US20030196728A1 - Nonchromate metallic surface-treating agent, nonchromate metallic surface-treating method, and aluminum or aluminum alloy - Google Patents

Nonchromate metallic surface-treating agent, nonchromate metallic surface-treating method, and aluminum or aluminum alloy Download PDF

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US20030196728A1
US20030196728A1 US10/421,578 US42157803A US2003196728A1 US 20030196728 A1 US20030196728 A1 US 20030196728A1 US 42157803 A US42157803 A US 42157803A US 2003196728 A1 US2003196728 A1 US 2003196728A1
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water
metallic surface
compound
treating
nonchromate
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Satoshi Nishimura
Tomoyuki Kanda
Masayuki Kamimura
Minoru Inoue
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Nippon Paint Co Ltd
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Nippon Paint Co Ltd
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Assigned to NIPPON PAINT CO., LTD. reassignment NIPPON PAINT CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INOUE, MINORU, KAMIMURA, MASAYUKI, KANDA, TOMOYUKI, NISHIMURA, SATOSHI
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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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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 present invention relates to a nonchromate metallic surface-treating agent, nonchromate metallic surface-treating method, and aluminum or an aluminum alloy.
  • a chromium phosphate surface-treating agent As surface treatment of aluminum plates, a chromium phosphate surface-treating agent has been used. Since chemical conversion coats formed with the chromium phosphate surf-ace-treating agent are excellent in the corrosion resistance of the coatings alone and in the corrosion resistance and adhesion after applying various resin base coatings, they are adopted in a wide range of uses of aluminum materials for construction materials, an electric home appliance, fin materials, car evaporators, beverage can materials and the like. However, in recent years, there is required a nonchromate metallic surface-treating agent, which can provide the high corrosion resistance and adhesion equal to a chromium phosphate surface-treating agent, from the view point of environmental protection.
  • nonchromate chemical conversion treating agent for example, a system where a zirconium or titanium compound is used in conjunction with a phosphoric acid compound for a beverage can material.
  • a nonchromate chemical conversion treating agent for example, a system where a zirconium or titanium compound is used in conjunction with a phosphoric acid compound for a beverage can material.
  • the chemical conversion coats formed by these systems are of inferior corrosion resistance and adhesion after applying coating in comparison with the coatings formed by the chromium phosphate surface-treating agent, these could not be used for a wide range of uses.
  • Japanese Kokai Publication Sho-56-33468 discloses a surface-treating agent for aluminum comprising zirconium and/or titanium, phosphate and fluoride.
  • a surface-treating agent for aluminum comprising zirconium and/or titanium, phosphate and fluoride.
  • it is insufficient in the high adhesion with a coating and the corrosion resistance as a coating material.
  • Japanese Kokai Publication Sho-63-30218 discloses a nonchromate metallic surface-treating agent comprising a water-soluble titanium and/or zirconium compound, a tannin and/or a water-soluble or water-dispersant high polymer.
  • a nonchromate surface-treating agent is insufficient in the corrosion resistance as a coated material.
  • an object of the present invention is to provide a nonchromate metallic surface-treating agent capable of achieving the corrosion resistance and adhesion with a coating film equal to a chromium phosphate surface-treating agent.
  • This invention is a nonchromate metallic surface-treating agent comprising
  • a content of zirconium and/or titanium of said water-soluble zirconium compound and/or the water-soluble titanium compound (1) is 40 to 1000 ppm on a mass basis
  • a content of said organic phosphonic acid compound (2) is 20 to 500 ppm on a mass basis
  • a content of said tannin (3) is 200 to 5000 ppm on a mass basis
  • a nonchromate metallic surface treating-agent has a pH of 1.6 to 4.0.
  • Said organic phosphonic acid compound is preferably a compound in which phosphorus atom forming a phosphonic group combines with carbon atom.
  • This invention is a nonchromate metallic surface-treating method comprising
  • a step (A) of treating a substrate to be treated with said nonchromate metallic surface-treating agent is a step (A) of treating a substrate to be treated with said nonchromate metallic surface-treating agent.
