CN102257178B - Surface treating agent for metallic materials - Google Patents

Surface treating agent for metallic materials Download PDF

Info

Publication number
CN102257178B
CN102257178B CN200880132453.2A CN200880132453A CN102257178B CN 102257178 B CN102257178 B CN 102257178B CN 200880132453 A CN200880132453 A CN 200880132453A CN 102257178 B CN102257178 B CN 102257178B
Authority
CN
China
Prior art keywords
mentioned
metallic
treating agent
compound
metallic materials
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200880132453.2A
Other languages
Chinese (zh)
Other versions
CN102257178A (en
Inventor
内田淳一
水野贤辅
佐藤世一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Publication of CN102257178A publication Critical patent/CN102257178A/en
Application granted granted Critical
Publication of CN102257178B publication Critical patent/CN102257178B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C23C22/73—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
    • C23C22/74—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 for obtaining burned-in conversion coatings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • C23C22/07—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 phosphates
    • 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
    • C23C22/34—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
    • C23C22/36—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 containing also phosphates
    • C23C22/362—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 containing also phosphates containing also zinc cations
    • 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
    • C23C22/42—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 phosphates
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

Disclosed is a surface treating agent for metallic materials that has various properties such as corrosion resistance and overcoating properties and, when used in coating-type surface treatment, particularly can form a film , which has excellent adhesion to the surface of metallic materials, and can fix, within the film, a component capable of functioning as a corrosion inhibitor for metallic materials. The surface treating agent for metallic materials comprises a silicic acid compound (A), an organoalkoxysilane (B), a metallic compound (C) containing at least one metal element selected from the group consisting of Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr, and Zn, at least one compound (D) selected from the group consisting of phosphoric acid compounds and fluoro compounds, water (E), and an alcohol (F) produced upon hydrolysis of the organoalkoxysilan (B). The molar concentration (mol/L) of the alcohol (F) in the treating agent has been regulated in a predetermined range.

Description

Surface treating agent for metallic materials
Technical field
The present invention relates to surface treating agent for metallic materials, use surface treatment method and the tunicate surface-treated metal material of tool of this surface treating agent for metallic materials.
Background technology
In order to obtain erosion resistance or coating, can implement surface treatment to metal species material.That is,, by surface treatment, it is important obtaining following effect: even if suppress corrosion of metal or do not make it film to peel off or film and peel off the corrosion that this part also can not occur when applying.In the past, as the surface treatment of metal species material, carried out making the phosphatizing of crystallization of metal-salt of phosphoric acid or the chromic salt that formation contains chromic tunicle to process.
In phosphatizing, first, metallic substance is contacted with the aqueous solution that contains phosphoric acid and metal ion.At this moment, metal dissolves in acid, and by this solubilizing reaction, hydrogen is consumed on the interface of metallic substance, therefore produces pH and raises.Because this pH raises, the metal-salt of the phosphoric acid that cannot moltenly deposit is separated out on the surface of metallic substance, forms phosphate coating.Because phosphate coating is separated out after the dissolving of metal material surface, therefore very good with the adhesivity of metallic substance.And, because the set of the crystallization by trickle forms tunicle, therefore by the anchor effect (anchor effect) of the concavo-convex generation by trickle, also good with the coated adhesivity of filming.So, be as the base treatment surface treatment that be still widely used so far, good applying.
But, owing to being, so that contacting with the acidic aqueous solution that contains phosphoric acid, metal produces solubilizing reaction as initial, so-called response type surface treatment, therefore, there is the problem of the composition change that causes the treatment solution that contains phosphoric acid because metallic substance kind is different.In addition, due to the phosphoric acid salt that cannot separate out on the surface of metallic substance, can swim in treatment solution as sludge (sludge), therefore be necessary to be removed.In addition, be also necessary suitably to change the contact conditions (temperature, time etc.) of the aqueous solution and metallic substance, and, also there is the problem that needs to carry out washing step (generation waste water) after surface treatment.In addition, reactive as also inapplicable in the material of stainless steel and so on to lacking.
