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
  • C23C22/48—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
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
  • C23C22/56—Treatment of aluminium or alloys based thereon

Definitions

• the present invention relates to a metal surface modification solution containing no fluorine and a metal surface treatment method.
• chromate treatment and phosphate treatment are generally performed to improve the corrosion resistance of metal surfaces.
• the toxicity of chromium has become a social problem in recent years, and the surface treatment method using chromate has a problem of scattering of chromate fume in the treatment process and requires a large amount of cost for wastewater treatment equipment.
• Patent Document 1 proposes a chemical conversion treatment agent for iron and / or zinc-based substrates that contains substantially no phosphate ions but contains zirconium ions and / or titanium ions and fluorine ions.
• Patent Document 2 discloses (I) a compound containing at least one metal element selected from Ti, Zr, Hf and Si, and (II) a surface treatment of a metal containing a fluorine-containing compound as a source of fluorine ions.
• a surface treatment film having excellent corrosion resistance can be deposited on the surface of a metal containing at least one of iron and zinc, and the surface adjustment (surface tone) step is not required, so that the treatment step is shortened. It is disclosed to save space.
• Patent Document 1 and Patent Document 2 both contain fluorine as an essential component, and due to restrictions on the fluorine content in industrial wastewater in recent years, a great amount of capital investment has been made to overcome these. It was necessary.
• Patent Document 3 in order to form a chemical conversion film having corrosion resistance and coating film adhesion on the surface of a metal substrate without containing fluorine, at least one selected from a water-soluble titanium compound and a water-soluble zirconium compound is used.
• Compound (A), and an organic compound (B) having a plurality of functional groups as a stabilizer the content of compound (A) is 0.1 to 10 mmol / L, and the content of organic compound (B) is compound ( It has been proposed to use a chemical conversion treatment solution for metal surfaces having a metal content of 2.5 to 10 times mol of the metal content of A) and having a pH of 2.0 to 6.5.
• the object of the present invention is to provide a metal surface modification that does not contain fluorine, particularly useful for chemical conversion treatment for iron-based materials, without causing the above-mentioned problems even when the treatment is performed continuously in chemical conversion treatment for iron-based materials.
• the object is to provide a liquid and metal surface modification method.
• the present inventors have determined that specific amounts of at least one element selected from Zr and Ti, oxycarboxylic acid, alkanoic acid having 1 to 7 carbon atoms, and nitrate ion are used. It has been found that the above-mentioned problems can be solved by the inclusion, and the present invention has been completed. That is, the present invention is as follows.
• Item 1 10 to 500 ppm of at least one element selected from Zr and Ti, 20 to 3,000 ppm of oxycarboxylic acid, 1 to 10,000 ppm of alkanoic acid having 1 to 7 carbon atoms, and 1 to 10,000 ppm of nitrate ions And a molar ratio of at least one element selected from Zr and Ti to oxycarboxylic acid (at least one element selected from Zr and Ti / oxycarboxylic acid) is 1/10 to 1/2, pH 2
• a metal surface modification solution containing no fluorine characterized by being an aqueous solution of 0.0 to 6.5.
• Item 2 The metal surface modification solution according to Item 1, wherein the oxycarboxylic acid is at least one selected from lactic acid, malic acid, citric acid, tartaric acid, gluconic acid and glycolic acid.
• the oxycarboxylic acid is at least one selected from lactic acid, malic acid, citric acid, tartaric acid, gluconic acid and glycolic acid.
• Item 3. The metal surface modifying solution according to Item 1 or 2, wherein the alkanoic acid having 1 to 7 carbon atoms is at least one selected from formic acid, acetic acid, propionic acid, and butyric acid.
• Zr is derived from at least one selected from zirconium oxynitrate, zirconium nitrate, zirconium oxyacetate, zirconium acetate, ammonium zirconium carbonate, ammonium zirconium nitrate, zirconium sulfate, zirconium oxysulfate, zirconium lactate and zirconium chloride.
• the metal surface modification liquid according to any one of the above.
• Item 5 The metal surface modification solution according to any one of Items 1 to 4, wherein Ti is derived from at least one selected from titanium nitrate, titanium oxynitrate, titanium sulfate, titanium oxysulfate and titanium ammonium nitrate.
• Item 6. The metal surface modifying solution according to any one of Items 1 to 5, which has a pH buffering action and is an aqueous solution having a pH of 3.5 to 5.5.
• At least one element selected from Zr and Ti is at least one of zirconium oxynitrate and titanium oxynitrate or titanium sulfate; the oxycarboxylic acid is selected from lactic acid, malic acid, and citric acid;
• Item 8 The metal surface modifying solution according to Item 1, wherein the alkanoic acid of ⁇ 7 is selected from formic acid, acetic acid, and propionic acid.
