EP2302097B1 - Procédé de traitement de surface - Google Patents

Procédé de traitement de surface Download PDF

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Publication number
EP2302097B1
EP2302097B1 EP05811597.3A EP05811597A EP2302097B1 EP 2302097 B1 EP2302097 B1 EP 2302097B1 EP 05811597 A EP05811597 A EP 05811597A EP 2302097 B1 EP2302097 B1 EP 2302097B1
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EP
European Patent Office
Prior art keywords
aforementioned
surface treatment
acid
component
treatment liquid
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.)
Not-in-force
Application number
EP05811597.3A
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German (de)
English (en)
Other versions
EP2302097A4 (fr
EP2302097A1 (fr
Inventor
Masayuki Yoshida
Katsuyuki Kawakami
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL05811597T priority Critical patent/PL2302097T3/pl
Publication of EP2302097A1 publication Critical patent/EP2302097A1/fr
Publication of EP2302097A4 publication Critical patent/EP2302097A4/fr
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Publication of EP2302097B1 publication Critical patent/EP2302097B1/fr
Not-in-force 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • 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
    • C23C22/50—Treatment of iron 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
    • C23C22/48—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
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel

Definitions

  • the present invention pertains to a method of surface treatment, and surface-treated metal materials obtained by said treatment method.
  • the method will allow deposition of a surface coating film with excellent corrosion resistance or bare corrosion resistance after coating the surface of metal material such as building materials and home electrical appliance materials.
  • the phosphoric acid zinc treatment method or the chromate treatment method is commonly used for deposition of a surface coating film with excellent corrosion resistance on the surface of metal materials after coating.
  • a film with excellent corrosion resistance can be deposited on a steel plate or zinc-plated steel plate such as a hot rolled steel plate or cold rolled steel plate.
  • a non-chrome coating for metal surface treatment that contains a compound having a nitrogen atom with a lone electron pair or that contains the aforementioned compound and a zirconium compound is used.
  • the purpose of this method is to obtain a surface coating film with excellent corrosion resistance and adherence with the use of the aforementioned compositions that contain no harmful hexavalent chromium.
  • a surface treatment agent and a treatment bath containing selenium, zirconium, phosphoric acid, and fluorine compounds are used for the deposition of a surface coating film with excellent tight bonding and corrosion resistance after coating by means of a formation reaction.
  • a metallic surface treatment composition consisting of a metal acetylacetonate and a water-soluble inorganic titanium compound or water-soluble inorganic zirconium compound is used for the deposition of a surface coating film with excellent corrosion resistance and adherence after coating.
  • This method can be used to treat metal materials other than aluminum alloys, such as magnesium, magnesium alloys, zinc, and zinc plated alloys.
  • this method cannot be used for the deposition of a surface coating film on the surface of iron-based metal materials such as hot rolled steel plate or cold rolled steel plate.
  • Patent Reference 4 a metal surface treatment using a chromium-free coating type acid composition has been described in Patent Reference 4.
  • an aqueous solution of components capable of forming a film with excellent corrosion resistance is coated on a metal surface and then a baking/drying process is carried out for fixing the formed film without a water washing process. Therefore, no chemical reaction is involved in the formation of the film and thus it is possible to use this method for the deposition of a film on the surface of metals such as hot rolled steel plate, cold rolled steel plate, zinc-plated steel plate, and aluminum alloys.
  • the film is formed by coating and drying as in the case of the method described in Patent Reference 1 and thus it is difficult to achieve a uniform film coating on a material with a complex structure.
  • Patent Reference 5 a metal chemical conversion method using a treatment bath containing zirconium ion and/or titanium ion and fluorine ion is described. This method is applicable to iron-based metal materials as well as aluminum and zinc.
  • this method requires using an oxidizing agent for controlling the iron ion concentration in the chemical conversion agent during the conversion process.
  • this method cannot be used to carry out a highly workable surface treatment capable of depositing a film with excellent corrosion resistance and adherence on metal materials such as iron-based metal materials, zinc-based metal materials, etc., using a treatment liquid containing none of the environmentally harmful components used in the conventional technique.
  • Patent References 6 and 7 disclose the passivating treatment for iron and/or zinc surfaces employing acidic solutions containing titanium or zirconium as well as yittrium or a lanthanide. While Patent Reference 6 teaches a technique to form a bright primary rust preventive coating mainly on zinc-based metallic material, Patent Reference 7 teaches a technique to form a crystalline coating without forming precipitates of Group IIa metal ions.
  • the purpose of the present invention is to provide a composition for surface treatment, treating liquid for surface treatment, method of surface treatment, and surface-treated metal materials obtained by said treatment method.
