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CN101487115B - Treatment liquid for metal surface treatment and surface treatment method - Google Patents

Treatment liquid for metal surface treatment and surface treatment method Download PDF

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Publication number
CN101487115B
CN101487115B CN2008101849496A CN200810184949A CN101487115B CN 101487115 B CN101487115 B CN 101487115B CN 2008101849496 A CN2008101849496 A CN 2008101849496A CN 200810184949 A CN200810184949 A CN 200810184949A CN 101487115 B CN101487115 B CN 101487115B
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surface treatment
compound
treatment
metallic substance
magnesium
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CN101487115A (en
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中山隆臣
佐藤裕之
相岛敏行
冈田荣作
吉田文也
盐田克博
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Nihon Parkerizing Co Ltd
Toyota Motor Corp
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Nihon Parkerizing Co Ltd
Toyota Motor Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

本发明提供不含有对环境有害的成分，不产生成为废弃物的淤渣，在金属表面可以析出涂装后的耐腐蚀性优良的表面处理被膜的表面处理用处理液和表面处理方法。本发明提供金属表面处理用处理液，该处理液是用于对选自铁系材料、锌系材料、铝系材料以及镁系材料的金属材料分别单独或2种以上同时进行表面处理的水系表面处理液，其含有5～5000ppm选自锆化合物和钛化合物的1种以上化合物的上述金属元素，还含有0.1～100ppm游离氟离子，且pH为2～6。进而在该处理液中也可以含有钙化合物、镁化合物或锶化合物、硝酸根、含氧酸和/或含氧酸盐、高分子化合物、表面活性剂。使金属材料与上述处理液接触，或在上述处理液中进行电解处理，形成被膜。

Figure 200810184949

The present invention provides a surface treatment solution and a surface treatment method that does not contain environmentally harmful components, does not generate waste sludge, and can deposit a surface treatment film that is excellent in corrosion resistance after coating on a metal surface. The present invention provides a treatment solution for metal surface treatment, the treatment solution is an aqueous surface for surface treatment of metal materials selected from iron-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials, either individually or simultaneously. The treatment liquid contains 5 to 5000 ppm of the above-mentioned metal element selected from one or more compounds selected from zirconium compounds and titanium compounds, further contains 0.1 to 100 ppm of free fluorine ions, and has a pH of 2 to 6. Furthermore, the treatment liquid may contain calcium compounds, magnesium compounds or strontium compounds, nitrates, oxoacids and/or oxoacid salts, polymer compounds, and surfactants. The metal material is brought into contact with the above-mentioned treatment solution, or electrolytically treated in the above-mentioned treatment solution to form a film.

Figure 200810184949

Description

Metal finishing treatment solution and surface treatment method
The application is that to be CN200380105947.9 (international filing date is on December 11st, 2003), denomination of invention be dividing an application that the PCT that enters country's stage of " metal finishing with treatment solution and surface treatment method " applies for to application number.
Technical field
The present invention relates to surface treatment treatment solution and surface treatment method, it is containing ferrous material, zinc series materials, aluminium system and magnesium based material separately or the metal material surface of its structure of 2 kinds to 4 kinds take body of motor vehicle as representative, the surface treatment capsule that can make respectively excellent corrosion resistance after application separately or its 2 kinds to 4 kinds separate out simultaneously.
Background technology
As the method that the surface treatment capsule of excellent corrosion resistance after making application in the metallic surface is separated out, generally use now Zinc Coslettising process or chromating.Zinc Coslettising process can be separated out in the steel such as cold-rolled steel sheet, steel plate galvanized and a part of aluminum alloy surface the tunicle of excellent corrosion resistance.But, carrying out zinc phosphate when processing, can not avoid the generation of byproduct of reaction sludge, and can not fully guarantee rust-preventing characteristic after application to different types of aluminium alloy.Can guarantee to have sufficient performance after application by implementing the chromic salt processing for aluminium alloy.But, the trend of avoiding containing the chromic salt processing that is harmful to 6 valency chromium in treatment solution is arranged in environment regulations now.Therefore as the surface treatment method that does not contain objectionable constituent in treatment solution, invention shown below is disclosed.
For example, proposed to contain the compound of the nitrogen-atoms with lone-pair electron and contain above-claimed cpd and the metallic surface of zirconium compounds with non-chromate coating agent (with reference to JP 2000-204485 communique).The method can obtain not containing erosion resistance and the good surface treatment capsule of adaptation after objectionable constituent 6 valency chromium, application by the coating above-mentioned composition.But, only limit to aluminium alloy as the object metallic substance, and make it form surface treatment capsule by being coated with drying, therefore be difficult to be coated with the complex structure thing that resembles body of motor vehicle and so on.
Therefore, the method (for example can reference: JP 56-136978 communique, Unexamined Patent 8-176841 communique, Unexamined Patent 9-25436 communique, Unexamined Patent 9-31404 communique) of separating out the surface treatment capsule of adaptation and excellent corrosion resistance after application by chemical reaction is disclosed a lot.But no matter which kind of method as the metallic substance of object, only limits to the aluminium alloy of material self excellent corrosion resistance, it is impossible separating out surface treatment capsule on ferrous material or zinc series materials surface.
In addition, disclose with the surface treating composition that contains metal acetylacetonates, water-soluble inorganic titanium compound or water-soluble inorganic zirconium compounds, can separate out the method (with reference to JP 2000-199077 communique) of the surface treatment capsule that erosion resistance and adaptation are good after application.By using the method, applicable metallic substance expands magnesium, magnesium alloy, zinc and the galvanized alloy beyond aluminium alloy to.But the method can not be separated out surface treatment capsule on the ferrous material such as cold-rolled steel sheet surface, can not process simultaneously ferrous material.
And then, propose to use the method for metal processing of Chrome-free application type acidic composition, for example, after the aqueous solution by film component that can form excellent corrosion resistance is coated the metallic surface, need not implement washing step, make the immobilized metal surface treating method of tunicle (with reference to Unexamined Patent 5-195244 communique) by toasting drying.This method generates tunicle without chemical reaction, therefore can implement tunicle in metallic surfaces such as steel plate galvanized, cold-rolled steel sheet and aluminium alloys and process.But with in above-mentioned JP 2000-204485 communique invention disclosed identical, generate tunicle by being coated with drying, therefore be difficult to that the complex structure thing of body of motor vehicle and so on is implemented uniform tunicle and process.