• Item 8 A metal surface modification method for modifying a surface of a metal material, the step of bringing the metal surface modification solution according to any one of Items 1 to 7 into contact with the metal material, and contacting the modification solution
• a metal surface modification method comprising: a water washing step of washing the metal material that has undergone the step of causing the metal material to wash.
• Item 9 The metal surface modification method according to Item 8, wherein the metal material is an iron-based material.
• Item 10 The method for modifying a metal surface according to Item 8 or 9, further comprising a step of subjecting the metal material to pickling with an acidic aqueous solution containing acetic acid and nitric acid before contacting the modifying solution.
• Item 11 A coating method of a metal material, wherein a baking paint is coated on a metal surface that has been surface-modified by the metal surface modification method according to any one of Items 8 to 10.
• composition of the present invention in particular, when the treatment is continuously performed in the chemical conversion treatment for the iron-based material, no trouble occurs, and the corrosion resistance and the upper coating film are not formed on the surface of the metal substrate without containing fluorine.
• a chemical conversion film having excellent adhesion can be formed.
• the metal surface modification liquid of the present invention is particularly useful for chemical conversion treatment for iron-based materials.
• the metal surface modification liquid of the present invention contains 10 to 500 ppm, preferably 25 to 300 ppm, of at least one element selected from Zr and Ti (the total when both Zr and Ti are included). If it is less than 10 ppm, sufficient corrosion resistance cannot be obtained, and if it exceeds 500 ppm, the corrosion resistance may be reduced, and the adhesion with the coating film formed on the treated film may also be reduced.
• Zr can be supplied from, for example, zirconium oxynitrate, zirconium nitrate, zirconium oxyacetate, zirconium acetate, ammonium zirconium carbonate, ammonium zirconium nitrate, zirconium sulfate, zirconium oxysulfate, zirconium lactate, zirconium chloride and the like.
• Ti can be supplied from, for example, titanium nitrate, titanium oxynitrate, titanium sulfate, titanium oxysulfate, and ammonium ammonium nitrate.
• the metal surface modifying liquid of the present invention contains 20 to 3,000 ppm, preferably 50 to 1,000 ppm of oxycarboxylic acid. If it is less than 20 ppm, Zr and Ti in the reforming solution may not be stabilized and precipitates may be formed. If it exceeds 3,000 ppm, Zr and Ti will not easily precipitate from the reforming solution, and will form on the surface of the metal substrate. A treatment film may not be formed.
• oxycarboxylic acid for example, lactic acid, malic acid, citric acid, tartaric acid, gluconic acid, glycolic acid and the like can be used, and lactic acid is particularly preferable.
• the molar ratio (at least one element selected from Zr and Ti / oxygen) of at least one element selected from Zr and Ti to the oxycarboxylic acid (the sum of both when Zr and Ti are included).
• Carboxylic acid) is preferably 1/10 to 1/2, and particularly preferably in the range of 1/8 to 1/3. If it is out of this range, the chemical conversion film may not be formed on the surface of the metal substrate.
• the metal surface modification liquid of the present invention contains 1 to 10,000 ppm, preferably 25 to 3,000 ppm of alkanoic acid having 1 to 7 carbon atoms. If it is less than 1 ppm, the pH of the reforming solution will increase with time and it will be difficult to control the reforming solution, and the corrosion resistance will be reduced. If it exceeds 10,000 ppm, Zr and Ti will not easily precipitate from the modifying solution, and the surface of the metal substrate In some cases, the chemical conversion film may not be formed.
• alkanoic acid having 1 to 7 carbon atoms for example, formic acid, acetic acid, propionic acid, butyric acid and the like can be used, and formic acid and acetic acid are particularly preferable.
• the metal surface modification liquid of the present invention contains 1 to 10,000 ppm, preferably 25 to 5,000 ppm of nitrate ions. If it is less than 1 ppm, the oxidized layer on the surface of the metal base material cannot be dissolved, and a chemical conversion treatment film may not be formed on the surface of the metal base material. Adhesion with the coating film may be reduced.
• the metal surface modification liquid of the present invention is further magnesium, zinc, calcium, aluminum, gallium, indium, copper, iron, manganese, nickel, cobalt, cerium, strontium, rare earth element, tin, It can contain at least one metal element selected from the group consisting of bismuth, yttrium, vanadium, barium, chromium, molybdenum, tungsten and silver.
• the supply source of these metal elements is not particularly limited, and for example, it can be blended in the metal surface modification liquid as a nitrate, a sulfate or the like. When these metal elements are contained, the content is suitably in the range of 0.1 to 5,000 ppm in terms of metal elements.
• the metal surface modification liquid of the present invention is further improved in terms of the corrosion resistance of the film and the adhesion to the coating film.
