Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • 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
  • C23C22/40—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 molybdates, tungstates or vanadates
  • C23C22/44—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 molybdates, tungstates or vanadates containing also 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
  • C23C22/73—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 characterised by the process
  • C23C22/76—Applying the liquid by spraying
• • 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
  • 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

Definitions

• the present invention is applied to the surface of a metal material of an iron-based material, a zinc-based material, an aluminum-based material, and a magnesium-based material represented by an automobile body, or a structure composed of two to four types thereof.
• the present invention relates to a surface treatment liquid and a surface treatment method that can deposit a surface treatment film having excellent corrosion resistance after coating, either alone or in combination of two or four of them. Background art
• the zinc phosphate treatment method can deposit a coating having excellent corrosion resistance on the surface of steel such as cold-rolled steel sheets, galvanized steel sheets, and some aluminum alloys.
• steel such as cold-rolled steel sheets, galvanized steel sheets, and some aluminum alloys.
• the generation of sludge, which is a by-product of the reaction is unavoidable, and depending on the type of aluminum alloy, it is not possible to ensure sufficient yarn resistance after coating. .
• sufficient post-painting performance can be ensured by applying chromium treatment.
• the following invention has been proposed as a surface treatment method in which no harmful components are contained in the treatment liquid.
• a compound containing a nitrogen atom having a lone pair of electrons and a non-chromium coating agent for a metal surface containing the compound and a zirconium compound have been proposed (Japanese Patent Application Laid-Open No. 2 00 0-2 0 4 4 8 5 See the official gazette).
• This method does not contain hexavalent chromium, which is a harmful component, by applying the composition.
• the target metal materials are limited to aluminum alloys, and since a surface treatment film is formed by coating and drying, it is difficult to apply to complex structures such as automobile bodies.
• a method has been proposed in which a surface treatment composition comprising a metal acetylacetonate and a water-soluble inorganic titanium compound or a water-soluble inorganic zirconium compound is used to deposit a surface treatment film having excellent corrosion resistance and adhesion after coating (special feature). Open 2 0 0 0-1 9 9 0 77).
• the applicable metal materials have been expanded to magnesium, magnesium alloys, zinc, and zinc-plated alloys in addition to aluminum alloys.
• it is impossible to deposit a surface treatment film on the surface of ferrous materials such as cold-rolled steel sheets, and ferrous materials cannot be treated simultaneously.
• a metal surface treatment method using a chromium-free coating-type acidic composition for example, an aqueous solution of a component capable of forming a film having excellent corrosion resistance is applied to the metal surface, and then the film is fixed by baking and drying without performing a water washing step.
• a metal surface treatment method has been proposed (refer to Japanese Patent Laid-Open No. 5-1952244). Since this method does not involve a chemical reaction in the formation of a film, it is possible to perform a film treatment on a metal surface such as a zinc-plated steel sheet, a cold-rolled steel sheet, and an aluminum alloy ( however, the above-mentioned JP-A-2000-2000).
• -2 0448 Similar to the invention disclosed in Japanese Patent Publication No. 5, in order to form a film by coating and drying, It is difficult to perform uniform film treatment on a rough structure.
• the conventional technology does not contain components that are harmful to the environment and does not generate sludge as waste, and it is a ferrous material such as cold-rolled steel sheet and zinc-based material such as galvanized steel sheet. Furthermore, it was impossible to treat two or four types of aluminum and magnesium materials at the same time for surface treatment with excellent corrosion resistance and adhesion. Disclosure of the invention
• the present invention does not contain components harmful to the environment, which is impossible with the prior art, and does not generate sludge as waste, and can be used for iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials.
• An aqueous surface treatment solution for surface treatment of a selected metal material consisting of a zirconium compound and titanium.
• One or more compounds selected from compounds are contained in an amount of 5 to 500 ppm as the above metal element, free fluorine ions are contained in an amount of 0.1 to 100 ppm, and pH is 2 to 6 It is a processing solution for the surface treatment of metal.
• This surface treatment liquid further includes a calcium compound and a magnesium compound.
• a calcium compound and a magnesium compound One or more compounds selected from the group consisting of a compound and a strontium compound may be included. The concentration of these compounds at that time is preferably 5 to 100 ppm for calcium compounds and 10 to 5000 ppm for magnesium compounds or tungsten compounds as these metal elements.
• This treatment liquid preferably further contains a nitrate group in an amount of 1000 to 50000 ppm.
• HC 10 3, HB r Os , the HN_ ⁇ 2, HN 0 3, H Mn0 4, HV0 3, H 2 ⁇ 2, H 2 W 0 4 and H 2 M o 0 4 and salts such It is preferable to contain at least one oxygen acid and / or oxyacid salt selected from among them.