  • Said nonchromate metallic surface-treating method preferably comprises an acid cleaning step followed by said step (A).
  • an alkaline cleaning step is performed and then an acid cleaning step is performed before said step (A) is performed.
  • This invention is aluminum or an aluminum alloy having a coat obtained by said nonchromate metallic surface-treating method.
  • Said coat after drying, preferably contains said water-soluble zirconium compound and/or the water-soluble titanium compound (1) with zirconium and/or titanium atom of 4.0 to 30 mg/m 2 , by mass per one surface, and said-organic phosphonic acid compound (2) with phosphorus atom of 0.05 to 0.3 and said tannin (3) with carbon atom of 0.5 to 3 relative to zirconium and/or titanium atom of said water-soluble zirconium compound and/or said water-soluble titanium compound (1), on a mass basis.
  • FIG. 1 is a schematic view illustrating the shape of a sample for evaluating corrosion resistance.
  • the nonchromate metallic surface-treating agent of the present invention is a surface-treating agent which can provide the excellent corrosion resistance and adhesion with a coating film after applying coatings and which does not contain chromium. Particularly, it is suitably applicable to aluminum or an aluminum alloy, and can provide the excellent corrosion resistance and adhesion with a coating film, for example, in applying it to aluminum or an aluminum alloy for beverage cans or an electric home appliance.
  • the nonchromate metallic surface-treating agent of the present invention contains a water-soluble zirconium compound and/or a water-soluble titanium compound (1).
  • the water-soluble zirconium compound is not limited in particular so long as it is a compound containing zirconium, a water-soluble zirconium compound containing fluorine is preferred since it has good stability in an applicable pH range and it is high in the formability of a coat.
  • Said water-soluble zirconium compound containing fluorine is not limited in particular, and examples thereof may include H 2 ZrF 6 , (NH 4 ) 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF6, Li 2 ZrF6 and the like. These compounds may be used alone or in combination of two kinds or more.
  • said water-soluble titanium compound is not limited in particular so long as it is a compound containing titanium, a water-soluble titanium compound containing fluorine is preferred since it has the good stability in an applicable pH range and it is high in the formability of a coat.
  • Said water-soluble titanium compound containing fluorine is not limited in particular, and examples thereof may include H 2 TiF 6 , (NH 4 ) 2 TiF 6 , K 2 TiF 6 , Na 2 TiF 6 and the like. These compounds may be used alone or in combination of two kinds or more.
  • the content of the water-soluble zirconium compound and/or the water-soluble titanium compound (1) with zirconium and/or titanium has a lower limit of 40 ppm and an upper limit of 1000 ppm on amass basis in the nonchromate metallic surface-treating agent.
  • the content is less than 40 ppm, there is a possibility that a sufficient amount of zirconium or titanium in coats could be not obtained in a short-time treatment and the adhesion and corrosion resistance could be degraded.
  • the content exceeds 1000 ppm there is a possibility that the adhesion with a coating film after applying coatings could be degraded and also a possibility of being relatively expensive since the enhancement of performances and the reduction in treatment time are not recognized.
  • the lower limit is 100 ppm and the upper limit is 300 ppm. It is noted that the content of the water-soluble zirconium compound and/or the water-soluble titanium compound is the sum of the masses of zirconium and titanium contained in the nonchromate metallic surface-treating agent.
  • the nonchromate metallic surface-treating agent of the present invention contains an organic phosphonic acid compound (2).
  • Said organic phosphonic acid compound (2) means an organic compound containing a phosphonic group (—PO 3 H 2 ), and this compound (2) is preferably compound in which the phosphonic group (—PO 3 H 2 ) combines with carbon atom.