• silane coupling agents such as aminosilane and epoxysilane; and epoxy resins, acrylic resins, polyester resins, poly Water-soluble or water-dispersible organic resins such as allylamine resin, polyvinylamine resin, polybutadiene resin, polyurethane resin, polyvinyl alcohol, and ethylene-vinyl acetate resin can be blended.
• the content thereof is suitably in the range of 0.1 to 300,000 ppm, preferably 5 to 5,000 ppm in terms of solid content.
• the metal surface modification liquid of the present invention can further contain a surfactant for the purpose of improving the stability and precipitation of the composition.
• a surfactant for the purpose of improving the stability and precipitation of the composition.
• the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
• the content thereof is suitably in the range of 5 to 300,000 ppm, preferably 25 to 100,000 ppm in terms of solid content.
• the metal surface modifying solution of the present invention is preferably an aqueous solution having a pH of 2.0 to 6.5, particularly 3.5 to 5.5.
• the metal surface modification liquid of the present invention desirably has a pH buffering action in the pH range from the viewpoint of improving the liquid stability after the treatment.
• the above-mentioned acidic compounds such as alkanoic acid such as formic acid and acetic acid and nitric acid, and basic compounds such as sodium hydroxide, potassium hydroxide and ammonia can be used.
• the metal surface modification liquid contains 10 to 500 ppm of at least one of zirconium oxynitrate and titanium oxynitrate or titanium sulfate, and 20 to oxycarboxylic acid selected from lactic acid, malic acid, and citric acid.
• the aqueous solution has a molar ratio of at least one element to oxycarboxylic acid of 1/10 to 1/2 and a pH of 2.0 to 6.5.
• the metal surface modification liquid of the present invention obtained as described above is for forming a chemical conversion film containing Zr and / or Ti on the surface of the metal material.
• the material iron is eluted, and the eluted iron ions form a complex with the oxycarboxylic acid, so that Zr and Ti are destabilized, and the hydroxide and / or oxide of Zr and / or Ti and the material metal It is possible to deposit a chemical conversion film layer containing a complex of (mainly Fe in the case of iron-based materials) and oxycarboxylic acid on the surface of the metal material.
• the metal surface modification method of the present invention includes a step of bringing a metal surface modification solution obtained as described above into contact with a metal material (hereinafter referred to as a modification solution contact step), and washing the metal material that has undergone the modification solution contact step with water. And a water washing step.
• the reforming liquid contact step is not particularly limited, and for example, a dipping method, a spray method, a roll coating method or the like can be employed. It is preferable to adjust the temperature of the treatment liquid to 20 to 70 ° C., particularly 30 to 55 ° C.
• steel materials such as cold-rolled steel plates and hot-rolled steel plates, iron-based materials such as cast iron, sintered materials and iron-zinc alloy-plated steel plates; aluminum-based materials such as aluminum die-casting and aluminum alloy plates; zinc Examples thereof include system materials.
• the metal surface modification method of the present invention is particularly useful for iron-based materials made of iron and / or alloys thereof.
• These metal materials are preferably subjected to a degreasing treatment, a post-degreasing water washing treatment, a pickling treatment, and the like before the modifying liquid contacting step, and a water washing step after the modifying liquid contacting step.
• the corrosion resistance can be improved by performing pickling with an acidic aqueous solution containing acetic acid and nitric acid before the modifying solution contacting step, and is usually performed after the pickling treatment. It is not necessary to remove the pickling solution.
• the acidic aqueous solution preferably has a concentration range of 0.1 to 10 g of acetic acid and 0.1 to 10 g of nitric acid in 1 L.
• a surfactant and a chelating agent can be further added to the acidic aqueous solution. When adding, if the kind of surfactant and / or chelating agent can be used in acidic aqueous solution, it will not be specifically limited.
• the pickling treatment conditions are not particularly limited, but it is preferable to treat at 5 to 80 ° C. for 3 to 30 minutes.
• the degreasing treatment is performed to remove oil and dirt adhering to the surface of the base material, and usually with a degreasing agent such as a phosphorus-free and nitrogen-free degreasing cleaning solution at 30 to 70 ° C. for several seconds. Immersion treatment is performed for about several minutes. If desired, a preliminary degreasing process can be performed before the degreasing process.
• a degreasing agent such as a phosphorus-free and nitrogen-free degreasing cleaning solution
• the water washing step after contact with the modifying liquid is carried out once or more so as not to adversely affect the adhesion, corrosion resistance, etc. after the various coatings.
• the final water washing is performed with pure water.
• This water washing treatment may be either spray water washing or immersion water washing, and these methods may be combined for water washing.
• a drying step can be further employed after the water washing step.
• cold air drying, hot air drying, etc. can be performed.