• These surface treatment liquids may further contain at least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound, a nonionic surfactant, At least one surfactant selected from an anionic surfactant and a cationic surfactant may be contained.
• the present invention provides a contact with the above-described surface treatment treatment liquid, either alone or in combination of two or more metal materials selected from iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials.
• a surface treatment method for a metal In this surface treatment method, after the metal material is brought into contact with the treatment liquid for surface treatment, it is washed with water or not with water, and further selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium. It may be brought into contact with an acidic aqueous solution of a compound containing one kind of element, or in contact with a treatment liquid containing at least one kind of polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound. Also good.
• the present invention provides the above-mentioned surface by using each of metal materials selected from iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials alone or in combination of two or more thereof, and using the metal material as a cathode.
• It is a metal surface treatment method characterized by performing an electrolytic treatment in a treatment solution.
• the metal material is electrolytically treated in a surface treatment solution and then washed with water.
• it may be contacted with an acidic aqueous solution of a compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium without being washed with water. You may make it contact with the process liquid containing the at least 1 sort (s) of high molecular compound chosen from a molecular compound and a water-dispersible high molecular compound.
• the present invention provides a metal material selected from iron-based material, zinc-based material, aluminum-based material and magnesium-based material that has not been degreased and cleaned, either alone or in combination of two or more thereof.
• a metal material selected from iron-based material, zinc-based material, aluminum-based material and magnesium-based material that has not been degreased and cleaned, either alone or in combination of two or more thereof.
• Degreasing the metal surface by contacting with a surface treatment solution containing at least one surfactant selected from the above-mentioned nonionic surfactants, anionic surfactants and cationic surfactants It is a method that can perform processing and film formation processing simultaneously.
• the present invention also provides a metal selected from titanium and zirconium formed on the surface of a metal material selected from iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials by the surface treatment method described above. It has a surface treatment film containing at least one element, and the amount of the surface treatment film is 30 mg / m ⁇ or more in the case of the surface of an iron-based metal material in terms of the metal element. 20 mg / m2 or more for zinc-based metal material surface, 10 mg / m2 or more for aluminum-based metal material surface, and 10 mg for magnesium-based metal material surface It is a metal material characterized by being / m2 or more.
• FIG. 1 is a plan view of a test plate used in Examples and Comparative Examples of the present invention.
• Fig. 2 is a front view of the test plate.
• the present invention relates to an iron-based material, a zinc-based material, an aluminum-based material, and magnesium.
• the present invention relates to a technique for depositing a surface-treated film with excellent corrosion resistance after coating, either by itself or by simultaneously treating two or more metal materials selected from the group materials.
• the iron-based material refers to steel plates such as cold-rolled steel plates and hot-rolled steel plates, and iron-based metals such as pig iron and sintered materials.
• the zinc-based material means zinc-containing metal plating.
• This zinc-containing metallurgy is a combination of zinc or zinc and other metals (eg, at least one metal such as nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead and antimony) and inevitable impurities.
• aluminum-based materials refer to aluminum alloy die-casts such as ADC-12, which are aluminum alloy plate materials such as 5000-series aluminum alloys and 6000-series aluminum alloys.
• the magnesium-based material refers to a plate material using a magnesium alloy, such as die casting.
• the present invention is applied to a structure including a single metallic material as a constituent member, or a structure including two to four metallic materials as a constituent member. And when applying to the structure which contains 2 to 4 types of the metal materials in the structural member, the surface of the 2 to 4 types of metal materials can be simultaneously surface treated (where 2 When surface treatment is performed simultaneously on seeds or four types of metal materials, the dissimilar metals may not be in contact with each other, or even if dissimilar metals are in contact with each other by a joining method such as welding, adhesion, riveting, etc.
• the treatment liquid for surface treatment of the present invention contains one or more compounds selected from a zirconium compound and a titanium compound as the above metal element in an amount of 5 to 5000 ppm, and contains free fluorine ions in an amount of 0.1 to LOO p pm and a treatment liquid having pH of 2 to 6.
• zirconium compound used in the present invention Z r C l 4 , Z r 0 C 1 2s Z r ( SO 4 ) 2 , Z rOS0 4 , Z r (N 0 3 ) 4 , Z r 0 (N 0 3 ) 2, H 2 Z r Fe s H 2 Z rFe salt, Z r0 2 , Z r 0 B r 2 , Z r F 4 and the like.
• a zirconium compound is preferably used.