  • Said method will allow deposition of a surface coating film having excellent corrosion resistance or bare corrosion resistance after coating on the surface of metal materials, for example, iron-based metal materials such as hot rolled steel plate, cold rolled steel plate used in building materials and home electrical appliance materials, zinc-based metal materials such as zinc-plated steel plate, etc.
  • said surface treatment method uses a treating liquid that contains none of the environmentally harmful components used in the conventional technique.
  • the method of surface treatment, of the present invention is an epoch-making technique capable of depositing a surface coating film with excellent corrosion resistance after coating on the surface of the metal material using a treatment bath that contains none of the environmentally harmful components used in the conventional technique.
  • composition for surface treatment of a metal according to a method of the present invention also to be called simply “the composition for use in a method of the present invention” in the following
  • a treatment method for metal surface treatment of the present invention also to be called simply “the treatment method of the present invention” in the following
  • the composition for use in a method of the present invention is diluted with water or dissolved in water at the time of its use to form the treatment liquid for use in a method of the present invention.
  • the materials to be surface-treated with the treatment liquid according to a method of the present invention are iron-based metal materials or zinc-based metal materials.
  • iron-based metal materials that can be used as long as they contain iron.
  • Suitable materials would include, for example, steel plate such as cold rolled steel plate, hot rolled steel plate, etc., cast iron, and sintered materials.
  • zinc-based metal materials that can be used as long as they contain zinc. Suitable materials would include, for example, zinc die-cast and zinc-containing plated materials.
  • the zinc-containing plated materials consist of zinc or alloys of zinc and at least one other element selected from among, for example, nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead, and antimony, and unavoidable impurities.
  • plating methods There are no particular limitations with regard to the plating methods that can be used. Suitable methods would include, for example, electroplating methods, fusion plating methods, vapor deposition plating methods, etc.
  • the present invention pertains to surface treatment of the surface of metal materials.
  • the metal materials can be surface-treated individually or combinations of two or more of them can be treated simultaneously.
  • the other metal material can be aluminum, magnesium, nickel, or their alloys.
  • the different metals may not be in contact with each other or they can be in contact with each other or joined together by a welding, adhesion, or riveting method.
  • composition for use in a method of the present invention contains the component (A), component (B), component (C), and component (D) as described below.
  • Component A is a compound containing at least one element selected from the group consisting of Ti, Zr, Hf, and Si.
  • Suitable compounds include, for example, TiCl 4 , Ti(SO 4 ) 2 , TiOSO 4 , Ti(NO 3 ) 4 , TiO(NO 3 ) 2 , Ti(OH) 4 , TiO 2 OC 2 O 4 , H 2 TiF 6 , salts of H 2 TiF 6 , TiO, TiO 2 , Ti 2 O 3 , TiF 4 , ZrCl 4 , ZrOCl 2 , Zr(OH) 2 Cl 2 , Zr(OH) 3 Cl, Zr(SO 4 ) 2 , ZrOSO 4 , Zr(NO 3 ) 4 , ZrO(NO 3 ) 2 , Zr(OH) 4 , H 2 ZrF 6 , salts of H 2 ZrF 6 , H 2 (Zr(CO 3 ) 2 (OH) 2 , salts of H 2 (Zr(CO 3 ) 2 (OH) 2 , H 2 Zr(OH) 2 (SO 4 ) 2 , salts of
  • Component (B) is a compound containing Y and/or a lanthanide element; i.e., a compound containing at least one element selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • Suitable compounds include, for example, oxides, sulfates, nitrates, and chlorides of these elements.
  • they include yttrium chloride, lanthanide chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, yttrium sulfate, lanthanide sulfate, cerium sulfate, praseodymium sulfate, neodymium sulfate, promethium sulfate, samarium sulfate, europium sulfate, gadolinium sulfate, terbium sulfate, dysprosium sulfate, holmium sulfate, erbium sulfate, hol
  • Component (C) is nitric acid and/or a nitric acid compound.
  • Suitable compounds include, for example, nitric acid, metal nitrates, etc.
  • Metal nitrates would include, for example, ferric nitrate, manganese nitrate, nickel nitrate, cobalt nitrate, silver nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, and calcium nitrate. Two or more of these compounds may also be used concomitantly.
  • a composition for use in a method of the present invention is diluted with water or dissolved in water at the time of its use for the surface treatment of a metal.
  • the treatment liquid for metal surface treatment is prepared and used.
  • water is added to the composition for metal surface treatment to bring the total mass concentration of the aforementioned elements (Ti, Zr, Hf, and Si) of the aforementioned component (A) within the range of 10 ppm to 10,000 ppm.
  • the total mass concentration A of the aforementioned elements contained in the aforementioned component (A) indicates “the concentration of the aforementioned elements contained in the aforementioned component (A) contained in the composition (in some cases, the treatment liquid) of the present invention". The same is true for the terms "the total mass concentration B" and "the total mass concentration C”.