Therefore, adopt prior art can not implement following surface treatment: to use the treatment solution that does not contain environmentally harmful composition, do not produce the sludge of waste, the zinc series materials such as the ferrous material such as the cold-rolled steel sheet of body of motor vehicle and so on and steel plate galvanized and aluminium system and magnesium based material 2 kinds to 4 kinds are processed simultaneously, and implemented erosion resistance and the good surface treatment of adaptation.
Summary of the invention
The objective of the invention is: provide prior art irrealizable, do not contain environmentally harmful composition, do not produce the sludge of waste, can separate out application on ferrous material, zinc series materials, aluminium system and magnesium based material surface after the surface treatment treatment solution of surface treatment capsule of excellent corrosion resistance.Be provided in addition combination as 2 kinds of metallic surfaces to 4 kinds of structures of ferrous material, zinc series materials, aluminium system and the magnesium based material of body of motor vehicle and so on, under identical conditions, the surface treatment of the surface treatment capsule of excellent corrosion resistance after the coating of same composition is gone out with the processing liquation, and provide and use this surface treatment with the surface treatment method for the treatment of solution.
The inventor is to solving the method process lucubrate of above-mentioned problem, and result has been completed unexistent surface treatment treatment solution and surface treatment method in prior art.
Be metal finishing treatment solution of the present invention be for to the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its carry out simultaneously surface-treated water system surface treatment liquid more than 2 kinds, it is characterized by: the above-mentioned metallic element that contains the compound more than a kind of 5～5000ppm selected among zirconium compound and titanium compound, contain in addition 0.1～100ppm free fluorine ion, and pH is 2～6.
With in treatment solution, also can and then contain the compound more than a kind that is selected from calcium cpd, magnesium compound and strontium compound in this surface treatment.This moment, the concentration of these compounds was preferred respectively to these metallic elements: calcium cpd is that 5～100ppm, magnesium compound or strontium compound are 10～5000ppm.Wherein, preferably contain 1000～50000ppm nitrate radical in this treatment solution.Preferably contain in addition and be selected from HClO 3, HBrO 3, HNO 2, HNO 3, HMnO 4, HVO 3, H 2O 2, H 2WO 4And H 2MoO 4And at least a kind of oxygen acid in its esters and/or oxysalt.These surface treatments are with in treatment solution, also can and then contain at least a kind of macromolecular compound that is selected from water-soluble high-molecular compound and water dispersible macromolecular compound, also can contain at least a kind of tensio-active agent that is selected from nonionic surface active agent, aniorfic surfactant and cationic surfactant.
Being characterized as of metal surface treating method of the present invention: the metallic substance that makes chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its contact simultaneously above-mentioned surface treatment treatment solution more than 2 kinds.In this surface treatment method, after metallic substance contacts with treatment solution with surface treatment, wash or do not wash, and then can contact with the acidic aqueous solution of the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium, or also can with contain the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound and contact.
Being characterized as of metal surface treating method of the present invention: the metallic substance that makes chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its more than 2 kinds simultaneously with this metallic substance as negative electrode, carry out electrolysis treatment in above-mentioned surface treatment in surface treatment liquid.In this surface treatment method, metallic substance is after above-mentioned surface treatment is carried out electrolysis treatment in treatment solution, wash or do not wash, and then its acidic aqueous solution with the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium is contacted, or also can make it and contain the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound and contact.
In addition, method of the present invention is that the metallic substance difference without the degreasing purifying treatment of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material is independent or they are more than 2 kinds, simultaneously with contain that to be selected from above-mentioned nonionic be that tensio-active agent, negatively charged ion be tensio-active agent are at least a kind of tensio-active agent of tensio-active agent with positively charged ion surface treatment liquid contact, the skimming treatment and the tunicle that carry out simultaneously the metallic surface form processing.
In addition, being characterized as of metallic substance of the present invention: on the metallic surface of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material, has the surface treatment capsule that contains the metallic element of at least a kind that is selected from titanium and zirconium that is formed by above-mentioned surface treatment method, and the adhesion amount of this surface treatment capsule, convert with above-mentioned metallic element, the Ferrious material material surface is 30mg/m 2Above, zinc is that metal material surface is 20mg/m 2Above, aluminum-based metal material surface is 10mg/m 2Above, magnesium is that metal material surface is 10mg/m 2Above.
The accompanying drawing summary
The orthographic plan for test plate (panel) of Fig. 1 for providing in embodiments of the invention and comparative example.Fig. 2 supplies the front elevation of test plate (panel) for this reason.
Embodiment
The present invention relates to the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its carry out simultaneously surface treatment more than 2 kinds, separate out the technology of the surface treatment capsule of excellent corrosion resistance after application.Wherein, ferrous material refers to the Ferrious materials such as the steel plates such as cold-rolled steel sheet and hot-rolled steel sheet, cast iron and agglomerated material.In addition, zinc series materials refers to die case zinc or contains zinc coating.This contains zinc coating and refers to be plated to by alloy and the inevitable impurity of zinc or zinc and other metals (at least a kind of metals such as nickel, iron, aluminium, manganese, chromium, magnesium, cobalt, lead and antimony), and its method for plating is not limited only to such as molten plating, plating, evaporation etc.The aluminium based material represents as the aluminum alloy plate materials of 5000 line aluminium alloys or 6000 line aluminium alloys and so on or the aluminium diecast alloy take ADC-12 as representative etc. in addition.The magnesium based material refers to adopt the sheet material of magnesium alloy or die-casting material etc.
The present invention is applicable to contain separately a kind of structure of above-mentioned metallic substance or contains 2 kinds to the structure of 4 kinds of above-mentioned metallic substance in structural member in structural member.Contain 2 kinds when using to the structure of 4 kinds of above-mentioned metallic substance in structural member, can carry out simultaneously surface treatment to 2 kinds to 4 kinds metal material surfaces.At this moment, when 2 kinds to 4 kinds metallic substance are carried out surface treatment simultaneously, can be discontiguous state between metal not of the same race, can be also to make by methods of attachment such as welding, bonding, riveteds the contact condition that connects between different metal.
Surface treatment treatment solution of the present invention is the above-mentioned metallic element that contains the compound more than a kind of 5～5000ppm selected among zirconium compound and titanium compound, contains free fluorine ion 0.1～100ppm, and pH is 2～6 treatment solution.Wherein, the zirconium compounds of the present invention's use can be enumerated ZrCl 4, ZrOCl 2, Zr (SO 4) 2, ZrOSO 4, Zr (NO 3) 4, ZrO (NO 3) 2, H 2ZrF 6, H 2ZrF 6Salt, ZrO 2, ZrOBr 2And ZrF 4Deng.Titanium compound can be enumerated TiCl in addition 4, Ti (SO 4) 2, TiOSO 4, Ti (NO 3) 4, TiO (NO 3) 2, TiO 2OC 2O 4, H 2TiF 6, H 2TiF 6Salt, TiO 2And TiF 4Deng.The preferred zirconium compounds that uses in the present invention.