In chromic salt is processed, also there is the reaction type same with phosphoric acid salt, after painting solution, only carry out dry application type chromic salt processing and be widely known by the people.It is to be coated on by containing the chromic aqueous solution the easy method being only dried after metal material surface that application type chromic salt is processed.Therefore,, owing to not needing washing step after surface treatment, form and do not produce the closed system of waste water, therefore be widely adopted in the surface treatment of coiled sheet (sheet coil).In addition, application type chromic salt tunicle has and in basic tunicle skeleton, has kept the form of the sexavalent chrome (chromic acid) of solubility take chromic high molecular, due to the tunicle screen effect on trivalent chromium basis and the oxygenizement (passivation, self-repair function) of sexavalent chrome generation, can give the erosion resistance that metallic substance is good.In addition, while using as the base treatment applying, by Ni being carried out to micro-displacement plating tunicle is become is difficult to peel off as its pre-treatment, be well-known.One of its reason, can enumerate: the adhesivity that has improved chromic salt tunicle and metallic surface by this displacement plating.
Surface-treated perfect condition as metallic substance is: with the good adhesion of metal material surface, the material that is high molecular by film component, and, in this tunicle, there is the corrosion inhibitor of solubility, formation can be by its long-term tunicle of preserving.In application type chromic salt is processed, can form the tunicle with characteristic as above.
But, by application type chromic salt, to process the tunicle forming and contain sexavalent chrome, this sexavalent chrome, by the stripping with contacting of moisture, therefore considers to have the tendency of keeping someone at a respectful distance from the viewpoint of environment aspect, security.So, carried out the various sexavalent chromes that can suppress from the research and development of chromic salt tunicle stripping.
Just, recently, chromic existence itself becomes and is out of favour, thereby has carried out the exploitation that more not chromyl non-chromate is processed.
As non-chromate, process, in patent documentation 1, disclose the steel plate that forms tunicle with the vanadium compound of P-compound, Si compound and tetravalence.But, use this technology, the adhesivity with metal material surface can not be fully guaranteed, and also sufficient erosion resistance cannot be obtained.
In patent documentation 2, disclose that to contain silane coupling agent, specific resin, F be 4 above metal complexs, and the treatment solution of metallic compound (Mn, Co, Zn, Mg, Ni, Ti, V, Zr).But, use this technology, the adhesivity with metal material surface can not be fully guaranteed, and also sufficient erosion resistance cannot be obtained.
In patent documentation 3, disclose by colloidal silicon-dioxide, organoalkoxysilane and the vinyl monomer with ethene unsaturated group being carried out to the water dispersible thing of core/shelly composite particles that the operation of polymerization obtains.But in this particle more than 80% is colloidal silicon-dioxide.This technology is for this particle-stabilised being blended in to the technology of resin, even also cannot form tunicle with the direct use of this state, and also cannot obtaining erosion resistance.
In patent documentation 4, the technology of using the composition that contains silane and metallo-chelate is disclosed.Metallo-chelate is taken on the effect of dissolved metal ions (particularly positively charged ion state), plays the effect of being combined with metal material surface simultaneously.But, in this technology, due to metal ion is carried out to chelating, form the form of easy dissolved metal ions, so result is fully to suppress their stripping, cannot obtain long-term erosion resistance.
In patent documentation 5, the treatment solution that contains silane coupling agent 0.01～100g/L, silicon-dioxide 0.05～100g/L, Zr0.01～50g/L and/or Ti0.01～50g/L, the compound 0.01～100g/L that contains thiocarbonyl, acrylic resin 0.1～100g/L is disclosed.This technology has good adhesivity, so coating is good, but erosion resistance when applying is insufficient.And, through aftertreatment fluid after a while, can there is gelation, therefore cannot be in industrial use.
In patent documentation 6, the technology of using the polyurethane resin, silane coupling agent, silicon-dioxide and the flakey silicon-dioxide that contain carboxyl is disclosed.
In patent documentation 7, the technology of using polyurethane resin, silane coupling agent and silicon-dioxide is disclosed.Disclosed technology in patent documentation 6 and 7, cannot fully guarantee the adhesivity with metal material surface.In addition, owing to cannot making silicon-dioxide fully immobilization in tunicle, therefore cannot obtain sufficient erosion resistance.