  • component A is a substance having excellent anti-acid and anti-alkali properties and is the main component of the surface coating film of the present invention.
  • Component (B) can promote the film deposition of component (A).
  • component (B) may be contained in the surface coating film so that the corrosion resistance and bare corrosion resistance of the film after coating can be expected to further improve.
  • Component (C) in the treatment liquid for surface treatment serves to maintain the stability of the treatment liquid by increasing the solubility of component (A) and component (B).
  • component (C) can also assist the film deposition of component (A), though not as effectively as component (B).
  • component (B) can not be expected to promote the film deposition of component (A) because of the reduced proportion of component (B). Consequently, the amount of film adhesion of component (A) will decrease compared to that obtained when the total mass concentration ratio of component (A) to component (B), i.e., K1, is within the range of 0.05 ⁇ K1 ⁇ 50 and the corrosion resistance of the treated metal material may decrease.
  • component (A) on the surface of the treated metal material may be lowered and the amount of film adhesion of component (A), that is the main component of the film and the component that provides the corrosion resistance to the film, will decrease even though the film deposition promoting effect of component (B) is present. Therefore, excellent corrosion resistance cannot be obtained and the adherence may also be adversely affected in some cases.
  • the aforementioned total mass concentration A of the aforementioned component (A) used in the treatment liquid for use in a method of the present invention is preferably adjusted to be in the range of 10 ppm to 10,000 ppm, and more preferably in the range of 50 ppm to 5,000 ppm.
  • the aforementioned total mass concentration A is too small, it will become difficult to obtain an amount of adhesion sufficient for acquiring the desired corrosion resistance within a practical treatment time due to the low concentration of the film main component, even though the aforementioned K1 and the aforementioned K2 are within the specified ranges.
  • the aforementioned total mass concentration A is too large, although a sufficient amount of adhesion can be obtained, the corrosion resistance cannot be improved further and thus an excessively high total mass concentration A is not economically desirable.
  • composition and treatment liquid for use in a method of the present invention additionally contain at least one fluorine-containing compound as component (D).
  • Suitable compounds include, for example, hydrofluoric acid, H 2 TiF 6 , salts of H 2 TiF 6 , TiF 4 , H 2 ZrF 6 , salts of H Z ZrF 6 , ZrF 4 , H 2 HfF 6 , salts of H 2 HfF 6 , HfF 4 , H 2 SiF 6 , HBF 4 , salts of HBF 4 , NaHF 2 , KHF 2 , NH 4 HF 2 , NaF, KF, and NH 4 H. Two or more of these fluorine-containing compounds may also be used concomitantly.
  • Component (D) is to be added to the treatment liquid for use in a method of the present invention, the concentration of at least one of the fluorine-containing compounds of component (D) is adjusted so that the free fluorine ion concentration D will be in the range of 0.001 ppm to 300 ppm, and more preferably in the range of 0.1 ppm to 100 ppm.
  • the term "free fluorine ion concentration D" means the fluorine ion concentration determined with the use of a commercially available ion electrode.
  • the free fluorine ion concentration D When the free fluorine ion concentration D is too high, the etching reaction on the raw material surface by HF will be too excessive and the amount of film deposition sufficient to achieve corrosion resistance of the surface of the treated metal material will tend to become difficult to obtain.
  • the corrosion resistance of the surface of the treated metal material can be achieved even when the free fluorine ion concentration D produced by the fluorine-containing compound of component (D) is too small, but the stability of the treatment liquid for surface treatment may be adversely affected and continuous operation may be hindered.
  • Film deposition by the treatment liquid for use in a method of the present invention is preferably induced by the formation reaction accompanying the etching of the metal base material. Therefore, the treatment is preferably carried out in a pH range in which an etching reaction will ordinarily occur, i.e., a pH value below 6.0, preferably below 5.0, and more preferably below 4.0.
  • acids such as hydrochloric acid, sulfuric acid, boric acid, and organic acids
  • alkalis such as lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, alkali metal salts, ammonia, ammonium salts, and amines may be used.
  • a treatment liquid for use in a method of the present invention may be contaminated by the metals contained in the base material which are eluted out by the etching reaction of the base material, or by the metals or compounds contained in the tap water and industrial water because component (B) can promote the film deposition of component (A) and the film deposition of component (A) will not be affected by other metal elements.
  • An anion component is preferably added to the treatment liquid for use in a method of the present invention to further promote the film-formation reaction.
  • Suitable anion components that may be added to the treatment liquid for use in a method of the present invention include, for example, HCl, H 2 SO 4 , HClO 3 , HBrO 3 , HNO 2 , HMnO 4 , HVO 3 , H 2 O 2 , H 2 WO 4 , H 2 MoO 4 , etc.