• the concentration of one or more compounds selected from the zirconium compound and the titanium compound used in the present invention is preferably 5 to 5000 ppm as the metal element (that is, as zirconium and Z or titanium), More preferably, it is 10 to 3000 ppm. Since the film obtained by using the surface treatment solution and the surface treatment method of the present invention is an oxide or hydroxide of zirconium or titanium, one or more kinds selected from the zirconium compound or titanium compound are used. When the concentration of the compound is less than 5 ppm as zirconium and / or titanium, it is difficult to obtain a sufficient amount of adhesion in a practical processing time to obtain corrosion resistance because the concentration of the main component of the film is small. In addition, when the concentration is higher than 5000 ppm, a sufficient amount of adhesion can be obtained, but there is no further effect of improving the corrosion resistance, which is only economically disadvantageous.
• Zirconium compounds or titanium compounds are relatively soluble in acidic solutions, but are unstable in alkaline solutions and readily precipitate as oxides or hydroxides of zirconium or titanium.
• the surface treatment solution of the present invention has a pH of 2 to 6, more preferably 3 to 6.
• a dissolution reaction of the metal material to be treated occurs.
• the pH increases at the interface of the metal material to be treated, and an oxide or hydroxide of zirconium and titanium is deposited as a film on the surface of the metal material to be treated ⁇
• free fluorine ions are present therein.
• a fluorinated compound is added to the surface treatment solution.
• Sources of this free fluoride ion include hydrofluoric acid, H 2 Z r Fe, H ⁇ salt Z rFe, H 2 T i Fe , salts of H ⁇ T i Fe, salts of H 2 S i F 6, H ⁇ S i Fe, salts of HBF 4, HBF 4, Examples include Na HF 2 , KHF 2 , NH 4 HF 2 , NaF, KF, and NH 4 F.
• Free fluorine has the effect of improving the stability of the zirconium compound and the titanium compound in the surface treatment solution.
• free fluorine ions are dissolved in an acidic solution in any of iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials, which are metal materials to be subjected to the surface treatment of the present invention. Has the effect of promoting the reaction. Therefore, by adding a fluorine compound to make free fluorine ions exist, it is possible to increase the stability of the surface treatment treatment liquid of the present invention and also improve the reactivity to the metal material to be treated. .
• the present applicant has previously described a surface treatment composition and a surface treatment solution for treating the surface of a metal containing at least one of iron or zinc, and a titanium compound, a zirconium compound, and a fluorine-containing compound.
• the iron-based material, the zinc-based material, A metal material selected from aluminum materials and magnesium materials can be surface-treated either alone or in combination of two or more thereof. Since iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials have different reactivities, it was impossible in the prior art to surface-treat two or more of the metal materials at the same time. In the present invention, the balance between the stability and reactivity of the surface treatment solution can be freely changed by adjusting the concentration of free fluorine ions. Two or more types of zinc-based materials, aluminum-based materials, and magnesium-based materials can be surface-treated simultaneously or independently.
• the concentration of free fluorine ion here refers to the concentration of fluorine ion measured using a commercially available ion electrode.
• the concentration of free fluorine ions in the surface treatment solution of the present invention is preferably 0.1 to 100 ppm, more preferably 2 to 70 ppm.
• concentration of free fluorine ions is higher than 100 ppm, the dissolution reaction of the metal material to be treated is promoted, but the zirconium compound and the titanium compound in the surface treatment solution are very stable. Therefore, even if pH increases at the metal material interface, it is difficult to deposit as a film.
• it is smaller than 0.1 ppm, the effect of improving the stability and reactivity of the surface treatment solution is small, and the meaning of containing free fluorine ions is lost.
• the free fluorine ions in the present invention have the effect of keeping the components eluted by dissolution of the metal material to be treated stably in the surface treatment liquid, in addition to the action of improving the stability and reactivity of the surface treatment liquid. Bear.
• sludge is generated because, for example, iron ions eluted from ferrous metal materials form iron phosphate, which is an insoluble salt with phosphoric acid.
• phosphate radicals can be contained in the treatment liquid, but if the concentration of phosphate radicals exceeds 1. O g / L, sludge may be generated.
• inorganic acids such as sulfuric acid and hydrochloric acid
• acetic acid, oxalic acid, tartaric acid
• organic acid such as acid, succinic acid, gluconic acid, or fuuric acid
• a chelating agent capable of chelating the elution component may be added alone or in combination.
• the treatment liquid for surface treatment of the present invention can contain at least one selected from the group consisting of calcium compounds, magnesium compounds and strontium compounds.