In patent documentation 8, disclose lower floor and formed the tunicle that contains organic resin and silane coupling agent, the organic resin tunicle that thiocarbonyl is contained on upper strata.This technology relates to 2 layers of lower floor in processing, by the combination with upper strata, has reached first object.Therefore as independent tunicle, still cannot obtain adhesivity and erosion resistance with metallic substance.
In patent documentation 9, the technology of use vanadium compound and Zr, Ti, Mo, W, Mn, Ce is disclosed.But the adhesivity of formed tunicle and metallic substance is insufficient in this technology, in addition, also cannot suppress the stripping of metallic compound.
In patent documentation 10, the technology of using silane coupling agent, silica dioxide gel and water-based organic resin is disclosed.In this technology, make silane coupling agent be combined with silica sphere, therefore can make silica composition immobilization, but cannot suppress the stripping of metallic compound.
As mentioned above, all methods all cannot obtain replacing the surface treated steel plate of chromic salt tunicle, strongly need to develop a kind of surface treatment agent: can comprehensively meet all characteristics such as erosion resistance and outer coating, particularly can improve formed tunicle and metallic substance adhesivity, can manufacture the corroded surface that can suppress metallic substance and process steel plate.
Patent documentation 1: TOHKEMY 2005-48199 communique
Patent documentation 2: TOHKEMY 2005-120469 communique
Patent documentation 3: No. 3818689 specification sheets of Japanese Patent
Patent documentation 4: Japanese Unexamined Patent Application Publication 2006-519307 communique
Patent documentation 5: TOHKEMY 2001-316845 communique
Patent documentation 6: TOHKEMY 2005-178213 communique
Patent documentation 7: TOHKEMY 2005-200757 communique
Patent documentation 8: No. 3722658 specification sheetss of Japanese Patent
Patent documentation 9: TOHKEMY 2002-30460 communique
Patent documentation 10: TOHKEMY 2001-98215 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide surface treating agent for metallic materials and use the surface treatment method for the treatment of agent for this metallic substance, in the tunicle that described surface treating agent for metallic materials forms in the surface treatment of using application type, there is all characteristics such as erosion resistance, outer coating, the good adhesion of formed tunicle and metal material surface particularly, composition immobilization in tunicle that can make the corrosion inhibitor as metallic substance play a role.
Solve the means of problem
The character of people of the present invention based on organoalkoxysilane, the result of carrying out deep research, finds the compound that contains regulation by uses and has controlled the treatment agent by the amount of the alcohol of the hydrolysis generation of organoalkoxysilane, can solve above-mentioned problem.
That is, the invention provides following (1)～(9).
(1) surface treating agent for metallic materials, it is the surface treating agent for metallic materials that contains following (A)～(F):
Silicate compound (A);
Organoalkoxysilane (B);
Containing the metallic compound (C) that is selected from least a kind of metallic element in Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and Zn;
Be selected from the compound of at least a kind (D) in phosphate cpd and fluorine cpd;
Water (E); With
The alcohol (F) being generated by the hydrolysis of above-mentioned organoalkoxysilane (B),
And make volumetric molar concentration (the mol/L) (C of above-mentioned alcohol (F) in treatment agent f1), with above-mentioned organoalkoxysilane (B) in contain the hydrolysis of whole alkoxyl group time the alcohol that generates volumetric molar concentration (the mol/L) (C in treatment agent f2) ratio (C f1/ C f2) be adjusted into 0.05～0.9 scope.
(2) surface treating agent for metallic materials described in (1), the scope that wherein mass ratio (C/F) of above-mentioned alcohol (F) and above-mentioned metallic compound (C) is 0.01～50.
(3) surface treating agent for metallic materials described in (1) or (2), wherein above-mentioned alcohol (F) is 0.01～25 with the mass ratio (D/F) of above-claimed cpd (D).
(4) surface treating agent for metallic materials described in any one of (1)～(3), wherein above-mentioned silicate compound (A) is 0.01～3.0 with the mass ratio (A/B) of above-mentioned organoalkoxysilane (B);
The total quality (A+B) of above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B) is 0.01～2.0 with the mass ratio of above-mentioned metallic compound (C) (C/ (A+B));
The total quality (A+B) of above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B) is 0.01～1.5 with the mass ratio of above-claimed cpd (D) (D/ (A+B)).