  • concentration of the anion component added a concentration in the range of about 10 ppm to 20,000 ppm is sufficient for providing the desired effect.
  • a chelating agent capable of chelating metal ions dissolved out by the etching reaction is preferably added.
  • Suitable chelating agents that can be used in the treatment liquid of the present invention include, for example, ethylenediamine tetraacetic acid (EDTA), gluconic acid, heptogluconic acid, glycolic acid, citric acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid, malic acid, salicylic acid, and their salts.
  • EDTA ethylenediamine tetraacetic acid
  • gluconic acid gluconic acid
  • heptogluconic acid glycolic acid
  • citric acid succinic acid
  • fumaric acid aspartic acid
  • tartaric acid, malonic acid, malic acid, salicylic acid and their salts.
  • a concentration in the range of about 1 ppm to 10,000 ppm is sufficient for providing the desired effect.
  • a water-soluble polymer compound and/or a water-dispersible polymer compound having an ionic reactive group in their molecule are preferably added to the treatment liquid for use in a method of the present invention.
  • Suitable compounds include, for example, copolymers of polyvinyl alcohol, poly(meth)acrylic acid or acrylic acid, and methacrylic acid, copolymers of ethylene and acryl-type monomers such as (meth)acrylic acid, (meth)acrylate, etc., copolymers of ethylene and vinyl acetate, polyurethane, amino modified phenol resins, polyester resins, epoxy resins, polyamide amines, polyamines, polyamine derivatives, polyallyl amines, polyallyl amine derivatives, polyamide amine derivatives, polyvinyl amine, polyvinyl amine derivatives, tannin, tannic acid and its salts, and phytic acid.
  • concentration of the aforementioned compounds added but a concentration in the range of 1 pp
  • At least one surfactant selected from a group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants is preferably added to the treatment liquid for use in a method of the present invention.
  • a treatment liquid for surface treatment of this kind is used for the surface treatment of a metal base material, as will be mentioned later, a good film can be formed without a preliminary degreasing treatment or cleansing treatment of the metal material to be treated.
  • the treatment liquid for use in a method of the present invention can be used as a degreasing surface treatment agent as well as a formation surface treatment agent.
  • the treatment method of the present invention is a surface treatment method for metals containing iron and/or zinc that includes a treatment liquid contact process in which the metal material containing iron and/or zinc is brought into contact with the treatment liquid of the present invention.
  • the only requirement of the surface treatment method of the present invention is to bring the aforementioned metal material containing iron and/or zinc into contact with the aforementioned treatment liquid for use in a method of the present invention.
  • a film made of oxides and/or hydroxides of the aforementioned elements of the aforementioned component (A) will be deposited on the surface of the metal base material and a surface coating film layer with excellent adherence and corrosion resistance can thus be formed.
  • Any method such as a spray treatment, immersion treatment, or cast liquid treatment can be used for the contact treatment mentioned above; the contact method used will not affect the performance of the film formed. It is chemically difficult to obtain the hydroxide of metals contained in the film of the aforementioned component (A) in the form of a pure hydroxide.
  • oxides of the aforementioned metals with attached water of hydration are also included in this group of oxides. Therefore, the aforementioned hydroxides of metal will eventually become oxides by heating.
  • the structure of the surface coating film of the present invention it is believed that the film is present in the state of a mixture of oxides and hydroxides when the film is dried at normal temperature or a low temperature after the surface treatment, whereas the film is present in a state in which oxides only or oxides as the majority component are present when the film is dried at a high temperature after the surface treatment.
  • the aforementioned metal material containing iron and/or zinc is preferably subjected to a cleansing process, such as a degreasing treatment.
  • a cleansing process such as a degreasing treatment.
  • the method used for degreasing i.e., any conventional method can be used.
  • the treatment liquid for use in a method of the present invention contains the aforementioned surfactant, a good film can be formed even without pre-cleansing of the aforementioned metal material containing iron and/or zinc by a degreasing treatment.
  • the degreasing treatment and the film-forming treatment of the aforementioned metal material containing iron and/or zinc are carried out at the same time.
  • the treatment temperature and treatment time can be altered freely in accordance with the reactivity of the treatment bath.
  • an electrolytic treatment with the aforementioned metal material containing iron and/or zinc as the cathode can be carried out while the metal material is in the state of contact with the treatment liquid of the present invention.
  • a hydrogen reducing reaction will occur at the interface of the aforementioned metal material containing iron and/or zinc serving as the cathode and the pH will rise.
  • the stability of the compound containing the elements of component (A) at the cathode interface will decrease and the surface treatment film will be deposited as an oxide or as a water-containing hydroxide.