The concentration of the selected among zirconium compound that uses in the present invention and the compound more than a kind of titanium compound is preferably 5～5000ppm, more preferably 10～3000ppm in above-mentioned metallic element (that is, in zirconium and/or titanium).Use surface treatment of the present invention to be zirconium or titanyl compound or oxyhydroxide with the tunicle that treatment solution and surface treatment method obtain, so the compound more than a kind that is selected from above-mentioned zirconium compounds and titanium compound is in the concentration of zirconium and/or titanium during less than 5ppm, because tunicle principal constituent concentration is little, in order to obtain erosion resistance, obtain sufficient adhesion amount in the treatment time when practicality and become difficult.In addition, concentration although can obtain sufficient adhesion amount, does not improve the effect of erosion resistance during greater than 5000ppm on this basis, and is just uneconomical.
Zirconium compounds or titanium compound are more soluble in acidic solution, but unstable in basic solution, easily separate out with zirconium or titanyl compound or oxyhydroxide.Surface treatment of the present invention is 2～6 with the pH for the treatment of solution, and more preferably selecting pH is 3～6.Contact with treatment solution with surface treatment of the present invention at this pH metal to be treated material, cause the solubilizing reaction of metal to be treated material.Then, due to the metal to be treated material dissolves, cause the rising of metal to be treated material contact surface pH, zirconium and titanyl compound or oxyhydroxide are separated out at the metal to be treated material surface as tunicle.
Surface treatment of the present invention makes and wherein has the free fluorine ion with in treatment solution.For the free fluorine ion is existed, add fluorochemical in surface treatment in treatment solution.As the supply source of this free fluorine ion, can enumerate hydrofluoric acid, H 2ZrF 6, H 2ZrF 6Salt, H 2TiF 6, H 2TiF 6Salt, H 2SiF 6, H 2SiF 6Salt, H 2BF 4, H 2BF 4Salt, NaHF 2, KHF 2, NH 4HF 2, NaF, KF and NH 4F etc.The free fluorine ion is improved surface treatment with the effect of zirconium compounds in treatment solution and titanium compound stability.And the free fluorine ion has the metallic substance that promotes as surface treatment object of the present invention: the effect of solubilizing reaction occurs in any one material of ferrous material, zinc series materials, aluminium based material and magnesium based material in acidic solution.Therefore, by adding fluorochemical, the free fluorine ion is existed, surface treatment of the present invention is improved with the stability for the treatment of solution, and also can improve the metal to be treated material reactive.
At first the applicant discloses following invention: to surface treatment composition and the surface treatment treatment solution for the treatment of the metallic surface of containing at least a kind of iron or zinc, use titanium compound or zirconium compounds and fluorochemicals, the ratio A/B of surface treatment molal weight B when in the total molal weight A of above-mentioned metallic element in treatment solution and fluorochemicals, whole fluorine atoms being scaled HF with composition and surface treatment is specified range 0.06～0.18 (WO02/103080).According to the present invention, metallic element concentration, pH, free fluorine ionic concn by regulation titanium compound or zirconium compounds, even outside above-mentioned specified range, also can to the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its carry out simultaneously surface treatment more than 2 kinds.
The reactivity separately of ferrous material, zinc series materials, aluminium system and magnesium based material is different, so prior art can not be carried out surface treatment simultaneously to above-mentioned metallic substance more than 2 kinds.In the present invention, can freely change surface treatment with stability and reactive balance for the treatment of solution by the concentration of regulating the free fluorine ion, therefore can to reactivity different, chosen from Fe based material, zinc series materials, aluminium be and the magnesium based material implement separately at the same time or separately surface treatment more than 2 kinds.
Wherein, the free fluorine ionic concn of indication refers to the fluorinion concentration with commercially available ion electrode mensuration.The free fluorine ionic concn preferred 0.1～100ppm of surface treatment of the present invention in treatment solution, more preferably 2～70ppm.The concentration of free fluorine ion is during higher than 100ppm, although can promote the solubilizing reaction of metal to be treated, but surface treatment is highly stable with zirconium compounds and titanium compound in treatment solution, is difficult to separate out as tunicle even therefore rise also to become at metal to be treated contact surface pH.In addition, during less than 0.1ppm, surface treatment is little to stability and the reactive effect that improves with treatment solution, has lost the meaning that contains the free fluorine ion.
Free fluorine ion of the present invention improves surface treatment with treatment solution stability and reactive effect except bearing, and the dissolving of also bearing by the metal to be treated material stably is kept at surface treatment with in treatment solution with dissolved element.In the zinc phosphate of one of prior art is processed, for example produced sludge owing to being generated as the insoluble salt tertiary iron phosphate from the iron ion of Ferrious material material stripping and phosphoric acid.Even with in treatment solution, also can contain phosphate radical in surface treatment of the present invention in treatment solution, but if the concentration of phosphate radical surpasses 1.0g/L, can produce sludge.Relatively to process the capacity of bath remarkable when many for the treatment capacity of metal to be treated material in addition, in order to make the dissolved element solubilization, also can add mineral acids such as sulfuric acid, hydrochloric acid; The organic acids such as acetic acid, oxalic acid, tartrate, citric acid, succsinic acid, gluconic acid, phthalic acid; But the sequestrant of chelating dissolved element etc. is one kind or two or more.
Surface treatment of the present invention is selected from calcium cpd, magnesium compound and strontium compound more than at least a kind with containing in treatment solution.The present invention by will contain certain specific concentrations zirconium compounds and the free fluorine ionic concn in the aqueous solution of titanium compound be controlled at certain limit, can make 2 kinds to the 4 kinds whiles of chosen from Fe based material, zinc series materials, aluminium system and magnesium based material or carry out separately respectively surface treatment.Wherein, the metallic element that contains in above-mentioned calcium cpd, magnesium compound or strontium compound (calcium, magnesium or strontium) has owing to generating the salt of fluorochemical with fluorine in the aqueous solution effect that the free fluorine ionic concn that makes in the aqueous solution remains on certain value.Due to this effect, even simultaneously various metal to be treated materials are carried out surface treatment, disobey its usage ratio, usually keep certain free fluorine ionic concn, therefore can obtain best tunicle adhesion amount to different metal to be treated materials.
As the calcium cpd that can use in the present invention, magnesium compound or strontium compound, can enumerate oxide compound, oxyhydroxide, muriate, vitriol, nitrate and the carbonate etc. of these metals.In addition, except calcium cpd, magnesium compound or strontium compound, so long as have the compound that keeps the effect of aqueous solution containing fluoride Free Fluoride ionic concn, no matter be inorganics, organism, all can be able to use in the present invention.