  • the compound in which the phosphonic group (—PO 3 H 2 ) combines with carbon atom is not limited in particular, and examples thereof may include aminotri(methylenephosphonic acid) represented by the following formula (a), 1-hydroxyethylidene-1,1-diphosphonic acid represented by the following formula (b), 2-phosphobutanone-1,2,4-tricarboxylic acid represented by the following formula (c), and the like.
  • Examples of the organic phosphonic acid compounds (2) may also include ethylenediaminetetra(methylenephosphonic acid) represented by the following formula (d), diethylenetriaminepenta(methylenephosphonic acid) represented by the following formula (e), and the like.
  • organic phosphonic acid compounds (2) aminotri (methylenephosphonic acid) represented by the formula (a), 1-hydroxyethylidene-1,1-diphosphonic acid represented by the formula (b), and 2-phosphobutanone-1,2,4-tricarboxylic acid represented by the formula (c) are preferred since these are excellent in the precipitability of coats and the corrosion resistance and adhesion with a coating film after applying coatings.
  • the organic phosphonic acid compounds (2) are water-soluble.
  • this is a water-soluble compound, the use of an organic solvent is not required and a burden on the environment can be reduced.
  • the organic phosphonic acid compounds (2) maybe used alone or in combination of two kinds or more. It is noted that it is not preferred to include salts of organic phosphonic acid compounds, which is obtained by replacing the hydrogen atom contained in a phosphonic group with alkaline metal, ammonium or the like, in the nonchromate metallic surface-treating agent since the corrosion resistance of the formed coat is decreased.
  • the content of the organic-phosphonic acid compound (2) has a lower limit of 20 ppm and an upper limit of 500 ppm on a mass basis in the nonchromate metallic surface-treating agent.
  • the content is less than 20 ppm, there is a possibility that an appropriate amount of phosphorus could be not obtained in the resulting coats to be formed and the adhesion with a coating film after applying coatings could be degraded.
  • the organic phosphonic acid compound exists just only excessively and does not have an effect of enhancing the adhesion and corrosion resistance, and therefore there is a possibility of being relatively expensive.
  • the lower limit is 50 ppm and the upper limit is 200 ppm.
  • the nonchromate metallic surface-treating agent of the present invention contains tannin (3).
  • Said tannin (3) is also referred to as tannic acid and is a generic name for aromatic compounds with a complicated structure, which has a number of phenolic hydroxyl groups being widely distributed over the plant kingdom.
  • Said tannin (3) may be hydrolyzable tannin or condensed tannin.
  • Examples of the tannin (3) may include hamameli tannin, Japanese persimmon tannin, tea tannin, gallan tannin, gallnut tannin, myrobaran tannin, divi-divi tannin, valonia tannin, catechin tannin and the like.
  • the tannin (3) may also be decomposed tannins which are formed by decomposing tannins contained in plants by a method such as hydrolysis.
  • tannin (3) commercial products such as “Tannin Acid Essence A”, “B Tannic Acid”, “N Tannic Acid”, “Industrial Tannic Acid”, “Purified Tannic Acid”, “Hi Tannic Acid”, “F Tannic Acid”, “Officinal Tannic Acid” (all manufactured by Dainippon Pharmaceutical Co., Ltd.), “Tannin Acid: AL” (manufactured by Fuji Chemical Industry Co., Ltd.) can also be used.
  • the above-mentioned tannins may be used alone or in combination of two kinds or more.
  • the tannin (3) has the number-average molecular weight of 200 or more. If decomposition of tannin proceeds too much and the decomposed tannin becomes a compound with low molecular weight less than 200 when a product formed through the decomposition of tannin are used as the tannin (3), there is a possibility that the adhesion with a coating film after applying coatings could not be enhanced for lack of properties as tannin.
  • a content of the tannin (3) has a lower limit of 200 ppm and an upper limit of 5000 ppm on a mass basis in the nonchromate metallic surface-treating agent.
  • the content is less than 200 ppm, there is a possibility that an appropriate amount of carbon could be not obtained in coats to be formed and the corrosion resistance and adhesion with a coating film after applying coatings could be degraded.