  • the aforementioned metal material containing iron and/or zinc has made contact with the treatment liquid for use in a method of the present invention or has been subjected to an electrolytic treatment following such contact, it may then be brought into contact with an acidic aqueous solution containing at least one element selected from a group consisting of cobalt, nickel, tin, copper, titanium, and zirconium or with a treatment solution containing at least one water-soluble polymer compound and/or water-dispersible polymer compound.
  • an acidic aqueous solution containing at least one element selected from a group consisting of cobalt, nickel, tin, copper, titanium, and zirconium or with a treatment solution containing at least one water-soluble polymer compound and/or water-dispersible polymer compound.
  • a surface coating film obtained by the present invention is a thin film with excellent coating performance.
  • the surface treatment film layer may end up with a very small defective portion. Therefore, the metal material is brought into contact with the acidic aqueous solution containing at least one element selected from a group consisting of cobalt, nickel, tin, copper, titanium, and zirconium or with a treatment solution containing at least one water-soluble polymer compound and/or water-dispersible polymer compound. In this way, any defective portion can be covered and the corrosion resistance can be further improved.
  • the source of supply of the aforementioned at least one element selected from a group consisting of cobalt, nickel, tin, copper, titanium, and zirconium there are no particular limitations with regard to the source of supply of the aforementioned at least one element selected from a group consisting of cobalt, nickel, tin, copper, titanium, and zirconium.
  • the source of supply of the aforementioned at least one element selected from a group consisting of cobalt, nickel, tin, copper, titanium, and zirconium Readily available oxides, hydroxides, fluorides, complex fluorides, chlorides, nitrates, oxynitrates, sulfates, oxysulfates, carbonates, oxycarbonates, phosphates, oxyphosphates, oxalates, oxyoxalates, and organometal compounds of the aforementioned metal elements can be used.
  • the acidic aqueous solution containing the aforementioned metal elements preferably has a pH value in the
  • Acids such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, and organic acids, and alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal salts, ammonia, ammonium salts, and amines can be used for pH adjustment.
  • the aforementioned at least one polymer compound selected from among water-soluble polymer compounds and water-dispersible polymer compounds can be, for example, a copolymer of polyvinyl alcohol, poly(meth)acrylic acid or acrylic acid, and methacrylic acid, copolymers of ethylene and acryl-type monomers such as (meth)acrylic acid, (meth) acrylate, etc., copolymers of ethylene and vinyl acetate, polyurethane, amino modified phenol resins, polyester resins, epoxy resins, polyamide amines, polyamines, polyamine derivatives, polyallyl amines, polyallyl amine derivatives, polyamide amine derivatives, polyvinyl amine, polyvinyl amine derivatives, tannin, tannic acid and its salts, and phytic acid.
  • a copolymer of polyvinyl alcohol, poly(meth)acrylic acid or acrylic acid, and methacrylic acid copolymers of ethylene and acryl-type monomers such as
  • the corrosion resistance of a metal material can be improved markedly by forming a film layer made of the oxides and/or hydroxides of the aforementioned component (A) or a film layer made of a mixture of film layers consisting of the film layer of the aforementioned component (A) and a film layer made of the oxides and/or hydroxides of the metal elements of the aforementioned component (B).
  • any films made of the oxides and/or hydroxides of the aforementioned component (A) are acid and alkali resistant and are chemically stable.
  • a film made of the oxides and/or hydroxides of the aforementioned component (A) used in the present invention is resistant to both acids and alkalis.
  • a thin and uniform surface coating film can be formed on the surface of the metal to be treated and thus the superior effect of the present invention can be maintained even in a corrosive environment.
  • the formed film is an excellent barrier film.
  • the corrosion of a metal material will vary depending on the environment in which the metal material is used. In general, however, corrosion will occur under the condition where water and oxygen are present and thus is usually of the oxygen requiring type. Therefore, the corrosion speed will be increased in the presence of components such as chlorides, etc. Since the film layer of the present invention has a barrier effect on water, oxygen, and corrosion-promoting components, it offers an excellent anti-corrosion property.
  • the adhering amount of the surface coating film in terms of component (A) is preferably greater than 20 mg/m 2 , more preferably greater than 30 mg/m 2 , and especially greater than 40 mg/m 2 .
  • the adhering amount of the surface coating film in terms of component (A) is preferably greater than 15 mg/m 2 , and more preferably greater than 20 mg/m 2 .
  • the adhering amount is too small, the aforementioned barrier effect will not be sufficient and it will be difficult to obtain excellent corrosion resistance.
  • the adhering amount on the iron-based metal material or zinc-based metal material is preferably no more than 1 g/m 2 , and especially no more than 800 mg/m 2 .