The magnesium compound that the present invention uses or the concentration of strontium compound, in above-mentioned metallic element, preferred 10～5000ppm, more preferably 100～3000ppm.For calcium cpd, because the solubleness of Calcium Fluoride (Fluorspan) is very little, in the preferred 5～100ppm of calcium, more preferably 5～50ppm.Wherein, when the concentration ratio higher limit of above-claimed cpd is large, may process the stability of using treatment solution by failure surface, produce the obstacle in operate continuously.In addition, the concentration ratio lower value of above-claimed cpd hour has the worry that reduces tunicle adhesion amount of the present invention especially on ferrous material.
In addition, surface treatment of the present invention is with adding the nitrate radical of 1000～50000ppm, more preferably 1000～30000ppm in treatment solution.Nitrate radical works as oxygenant, has the effect that promotes the tunicle evolution reaction in the present invention, and improves calcium cpd, magnesium compound or strontium compound in the effect of surface treatment with solubleness in treatment solution.Therefore, even the concentration of nitrate radical during less than 1000ppm, also can be separated out the tunicle of excellent corrosion resistance, still, when above-mentioned calcium cpd, magnesium compound or strontium compound concentration are high, may process with treatment solution stability by failure surface.In addition, the concentration of nitrate radical is that 50000ppm is enough, can only be uneconomic even add more nitrate radical.
In addition, can add in treatment solution in surface treatment of the present invention and be selected from HClO 3, HBrO 3, HNO 3, HNO 2, HMnO 4, HVO 3, H 2O 2, H 2WO 4And H 2MoO 4At least a kind of oxygen acid and/or the salt of these oxygen acid.Oxygen acid or its salt work to treated material as oxygenant, promote tunicle of the present invention to form reaction.Interpolation concentration to above-mentioned oxygen acid or these oxygen acid salts does not have particular determination, can give full play to the effect as oxygenant under the addition of 10～5000ppm left and right.
And then, can add at least a kind of macromolecular compound that is selected from water-soluble high-molecular compound and water dispersible macromolecular compound in surface treatment of the present invention in treatment solution.Use surface treatment of the present invention to make the surface-treated metallic substance that sufficient erosion resistance be arranged with treatment solution, but when further requiring the function such as oilness, select to add and the corresponding macromolecular compound of desired function, also can change the physical property of tunicle.Can use as acrylic acids such as multipolymer, ethene and (methyl) vinylformic acid of polyvinyl alcohol, poly-(methyl) vinylformic acid, vinylformic acid and methacrylic acid or (methyl) acrylate as above-mentioned water-soluble high-molecular compound and water dispersible macromolecular compound is the multipolymer of monomer; The macromolecular compound of commonly using in the metal finishing such as the multipolymer of ethene and vinyl acetate, polyurethane(s), amino modified resol, vibrin, epoxy resin.
When using surface treatment of the present invention with treatment solution, the metallic surface to be processed, well-established law only has the metal to be treated material that skimming treatment, purifying treatment are carried out in the surface to contact with treatment solution with surface treatment.Thus, separate out the oxide compound of the metallic element that contains selected among zirconium and titanium and/or the tunicle of oxyhydroxide at metal material surface, and form adaptation and the good surface treatment capsule layer of erosion resistance.This contact is processed and can be used the either method such as spraying plating processing, dip treating and flow coat processing, and this contact method does not affect performance.Above-mentioned metal hydroxides will obtain its pure oxyhydroxide, is being chemically difficult, usually the form of above-mentioned metal oxide band water of hydration is also brought into the category of oxyhydroxide.Therefore, above-mentioned metal hydroxides finally becomes oxide compound through heating.Think the structure of the surface treatment capsule layer in the present invention, when dry under normal temperature or low temperature after the enforcement surface treatment, be that oxide compound and oxyhydroxide mix the state that exists, and implement after surface treatment when at high temperature dry, only become as acidulants or mostly be the state of oxide compound.
Surface treatment in the present invention does not have particular determination with the working conditions for the treatment of solution.The reactivity of surface treatment liquid of the present invention can freely regulate and control with the zirconium compounds in treatment solution or concentration and the free fluorine ionic concn of titanium compound by changing surface treatment.Therefore treatment temp and treatment time by making up with processing the reactivity of bathing, may change arbitrarily.
In addition, to be selected from nonionic be that tensio-active agent, negatively charged ion are that tensio-active agent and positively charged ion are at least a kind of tensio-active agent of tensio-active agent and are used for surface treatment with adding in treatment solution in above-mentioned surface treatment.When adopting this surface treatment with treatment solution, metallic substance to be carried out surface treatment, the metal to be treated material also can form good tunicle without skimming treatment in advance, purification.That is to say, this surface treatment can be used as with treatment solution the surface treatment agent that doubles as degreasing and uses.
In addition, when adopting surface treatment of the present invention to carry out metal finishing with treatment solution, also can adopt take the metal to be treated material as negative electrode the method for carrying out electrolysis in treatment solution in surface treatment.Wherein, if carry out electrolysis treatment with the metal to be treated material as negative electrode, hydrogen reduction reaction occurs and the pH rising on the negative electrode contact surface.Follow the rising of pH, the zirconium compounds on the negative electrode contact surface and/or the stability of titanium compound reduce, and separate out surface treatment capsule with oxide compound or aqueous hydroxide.
In addition, after metal to be treated material and surface treatment contact with treatment solution or after surface treatment is carried out electrolysis treatment in treatment solution, wash or do not wash, by with the acidic aqueous solution of the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium, or contact with containing the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound, and then can improve effect of the present invention.
The surface treatment capsule layer that obtains by the present invention is film and shown good coating performance, but according to the condition of surface of metal to be treated material, the surface treatment capsule layer may have trickle defect part.Therefore, by making it the acidic aqueous solution with the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium, or contact with containing the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound, further improve erosion resistance thereby coat above-mentioned fine defects part.
The above-mentioned compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium does not have particular determination, can use oxide compound, oxyhydroxide, fluorochemical, fluorinated complex, muriate, nitrate, nitric acid oxonium salt, vitriol, sulfuric acid oxonium salt, carbonate, carbonic acid oxonium salt, phosphoric acid salt, phosphoric acid oxonium salt, oxalate, oxalic acid oxonium salt and the organometallic compound etc. that hold facile above-mentioned metallic element.In addition, contain the pH of acidic aqueous solution of above-mentioned metallic element preferred 2～6, the acid such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid and organic acid, or the alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, an alkali metal salt, ammonium salt and amine are regulated.