  • the content exceeds 5000 ppm, there is a possibility of being relatively expensive since the enhancement of performances such as the corrosion resistance and adhesion with a coating and the reduction in treatment time are not recognized.
  • the lower limit is 500 ppm and the upper limit is 2000 ppm.
  • the nonchromate metallic surface-treating agent of the present invention has a pH within a range from a lower limit of 1.6 to an upper limit of 4.0.
  • the pH is less than 1.6, the coat appearance becomes bad since the etching of the metal surface become excessive, and the corrosion resistance of the obtained coat is degraded.
  • the lower limit is preferably 1.8, more preferably 2.2.
  • the upper limit is preferably 3.4, more preferably 2.8.
  • an etching assistant agent a chelating agent and a pH regulator can be further used as required in addition to the above-mentioned components.
  • Examples of the etching assistant agent may include hydrofluoric acid, hydrofluoride, fluoboride and the like. Further, when as a source of fluorine ion, zirconium- or titanium complex which has been mentioned as the water-soluble zirconium compound or the water-soluble titanium compound (1) is used, it is preferred to use the fluorine compound in conjunction with this complex since the amount of produced fluorine ion is insufficient.
  • Examples of the chelating agents may include acids, which form complexes with aluminum, such as citric acid, tartaric acid and gluconic acid, and metal salts thereof.
  • Examples of the pH regulator may include acids or bases, which do not adversely affect surface treatments, such as nitric acid, perchloric acid, sulfuric acid, sodium nitrate, ammonium hydroxide, sodium hydroxide and ammonia.
  • a nonchromate metallic surface-treating method of the present invention comprises a step (A) of treating a substrate to be treated with the nonchromate metallic surface-treating agent.
  • step (A) By performing the step (A), it is possible to provide the excellent corrosion resistance and adhesion with a coating film after applying coatings to the substrate.
  • An example of the substrate to be treated includes metallic base materials, and aluminum or an aluminum alloy is preferred.
  • aluminum alloys an aluminum alloy 5182 material, an aluminum alloy 5021 material, an aluminum alloy 5022 material, an aluminum alloy 5052 material, an aluminum alloy 3004 material, an aluminum alloy 3005 material, an aluminum alloy 1050 material, an aluminum alloy 1100 material and the like are suitably used.
  • Applications of the substance to be treated are not limited in particular, and examples thereof include an electric home appliance, cases for food and beverage, construction materials and the like.
  • a method of treating the substrate to be treated is not limited in particular so long as it is a method of allowing the substrate to bring into contact with the nonchromate metallic surface-treating agent, and examples of ordinary methods may include a spray method, a immersion method and the like. Among them, a spray method is preferably used.
  • Said step (A) is preferably performed at a temperature range from a lower limit of 30° C. to an upper limit of 80° C.
  • a reaction rate is lowered and the precipitability of coats is degraded. Therefore, an extension of treatment time is required to obtain a sufficient amount of coats, and productivity is decreased.
  • the temperature exceeds 80° C., there is a possibility that energy losses become large. More preferably, the lower limit is 50° C. and the upper limit is 70° C.
  • a treatment time preferably is within a range from a lower limit of 1 second to an upper limit of 20 seconds.
  • the treatment time is less than 1 second, the amount of coats formed is insufficient and there is a possibility that the corrosion resistance and adhesion could be degraded.
  • the treatment time exceeds 20 seconds, there is a possibility that etching proceeds excessively in formation of coatings and the adhesion and corrosion resistance could be degraded. More preferably, the lower limit is 3 seconds and the upper limit is 8 seconds.
  • water-washing treatment may be performed as required.
  • the water-washing treatment is performed once or more not to adversely affect on the appearances of coating film and the like. In this case, it is appropriate to perform the final water-washing with pure water.
  • this water-washing treatment either spray or immersion method may be used, and the combination thereof may also be used.
  • the coats obtained through the step (A) are preferably dried after water-washing.