• the present invention provides a specific concentration of zirconium compound and By adjusting the concentration of free fluorine ions in an aqueous solution containing a titanium compound within a certain range, surface treatment can be applied to two to four types of iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials simultaneously or independently. It is possible to apply.
• the metal element (calcium, magnesium or strontium) contained in the calcium compound, the magnesium compound or the strontium compound is free fluorine in the aqueous solution by generating a salt of fluorine and fluoride in the aqueous solution.
• Examples of calcium compounds, magnesium compounds or strontium compounds that can be used in the present invention include oxides, hydroxides, chlorides, sulfates, nitrates and carbonates of these metal elements.
• any compound can be used in the present invention, whether it is an inorganic substance or an organic substance, as long as the compound has an action of keeping the free fluorine ion concentration in the fluorine-containing aqueous solution constant. Can be used.
• the concentration of the magnesium compound or stoichiometric compound used in the present invention is preferably 10 to 500 ppm, more preferably 100 to 300 ppm, as the metal element.
• the solubility of calcium fluoride is remarkably small, so that calcium is preferably 5 to 1 OO ppm, more preferably 5 to 50 ppm.
• the concentration of the compound is larger than the upper limit value, the stability of the treatment liquid for surface treatment may be impaired, and there may be a problem in continuous operation.
• the concentration of the compound is smaller than the lower limit, the amount of the coating of the present invention on the iron-based material may be lowered.
• nitrate radicals can be added to the surface treatment solution of the present invention at 100 00 to 5 00 000 ppm, more preferably 10 00 to 30 00 ppm.
• the nitrate radical acts as an oxidant, has the effect of promoting the film deposition reaction in the present invention, and the effect of increasing the solubility of the calcium compound, magnesium compound or strontium compound in the surface treatment solution. Therefore, even when the concentration of nitrate radical is less than 100 ppm, it is possible to deposit a film having excellent corrosion resistance, but the concentration of the calcium compound, the magnesium compound, or the tungsten compound is low. If it is high, the stability of the surface treatment solution may be impaired.
• the concentration of nitrate radicals is sufficient as 500,000 ppm, and adding more nitrate radicals is only economically disadvantageous. .
• the surface treatment solution of the present invention includes HC 10 3 , HB r 0 3 , ⁇ 0, HN0 2 , HMn0 4 , HV0 3 , ⁇ 2 0 2 , H 2 W0 4 and ⁇ 2 ⁇ ⁇ C
• At least one oxygen acid selected from the group consisting of oxyacids and soot or salts of these oxygen acids can be added.
• Oxygen acid or a salt thereof acts as an oxidizing agent for the material to be treated, and accelerates the film formation reaction in the present invention.
• concentration of the above-mentioned oxygen acids or salts of these oxygen acids but the effect as an oxidizing agent is sufficiently exerted with an addition amount of about 10 to 500 ppm.
• At least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound may be added to the surface treatment treatment liquid of the present invention.
• the metal material surface-treated with the treatment liquid for surface treatment of the present invention has sufficient corrosion resistance.
• the polymer compound is selected according to the desired function. May be selected and added to modify the physical properties of the film.
• the water-soluble polymer compound and the water-dispersible polymer compound include polyvinyl alcohol, poly (meth) acrylic acid, a copolymer of acrylic acid and methacrylic acid, and ethylene and (meth) acrylic acid.
• Copolymers with acrylic monomers such as (meth) acrylic acid salts, ethylene and vinyl acetate
• Acrylic monomers such as (meth) acrylic acid salts, ethylene and vinyl acetate
• Polymers commonly used for surface treatment of metals such as copolymers, polyurethane, amino-modified phenolic resin, polyester resin, and epoxy resin can be used.
• the structure of the surface treatment film layer in the present invention is the state in which oxides and hydroxides are mixed when dried at room temperature or low temperature after the surface treatment, and also when oxidized at high temperature after surface treatment. It is thought that there are many things or oxides.
• the reactivity of the surface treatment liquid of the present invention can be freely controlled by changing the concentration of the zirconium compound or titanium compound in the surface treatment liquid and the free fluorine ion concentration. Therefore, the treatment temperature and treatment time can be changed in any way in combination with the reactivity of the treatment bath.
• At least one surfactant selected from the group of nonionic surfactants, anionic surfactants and cationic surfactants is added to the above surface treatment treatment solution for surface treatment.
• a surfactant selected from the group of nonionic surfactants, anionic surfactants and cationic surfactants is added to the above surface treatment treatment solution for surface treatment.
• this surface treatment solution can be used as a degreasing and surface treatment agent.