In addition, as at least a kind of macromolecular compound that is selected from above-mentioned water-soluble high-molecular compound and water dispersible macromolecular compound, can use acrylic acids such as polyvinyl alcohol, the multipolymer, ethene and (methyl) vinylformic acid that gather (methyl) vinylformic acid, vinylformic acid and methacrylic acid or (methyl) acrylate is the multipolymer of monomer; The multipolymer of ethene and vinyl acetate, polyurethane(s), amino modified resol, vibrin, epoxy resin, tannin and Weibull and salt and phytinic acid etc.
The present invention is provided with the oxide compound of the metallic element that contains selected among zirconium or titanium and/or the surface treatment capsule layer of oxyhydroxide on the metal to be treated material surface, therefore can improve the erosion resistance of metallic substance tremendously.Wherein, the oxide compound of above-mentioned metallic element and oxyhydroxide have the chemically stable character that is difficult to by acid or alkali erosion.In the environment of actual corroding metal, the pH that the anode portion of metal dissolving occurs reduces, and causes that the pH of the negative pole part that reduction reaction occurs rises.Therefore, the surface treatment capsule that acid resistance and alkali resistance are poor, dissolving under corrosive atmosphere and lose its effect.The principal constituent of the surface treatment capsule layer in the present invention is difficult to be corroded by acid or alkali, therefore also can keep good effect under corrosive atmosphere.
In addition, the oxide compound of above-mentioned metallic element and oxyhydroxide owing to having formed the reticulated structure of being got involved by metal and oxygen, have formed very good barrier tunicle.The corrosion condition of metallic substance according to environment for use and difference, but is generally aerobic-type corrosion under water and oxygen existence, and this corrosion speed is because the existence of the compositions such as muriate is promoted.Wherein, surface treatment capsule layer of the present invention has screen effect to the composition of water, oxygen and promotion corrosion, therefore can bring into play good erosion resistance.
At this, utilize above-mentioned screen effect, in order to improve the erosion resistance of the ferrous materials such as cold-rolled steel sheet, hot-rolled steel sheet, cast iron and agglomerated material, with above-mentioned metallic element conversion 30mg/m 2Above adhesion amount is necessary, preferred 40mg/m 2Above adhesion amount, more preferably 50mg/m 2Above adhesion amount.In addition, the erosion resistance that is in order to improve the zinc such as zinc, steel plate galvanized, alloy galvanized steel plate is with above-mentioned metallic element conversion 20mg/m 2Above adhesion amount is necessary, preferred 30mg/m 2Above adhesion amount.And then, in order to improve the erosion resistance of the aluminium based materials such as aluminium casting and aluminium alloy plate, with above-mentioned metallic element conversion 10mg/m 2Above adhesion amount is necessary, preferred 20mg/m 2Above adhesion amount.In addition, the erosion resistance that is in order to improve the magnesium such as magnesium alloy plate and magnesium foundry goods is with above-mentioned metallic element conversion 10mg/m 2Above adhesion amount is necessary, preferred 20mg/m 2Above adhesion amount.The upper limit to adhesion amount does not have particular determination, but if adhesion amount surpasses 1g/m 2, easily generating sludge on surface treatment capsule, the operation that obtains uniform tunicle becomes difficult.Therefore, the equal preferred 800mg/m of the adhesion amount upper limit of ferrous material, zinc series materials and aluminium based material 2But not 1g/m 2
Embodiment
Enumerate embodiment and comparative example when as follows, illustrate the effect that treatment solution and surface treatment method are used in surface treatment of the present invention.And the treated material that uses in embodiment, grease-removing agent and coating are selected arbitrarily in the commercially available material, and the non-limiting surface treatment of the present invention practical use for the treatment of solution and surface treatment method.
[for test plate (panel)]
Use cold-rolled steel sheet, hot-dip galvanized steel sheet, aluminium alloy and magnesium alloy plate as the test plate (panel) that supplies of embodiment and comparative example.This brevity code and detail for test plate (panel) is expressed as follows.Adopt when estimating the outward appearance after surface treatment SPC, GA are connected with Al state that 3 kinds of metallic substance connect with spot welding for test plate (panel).Adopt separately respectively SPC, GA, Al, Mg for test plate (panel) when estimating the adhesion amount of surface treatment capsule layer, with the state of SPC, GA being connected spot welding connect with Al3 kind metallic substance for test plate (panel).When estimating coating performance, adopt SPC, GA are connected with Al3 kind metallic substance state that spot welding connects for test plate (panel), implement the series of experiments that surface treatment, coating, coating performance are estimated.Fig. 1 is that SPC, GA are connected the orthographic plan for test plate (panel) that 3 kinds of metallic substance connect with spot welding with Al, and Fig. 2 is its front elevation.1 expression spot welding position.
SPC (cold-rolled steel sheet: JIS-G-3141)
GA (two sides alloy galvanized steel plate: plating amount 45g/m 2)
Al (aluminium alloy plate: 6000 line aluminium alloys)
Mg (magnesium alloy plate: JIS-H-4201)
[treatment process]
The treatment process of embodiment, comparative example is as follows.
Embodiment 1-4, embodiment 7 and comparative example 1-4: alkali degreasing → washing → formation tunicle processing → washing → pure water is washed → drying
Embodiment 5: alkali degreasing → washing → formation electrolysis tunicle processing → washing → pure water is washed → drying
Embodiment 6: form tunicle processing (dual-purpose skimming treatment) → washing → pure water and wash → drying
Embodiment 8: alkali degreasing → washing → formation tunicle processing → washing → aftertreatment → pure water is washed → drying
Embodiment 9: form tunicle processing (dual-purpose skimming treatment) → washing → aftertreatment → pure water and wash → drying
Comparative example 5: alkali degreasing → washing → surface adjustment → zinc phosphate processing → washing → pure water is washed → drying
In above-mentioned, it is all with FINE CLEANERL4460 (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to 2%, 40 ℃ with tap water, sprayed 120 seconds to processed plate that embodiment, comparative example are carried out alkali degreasing.It is all at room temperature to spray 30 seconds to processed plate that embodiment, comparative example are carried out that washing after tunicle is processed and pure water wash.
Embodiment 1
Use Zircosol ZN reagent and nitric acid, preparation zirconium concentration is the aqueous solution of 200ppm.After heating under 45 ℃, using sodium hydroxide reagent and hydrofluoric acid is 3.0 with pH regulator with this solution, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 1ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 50ppm with whole fluorinion concentrations in treatment solution.