  • heat drying is preferred, and an example thereof includes oven-drying and/or heat drying through a forced circulation of hot air. These heat drying are generally performed at a temperature of 40 to 120° C. for 6 to 60 seconds.
  • an acid cleaning step is performed before the step (A) is performed.
  • an alkaline cleaning step is performed before the acid cleaning step is performed.
  • the most preferable aspect is a method comprising an alkaline cleaning, a water-washing, an acid cleaning, a water-washing, nonchromate metallic surface treatment, water-washing and drying in this order.
  • the alkaline cleaning treatment is not limited in particular, and for example alkaline cleaning which has been adopted in the alkaline cleaning of the metals such as aluminum and aluminum alloys can be performed.
  • the alkaline cleaning treatment generally, the alkaline cleaning is performed through the use of an alkaline cleaner.
  • the acid cleaning is performed through the use of an acid cleaner.
  • the alkaline cleaner is not limited in particular, and for example an alkaline cleaner used in a usual alkaline cleaning can be adopted.
  • An example of the alkaline cleaner includes “SURF CLEANER 360” manufactured by Nippon Paint Co., Ltd.
  • the acid cleaner is not limited in particular, and examples thereof include inorganic acids such as sulfuric acid, nitric acid and hydrochloric acid, and “SURF CLEANER ST160” manufactured by Nippon Paint Co., Ltd.
  • the acid cleaning and alkaline cleaning treatments are generally performed through a spray method. After the acid cleaning or alkaline cleaning treatment is performed, water-washing is performed to remove an acid cleaning agent or an alkaline cleaning agent remaining on the surface of the basis material.
  • the coat obtained by the nonchromate metallic surface-treating method contains the water-soluble zirconium compound and/or the water-soluble titanium compound (1) with zirconium and/or titanium atom within a range having a lower limit of 4 mg/m 2 and an upper limit of 30 mg/m 2 by mass per one surface.
  • the content thereof is less than 4 mg/m 2 , there is a possibility that the corrosion resistance after applying coatings could be degraded and when the content thereof exceeds 30 mg/m 2 , there is a possibility that the adhesion with a coating after applying coatings could be degraded.
  • the lower limit is 10 mg/m 2 and the upper limit is 20 mg/m 2 .
  • the term mass per one surface, after drying, of the water-soluble zirconium compound and/or the water-soluble titanium compound means the sum of the masses of zirconium and titanium contained in the coat obtained by the nonchromate metallic surface-treating method.
  • the amounts of the respective component forming the coat can be obtained in desired amounts by appropriately setting the composition of the nonchromate metallic surface-treating agent, treatment temperature and treatment time.
  • the coat obtained by the nonchromate metallic surface-treating method contains the organic phosphonic acid compound (2) with phosphorus atom within a range having a lower limit of 0.05 and an upper limit of 0.3 relative to zirconium and/or titanium atom of said water-soluble zirconium compound and/or said water-soluble titanium compound (1), on a mass basis.
  • this rate is less than 0.05, there is a possibility that the adhesion with a coating film after applying coatings could be degraded and even if this rate exceeds 0.3, the organic phosphonic acid compound exists just only excessively and does not have an effect of enhancing the adhesion, and therefore there is a possibility of being relatively expensive.
  • the lower limit is 0.1 and the upper limit is 0.15.
  • the coat obtained by the nonchromate metallic surface-treating method contains the tannin (3) with carbon atom within a range having a lower limit of 0.5 and an upper limit of 3 relative to zirconium and/or titanium atom-of said water-soluble zirconium compound and/or said water-soluble titanium compound (1), on a mass basis.
  • this rate is less than 0.5, there is a possibility that the adhesion with a coating after applying coating could be degraded and when this rate exceeds 3, there is a possibility that the corrosion resistance after applying coating could be degraded.
  • the lower limit is 1.0 and the upper limit is 1.5.