• a method of performing electrolysis in the surface treatment liquid using a metal material to be treated as a cathode may be employed.
• electrolytic treatment is performed using the metal material to be treated as a cathode
• a reduction reaction of hydrogen occurs at the cathode interface and pH increases.
• the stability of the zirconium compound and the titanium or titanium compound at the cathode interface decreases, and the surface treatment film is deposited as an oxide or a hydroxide containing water.
• the surface-treated film layer obtained by the present invention is a thin film and exhibits excellent coating performance. However, depending on the surface state of the metal material to be treated, there may be a fine defect in the surface-treated film layer. . Therefore, an acidic aqueous solution of a compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, or at least selected from a water-soluble polymer compound and a water-dispersible polymer compound. By contacting with a treatment liquid containing one kind of polymer compound, the fine defects are covered and the corrosion resistance is further enhanced.
• the compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium is not particularly limited, but is easily available as an oxide or hydroxide of the metal element.
• Fluoride Use complex fluoride, chloride, nitrate, oxynitrate, sulfate, oxysulfate, carbonate, oxycarbonate, phosphate, oxyphosphate, oxalate, oxyoxalate and organometallic compounds Can do.
• the pH of the acidic aqueous solution containing the metal element is preferably 2 to 6, and acids such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, and organic acids, sodium hydroxide, It can be adjusted with the strength of potassium hydroxide, lithium hydroxide, alkali metal salt, ammonium salt, and amines.
• Examples of at least one polymer compound selected from the above water-soluble polymer compounds and water-dispersible polymer compounds include polyvinyl alcohol, poly (meth) acrylic acid, acrylic acid and methacrylic acid. Copolymers of ethylene and copolymers of acrylic monomers such as (meth) acrylic acid and (meth) acrylate, copolymers of ethylene and vinyl acetate, polyurethanes, amino-modified phenolic resins Polyester resin, epoxy resin, tannin and botheric acid and salts thereof, and phytic acid can be used.
• the present invention is to dramatically improve the corrosion resistance of a metal material by providing a surface treatment film layer made of an oxide and / or hydroxide of a metal element selected from zirconium and / or titanium on the surface of the metal material to be treated.
• the oxide and hydroxide of the metal element have a chemically stable property that is hardly affected by acid and alkali.
• the pH decreases at the anode where metal elution occurs, and the pH increases at the force sword where the reduction reaction occurs. Therefore, the surface treatment film with poor acid resistance and alkali resistance dissolves in a corrosive environment and loses its effect. Since the main component of the surface treatment film layer in the present invention is not easily affected by acid or alkali, excellent effects continue even in a corrosive environment.
• the metal element oxides and hydroxides form a network structure through the metal and oxygen, so that a very good barrier film is obtained.
• Corrosion of metal materials varies depending on the environment in which it is used, but generally water and oxygen are present. In this situation, the oxygen demand type corrosion is accelerated by the presence of components such as chloride.
• the surface-treated film layer of the present invention since the surface-treated film layer of the present invention has a barrier effect against water, oxygen and corrosion promoting components, it can exhibit excellent corrosion resistance.
• the above adhesion amount is necessary, preferably 40 mg / m ⁇ or more, and more preferably 50 mg / ms or more.
• an amount of adhesion of 20 mg m ⁇ or more in terms of the above metal elements is required. Is a deposit of 30 mg m ⁇ or more.
• an amount of deposit of 10 mgZm2 or more is required in terms of the metal element, and preferably an amount of deposit of 20 mg / ma or more. It is.
• an amount of deposit of 10 mgZms or more in terms of the metal element is required, and preferably an amount of deposit of 20 mg / m2 or more It is.
• the upper limit of the adhesion amount is not particularly limited, but if the adhesion amount exceeds 1 g / ms, cracks are likely to occur in the surface treatment film layer, making it difficult to obtain a uniform film. Therefore, the upper limit of the adhesion amount for iron-based materials, zinc-based materials, and aluminum-based materials is more preferably 800 mg m ⁇ than l g / ma.
• Fig. 1 is a plan view of a test plate spot-welded with three kinds of metallic materials, SPC, GA and A1
• Fig. 2 is a front view thereof. 1 indicates a spot weld.
