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EP0817871B1 - Produit de nettoyage anticorrosion pour acier etame - Google Patents

Produit de nettoyage anticorrosion pour acier etame Download PDF

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Publication number
EP0817871B1
EP0817871B1 EP96908053A EP96908053A EP0817871B1 EP 0817871 B1 EP0817871 B1 EP 0817871B1 EP 96908053 A EP96908053 A EP 96908053A EP 96908053 A EP96908053 A EP 96908053A EP 0817871 B1 EP0817871 B1 EP 0817871B1
Authority
EP
European Patent Office
Prior art keywords
ppm
weight
solution
corrosion
cans
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 - Lifetime
Application number
EP96908053A
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German (de)
English (en)
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EP0817871A1 (fr
Inventor
Henry Rossmaier
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 AG and Co KGaA
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Henkel AG and Co KGaA
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Filing date
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Publication of EP0817871A1 publication Critical patent/EP0817871A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C23C22/34—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
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals

Definitions

  • the invention is in the field of cleaning and corrosion protection of tinned steel, especially food or beverage cans made of this material, so-called tinplate cans, in the can manufacturing process between can molding and Painting.
  • Tin cans are usually made by pre-forming, deep drawing and smoothing. They have a desirable metallic shiny surface so that after a coating treatment with a clear or opaque organic varnish or printing the outer surface are suitable as attractive packaging.
  • the Process sequence in the manufacture of tin cans exists usually in the unwinding provided with a protective oil layer Tinplate tape from the coil, in the application of drawing lubricants, in a first preliminary deformation into a cup and in deep drawing and smoothing to form the final shape.
  • additional cooling lubricants such as Water or aqueous emulsions that facilitate the deep-drawing process, used.
  • the Remains of the protective oiling and the drawing aids as well as any metal abrasion away.
  • the containers passed through one or more water rinsing stages and then in dried in a drying oven. Then there is an on or multi-stage painting and a decorative print on the outer Surface.
  • the metallic surface must be such be that the paint has sufficient adhesion and a reliable corrosion protection.
  • this problem can be solved tin-free steel cans, so-called black tin cans solve that the cans with after the actual cleaning step treated with an aqueous anti-corrosion solution 10 to 5,000 ppm aluminum ions, 10 to 200 ppm fluoride ions and up to 1,000 ppm ions of at least one of the metals titanium, zircon and / or hafnium and which has a pH of 2 to 5.5.
  • an aqueous anti-corrosion solution 10 to 5,000 ppm aluminum ions, 10 to 200 ppm fluoride ions and up to 1,000 ppm ions of at least one of the metals titanium, zircon and / or hafnium and which has a pH of 2 to 5.5.
  • US-A-4370177 describes acidic, aqueous coating solutions for aluminum surfaces, whose pH is preferably in the range from 3.5 to 4.5. These solutions contain zirconium, titanium and / or hafnium ions in a concentration of at least 0.5 mmol / l, sufficient amounts of fluoride to deal with the above metals to form soluble complexes, and at least two surfactants, preferably nonionic Surfactants. Furthermore, such solutions can be polyhydroxy compounds, preferably Contain gluconic acid or its salts, as well as boron compounds or tannin. Such Solutions form adherent, corrosion-resistant on the aluminum surfaces Coatings which also have the adhesive strength of subsequently applied further coatings, for example, based on paint, improve.
  • US-A-4313769 discloses similar acidic, aqueous coating solutions for aluminum surfaces, such as the U.S. patent discussed above. These solutions also contain zirconium titanium and / or hafnium ions and fluoride, but only one surfactant, preferably a nonionic Surfactant. Possible additional components and the intended use of these Solutions correspond to the disclosure of the U.S. patent discussed above.
  • the object of the invention was to provide a treatment solution, a concentrate Manufacture and provide a treatment process with which Tin cans cleaned in a single treatment step and with one Corrosion-protected surfaces are provided, so that corrosion of the surfaces prevented before painting and good paint adhesion can be achieved.
  • the invention relates to the use of an aqueous solution which has a pH in the range from 3 to 6, comprising: 100 to 400 ppm complex fluorides of the elements boron, titanium, zirconium and / or hafnium, based on the complex fluorides of the elements mentioned, 100 to 2000 ppm non-ionic surfactants, 100 to 1000 ppm corrosion inhibitor and the remainder water or an aqueous solution of further active ingredients or auxiliaries, selected from aluminum ions, hydroxycarboxylic acids and solubilizers, for cleaning, for protection against corrosion and / or for improving the paint adhesion of tinned steel.
  • concentration ranges are therefore particularly preferred for the individual active compounds.
  • the source of the aluminum ions is preferably one given in Concentration range of soluble aluminum salt used.