  • the respective amounts of zirconium and titanium of the water-soluble zirconium compound and/or the water-soluble titanium compound (1) and the amount of phosphorus of the organic phosphonic acid compound (2) in the coat obtained by the nonchromate metallic surface-treating method can be measured by a X-ray fluorescence spectrometer, and the amount of the tannin (3) can be determined from the amount of organic carbon measured by a carbon/moisture content phase analyzer.
  • Aluminum or aluminum alloy according to the present invention is obtained by the nonchromate metallic surface-treating method. Since thus obtained aluminum or aluminum alloy is excellent in the corrosion resistance and adhesion with a coating film after applying coatings, it can be suitably used for uses such as a case for beverages, an electric home appliance and construction materials.
  • the nonchromate metallic surface-treating agent of the present invention comprises a water-soluble zirconium compound and/or a water-soluble titanium compound (1), an organic phosphonic acid compound (2) and a tannin (3), wherein a content of zirconium and/or titanium of the water-soluble zirconium compound and/or the water-soluble titanium compound (1) is 40 to 1000 ppm on a mass basis, a content of the organic phosphonic acid compound (2) is 20 to 500 ppm on a mass basis, a content of the tannin (3) is 200 to 5000 ppm on a mass basis, and the nonchromate metallic surface-treating agent has a pH of 1.6 to 4.0.
  • the nonchromate metallic surface-treating agent according to the present invention contains not only the water-soluble zirconium compound and/or the water-soluble titanium compound (1) but also the organic phosphonic acid compound (2) and the tannin (3), the corrosion resistance and adhesion with a coating film after applying coatings can be enhanced by using said nonchromate metallic surface-treating agent.
  • metallic base materials such as aluminum or an aluminum alloy
  • the nonchromate metallic surface-treating agent, the nonchromate metallic surface-treating method, and aluminum or an aluminum alloy of the present invention comprise the constitutions described above, they can obtain the corrosion resistance and adhesion with a coating film equal to a chromium phosphate surface-treating agent. Thereby, they can be suitably adopted in a wide range of uses of aluminum materials for construction materials, an electric home appliance, fin materials, car evaporators, beverage can materials and the like, particularly uses for an electric home appliance, construction materials, and materials of beverage can cover.
  • hydrofluoric acid was compounded in such a manner that the concentration of free fluorine was 12 ppm to this treating agent and then ammonia was added to adjust pH of the treating agent to 2.6.
  • the agitation was continued for 10 minutes to obtain a slightly brown aqueous solution which contains fluorozirconic acid with zirconium of 40 ppm, 1-hydroxyethylidene-1,1-diphosphonic acid with phosphorus of 20 ppm, and tannin of 200 ppm.
  • Ion-exchanged water 9989.1 parts was charged into the vessel equipped with an agitation apparatus.
  • “Fluorotitanic acid” 1.5 parts: containing 29.3% of Ti) manufactured by Morita Chemical Industries Co., Ltd. was added gradually while agitating at room temperature. While further agitating, 1.4 part of “1-hydroxyethylidene-1,1-diphosphonic acid” manufactured by Morita Chemical Industries Co., Ltd. was added gradually.
  • 8 parts of “Tannic Acid Essence A” nonvolatile matter 50% manufactured by Dainippon Pharmaceutical Co., Ltd. was added gradually while agitating.
  • hydrofluoric acid was compounded in such a manner that the concentration of free fluorine was 12 ppm to this treating agent and then ammonia was added to adjust pH of the treating agent to 2.6.
  • the agitation was continued for 10 minutes to obtain a slightly brown aqueous solution which contains fluorotitanic acid with titanium of 45 ppm, 1-hydroxyethylidene-1,1-diphosphonic acid with phosphorus of 40 ppm, and tannin of 400 ppm.