  • the effect of the surface treatment liquid and the surface treatment method of the present invention will now be explained in detail with the use of actual examples and comparison examples.
  • the material to be treated, the degreasing agent, and the coating material used were selected arbitrarily from among commercially available products and should not restrict in any way the surface treatment method.
  • Example 5 the surface treatment was carried out in accordance with the following treatment process: Alkaline degreasing ⁇ water washing ⁇ film formation treatment ⁇ water washing ⁇ post treatment ⁇ deionized water washing ⁇ drying.
  • Example 6 the surface treatment was carried out in accordance with the following treatment process:. Alkaline degreasing ⁇ water washing ⁇ electroformation treatment ⁇ water washing ⁇ deionized water washing ⁇ drying.
  • Fine Cleaner L4460A registered trade name, manufactured by Nihon Parkerizing Co., Ltd.
  • Fine Cleaner L4460B registered trade name, manufactured by the Nihon Parkerizing Co., Ltd.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the zirconium element to 100 ppm.
  • Hydrofluoric acid and ammonia were then used to obtain a surface treatment treatment liquid with a free fluorine concentration of 25 ppm (fluorine ion meter: IM-55G, manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH value of 3.6.
  • a test plate that had been degreased and water-washed was immersed in the aforementioned surface treatment liquid at 45°C for 150 seconds for surface treatment.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the zirconium element and the mass concentration of hafnium element to a combined mass concentration of 50 ppm.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the zirconium element to 20 ppm.
  • Hydrofluoric acid and calcium hydroxide were then used to obtain a treatment liquid for surface treatment with a free fluorine concentration of 15 ppm (fluorine ion meter: IM-55G, manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH value of 3.0.
  • a test plate that had been degreased and water-washed was sprayed with the aforementioned surface treatment liquid at 55°C for 120 seconds for surface treatment.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the zirconium element and the mass concentration of the silicon element to a combined mass concentration of 2,500 ppm.
  • Ammonium fluoride and ammonia were then used to obtain a treatment liquid for surface treatment with a free fluorine concentration of 100 ppm (fluorine ion meter: IM-55G, manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH value of 2.9.
  • a test plate that had been degreased and water-washed was sprayed with the aforementioned surface treatment liquid at 65°C for 300 seconds for surface treatment.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the the mass concentration of the zirconium element and the mass concentration of the titanium element to a combined mass concentration of 200 ppm.
  • Ammonium fluoride and potassium hydroxide were then used to obtain a treatment liquid for surface treatment with a free fluorine concentration of 50 ppm (fluorine ion meter: IM-55G, manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH value of 4.2.
  • a test plate that had been degreased and water-washed was immersed in the aforementioned surface treatment liquid at 60°C for 200 seconds for surface treatment. After water washing, the plate was subjected to a post treatment.
  • an aqueous hexafluoro titanium solution and nickel nitrate were used to prepare an aqueous solution with a titanium mass concentration of 200 ppm and a nickel mass concentration in terms of the metal element of 50 ppm.
  • This aqueous solution was heated to 45°C and then sodium hydroxide was used to adjust its pH to 4.5. The solution thus obtained was used in the post treatment.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the zirconium element to 200 ppm.
  • EDTA 50 ppm of EDTA was added to the liquid, then hydrofluoric acid and sodium hydroxide were used to obtain a treatment liquid for surface treatment with a free fluorine concentration of 80 ppm (fluorine ion meter: IM-55G, manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH value of 2.8.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the zirconium element to 100 ppm.
  • Sodium hydroxide was then used to obtain a treatment liquid for surface treatment with a pH value of 3.0.
  • a test plate that had been degreased and water-washed was immersed in the aforementioned surface treatment liquid at 55°C for 180 seconds for surface treatment.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the zirconium element to 4 ppm. Potassium fluoride and potassium hydroxide were then used to obtain a treatment liquid for surface treatment with a free fluorine concentration of 20 ppm (fluorine ion meter: IM-55G, manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH value of 3.8.
  • a test plate that had been degreased and water-washed was immersed in the aforementioned surface treatment liquid at 60°C for 120 seconds for surface treatment.
  • the aforementioned composition for surface treatment was diluted with deionized water to adjust the mass concentration of the titanium element to 50 ppm.
  • Ammonium fluoride and ammonia were then used to obtain a treatment liquid for surface treatment with a free fluorine concentration of 400 ppm (fluorine ion meter: IM-55G, manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH value of 2.8.
  • a test plate that had been degreased and water-washed was sprayed with the aforementioned surface treatment liquid at 50°C for 150 seconds for surface treatment.
  • a test plate that had been degreased and water-washed was sprayed at room temperature for 30 seconds with a liquid obtained by diluting Preparen ZN (registered trade name, manufactured by the Nihon Parkerizing Co., Ltd.) (a surface preparation agent) to 0.1 % with tap water.