(5) surface treating agent for metallic materials described in any one of (1)～(4), wherein above-mentioned organoalkoxysilane (B) has amino and/or epoxy group(ing).
(6) surface treating agent for metallic materials described in any one of (1)～(5), wherein further contains the compound of at least a kind (G) being selected from water-soluble polymer and water system emulsifying resins.
(7) surface treating agent for metallic materials described in (6), wherein the total quality (A+B) of the above-mentioned silicate compound (A) in treatment agent and above-mentioned organoalkoxysilane (B) and the mass ratio of above-claimed cpd (G) (G/ (A+B)) are 0.01～0.3.
(8) surface treatment method of metallic substance, its be on metal material surface coating (1)～(7) any one described in surface treating agent for metallic materials, heat drying forms tunicle amount and counts 2～1000mg/m with Si adhesion amount on above-mentioned metal material surface 2tunicle.
(9) surface-treated metal material, it is to use on that the surface treatment method of the metallic substance described in (8) obtains and surface to have tunicle.
Invention effect
The surface treatment method that the invention provides surface treating agent for metallic materials and use this surface treating agent for metallic materials, in the tunicle that described surface treating agent for metallic materials forms in the surface treatment of using application type, there is all characteristics such as good erosion resistance, outer coating, the good adhesion of formed tunicle and metal material surface particularly, composition immobilization in tunicle that can make the corrosion inhibitor as metallic substance play a role.
Embodiment
Below, to surface treating agent for metallic materials of the present invention and use the surface treatment method of this surface treating agent for metallic materials to describe.
First, surface treating agent for metallic materials is elaborated.
< surface treating agent for metallic materials >
Surface treating agent for metallic materials of the present invention is the surface treating agent for metallic materials that contains following (A)～(F): silicate compound (A); Organoalkoxysilane (B); Containing the metallic compound (C) that is selected from least a kind of metallic element in Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and Zn; Be selected from the compound (D) in phosphate cpd and fluorine cpd; Water (E) and the alcohol (F) being generated by the hydrolysis of above-mentioned organoalkoxysilane (B).And, make volumetric molar concentration (the mol/L) (C of alcohol (F) in treatment agent f1), with organoalkoxysilane (B) in contain the hydrolysis of whole alkoxyl group time the alcohol that generates volumetric molar concentration (the mol/L) (C in treatment agent f2) ratio (C f1/ C f2) be adjusted into 0.05～0.9 scope.
First, to forming the various compositions of surface treating agent for metallic materials, describe.
< silicate compound (A) >
In surface treating agent for metallic materials of the present invention, contain silicate compound (A).By using silicate compound, can form all well behaved tunicles such as erosion resistance, outer coating, thermotolerance, weldability, continuous processibility.
Silicate compound is to using silicon and oxygen as the material of main composition composition, and to its kind, there is no particular limitation.For example, can enumerate: the alkaline silicates such as water glass, potassium silicate, lithium silicate, the colloid silica or the liquid phase silica that use ion exchange method to remove sodium, potassium or lithium and use the methods such as gelation to obtain from these silicate, the aerosil that silicon chlorides is made in combustion synthesis in air oxidation is dispersed in water the dispersion of formation, and the hydrolyzate of organoalkoxysilane etc.Wherein, better from the viewpoint of the performance of gained tunicle, preferred colloid silica and liquid phase silica.
For example, as liquid phase silica, can enumerate: Snowtex C, Snowtex CS, Snowtex CM, Snowtex O, Snowtex OS, Snowtex OM, Snowtex NS, Snowtex N, Snowtex NM, Snowtex S, Snowtex20, Snowtex30, Snowtex40, ア デ ラ イ ト AT-20N, ア デ ラ イ ト AT-20A, ア デ ラ イ ト AT-20Q etc., can enumerate in addition: the Snowtex UP that is processed into special chain shape, Snowtex OUP, Snowtex PS-S, Snowtex PS-SO, Snowtex PS-M, Snowtex PS-MO, Snowtex PS-L, Snowtex PS-LO etc.
