016205A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP95940171A EP0793738B1 (de) 1994-11-23 1995-11-14 Korrosionsschutz und reibungsverminderung von metalloberflächen
AU41719/96A AU698370B2 (en) 1994-11-23 1995-11-14 Preventing corrosion and reducing friction on metal surfaces
BR9509759A BR9509759A (pt) 1994-11-23 1995-11-14 Solução aquosa para o tratamento de superfícies de alumínio ou estanho concentrado aquoso e processo para a produção de uma camada protetora anticorrosiva redutora de atrito
DE59505673T DE59505673D1 (de) 1994-11-23 1995-11-14 Korrosionsschutz und reibungsverminderung von metalloberflächen
JP8516528A JPH10509766A (ja) 1994-11-23 1995-11-14 金属表面の抗腐食および摩擦低下処理

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4441710.1 1994-11-23
DE4441710A DE4441710A1 (de) 1994-11-23 1994-11-23 Korrosionsschutz und Reibungsverminderung von Metalloberflächen

Publications (1)

Publication Number Publication Date
WO1996016205A1 true WO1996016205A1 (de) 1996-05-30

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Application Number Title Priority Date Filing Date
PCT/EP1995/004466 WO1996016205A1 (de) 1994-11-23 1995-11-14 Korrosionsschutz und reibungsverminderung von metalloberflächen

Country Status (12)

Country Link
EP (1) EP0793738B1 (enrdf_load_stackoverflow)
JP (1) JPH10509766A (enrdf_load_stackoverflow)
AR (1) AR000259A1 (enrdf_load_stackoverflow)
AT (1) ATE178951T1 (enrdf_load_stackoverflow)
AU (1) AU698370B2 (enrdf_load_stackoverflow)
BR (1) BR9509759A (enrdf_load_stackoverflow)
CA (1) CA2205996A1 (enrdf_load_stackoverflow)
DE (2) DE4441710A1 (enrdf_load_stackoverflow)
TR (1) TR199501469A2 (enrdf_load_stackoverflow)
TW (1) TW283740B (enrdf_load_stackoverflow)
WO (1) WO1996016205A1 (enrdf_load_stackoverflow)
ZA (1) ZA959938B (enrdf_load_stackoverflow)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19654642C2 (de) * 1996-12-28 2003-01-16 Chemetall Gmbh Verfahren zur Behandlung metallischer Oberflächen mit einer wässerigen Lösung
US6379474B1 (en) 1997-08-06 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Phosphating method accelerated by N-oxides
DE19933189A1 (de) * 1999-07-15 2001-01-18 Henkel Kgaa Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen
JP3998057B2 (ja) * 2002-04-23 2007-10-24 日本ペイント株式会社 ノンクロム金属表面処理方法、及び、アルミニウム又はアルミニウム合金板
JP3998056B2 (ja) * 2002-04-23 2007-10-24 日本ペイント株式会社 熱可塑性ポリエステル系樹脂被覆金属板の製造方法及び熱可塑性ポリエステル系樹脂被覆金属板
ES2574561T3 (es) * 2007-07-10 2016-06-20 Atotech Deutschland Gmbh Solución y proceso para incrementar la capacidad de soldadura y la resistencia a la corrosión de la superficie de un metal o de una aleación metálica
EP2376678B1 (en) * 2009-01-14 2012-09-12 Atotech Deutschland GmbH Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface
CN103097583B (zh) * 2010-09-15 2015-11-25 杰富意钢铁株式会社 容器用钢板及其制造方法
WO2016167928A1 (en) * 2015-04-15 2016-10-20 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers
DE102015206812A1 (de) 2015-04-15 2016-10-20 Henkel Ag & Co. Kgaa Polymerhaltige Vorspüle vor einer Konversionsbehandlung
DE102015209910A1 (de) * 2015-05-29 2016-12-01 Henkel Ag & Co. Kgaa Vorspüle enthaltend ein quartäres Amin zur Konditionierung vor einer Konversionsbehandlung

Citations (7)

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GB875972A (en) * 1960-01-18 1961-08-30 Collardin Gmbh Gerhard Improvements in or relating to the phosphatising of metals
GB2059445A (en) * 1979-09-06 1981-04-23 Richardson Chemical Co Chromium-free or low-chromium metal surface passivation
US4273592A (en) * 1979-12-26 1981-06-16 Amchem Products, Inc. Coating solution for metal surfaces
WO1985005131A1 (en) * 1984-05-04 1985-11-21 Amchem Products, Inc. Metal treatment
JPH05320936A (ja) * 1991-09-20 1993-12-07 Mitsubishi Heavy Ind Ltd 鉄鋼表面の錆転化による防錆処理剤
WO1994001517A1 (en) * 1992-07-08 1994-01-20 Henkel Corporation Aqueous lubrication and surface conditioning for formed metal surfaces
WO1995002660A1 (en) * 1993-07-13 1995-01-26 Henkel Corporation Aqueous lubricant and surface conditioner for formed metal surfaces

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB875972A (en) * 1960-01-18 1961-08-30 Collardin Gmbh Gerhard Improvements in or relating to the phosphatising of metals
GB2059445A (en) * 1979-09-06 1981-04-23 Richardson Chemical Co Chromium-free or low-chromium metal surface passivation
US4273592A (en) * 1979-12-26 1981-06-16 Amchem Products, Inc. Coating solution for metal surfaces
WO1985005131A1 (en) * 1984-05-04 1985-11-21 Amchem Products, Inc. Metal treatment
JPH05320936A (ja) * 1991-09-20 1993-12-07 Mitsubishi Heavy Ind Ltd 鉄鋼表面の錆転化による防錆処理剤
WO1994001517A1 (en) * 1992-07-08 1994-01-20 Henkel Corporation Aqueous lubrication and surface conditioning for formed metal surfaces
WO1995002660A1 (en) * 1993-07-13 1995-01-26 Henkel Corporation Aqueous lubricant and surface conditioner for formed metal surfaces

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Title
PATENT ABSTRACTS OF JAPAN vol. 018, no. 150 (C - 1179) 14 March 1994 (1994-03-14) *

Also Published As

Publication number Publication date
AU4171996A (en) 1996-06-17
MX9703762A (es) 1998-07-31
CA2205996A1 (en) 1996-05-30
ZA959938B (en) 1996-05-23
DE59505673D1 (de) 1999-05-20
DE4441710A1 (de) 1996-05-30
JPH10509766A (ja) 1998-09-22
ATE178951T1 (de) 1999-04-15
EP0793738B1 (de) 1999-04-14
BR9509759A (pt) 1997-09-16
TW283740B (enrdf_load_stackoverflow) 1996-08-21
TR199501469A2 (tr) 1996-07-21
AU698370B2 (en) 1998-10-29
AR000259A1 (es) 1997-06-18
EP0793738A1 (de) 1997-09-10

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