• a 1 (Aluminum alloy plate: 6000 series aluminum alloy)
• Mg magnesium alloy plate: J I S— H— 420 1
• Example 5 Alkaline degreasing Water washing Electrochemical conversion treatment “ ⁇ Washing Pure water washing Drying Example 6 Film formation treatment (degreasing chemical combined use) Water washing ⁇ Pure water washing Drying Example 8 Al force degreasing Water film formation treatment Water washing Post-treatment Pure water washing ⁇ Dry
• Example 9 Film chemical conversion treatment (degreasing chemical combined use) Washing After treatment Pure water washing Drying Comparative example 5: Alkaline degreasing Water washing Surface conditioning Zinc phosphate treatment Water washing Pure Washing and drying
• alkaline degreasing was performed by diluting Fine Cleaner L4460 (registered trademark: Nippon Pakaraizing Co., Ltd.) to 2% with tap water in both Examples and Comparative Examples, 40 ° C, 120 seconds. Used by spraying on the plate to be treated. In the examples and comparative examples, water washing after the coating treatment and pure water washing were sprayed on the plate to be treated at room temperature for 30 seconds.
• an aqueous solution having a zirconium concentration of 200 ppm was prepared. After heating this aqueous solution to 45 ° C, the pH was adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and the fluoride ion memory (IM-55G; Toa Radio) The surface treatment solution was prepared by adjusting the free fluorine ion concentration measured by Kogyo Co., Ltd. to 1 ppm. After adjusting the free fluorine ion concentration, the total fluorine concentration in the surface treatment solution was 50 ppm.
• test plate that had been degreased and washed with water was immersed in the above-mentioned surface treatment solution for 120 seconds for surface treatment.
• zirconium zirconium nitrate reagent Using zirconium zirconium nitrate reagent, magnesium nitrate reagent and strontium nitrate reagent, the zirconium concentration was 100 ppm, the magnesium concentration was 500,000 ppm, the nitrogen concentration was 2 000 ppm, and the nitrate radical An aqueous solution of 2 8 470 ppm was prepared. After heating this aqueous solution to 50 ° C, the pH was adjusted to 4.0 using ammonia water reagent and hydrofluoric acid, and a fluorine ion meter (IM-55G; Toa Denpa Kogyo Co., Ltd.) The free fluorine ion concentration measured in (1) was adjusted to 80 ppm and used as a surface treatment solution. After adjusting the free fluoride ion concentration, the total fluorine concentration in the surface treatment solution was 2000 ppm.
• IM-55G fluorine ion meter
• test plate that has been degreased and washed with water is immersed in the above surface treatment solution for 60 seconds. It was crushed and surface-treated.
• the pH is adjusted to 5.0 using a potassium hydroxide reagent and hydrofluoric acid, and a fluorine ion meter (IM-55G; Toa Denpa Kogyo Co., Ltd.)
• IM-55G Toa Denpa Kogyo Co., Ltd.
• the free fluorine ion concentration measured in (1) was adjusted to 25 ppm and used as a surface treatment solution.
• the total fluorine concentration in the surface treatment solution after adjusting the free fluorine ion concentration was 2 It was 2 50 ppm.
• test plate that had been degreased and washed with water was immersed in the above surface treatment solution for 90 seconds for surface treatment.
• An aqueous solution having a root of 70.80 ppm and a nitrite root of 40 ppm was prepared. After heating this aqueous solution to 35 ° C, the pH is adjusted to 4.0 using triethanolamine reagent and hydrofluoric acid, and a fluorine ion meter (IM-5 5 G: The free fluorine ion concentration measured by Toa Denpa Kogyo Co., Ltd. was adjusted to 10 ppm and used as a surface treatment solution. After adjusting the free fluorine ion concentration, the total fluorine concentration in the surface treatment solution was 1 1900 ppm.
• the surface treatment was performed by spraying the above-mentioned surface treatment solution on a test plate that had been degreased and washed with water for 120 seconds.
• zirconium oxynitrate reagent and hexafluorotitanic acid IV
• aqueous solution Using magnesium nitrate reagent, nitric acid and sodium chlorate reagent, the zirconium concentration was 5 p pm, the titanium concentration was 5 p pm, the magnesium concentration was 10 0 p ppm, and the nitrate radical was 3 0 5 2 0 p pm, an aqueous solution having a chlorate radical of 100 ppm was prepared. After heating this aqueous solution to 30 ° C, the pH was adjusted to 6.0 using an aqueous ammonia reagent and hydrofluoric acid. ) The surface treatment solution was prepared by adjusting the free fluorine ion concentration measured in (5) to 0.5 ppm. After adjusting the free fluorine ion concentration, the total fluorine concentration in the surface treatment solution is 12 p pm.
• a test plate that had been degreased and washed with water was used as a cathode, and a carbon electrode was used as the anode, and surface treatment was performed by electrolysis for 5 seconds in the above-mentioned surface treatment solution under an electrolytic condition of 5 A / dms.