In addition, as the micropartical silicon-dioxide that is called as aerosil, can enumerate: AEROSIL50, AEROSIL130, AEROSIL200, AEROSIL300, AEROSIL380, AEROSIL TT600, AEROSIL MOX80, AEROSIL MOX170 etc., also can be dispersed in water use by them.
To the content of the silicate compound in surface treating agent for metallic materials (A), there is no particular limitation, but from better viewpoint considerations such as the erosion resistance of gained tunicle, outer coating, thermotolerance, weldability, continuous processibilities, with respect to the total solid composition in treatment agent, be preferably 0.1～70 quality %, more preferably 1～50 quality %.In addition, the total solid composition in treatment agent, refers to the solid composition that forms tunicle described later, does not comprise solvent etc.
< organoalkoxysilane (B) >
In surface treating agent for metallic materials of the present invention, contain organoalkoxysilane (B).By by organoalkoxysilane (B) and above-mentioned silicate compound (A) use, can form the tunicle of the three-dimensional structure with the generation of being combined with the siloxanes of organoalkoxysilane (B) by silicate compound (A).Thus, can infer the erosion resistance of gained tunicle, outer coating, thermotolerance, weldability, continuously processibility, ground connection (earth) property, with the raisings such as adhesivity of metal material surface.
To the organoalkoxysilane using in the present invention, there is no particular limitation, for example, can enumerate: tetramethoxy-silicane, tetraethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, Union carbide A-162, Cyclohexyl Methyl Dimethoxysilane, n-hexyl Trimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, decyl Trimethoxy silane, octadecyl Trimethoxy silane, octadecyltriethoxy silane, isobutyl-Trimethoxy silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl-triethoxysilicane, N-β (amino-ethyl) gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, γ-sulfydryl propyl group methyl dimethoxysilane, to styryl Trimethoxy silane, γ-acryloxy propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-uride propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, γ-isocyanic ester propyl-triethoxysilicane, γ-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-(vinyl benzyl amine)-beta-aminoethyl-gamma-amino propyl trimethoxy silicane etc.
Wherein, from the viewpoint of easy adjustment determining alcohol, preferably there is the trialkoxy silane of the alkoxyl group of 3mol activity.
In addition, organoalkoxysilane (B) preferably has the functional group of at least a kind being selected from amino and epoxy group(ing).Infer that organoalkoxysilane (B), by having these functional groups, further promotes above-mentioned silicate compound (A) to be combined with the siloxanes of above-mentioned organoalkoxysilane (B), and then form the three-dimensional cross-linked tunicle with densification.Thus, the composition that tunicle can play a role the corrosion inhibitor as metallic substance is more fixed, and further improves erosion resistance.
A kind of as the suitable embodiment of organoalkoxysilane, can enumerate the following compound representing with general formula (I).
[changing 1]
General formula (I)
Figure GDA00003265479900091
In general formula (I), X represents to be selected from any the functional group in epoxy group(ing), amino, sulfydryl, acryloxy, uride base, isocyanate group and vinyl.L represents linking group or the singly-bound of divalence.R represents alkyl or hydrogen atom.N represents 1～3 integer.
In general formula (I), X represents to be selected from any the functional group in epoxy group(ing), amino, sulfydryl, acryloxy, uride base, isocyanate group and vinyl.Wherein, preferred epoxy group(ing), amino.In addition, n is 2 when above, and X can be the same or different.
In general formula (I), L represents linking group or the singly-bound of divalence.
The linking group representing as L, for example, can enumerate: alkylidene group (preferably carbonatoms 1～20) ,-O-,-S-, arylidene ,-CO-,-NH-,-SO 2-,-COO-,-CONH-or by their combination group.Wherein, preferred alkylidene group.When L represents singly-bound, refer to that the X of general formula (I) is directly connected with Si (Siliciumatom).In addition, n is 2 when above, and L can be the same or different.
In general formula (I), R represents respectively alkyl (preferably carbonatoms 1～4) or hydrogen atom independently.
In general formula (I), n represents 1～3 integer.Wherein preferably 1.
In addition, organoalkoxysilane (B) can be also the hydrolyzate after the part hydrolysis of alkoxyl group.