• the film obtained by the method of the present invention has a coating amount of 0.1 to 100 mg / m 2 , particularly 1 to 50 mg / m 2 in terms of the metal element contained in the treatment agent, so that the corrosion resistance of the film is improved. This is preferable from the viewpoint of improving adhesion to the coating film.
• a paint film layer may be appropriately formed by coating with a conventionally known paint, and an organic resin coating layer may be provided via an adhesive layer.
• a conventionally known paint can be used without any particular limitation.
• a baking paint such as an organic solvent-diluted paint, a water-based paint, and a powder paint can be applied.
• Preparation Examples 1 to 20 and Comparative Examples 1 to 9 of Metal Surface Modification Liquid Zirconium oxynitrate, titanium oxynitrate, titanium sulfate, lactic acid, malic acid, citric acid, acetic acid, formic acid, propionic acid, nitric acid, ammonia, sodium hydroxide, etc. are used to modify the metal surface having the composition and pH shown in Table 1.
• a fluid was prepared.
• Table 1 the concentration of each metal component is shown in terms of metal element, and the concentration of the other components indicates the solid content concentration.
• the content of nitrate ions when zirconium oxynitrate and titanium oxynitrate are used means the total amount of carry-in and the amount due to the addition of nitric acid.
• Table 2 shows the liquid state of the metal surface modification liquid. Y is defined as no abnormality.
• (Note 1) to (Note 3) indicate the following.
• Surfactant “New Coal 1100”, trade name, manufactured by Nippon Emulsifier Co., Ltd.
• Nonionic surfactant (Note 3) Organic resin: “Adekabon titer UX206”, trade name, manufactured by ADEKA, water-based polyurethane resin.
• the substrate was immersed in a commercially available degreasing solution adjusted to 40 ° C. for 2 minutes for degreasing treatment, and then washed with tap water for 30 seconds.
• the metal substrate after washing with water was immersed in the metal surface modification liquids of Examples and Comparative Examples adjusted for pH and temperature for 10 to 300 seconds.
• the metal surface modifying solution was used by adjusting the pH to 3.2 to 4.2 using nitric acid or sodium hydroxide, and adjusting the temperature to 35 to 50 ° C.
• test coating plate (1) On each surface-modified plate obtained above, “Magiclon # 1000” (manufactured by Kansai Paint Co., Ltd., acrylic / melamine resin-based organic solvent dilution type paint) is adjusted to a dry film thickness of 30 ⁇ m. Each of the test coating plates was made by air spray coating and heating and baking at 160 ° C. for 30 minutes. Each obtained test coating board was used for the following evaluation test. The results are shown in Table 2.
• Evaluation test 1 Corrosion resistance: Cross-cut flaws were made in the coating plate (1) of each example and comparative example with a knife so as to reach the substrate, and this was subjected to a salt spray corrosion test (SST: JIS Z-2371. Salt water temperature 35) C.) for 240 hours, and then the adhesive tape was attached to and peeled from the knife wound, and the peel width of the coating film on one side was measured from the cut wound.
• SST JIS Z-2371. Salt water temperature 35
• Adhesiveness The test coating plate (1) of each example and comparative example was immersed in warm water (40 ° C.) for 240 hours, and immediately after being pulled up, cuts of grids (10 ⁇ 10 pieces, 1 mm interval) were added. Then, adhesion and peeling with an adhesive tape were performed, and the number of peeling masses of the coating film was examined.
• the evaluation criteria are as follows.
• the iron ion concentration (ppm) of the modified liquid after the treatment was measured by ICP emission spectroscopic analysis, and then the modified liquid after the treatment was left at 40 ° C. for 1 day. Thereafter, one step using a commercially available cold-rolled steel plate (SPCC-SD, manufactured by Nippon Test Panel Co., Ltd., 70 mm ⁇ 150 mm ⁇ 0.8 mm) as a base material, the above-described process ( A metal surface modification treatment was performed under the conditions 1) to (4) and Table 1 to obtain a surface modification treatment plate. The amount of the metal film on each surface-modified plate was analyzed as a total amount (mg / m 2 ) of adhered metal using “XRF1700” (manufactured by Shimadzu Corporation, fluorescent X-ray analyzer).
• test coating plate (2) “Magiclon # 1000” (manufactured by Kansai Paint Co., Ltd., acrylic / melamine resin organic solvent dilution type paint) with a dry film thickness on each surface modified plate obtained by the above-mentioned continuous treatment.
• Each test coating plate (2) was prepared by performing air spray coating to 30 ⁇ m, heating and baking at 160 ° C. for 30 minutes.
• Each obtained test coated plate (2) was subjected to the above corrosion resistance test and (after water resistance) adhesion test. The results are shown in Table 2.

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• 2013
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