  • the nitrate and in particular the sulfate are suitable, while the chloride is less preferred for corrosion reasons is.
  • the solution is additionally considered further active ingredient or auxiliary 200 to 800 ppm one or more one, two or three-base Hydroxycarboxylic acids with 4 to 7 carbon atoms in the molecule, the Sum of hydroxyl and carboxyl groups is at least 3.
  • the hydroxycarboxylic acid is or are Hydroxycarboxylic acids are preferably selected from mono- or dibasic Hydroxycarboxylic acids with 6 carbon atoms and at least 4 hydroxyl groups. Gluconic acid is particularly preferred. It is it is immaterial whether the acids as such or in the form of their im specified concentration range soluble salts, especially in Form of their sodium salts, are used.
  • the pH of the Solution in the range of 3 to 6 will depend on the acids their acid constants partly in their acid form and partly are present as carboxylate anions.
  • boron, titanium, zirconium and / or Hafnium is also considered to be in the form of its acids, for example the tetrafluoroboric acid or the hexafluoro acids of titanium, Zircon and hafnium, or in the form of in the specified concentration range soluble salts, for example the alkali metal salts, can be used. Because these complex fluoride anions strong acids, they are in the pH range from 3 to 6 are largely in ionic form.
  • the solution be complex Fluorides of boron in addition to complex fluorides of at least one of the Contains metals titanium, zircon and hafnium, especially of zircon.
  • a solution that is complex is particularly preferred Fluoride of boron and zircon in a weight ratio between 4: 1 and 1: 1, especially in the weight ratio between 3: 1 and 1.5: 1.
  • Such surfactants or surfactant mixtures are nonionic surfactants preferred, which has a cloud point below about 40 to about Have 45 ° C. This makes it possible to add the cleaning solution a working temperature between about 50 and about 70 ° C in spraying to be used without excessive and disruptive foaming occurs.
  • ethoxylates and Ethoxylate propoxylates of alkanols with about 10 to about 18 carbon atoms into consideration.
  • the ethoxylates and / or the Ethoxylate propoxylates may also be end group capped and, for example exist as butyl ether.
  • the ethoxylates preferably wear 4 to 12 ethylene oxide groups, especially about 6 to 10 Ethylene oxide groups which preferably carry ethoxylate propoxalates 3 to 7 ethylene oxide groups and 2 to 6 propylene oxide groups, preferably 4 to 6 ethylene oxide groups and 3 to 5 propylene oxide groups.
  • a pure compound with a certain C chain length can be selected.
  • alkanols Olethoxylates
  • a surfactant mixture which both Contains alkanol ethoxylates as well as alkanol ethoxylate propoxylates, for example in a weight ratio between 1: 3 and 1: 1.
  • the corrosion inhibitor or the corrosion inhibitors can for example can be selected from mono-, di- or triethanolamine, aromatic carboxylic acids, pyridine or pyrimidine derivatives and Diethylthiourea.
  • the ethanolamines are toxicological Reasons (avoidance of nitrosamine formation) especially triethanolamine prefers.
  • Aromatic carboxylic acids in particular come Benzoic acid and its substitution products into consideration. Examples for this are methylbenzoic acids, nitrobenzoic acids, Aminobenzoic acids such as anthranilic acid or p-aminobenzoic acid and hydroxybenzoic acids such as salicylic acid.
  • pyridine or pyrimidine derivatives are pyridine or pyrimidine derivatives as well Diethylthiourea less preferred.
  • An example of a usable Inhibitor combination is a mixture of triethanolamine and benzoic acid, for example in a weight ratio between 3: 1 and 1: 3. Triethanolamine can also act as the only corrosion inhibitor be used.
  • Fluorides in the form of their acids, may be required by Base addition the pH to the desired range between about 3 and about 6, preferably between about 4 and about 5.
  • basic alkali metal compounds such as Hydroxides or carbonates are suitable.
  • the invention relates to the use of the Solution for cleaning, characterized above Corrosion protection and / or to improve paint adhesion on objects made of tinned steel, especially for food or beverage cans.
  • This procedure has the advantage of being in a single treatment step cleaning and temporary corrosion protection at the same time to achieve.
  • the corrosion protection prevents corrosion of the Metal surfaces before painting, such as in Plant downtimes could occur.
  • the Paint adhesion and corrosion protection in the painted state improved, without another for this after the cleaning stage Treatment level is required.
  • the cans are usually rinsed with water, dried at elevated temperature and then painted.
  • the invention relates to a method for cleaning, for Corrosion protection and / or to improve the paint adhesion of objects made of tinned steel, especially of food or beverage cans, the cans having the one described above Solution for a period between about 30 and about 150 seconds at a temperature between about 50 and treated at about 70 ° C.
  • the treatment can be by spraying the cans with the solution or by immersing the cans into the solution. Treatment by splashing is preferred.
  • the invention relates to an aqueous cleaning solution for tinned steel, the 150 to 300 ppm complex fluorides of the elements, boron, titanium, zirconium and / or hafnium, based on the complex fluorides of the elements mentioned, 50 to 300 ppm aluminum, 300 to 1000 ppm non-ionic surfactants, 150 to 500 ppm corrosion inhibitor and the remainder contains water or an aqueous solution of further active ingredients or auxiliaries selected from hydroxycarboxylic acids and solubilizers and has a pH in the range from 3 to 6.