Impregnated in above-mentioned surface treatment treatment solution 120 seconds with what implement washing after degreasing for test plate (panel), carry out surface treatment.
Embodiment 2
Use Zircosol ZN reagent, magnesium nitrate reagent and strontium nitrate reagent, preparation zirconium concentration is that 100ppm, magnesium density are that 5000ppm, strontium concentration are that 2000ppm, nitrate radical are the aqueous solution of 28470ppm.After this solution was heated to 50 ℃, using ammoniacal liquor reagent and hydrofluoric acid to regulate pH was 4.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 80ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 2000ppm with whole fluorinion concentrations in treatment solution.
Impregnated in above-mentioned surface treatment treatment solution 60 seconds with what implement washing after degreasing for test plate (panel), carry out surface treatment.
Embodiment 3
Use hexafluoro zirconate (IV) aqueous solution, titanium sulfate (IV) aqueous solution, calcium sulfate reagent and nitric acid, preparation zirconium concentration is that 1000ppm, titanium concentration are that 2000ppm, calcium concn are that 5ppm, nitrate radical are the aqueous solution of 1000ppm.After this solution was heated to 40 ℃, using potassium hydroxide reagent and hydrofluoric acid to regulate pH was 5.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 25ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 2250ppm with whole fluorinion concentrations in treatment solution.
Impregnated in above-mentioned surface treatment treatment solution 90 seconds with what implement washing after degreasing for test plate (panel), carry out surface treatment.
Embodiment 4
Use hexafluoro metatitanic acid (IV) aqueous solution, strontium nitrate reagent and Sodium Nitrite reagent, preparation titanium concentration is that 5000ppm, strontium concentration are that 5000ppm, nitrate radical are that 7080ppm, nitrite anions concentration are the aqueous solution of 40ppm.After this solution was heated to 35 ℃, using trolamine reagent and hydrofluoric acid to regulate pH was 4.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 10ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 11900ppm with whole fluorinion concentrations in treatment solution.
By nozzle, above-mentioned surface treatment is sprayed to upper 120 second of confession test plate (panel) of implementing washing after degreasing with treatment solution, carries out surface treatment.
Embodiment 5
Use Zircosol ZN reagent, hexafluoro metatitanic acid (IV) aqueous solution, magnesium nitrate reagent and sodium chlorate reagent, preparation zirconium concentration is that 5ppm, titanium concentration are that 5ppm, magnesium density are that 100ppm, nitrate radical are that 30520ppm, chlorate anions are the aqueous solution of 100ppm.After this solution was heated to 30 ℃, using ammoniacal liquor reagent and hydrofluoric acid to regulate pH was 6.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 0.5ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 12ppm with whole fluorinion concentrations in treatment solution.
Supply test plate (panel) as negative electrode with what implement after degreasing to wash, anode uses carbon dioxide process carbon electrode, at above-mentioned surface treatment 5A/dm in treatment solution 2Electrolytic condition under, surface treatment is carried out in electrolysis 5 seconds.
Embodiment 6
Use Zircosol ZN reagent, magnesium oxide reagent, nitric acid and aquae hydrogenii dioxidi reagent, preparation zirconium concentration is that 150ppm, magnesium density are that 10ppm, nitrate radical are that 5200ppm, hydrogen peroxide are the aqueous solution of 10ppm.After this solution was heated to 50 ℃, using ammoniacal liquor reagent and hydrofluoric acid to regulate pH was 5.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 50ppm, and then add the non-ionic surfactant polyoxyethylene nonylplenyl ether (ethyleneoxide addition mole number: 12 moles) of 2g/L, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 170ppm with whole fluorinion concentrations in treatment solution.
Do not carry out skimming treatment, by nozzle, above-mentioned surface treatment is sprayed to upper 90 second of confession test plate (panel) that is coated with oil condition with treatment solution, carry out surface treatment in the time of degreasing.
Embodiment 7
Use titanium sulfate (IV) aqueous solution, nitrocalcite reagent, magnesium nitrate reagent and potassium permanganate, preparation titanium concentration is that 100ppm, calcium concn are that 50ppm, magnesium density are that 5000ppm, nitrate radical are that 25660ppm, permanganic acid are the aqueous solution of 10ppm.And then add in this aqueous solution water-soluble propenoic-acids macromolecular compound (ジ ユ リ マ-AC-10L: Japanese pure medicine company limited system) make solid minute concentration be 1% and be heated to 50 ℃ after, using sodium hydroxide reagent and hydrofluoric acid to regulate pH is 3.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 95ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 2000ppm with whole fluorinion concentrations in treatment solution.
Impregnated in above-mentioned surface treatment treatment solution 60 seconds with what implement washing after skimming treatment for test plate (panel), carry out surface treatment.
Embodiment 8
Preparation take solid divide densitometer water-soluble propenoic-acids macromolecular compound (ジ ユ リ マ-AC-10L: Japanese pure medicine company limited system) as 1%, Phosphoric Acid counts the aqueous solution of 2g/L with phosphate radical.After this solution was heated to 40 ℃, using ammoniacal liquor reagent to regulate pH was 4.5, the preparation aftertreatment fluid.To impregnated in above-mentioned aftertreatment fluid 30 seconds for test plate (panel) by what embodiment 5 surface treatments had implemented to form tunicle and washing, carry out aftertreatment.
Embodiment 9
Use hexafluoro zirconate (IV) aqueous solution and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES reagent, preparation zirconium concentration is that 50ppm, cobalt concentration are the aqueous solution of 50ppm, and then after the above-mentioned aqueous solution was heated to 40 ℃, using ammoniacal liquor reagent to regulate pH was 5.0, the preparation aftertreatment fluid.To impregnated in above-mentioned aftertreatment fluid 30 seconds for test plate (panel) by what embodiment 6 surface treatments had implemented to form tunicle and washing, carry out aftertreatment.
Comparative example 1
Use Zircosol ZN reagent, magnesium nitrate reagent and nitric acid, preparation zirconium concentration is that 500ppm, magnesium density are that 1000ppm, nitrate radical are the aqueous solution of 6780ppm.After this solution was heated to 45 ℃, using sodium hydroxide reagent to regulate pH was 4.0, with this as the surface treatment treatment solution.With commercially available fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of the above-mentioned surface treatment of mensuration in treatment solution, consequently 0ppm.
Impregnated in above-mentioned surface treatment treatment solution 120 seconds with what implement washing after degreasing for test plate (panel), carry out surface treatment.
Comparative example 2
Use titanium sulfate (IV) aqueous solution, preparation titanium concentration is the aqueous solution of 2000ppm.After this solution was heated to 50 ℃, using ammoniacal liquor reagent and hydrofluoric acid was 3.5 with pH regulator, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 400ppm, with this as the surface treatment treatment solution.