Content to the organoalkoxysilane in surface treating agent for metallic materials (B), there is no particular limitation, but from the erosion resistance of gained tunicle, outer coating, thermotolerance, weldability, continuously processibility, ground connection property, consider with the better viewpoint of adhesivity of metal material surface, with respect to the total solid composition in treatment agent, be preferably 0.1～70 quality %, more preferably 1～50 quality %.
< metallic compound (C) >
In surface treating agent for metallic materials of the present invention, contain metallic compound (C), described metallic compound (C) contains at least a kind of metallic element being selected from Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and Zn.By by metallic compound (C) and phosphate cpd described later and/or fluorine cpd use, can in tunicle, form the salt of insoluble.Infer that the salt of this insoluble is by promoting the crosslinking reaction of above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B), and then form and to there is fine and close cancellated tunicle, metallic compound (C) easily immobilization in tunicle that the corrosion inhibitor as metallic substance is played a role.
Metallic compound (C) is if contain above-mentioned metallic element, and there is no particular limitation, for example, can enumerate: the nitrate that contains above-mentioned metal, acetate, phosphoric acid salt, vitriol, ammonium salt, fluorochemical etc.
As the object lesson of metallic compound (C), as the metallic compound containing Zr, for example, can enumerate: zirconium nitrate, Zircosol ZN, acetic acid zirconium, zirconium sulfate, zirconium carbonate ammonium, potassium zirconium carbonate, sodium zirconium carbonate and zirconium colloidal sol etc.In addition, also can enumerate zirconic acid and the salt thereof that the aqueous solution of water-soluble zirconates is carried out to the neutralization of ion-exchange or alkali and make.
As the metallic compound that contains Ti, for example, can enumerate: titanyl sulfate, titanyl nitrate, Titanium Nitrate, chlorination oxygen titanium, titanium chloride, titanium oxide sol, titanium oxide, oxalic acid potassium titanate, lactic acid titanium, four isopropyl oxygen titaniums, titanium acetylacetone, di-isopropyl titanium bis-acetylacetonate etc.In addition, also can enumerate the aqueous solution of titanyl sulfate is carried out to metatitanic acid, the titanic hydroxide obtaining with alkali neutralization and their salt that thermal hydrolysis obtains.
As the metallic compound that contains Co, for example, can enumerate: rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous carbonate, cobaltous phosphate, cobalt chloride, cobalt oxide, cobaltous hydroxide etc.
As the metallic compound that contains Fe, for example, can enumerate: ferric sulfate, iron nitrate, iron(ic) chloride, tertiary iron phosphate, ferric oxide, ironic hydroxide, iron powder etc.
As the metallic compound that contains V, for example, can enumerate: vanadium pentoxide, ammonium meta-vanadate, sodium metavanadate, vanadylic chloride, three vanadium oxides, vanadium dioxide, vanadylic sulfate, methyl ethyl diketone vanadyl, vanadium acetylacetonate, vanadium trichloride, molybdenum vanadium phosphate, Vanadosulfuric acid etc.
As the metallic compound that contains Ce, for example, can enumerate: cerous nitrate, cerous acetate, Cerium II Chloride, cerium colloidal sol etc.
As the metallic compound that contains Mo, for example, can enumerate: ammonium molybdate, Sodium orthomolybdate, potassium molybdate, ammonium phosphomolybdate etc.
As the metallic compound that contains Mn, for example, can enumerate: potassium permanganate, ammonium permanganate, sodium permanganate, permanganate, manganous sulfate, manganous nitrate, manganese oxide, manganous carbonate, Manganous chloride tetrahydrate, manganous phosphate etc.
As the metallic compound that contains Mg, for example, can enumerate: magnesium sulfate, magnesium nitrate, magnesiumcarbonate, trimagnesium phosphate, magnesium chloride, magnesium oxide, magnesium hydroxide etc.
As the metallic compound that contains Al, for example, can enumerate: aluminum oxide, aluminium hydroxide, Tai-Ace S 150, aluminum nitrate, aluminum phosphate, aluminum chloride etc.
As the metallic compound that contains Ni, for example, can enumerate: nickel oxide, nickel hydroxide, single nickel salt, nickelous nitrate, nickelous phosphate, nickelous chloride etc.