  • the cleaning solution according to the invention can in principle be prepared by mixing the individual components together on site in the specified concentration ranges.
  • it is customary to sell such solutions in the form of aqueous concentrates, which the user can adjust to the desired concentration range by diluting with water on site. Therefore, in a further aspect, the invention comprises an aqueous concentrate which, when prepared in water at a concentration between about 0.5 and about 2.5% by weight, gives the cleaning solution according to the invention.
  • this concentrate preferably contains 1.5 to 3% by weight of complex fluorides of the elements boron, titanium, zirconium and / or hafnium, based on the complex fluorides of the elements mentioned, 0.5 to 3% by weight of aluminum ions, 3 to 10% by weight of nonionic surfactants and 1.5 to 5 wt .-% corrosion inhibitor.
  • an aluminum-containing concentrate it is preferable that it be used as further active substances or auxiliaries 2 to 8% by weight one or more mono-, di- or tri-basic hydroxycarboxylic acids with 4 to 7 carbon atoms in the molecule, the sum of hydroxyl and Carboxyl groups is at least 3 contains.
  • solubilizers in addition to the actual active ingredients, preferably in a concentration range between about 1 and about 10% by weight and in particular from about 3 to about 7% by weight.
  • Suitable solubilizers are substances known in the art, such as xylene sulfonates, alkyl phosphates (for example Triton R H66, Union Carbide) and in particular cumene sulfonate.
  • alkyl phosphates for example Triton R H66, Union Carbide
  • cumene sulfonate can preferably be used as alkali metal salts, for example as sodium and / or potassium salts.
  • a cleaner concentrate according to the invention with the following composition was produced by mixing the individual components together in the order given: water 70.8% by weight Fluoroboric acid 1.1% by weight Potassium hexafluorozirconate 0.7% by weight Aluminum sulfate ⁇ 17 H 2 O 12.4% by weight Sodium gluconate 3.3% by weight C 12/14 fatty alcohol x 5 ethylene oxide x 4 propylene oxide 3.7% by weight C 12-15 oxo alcohol x 8 ethylene oxide 1.2% by weight Na cumene sulfonate (40% solution) 4.3% by weight Triethanolamine 2.5% by weight
  • aqueous cleaner solutions with a pH value between 4 and 4.5 were produced with various batch concentrations, with which tinplate cans soiled by residues of corrosion protection oils and deep-drawing aids were cleaned by spraying for various times at a temperature of 63 ° C.
  • the cleaning effect was assessed by visual assessment of the water-free area (0: no cleaning, 100%: good cleaning).
  • the results are summarized in Table 1.
  • Cleaning effect of the concentrate from Example 1 with different batch concentrations Batch concentration (% by weight) Spraying time (seconds) % water-free area outside inside 0.7 45 60-65 / 100 90 85-90 / 100 60 75/100 0.9 45 75 / 85-90 60 85-90 / 100 90 100/100 1.2 45 90/100 60 100/100
  • concentrates were prepared in accordance with Example 1, the corrosion inhibitor triethanolamine being omitted or being completely or partially substituted. Resulting differences in composition were compensated for by water.
  • Corrosion protection effect Corrosion inhibitor in the concentrate (% by weight) Assessment grade without 6 2.5 triethanolamine 3rd 0.83 triethanolamine + 0.83 benzoic acid 3.5 1.67 triethanolamine + 1.67 benzoic acid 2nd 1.67 triethanolamine + 1.67 benzoic acid + 0.8 diethylthiourea 1.5 2.5 benzoic acid 3.5 1.5 triethanolamine + 1.5 salicylic acid 2nd
  • tin cans were cleaned with different solutions, rinsed for 15 seconds with tap water and with deionized water, dried in a drying cabinet at 170 ° C and painted once. (In practice, however, double painting is usual.) 288 cans treated in this way were filled with Coca Cola R (Coke R ) and stored for 4 months. The number of rusted cans was then determined. The results are shown in Table 3. Corrosion test (288 cans filled with Coca Cola R ) cleaning perforated cans Cf. 1 40 Cf. 2nd 20th Ex. 1 14
  • a cleaner concentrate according to the invention with the following composition was produced by mixing the individual components together in the order given: water 68.1% by weight Fluoroboric acid (49% solution) 1.1% by weight Potassium hexafluorozirconate 0.7% by weight Aluminum sulfate ⁇ 18 H 2 O 12.4% by weight Sodium gluconate 3.3% by weight C 12/14 fatty alcohol x 5 ethylene oxide x 4 propylene oxide 3.7% by weight C 12/14 fatty alcohol x 6 ethylene oxide 1.2% by weight Na cumene sulfonate (40% solution) 5.3% by weight Triethanolamine 4.2% by weight
  • a 1.1% by weight aqueous solution was also made from this concentrate a pH of 4.6.
  • tin cans were made by spraying at 60 ° C for one minute cleaned, then with tap water for 15 seconds each and rinsed with deionized water in a drying cabinet Dried 170 ° C and varnished twice. Subsequently, both carried out a paint adhesion text on the side and on the neck of the cans.
  • the cans were placed in a boiling 1 for 30 minutes % detergent solution, rinsed with water and dried. Then a cross cut was made, a Scotch tape (no. 610) stuck on and peeled off. For some samples, an almost full, but usually complete paint adhesion found.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (13)