Impregnated in above-mentioned surface treatment treatment solution 90 second for test plate (panel) with implementing after degreasing after washing, carry out surface treatment.
Comparative example 3
(Network ロ ミ Star Network Network ロ メ-ト) reagent treatment ア Le Network ロ system 713 (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) makes) is diluted to 3.6% with tap water, and then regulates full acidity, free acidity centered by the goods catalogue value with commercially available chromium-chromic salt.
Impregnated in the above-mentioned chromic salt treatment solution that is heated to 35 ℃ 60 seconds with what implement washing after degreasing for test plate (panel), carry out chromic salt and process.
Comparative example 4
With commercially available non-chromate reagent treatment パ Le コ-ト 3756 (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to 2% with tap water, and then regulate full acidity, free acidity centered by the goods catalogue value.Impregnated in the above-mentioned non-chromate treatment solution that is heated to 40 ℃ 60 seconds with what implement washing after degreasing for test plate (panel), carry out non-chromate and process.
Comparative example 5
under room temperature, by nozzle with the surface adjust treatment agent プ レ パ レ Application ZN (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to tap water 0.1% liquid spray implement after the degreasing washing for test plate (panel) after upper 30 second, be impregnated in the zinc phosphate tunicle is separated out, wherein, this treatment solution is prepared as follows: with パ Le ボ Application De L3020 (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to 4.8% with tap water, and then interpolation is in the sodium hydrogen fluoride reagent of fluorine 200ppm, then regulate full acidity centered by the goods catalogue value, free acidity, make the zinc phosphate chemical synthesis treatment liquid of 42 ℃.
[evaluation of surface treatment capsule]
The outward appearance for test plate (panel) after visual assessment embodiment and comparative example surface treatment.Its result is as shown in table 1.(System 3270 to use fluorescent x-ray analyzer; Electrical industry of science (strain) system) measure the adhesion amount of surface treatment capsule layer.Its result is as shown in table 2 and table 3.In addition, the adhesion amount of surface treatment capsule layer is that each metallic substance is not engaged and the situation (without engaging) processed respectively, and merges with spot weld the situation (joint is arranged) of processing and measure.
Table 1
Figure G2008101849496D00161
The ocular estimate result of the surface treatment capsule that obtains in table 1 expression embodiment and comparative example.For whole metallic substance kinds of test plate (panel), embodiment can obtain uniform tunicle for all.And the spot welding part for test plate (panel) that uses is in an embodiment also observed the situation that surface treatment capsule is separated out.To this, for whole test plate (panel)s that supplies, all do not separate out uniform tunicle in comparative example.Particularly comparative example 3,4 and 5, do not separate out tunicle fully at spot welding part.In addition, although comparative example 5 is the zinc phosphate treatment solutions when processing simultaneously cold-rolled steel sheet, steel plate galvanized and aluminium alloy, but as this test, by welding under the condition that each testing plate engages, the exposed portions serve of the metallic substance base substrate of open country (ス ケ) has appearred on cold-rolled steel sheet being called as.
Table 2
Figure G2008101849496D00171
Table 3
Figure G2008101849496D00172
The measurement result of the surface treatment capsule adhesion amount that obtains in table 2 and table 3 expression embodiment and comparative example.In an embodiment, for whole metallic substance kinds of test plate (panel), can obtain the adhesion amount of target for all.In addition, the surface treatment capsule adhesion amount in embodiment is certain, does not rely on for having or not that test plate (panel) engages.Yet in comparative example, shown by tunicle ocular estimate result, for whole test plate (panel)s that supplies, all can not separate out uniform tunicle.
[evaluation of coating performance]
(coating performance is estimated the making of plate)
Coating performance for Evaluation operation example and comparative example surface treatment plate is coated with according to following operation: cation electrodeposition electrophoresis painting dressing → pure water washes → cures → and the middle level application → cure → the top layer application → cure.Cation electrodeposition electrophoresis painting dressing, middle level application, top layer application are as follows.
The cation electrodeposition electrophoresis painting dressing: the epoxy resin cation electrophoretic coating (エ レ Network ロ Application 9400: Northwest pigment (strain) system), voltage 200V, thickness 20 μ m cured 20 minutes at 175 ℃.
The middle level application: alkyd amino is that (ア ミ ラ Star Network TP-37 ash: Northwest pigment (strain) system), spray, thickness 35 μ m cured 20 minutes at 140 ℃ coating.
The top layer application: alkyd amino is that (TM-13 is white for ア ミ ラ Star Network: Northwest pigment (strain) system), spray, thickness 35 μ m cured 20 minutes at 140 ℃ coating.
(coating performance evaluation)
Carry out the evaluation of embodiment and comparative example coating performance.Its result is as shown in table 4 and table 5.Assessment item and mark are as follows.Filming when in addition, electrophoretic painting finishes is called that electrophoresis is filmed, filming when the top layer application finishes is called 3 and is coated with coating film.
1. SST: salt spray testing (electrophoresis is filmed)
2. SDT: salt warm water test (electrophoresis is filmed)
3. ADH:1 adaptation of 1st (3 are coated with coating film)
4. 2nd ADH: water-fast 2 adaptations (3 are coated with coating film)
SST: with sharp cutting knife with the crosscut of electrophoretic painting plate, to this electrophoretic painting plate spraying 5% salt solution 840 hours (take JIS-Z-2371 as standard).After spraying finishes, measure the maximum swelling amplitude of crosscut section both sides.
SDT: the electrophoretic painting plate be impregnated in the NaCl aqueous solution of the 5wt% that is warming up to 50 ℃ 840 hours.After dipping finishes, peel off with adhesive tape with whole faces of the testing plate of tap water washing → Air drying, that films on each metallic substance of range estimation judgement peels off area.
1st ADH: be coated with 3 checker that cuts out 100 2mm intervals on coating film with sharp cutting knife.The checker part is peeled off with fiber band, and number goes out the tessellated number of peeling off.
2nd ADH: be coated with in the deionized water that the coating film plate impregnated in 40 ℃ 240 hours with 3.Cut out the checker at 100 2mm intervals after dipping with sharp cutting knife.The checker part is peeled off with fiber band, and number goes out the tessellated number of peeling off.