  • Ion-exchanged water 9987.9 parts was charged into the vessel equipped with an agitation apparatus. Fluorozirconic acid (1.7 parts) and in succession 1.0 parts of fluorotitanic acid were added gradually to the ion-exchanged water while agitating at room temperature. While further agitating, 1.4 parts of 1-hydroxyethylidene-1,1-diphosphonic acid was added gradually. Next, 8 parts of “Tannic Acid Essence A” (nonvolatile matter 50%) manufactured by Dainippon Pharmaceutical Co., Ltd. was added gradually while agitating.
  • hydrofluoric acid was compounded in such a manner that the concentration of free fluorine was 12 ppm to this treating agent and then ammonia was added to adjust pH of the treating agent to 2.6.
  • the agitation was continued for 10 minutes to obtain a slightly brown aqueous solution which contains fluorozirconic acid with zirconium of 30 ppm, fluorotitanic acid with titanium of 30 ppm, 1-hydroxyethylidene-1,1-diphosphonic acid with phosphorus of 40 ppm, and tannin of 400 ppm.
  • Aluminum alloy 5182 plate materials were degreased (treated at 65° C. for 3 seconds) using a 1% dilute solution of “Surf Cleaner 360” manufactured by Nippon Paint Co., Ltd., washed with water, and in succession cleaned using a 1% dilute solution of sulfuric acid (treated at 50° C. for 3 seconds) and then washed with water.
  • the resulting aluminum materials were treated at 58° C. for 5 seconds with the nonchromate metallic surface-treating agent of the examples and comparative examples using a spraying apparatus, and dried at a material temperature of 80° C. for 30 seconds to obtain surface treated metal plates.
  • Masses of zirconium, titanium, phosphorus and chromium of the dried coats obtained through examples and comparative examples were measured by using X-ray fluorescence spectrometer “XRF-1700” manufactured by Shimadzu Corp.
  • XRF-1700 X-ray fluorescence spectrometer
  • the mass of carbon atoms derived from tannin were determined by using a carbon/moisture content phase analyzer “RC 412” by LECO Corp. (USA). And, the masses of carbon atoms derived from tannin were determined with the following method.
  • Solvent-borne polyester-based coating “Flekicoat #5000 White” (nonvolatile matter 50%) manufactured by Nippon Fine Coatings Inc., Ltd. was applied to the resulting chemical conversion treatment plates so as to form a coat of 15 g/m 2 on a wet mass basis per one surface using a reverse roll coater and this coat was baked at a material temperature of 230° C. for 60 seconds using a conveyer type oven to obtain a coated aluminum material having a coat with the mass of 7.5 g/m 2 after drying.
  • the metallic surface-treating agents prepared in the manners were stored at 40° C. for 30 days, and the appearances of the treating agents were visually tested.
  • Tables 3 and 4 to the samples which did not exhibit abnormal conditions such as occurrences of a whitish portion, precipitations and coagulating substances and had better appearances, there were put an expression by“ ⁇ ”, and to the samples which caused abnormal conditions, there were put descriptions of the content of abnormal conditions.
  • Respective coated surfaces of the two same coated plates were mutually bonded by using a hot-melt polyamide film “Diamide Film #7000” manufactured by Daicel Chemical Industries, Co., Ltd. Bonding was performed by fixing two plates to each other by applying pressure at 200° C. and at a pressure of 7 kg/cm 2 for 1 minute with a hot press tester. The resulting bonded plate was cut out in width of 5 mm, and peeled off at a speed of 200 mm/min with a tensilon tester and a force applied then was measured (unit: kgf/5 mm) (Polyester-based coatings cannot be bonded in such a bonding-way and therefore cannot be tested.).
  • the coated aluminum plates were immersed for 60 minutes in boiled water of 100° C. Immediately after the coated aluminum plates were removed out of the boiled water, 100 of cross-hatch were provided with distances of 1 mm, and tape-peeling test were performed with cellophane tapes and the number of peeling were counted. It was taken as an accepted level that there were no peeling portions.
  • the coated aluminum plates were processed to the cups having the configuration illustrated in FIG. 1 so that the coated surface of the aluminum plates became convex.