  1. Utilisation d'une solution aqueuse qui présente un pH compris entre 3 et 6 contenant :
    100 à 400 ppm de fluorures complexes des éléments bore, titane, zirconium et/ou hafnium, par rapport aux fluorures complexes des éléments mentionnés,
    100 à 2000 ppm d'agents tensioactifs non ioniques,
    100 à 1000 ppm d'inhibiteur de corrosion
    le reste étant de l'eau ou une solution aqueuse d'autres matières actives ou adjuvants, choisis parmi les ions aluminium, les acides hydroxycarboxyliques et les tiers solvants, aux fins de nettoyage, de protection contre la corrosion et/ou pour améliorer l'adhérence des vernis sur l'acier étamé.
  2. Utilisation selon la revendication 1,
    caractérisée en ce que
    la solution contient :
    150 à 300 ppm de fluorures complexes des éléments bore, titane, zirconium et/ou hafnium,
    50 à 300 ppm d'ions aluminium,
    300 à 1000 ppm d'agents tensioactifs non ioniques,
    150 à 500 ppm d'inhibiteur de corrosion
  3. Utilisation selon l'une des revendications 1 ou 2, ou les deux,
    caractérisée en ce que
    la solution contient comme autres matières actives ou adjuvants :
    200 à 800 ppm d'un ou plusieurs acides hydroxycarboxyliques, mono-, di- ou tribasiques ayant de 4 à 7 atomes de carbone dans la molécule, la somme des groupes hydroxyle et carboxyle s'élevant à au moins 3.
  4. Utilisation selon la revendication 3,
    caractérisée en ce que
    le ou les acides hydroxycarboxyliques est(sont) choisi(s) parmi les acides hydroxycarboxyliques mono- ou dibasiques ayant 6 atomes de carbone et au moins 4 groupes hydroxyle.
  5. Utilisation selon une ou plusieurs des revendications 1 à 4,
    caractérisée en ce que
    la solution contient des fluorures complexes de bore et de zirconium dans un rapport pondéral compris entre 4:1 et 1:1.
  6. Utilisation selon une ou plusieurs des revendications 1 à 5,
    caractérisée en ce que
    les agents tensioactifs non ioniques sont choisis parmi les éthoxylates d'alcanol et les éthoxylates-propoxylates d'alcanol ayant de 10 à 18 atomes de carbone et de 4 à 12 groupes oxyde d'éthylène dans le cas des éthoxylates d'alcanol et ayant de 3 à 7 groupes oxyde d'éthylène et de 2 à 6 groupes oxyde de propylène dans le cas des éthoxylates-propoxylates.
  7. Utilisation selon une ou plusieurs des revendications 1 à 6,
    caractérisée en ce que
    les inhibiteurs de corrosion sont choisis parmi les mono-, di-, ou triéthanolamines, les acides carboxyliques aromatiques, les dérivés de pyridine ou des pyrimidine et la diéthylthiourée.
  8. Utilisation selon une ou plusieurs des revendications 1 à 7 pour le nettoyage, pour la protection contre la corrosion et pour l'amélioration de l'adhérence des vernis sur les boítes en acier étamé pour aliments ou poissons.
  9. Procédé de nettoyage, de protection contre la corrosion et/ou de l'amélioration de l'adhérence des vernis sur les boítes pour aliments ou boissons en acier étamé,
    caractérisé en ce qu'
    on traite les boítes avec une solution à utilise selon une ou plusieurs des revendications 1 à 7 pendant une durée comprise pendant 30 et 150 secondes à une température comprise entre 50 et 70°C par pulvérisation sur les boítes de la solution de nettoyage ou par immersion des boítes dans la solution de nettoyage.
  10. Solution de nettoyage aqueuse pour acier étamé qui contient
    150 à 300 ppm de fluorures complexes des éléments bore, titane, zirconium et/ou hafnium, par rapport aux fluorures complexes des éléments mentionnés,
    50 à 300 ppm d'ions aluminium
    300 à 1000 ppm d'agents tensioactifs non ioniques,
    150 à 500 ppm d'inhibiteur de corrosion
    le reste étant de l'eau ou une solution aqueuse d'autres matières actives ou adjuvants, choisis parmi les acides hydroxycarboxyliques et les tiers solvants, et qui présente un pH compris entre 3 et 6.
  11. Concentré aqueux pour la préparation de la solution de nettoyage selon la revendication 10 par dilution avec de l'eau qui contient
    1,5 à 3 % en poids de fluorures complexes des éléments bore, titane, zirconium et/ou hafnium, par rapport aux fluorures complexes des éléments mentionnés,
    0,5 à 3 % en poids d'ions aluminium,
    3 à 10 % en poids d'agents tensioactifs non ioniques,
    1,5 à 5 % en poids d'inhibiteur de corrosion,
    le reste étant de l'eau ou une solution aqueuse d'autres matières actives et adjuvants, choisis parmi les acides hydroxycarboxyliques et les tiers solvants.
  12. Concentré aqueux selon la revendication 11,
    caractérisé en ce qu'
    il contient comme autres matières actives ou adjuvants:
    2 à 8 % en poids d'un ou plusieurs acides hydroxycarboxyliques mono-, di- ou tribasiques ayant de 4 à 7 atomes de carbone dans la molécule, la somme des groupes hydroxyle et carboxyle étant au moins de 3.
  13. Concentré aqueux selon au moins l'une des revendications 11 ou 12, ou les deux,
    caractérisé en ce qu'
    il contient en outre comme additif
    de 1 à 10 % en poids d'un tiers solvant.
EP96908053A 1995-03-24 1996-03-15 Produit de nettoyage anticorrosion pour acier etame Expired - Lifetime EP0817871B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19510825A DE19510825A1 (de) 1995-03-24 1995-03-24 Korrosionsschützender Reiniger für verzinnten Stahl
DE19510825 1995-03-24
PCT/EP1996/001137 WO1996030558A1 (fr) 1995-03-24 1996-03-15 Produit de nettoyage anticorrosion pour acier etame