Table 4
Figure G2008101849496D00191
The coating performance evaluation result that table 4 expression electrophoresis is filmed.The test plate (panel)s that supply whole in embodiment show good erosion resistance.Yet in comparative example 1, owing to not containing free fluorion in surface treatment fully in treatment solution, therefore can not fully separate out surface treatment capsule, corrosion-resistant.In addition, in comparative example 2, due to high with treatment solution Free Fluoride ionic concn in surface treatment, so the tunicle adhesion amount on SPC is especially little, and result is corrosion-resistant.Although embodiment 5 and 6 shows the coating performance good than comparative example, compares with other embodiment, the erosion resistance after electrophoretic painting is slightly poor.But, as shown in embodiment 8 and 9, by implementing aftertreatment, further improve erosion resistance.
Comparative example 3 is that aluminium alloy is aluminium alloy non-chromate treatment agents with chromic salt treatment agent, comparative example 4, so the excellent corrosion resistance of Al, but other the erosion resistance for test plate (panel) is obviously poor than embodiment.Comparative example 5 now as cation electrodeposition electrophoresis painting dressing undercoat, is that normally used zinc phosphate is processed.But, as this test, even in comparative example 5, by welding under the condition that each testing plate engages, to compare with embodiment, its result is also poor.
Table 5
Table 5 expression 3 is coated with the adaptation evaluation result of coating film plate.The test plate (panel)s that supply whole in embodiment show good adaptation.Even 1st ADH also shows good result in comparative example, and for 2nd ADH, the erosion resistance of filming with electrophoresis is identical, the test plate (panel) that supplies for whole does not reach the standard that shows good adaptation.In addition, in comparative example 5, during the processing after surface treatment is bathed, the by product sludge when producing the zinc phosphate processing.But, in an embodiment, all do not find to produce sludge in any standard.
Above result shows, the surface treatment of the application of the invention product need not change to process and bathe and treatment condition with treatment solution and surface treatment method, and treatment S PC, GA and Al simultaneously can separate out the surface treatment capsule of adaptation and excellent corrosion resistance.And then the application of the invention, can separate out the surface treatment capsule of excellent corrosion resistance on weld part.In addition, surface treatment method of the present invention only makes the metal to be treated material contact with treatment solution with surface treatment and gets final product, and therefore as in the bag inside configuration, at the position that does not wish mixing effect, surface treatment capsule is separated out seek to improve erosion resistance.
Industrial applicability
Surface treatment according to the present invention is with treatment solution and the surface treatment method that uses this treatment solution, can can not be that realize, that do not contain environmentally harmful composition during processing bathes in prior art, do not produce sludge, contain separately at the same time or separately on the metallic surface of 2 kinds to 4 kinds of ferrous material, zinc series materials, aluminium system and magnesium based material, separate out the surface treatment capsule of excellent corrosion resistance after application.In addition, adjust operation even do not carry out the surface of metal to be treated material, also can separate out surface treatment capsule, in this case, can shorten treatment process, save the space.

Claims (8)

1. the surface treatment treatment solution of metallic substance of the same race not, this treatment solution is to carry out simultaneously surface-treated water system surface treatment liquid for the metallic substance not of the same race more than 2 kinds to chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material, it is characterized by:
(1) contain the compound more than a kind of selected among zirconium compound and titanium compound, its concentration is counted 5～5000ppm with zirconium and/or titanium;
(2) contain 0.1～100ppm free fluorine ion,
(3) contain the compound more than a kind that is selected from calcium cpd, magnesium compound and strontium compound, the concentration of above-mentioned calcium cpd, magnesium compound and strontium compound, in calcium, magnesium and/or strontium, be 10～5000ppm when being 5～50ppm, magnesium compound or strontium compound during calcium cpd
(4) contain 1000～50000ppm nitrate radical,
(5) contain and be selected from HNO 2, HNO 2Salt and H 2O 2In at least a kind, and
(6) pH is 3～6.
2. the surface treatment treatment solution of not metallic substance of the same race as claimed in claim 1, wherein, engage between the various metals of above-mentioned not metallic substance of the same race or contact.
3. the surface treatment treatment solution of not metallic substance of the same race as claimed in claim 1, this treatment solution and then contain at least a kind of macromolecular compound that is selected from water-soluble high-molecular compound and water dispersible macromolecular compound.
4. the surface treatment treatment solution of not metallic substance of the same race as described in claim 1 or 3, this treatment solution and then contain at least a kind of tensio-active agent that is selected from nonionic surface active agent, aniorfic surfactant and cationic surfactant.
5. the surface treatment method of metallic substance of the same race not, this treatment process is that the metallic substance not of the same race more than 2 kinds in chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material is contacted simultaneously with following water system surface treatment liquid, described water system surface treatment liquid
(1) contain the compound more than a kind of selected among zirconium compound and titanium compound, its concentration is counted 5～5000ppm with zirconium and/or titanium;
(2) contain 0.1～100ppm free fluorine ion,
(3) contain the compound more than a kind that is selected from calcium cpd, magnesium compound and strontium compound, the concentration of above-mentioned calcium cpd, magnesium compound and strontium compound, in calcium, magnesium and/or strontium, be 10～5000ppm when being 5～50ppm, magnesium compound or strontium compound during calcium cpd
(4) contain 1000～50000ppm nitrate radical,
(5) contain and be selected from HNO 2, HNO 2Salt and H 2O 2In at least a kind, and
(6) pH is 3～6.
6. the surface treatment method of not metallic substance of the same race as claimed in claim 5, it is characterized by: after metallic substance is contacted with treatment solution with surface treatment, wash or do not wash, and then it is contacted with the acidic aqueous solution that contains the compound that is selected from a kind of element in cobalt, nickel, tin, copper, titanium and zirconium at least.
7. the surface treatment method of not metallic substance of the same race as claimed in claim 5, it is characterized by: after metallic substance is contacted with treatment solution with surface treatment, washing or do not wash, and then make it and contain the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound and contact.
8. metallic substance, it is characterized by: be that metallic substance, zinc are that metallic substance, aluminum-based metal material and magnesium are at least 2 kinds of metal material surfaces not of the same race of metallic substance at chosen from Fe, has the surface treatment capsule that is selected from the metallic element of at least a kind of titanium and zirconium by the described surface treatment method of claim 5～7 any one containing of forming, and the adhesion amount of this surface treatment capsule, in the situation that Ferrious material material, for the surface treatment capsule amount, be 30mg/m as zirconium and/or titanium 2Above, in the situation that zinc is metallic substance, for the surface treatment capsule amount, be 20mg/m as zirconium and/or titanium 2Above, in the situation that the aluminum-based metal material for the surface treatment capsule amount, is 10mg/m as zirconium and/or titanium 2Above, in the situation that magnesium is metallic substance, for the surface treatment capsule amount, be 10mg/m as zirconium and/or titanium 2Above.
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CX01 Expiry of patent term