• zirconium oxide nitrate reagent Using zirconium oxide nitrate reagent, magnesium oxide reagent, nitric acid and hydrogen peroxide reagent, zirconium concentration was 1550 ppm, magnesium concentration was 10 ppm, nitrate radical was 5200 ppm, peroxide An aqueous solution with hydrogen at 10 ppm was prepared.
• the surface treatment solution was sprayed for 90 seconds on a test plate that had been oiled without degreasing treatment, and surface treatment was performed simultaneously with degreasing.
• Titanium (IV) sulfate aqueous solution, calcium nitrate reagent, magnesium nitrate reagent, and potassium permanganate reagent were used. Titanium concentration was 100 ppm, calcium concentration was 50 ppm, magnesium concentration was 500 ppm, nitric acid An aqueous solution having roots of 2 5 6 60 ppm and permanganic acid of 10 ppm was prepared. Further, a water-soluble acrylic polymer compound (Diyurima AC-10L: manufactured by Nippon Pure Chemical Co., Ltd.) was added to this aqueous solution so that the solid concentration was 1%, and the mixture was heated to 50 ° C.
• a water-soluble acrylic polymer compound Diyurima AC-10L: manufactured by Nippon Pure Chemical Co., Ltd.
• test plate that had been degreased and washed with water was immersed in the above surface treatment solution for 60 seconds for surface treatment.
• aqueous solution was prepared in which a water-soluble acryl-based polymer compound (Julima AC-10L: manufactured by Nippon Pure Chemical Co., Ltd.) was 1% in terms of solid concentration and the phosphate reagent was 2 g / L as a phosphate radical.
• This aqueous solution was heated to 40 ° C. and adjusted to pH 4.5 with an aqueous ammonia reagent to prepare a post-treatment solution.
• the test plate subjected to film formation and water washing in the surface treatment of Example 5 was subjected to a post-treatment by being immersed in the post-treatment liquid for 30 seconds.
• hexafluorozirconic acid (IV) aqueous solution and cobalt nitrate reagent prepare an aqueous solution with a zirconium concentration of 50 ppm and a cobalt concentration of 50 ppm, and further heat the aqueous solution to 40 ° C. Thereafter, the pH was adjusted to 5.0 with an aqueous ammonia reagent to prepare a post-treatment liquid.
• the test plate that had been subjected to film formation and water washing in the surface treatment of Example 6 was submerged in the above-mentioned post-treatment liquid for 30 seconds to carry out post-treatment. Comparative Example 1
• an aqueous solution having a zirconium concentration of 500 ppm, a magnesium concentration of 100 ppm, and a nitrate radical of 6780 ppm was prepared.
• This aqueous solution was heated to 45 ° C., and then the pH was adjusted to 4.0 with a sodium hydroxide reagent to obtain a surface treatment solution.
• the free fluorine ion concentration in the surface treatment solution was measured with a commercially available fluorine ion meter (IM-55G; manufactured by Toa Denpa Kogyo Co., Ltd.).
• test plate that had been degreased and washed with water was immersed in the above surface treatment solution for 120 seconds for surface treatment.
• an aqueous solution having a titanium concentration of 20 Oppm was prepared. After heating the aqueous solution to 50 ° C, the pH was adjusted to 3.5 with an aqueous ammonia reagent and hydrofluoric acid, and Fluorine Ion-Meiichi (IM-55G; manufactured by Toa Denpa Kogyo Co., Ltd.) The surface treatment solution was prepared by adjusting the free fluorine ion concentration measured in step 1) to 400 ppm.
• test plate that had been degreased and washed with water was immersed in the above surface treatment solution for 90 seconds for surface treatment.
• a commercially available chromic chromate treatment agent Alchrome 7 13 (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.) is diluted to 3.6% with tap water, and the total acidity and free acidity are adjusted to the center of the catalog value. did.
• test plate that had been degreased and washed with water was submerged in the chromate treatment solution heated to 35 ° C. for 60 seconds to perform chromate treatment.
• a test plate that has been degreased and washed with water is sprayed with a solution prepared by diluting 0.1% of preparen ZN (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.) with tap water at room temperature for 30 seconds
• Parbond L 3 0 20 registered trademark: manufactured by Nippon Parkerizing Co., Ltd.
• sodium hydrogen fluoride reagent was used as the fluorine.
• Table 1 shows the appearance evaluation results of the surface treatment films obtained in the examples and comparative examples.
• a uniform film could be obtained for all the metal material types of all the test plates.
• the surface treatment film was deposited on the spot welds of the test plates used in the examples.
• a uniform film could not be deposited on all the test plates.
• Comparative Examples 3, 4, and 5 no film was deposited on the spot welds.