Publications (2)

Publication Number Publication Date
EP0817871A1 EP0817871A1 (fr) 1998-01-14
EP0817871B1 true EP0817871B1 (fr) 1999-06-09

Family

ID=7757642

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96908053A Expired - Lifetime EP0817871B1 (fr) 1995-03-24 1996-03-15 Produit de nettoyage anticorrosion pour acier etame

Country Status (12)

Country Link
US (1) US6060122A (fr)
EP (1) EP0817871B1 (fr)
JP (1) JP3812950B2 (fr)
KR (1) KR100394601B1 (fr)
AU (1) AU702394B2 (fr)
BR (1) BR9607763A (fr)
CA (1) CA2216462A1 (fr)
DE (2) DE19510825A1 (fr)
ES (1) ES2133191T3 (fr)
MX (1) MX9707196A (fr)
TR (1) TR199701024T1 (fr)
WO (1) WO1996030558A1 (fr)

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DE19510825A1 (de) 1996-09-26
DE59602170D1 (de) 1999-07-15
US6060122A (en) 2000-05-09
CA2216462A1 (fr) 1996-10-03
AU5144896A (en) 1996-10-16
AU702394B2 (en) 1999-02-18
MX9707196A (es) 1998-02-28
JP3812950B2 (ja) 2006-08-23
KR100394601B1 (ko) 2003-11-17
EP0817871A1 (fr) 1998-01-14
ES2133191T3 (es) 1999-09-01
BR9607763A (pt) 1999-01-19
TR199701024T1 (xx) 1998-02-21
JPH11502568A (ja) 1999-03-02
KR19980703273A (ko) 1998-10-15
WO1996030558A1 (fr) 1996-10-03

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