  • the resulting cups were immerged in the mixed aqueous solution of 2% citric acid solution and 2% salt water, being kept at 50° C., for 72 hours, and after taking it out, states of corrosion of the respective portions, that is, a plane portion 1 , an edge portion 2 and a side portion 3 , which are shown in FIG. 1, were rated on a scale of 5 points according the following criteria and the average points of the respective portions were determined.
  • the nonchromate metallic surface-treating agents obtained through examples were high in the stability of liquid and the coats obtained with the treating agents were excellent in the adhesion and corrosion resistance.
  • Comparative Examples 9 and 10 in which pHs ranged out of the ranges of the present invention, were not only low in the adhesion and corrosion resistance but also poor in the stability of treating agents, and the obtained coats whitened.
  • the coating films obtained with the nonchromate metallic surface-treating agent of the examples exhibited the adhesion and corrosion resistance which is equal to or higher than that obtained with the treating agents of Comparative Examples 11 to 13.

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US10/421,578 2002-04-23 2003-04-23 Nonchromate metallic surface-treating agent, nonchromate metallic surface-treating method, and aluminum or aluminum alloy Abandoned US20030196728A1 (en)

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US20060151070A1 (en) * 2005-01-12 2006-07-13 General Electric Company Rinsable metal pretreatment methods and compositions
US20100089755A1 (en) * 2008-10-10 2010-04-15 Wealtec Bioscience Co., Ltd. Technical measure for gel electrophoresis shaping
EP3997180B1 (en) * 2019-09-18 2023-08-30 Novelis Inc. Metal surface coatings for improving bond performance and methods of making the same

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JP5611128B2 (ja) * 2011-06-27 2014-10-22 新日鐵住金株式会社 表面処理アルミめっき鋼板とその製造方法
CN104651821A (zh) * 2015-02-11 2015-05-27 常州君合科技股份有限公司 一种新型铝及铝合金高分子无铬成膜剂
DE102017206940A1 (de) * 2017-04-25 2018-10-25 Mahle International Gmbh Verfahren zur Herstellung eines Wärmetauschers

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EP1571237A4 (en) * 2002-12-13 2007-11-21 Nihon Parkerizing TREATMENT FLUID FOR METAL SURFACE TREATMENT AND SURFACE TREATMENT METHOD
EP1571237A1 (en) * 2002-12-13 2005-09-07 Nihon Parkerizing Co., Ltd. Treating fluid for surface treatment of metal and method for surface treatment
AU2006205215B2 (en) * 2005-01-12 2011-08-18 Chemetall Corp. Rinsable metal pretreatment methods and compositions
WO2006076197A1 (en) * 2005-01-12 2006-07-20 General Electric Company Rinsable metal pretreatment methods and compositions
US20080245444A1 (en) * 2005-01-12 2008-10-09 General Electric Company Rinsable metal pretreatment methods and compositions
US20060151070A1 (en) * 2005-01-12 2006-07-13 General Electric Company Rinsable metal pretreatment methods and compositions
AU2006205215C1 (en) * 2005-01-12 2012-01-19 Chemetall Corp. Rinsable metal pretreatment methods and compositions
TWI392769B (zh) * 2005-01-12 2013-04-11 Chemetall Gmbh 可沖洗的金屬預處理方法及組合物
US8585834B2 (en) * 2005-01-12 2013-11-19 Edward A. Rodzewich Rinsable metal pretreatment methods and compositions
EP2942422A1 (en) 2005-01-12 2015-11-11 Chemetall Corp. Rinsable metal pretreatment methods and compositions
EP2949781A1 (en) 2005-01-12 2015-12-02 Chemetall Corp. Rinsable metal pretreatment methods and compositions
US20100089755A1 (en) * 2008-10-10 2010-04-15 Wealtec Bioscience Co., Ltd. Technical measure for gel electrophoresis shaping
EP3997180B1 (en) * 2019-09-18 2023-08-30 Novelis Inc. Metal surface coatings for improving bond performance and methods of making the same

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