• Comparative Example 5 is a zinc phosphate treatment solution used when simultaneously processing cold-rolled steel sheets, zinc-plated steel sheets, and aluminum alloys. As in this test, each test piece was joined by welding. Under these conditions, there was an exposed portion of the metal material base called Suke on the cold-rolled steel sheet.
• Table 2 shows the appearance evaluation results of the surface treatment films obtained in the examples and comparative examples.
• Table 2 shows the appearance evaluation results of the surface treatment films obtained in the examples and comparative examples.
• a uniform film could be obtained for all the metal material types of all the test plates.
• the surface treatment film was
• Tables 2 and 3 show the measurement results of the adhesion amount of the surface treatment film obtained in Examples and Comparative Examples.
• the target adhesion amount could be obtained.
• the adhesion amount of the surface-treated film layer in the example was constant regardless of whether or not the test plate was joined.
• a uniform film could not be deposited on all the test plates, as is apparent from the film appearance evaluation results.
• Cationic electrodeposition coating, intermediate coating, and top coating are as follows.
• Cationic electrodeposition coating Epoxy-based cationic electrodeposition paint (Electron 94 400: manufactured by Kansai Paint Co., Ltd.), voltage 20 0 V, film thickness 20 mm, 1 75 ° C 20 minutes baking
• Top coat Aminoalkyd paint (Amirac TM 13-3 White: manufactured by Kansai Paint Co., Ltd.), spray coating, film thickness 35 mm, 140 ° C 20 minutes baking (evaluation of coating performance)
• the coating performance of Examples and Comparative Examples was evaluated. The results are shown in Tables 4 and 5. Evaluation items and abbreviations are shown below.
• the coating film at the completion of electrodeposition coating is referred to as the electrodeposition coating film, and the coating film at the completion of top coating is referred to as the 3coats coating film.
• the electrodeposition coated plate was immersed in a 5 wt% NaC1 aqueous solution heated to 50 ° C. for 84 hours. After immersion, the entire surface of the test beads washed with tap water and dried at room temperature was peeled off with gummed tape, and the peeled area of the coating on each metal material was visually determined.
• 1st ADH Cut 100 mm grids at 2 mm intervals with sharp force on 3 coats coating. The tape was peeled off from the grid area, and the number of peeled grids was counted.
• 2nd ADH 3coats coated plate was immersed in 40 ° C. deionized water for 24 hours. After immersion, 100 grids at intervals of 2 mm were cut with a sharp cutter. The tape was peeled off from the grid area, and the number of peeled grids was counted.
• Table 4 shows the coating performance evaluation results for the electrodeposition coating. Examples are all test plates Shows good corrosion resistance. On the other hand, in Comparative Example 1, since the surface treatment liquid did not contain any free fluorine ions, the surface treatment film was not sufficiently deposited and the corrosion resistance was poor. In Comparative Example 2, since the free fluorine ion concentration in the surface treatment solution was high, the coating amount on the SPC was particularly small and the corrosion resistance was poor. Examples 5 and 6 showed coating performance superior to that of the comparative example, but were slightly inferior in corrosion resistance after electrodeposition coating as compared with other examples. However, as shown in Examples 8 and 9, the corrosion resistance was further improved by applying the post-treatment.
• Comparative Example 3 is a chromate treatment agent for aluminum alloys and Comparative Example 4 is a non-chromate treatment agent for aluminum alloys, the corrosion resistance of A1 was excellent, but the corrosion resistance of other test plates was clearly an example. It was inferior to.
• Comparative Example 5 is a zinc phosphate treatment that is currently commonly used as a cathodic electrodeposition coating base. However, even in Comparative Example 5, the results were inferior to those in Examples under the conditions in which each test piece was joined by welding as in this test. Table 5
• Table 5 shows the results of evaluating the adhesion of the 3coats board. Examples apply to all test plates Good adhesion was shown. As for 1st ADH, good results were obtained in the comparative examples, but 2nd ADH did not show a level of good adhesion to all the test plates as well as the corrosion resistance of the electrodeposition coating film. In Comparative Example 5, sludge, which is a by-product during the zinc phosphate treatment, was generated in the treatment bath after the surface treatment. However, in the examples, no sludge was observed at any level.
• a surface-treated film having excellent corrosion resistance after coating can be deposited on a metal surface composed of two or four of iron-based material, zinc-based material, aluminum-based material, and magnesium-based material simultaneously or individually.
• the surface treatment film can be deposited without performing the surface adjustment process of the metal material to be treated. In this case, the treatment process can be shortened and the space can be saved.

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