  • the test plate was then immersed in a zinc phosphate formation treatment liquid at 43°C for deposition of a zinc phosphate film.
  • the aforementioned zinc phosphate formation liquid was prepared as follows: Parbond L3020 (registered trade name, manufactured by the Nihon Parkerizing Co., Ltd.) was diluted with tap water to 4.8%.
  • a sodium hydrofluoride reagent in a quantity equivalent to 200 ppm of fluorine was then added at 43°C and the total acidity and free acidity were adjusted to be central values of the catalogue values provided.
  • test plates obtained in accordance with the actual examples and comparison examples after the surface treatment were evaluated visually by the naked eye and the adhering quantity of the surface coating film layer was determined with the use of a fluorescence X-ray analyzer (System 3270, manufactured by Rigaku Denki Kogyo Co., Ltd.).
  • the coating was carried out according to the following process: cation electrodeposition ⁇ deionized water washing ⁇ baking ⁇ midcoat application ⁇ baking ⁇ topcoat application ⁇ baking.
  • Cation Electrodeposition epoxy-based cation electrodeposition coating material (Elecron 9400, manufactured by Kansai Paint Co., Ltd.), voltage 200 V, film thickness 20 ⁇ m, baking at 175°C for 20 minutes.
  • Midcoat Application aminoalkyd-based coating material (Amilac TP-37 White, manufactured by Kansai Paint Co., Ltd.), spray coating, film thickness 35 ⁇ m, baking at 140°C for 20 minutes.
  • Topcoat Application aminoalkyd-based coating material (Amilac TM-13 Gray, manufactured by Kansai Paint Co., Ltd.), spray coating, film thickness 35 ⁇ m, baking at 140°C for 20 minutes.
  • the coating performance of the actual examples and comparison examples was evaluated according to JIS specification. The evaluation items are described below.
  • the coated film obtained at the time of completion of the electodeposition coating was called the electrodeposition coated film and the coated film obtained at the time of completion of the topcoat application was called a 3-coat coated film.
  • a crosscut was made with the use of a sharp cutter on the electrodeposition coating plate. This plate was sprayed with 5% salt water for 720 hours (according to JIS-Z-2371). After spraying, the widths of the maximum swelling from both sides of the crosscut area were measured and evaluated according to the following evaluation standards:
  • a sharp cutter was used to make 6 cuts in both the vertical and horizontal directions at 2 mm interval on the 3-coat coated film to obtain 25 squares (according to JIS-K-5600-5-6).
  • the squares were peeled off by a tape and evaluated by the evaluation method according to the aforementioned JIS specification.
  • Table 3 shows the results of coating performance evaluation of the electrodeposition-coated film.
  • the SPC material and EG material obtained from the actual examples all showed excellent corrosion resistance.
  • the promoting effect of component (B) on the film formation of component (A) was not sufficient in Comparison Example 1 because of the small value of the total mass concentration ratio K1. Accordingly, there was not very much deposition of a surface coating film on either the SPC material or the EG material and the corrosion resistance of the deposited film was poor.
  • the targeted adhering quantity could not be achieved and the corrosion resistance was poor because the content of component (A) was too low.
  • Table 4 shows the results of evaluation of the adherence property of the 3-coat plate.
  • the adherence property with regard to all the test plates used in the actual examples was excellent.
  • the adherence property with regard to the test plates used in all the comparison examples except for Comparison Example 4 was not as good as that obtained with the actual examples.

Claims (10)

  1. Procédé de traitement de surface pour des métaux contenant du fer et/ou du zinc, qui englobe un procédé de mise en contact avec un liquide de traitement, dans lequel on met une matière métallique contenant du fer et/ou du zinc en contact avec un liquide de traitement qui comprend un composant (A), un composant (B), un composant (C) et un composant (D) tels que décrits ci-dessous :
    (A) un composé contenant au moins un élément choisi parmi Zr et/ou Ti avec une concentration massique totale A de l'élément susmentionné dans la plage de 10 ppm ≤ A ≤ 10.000 ppm ;
    (B) un composé contenant Y et/ou un élément des lanthanides ;
    (C) de l'acide nitrique et/ou un composé d'acide nitrique ;
    (D) au moins un composé contenant du fluor ;
    le rapport de la concentration massique totale B du Y et/ou de l'élément des lanthanides contenus dans le composant susmentionné (B) à la concentration massique totale A des éléments susmentionnés contenus dans le composant susmentionné (A), c'est-à-dire K1 = B/A, se situant dans la plage de 0,05 ≤ K1 ≤ 50 et le rapport de la concentration massique totale C des atomes d'azote contenus dans le composant susmentionné (C) en termes de concentration de NO3 à la concentration massique totale susmentionnée A, c'est-à-dire K2 = C/A, se situant dans la plage de 0,01 ≤ K2 ≤ 200 ; et
    dans lequel la concentration D des ions de fluor libre se situe dans la plage de 0,001 ppm ≤ D ≤ 300 ppm.
  2. Procédé de traitement de surface tel que décrit à la revendication 1, dans lequel le liquide de traitement possède une valeur de pH qui n'est pas supérieure à 6,0.
  3. Procédé de traitement de surface tel que décrit à la revendication 1 ou 2, dans lequel le liquide de traitement contient au moins un composé choisi parmi le groupe constitué par HCl, H2SO4, HClO3, HBrO3, HNO2, HMnO4, HVO3, H2O2, H2WO4, H2MoO4, et leurs sels en une concentration dans la plage de 10 à 20.000 ppm.
  4. Procédé de traitement de surface tel que décrit dans l'une quelconque des revendications 1 à 3, dans lequel le liquide de traitement contient au moins un composé choisi parmi le groupe constitué par l'acide éthylènediaminetétracétique, l'acide gluconique, l'acide heptagluconique, l'acide glycolique, l'acide citrique, l'acide succinique, l'acide fumarique, l'acide aspartique, l'acide tartrique, l'acide malonique, l'acide malique, l'acide salicylique et leurs sels en une concentration dans la plage de 1 à 10.000 ppm.
  5. Procédé de traitement de surface tel que décrit dans l'une quelconque des revendications 1 à 4, dans lequel le liquide de traitement contient un composé polymère soluble dans l'eau et/ou un composé polymère apte à être dispersé dans l'eau.
  6. Procédé de traitement de surface tel que décrit dans l'une quelconque des revendications 1 à 5, dans lequel le liquide de traitement contient au moins un agent tensioactif choisi parmi le groupe constitué par des agents tensioactifs non ioniques, des agents tensioactifs anioniques et des agents tensioactifs cationiques.
  7. Procédé de traitement de surface tel que décrit dans l'une quelconque des revendications 1 à 6, dans lequel le liquide de traitement contenant du fer et/ou du zinc représente une matière métallique qui a été nettoyée via un traitement de dégraissage.
  8. Procédé de traitement de surface tel que décrit dans l'une quelconque des revendications 1 à 7, dans lequel le procédé de mise en contact avec un liquide de traitement implique un traitement électrolytique dans lequel on utilise la matière métallique susmentionnée contenant du fer et/ou du zinc à titre de cathode.
  9. Procédé de traitement de surface tel que décrit dans l'une quelconque des revendications 1 à 8, qui englobe un procédé dans lequel on amène la matière métallique susmentionnée contenant du fer et/ou du zinc en contact avec une solution aqueuse contenant au moins un élément choisi parmi le groupe constitué par du cobalt, du nickel, de l'étain, du cuivre, du titane et du zirconium après le procédé de mise en contact avec un liquide de traitement.
  10. Procédé de traitement de surface tel que décrit dans l'une quelconque des revendications 1 à 8, qui englobe un procédé dans lequel on amène la matière métallique susmentionnée contenant du fer et/ou du zinc en contact avec une solution aqueuse contenant un composé polymère soluble dans l'eau ou un composé polymère apte à être dispersé dans l'eau après le procédé de mise en contact avec un liquide de traitement.
EP05811597.3A 2004-12-08 2005-12-02 Procédé de traitement de surface Not-in-force EP2302097B1 (fr)

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PCT/JP2005/022176 WO2006062037A1 (fr) 2004-12-08 2005-12-02 Composition pour le traitement de surface d'un métal, liquide de traitement pour traitement de surface, procédé de traitement de surface et matériau métallique traité en surface

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Cited By (3)

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US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers

Also Published As

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JP4242827B2 (ja) 2009-03-25
US20070272900A1 (en) 2007-11-29
PL2302097T3 (pl) 2015-04-30
CN101076615A (zh) 2007-11-21
CA2591214A1 (fr) 2006-06-15
ES2529318T3 (es) 2015-02-19
CA2591214C (fr) 2017-07-25
CN101076615B (zh) 2010-09-08
EP2302097A4 (fr) 2011-04-06
WO2006062037A1 (fr) 2006-06-15
RU2395622C2 (ru) 2010-07-27
RU2007125572A (ru) 2009-01-20
JP2006161117A (ja) 2006-06-22
AU2005312758A1 (en) 2006-06-15
EP2302097A1 (fr) 2011-03-30
BRPI0518423A2 (pt) 2008-11-25
MX2007006729A (es) 2007-07-25
BRPI0518423B1 (pt) 2018-01-23
AU2005312758B2 (en) 2010-06-10

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