As the metallic compound that contains Ca, for example, can enumerate: calcium oxide, calcium hydroxide, calcium sulfate, nitrocalcite, calcium phosphate, calcium chloride etc.
As the metallic compound that contains W, for example, can enumerate: ammonium metawolframate, metatungstic acid sodium, metatungstic acid potassium, para-tungstic acid, ammonium paratungstate, sodium paratungstate etc.
As the metallic compound that contains Nb, for example, can enumerate: niobium oxalate, niobium oxides, niobium colloidal sol etc.
As the metallic compound that contains Cr, for example, can enumerate the chromium of trivalent, can enumerate: chromium sulphate, chromium nitrate, chromium chloride, chromium hydroxide, chromic oxide, Plessy's green etc.
As the metallic compound that contains Zn, for example, can enumerate: zinc oxide, zinc hydroxide, zinc sulfate, zinc nitrate, zinc chloride, zinc phosphate, acetyl zinc etc., in addition, because zinc is amphoteric metal, therefore can also enumerate the sodium zincate that generated by basic side chain (ア Le カ リ サ イ De, alkali side), potassium zincate etc.
Wherein, from the viewpoint of improving the effective of erosion resistance, more preferably contain the metallic compound being selected from containing Zr, V, Al or Zn, and in their salt more than at least a kind.
Content to the metallic compound in surface treating agent for metallic materials (C), there is no particular limitation, but consider from the better viewpoint of erosion resistance, ground connection property of gained tunicle, with respect to the total solid composition in treatment agent, be preferably 0.05～50 quality %, more preferably 0.1～30 quality %.
< phosphate cpd and/or fluorine cpd >
In surface treating agent for metallic materials of the present invention, contain the compound of at least a kind (D) being selected from phosphate cpd and fluorine cpd.As mentioned above, phosphate cpd and/or fluorine cpd, by metallizing thing (C) use, can promote the crosslinking reaction of above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B).And, phosphate cpd and/or fluorine cpd, can etching as the metal of body material, form the tunicle of being combined with substrate material surface, therefore infer erosion resistance, and the adhesivity of metal material surface that can further improve tunicle.
As phosphate cpd, can enumerate: the ammonium salt of phosphoric acid, metal-salt (as metal, for example, can be enumerated: basic metal, V, Co, W, Ti, Zr, Al, Zn.); The condensed phosphoric acids such as tetra-sodium; Phytic acid, there is the organic phospho acid compound of phosphonate group (ホ ス ホ Application base), phosphino-(ホ ス Off イ Application base) etc.For example, can enumerate: phosphoric acid, metaphosphoric acid, tetra-sodium, ortho-phosphoric acid, triphosphoric acid, four phosphoric acid and their ammonium salt, aluminium salt, magnesium salts, cyano group trimethylene phosphonic, cyano group Sanya propyl phosphonous acid, cyano group diethyl methylene phosphonic acid, cyanopropyl dimethylene phosphonic acids methane, 1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid etc.
Phosphate cpd can separately or be used in combination two or more.
As fluorine cpd, for example, can enumerate: hydrofluoric acid, its ammonium salt, its an alkali metal salt; The metal fluorides such as Tin tetrafluoride., manganous fluoride, ferrous fluoride, ferric fluoride, aluminum fluoride, zinc fluoride, vanadium fluoride; The acid fluoride of fluorine oxide, acetylfluoride, benzoyl fluoride etc.
Preferred applicable use has the material that is selected from least one element in Ti, Zr, Hf, Si, Al and B, particularly, for example, can enumerate: to (TiF 6) 2-, (ZrF 6) 2-, (HfF 6) 2-, (SiF 6) 2-, (AlF 6) 3-, (BF 4oH) -deng negatively charged ion, carry out the complex compound that hydrogen atom is 1～3 atom addition, the ammonium salt of these negatively charged ion, the metal-salt of these negatively charged ion etc.More specifically, can enumerate: hydrofluotitanic acid, fluorine zirconic acid, silicofluoric acid etc.
Fluorine cpd can separately or be used in combination two or more.
Total content to the compound in surface treating agent for metallic materials (D), there is no particular limitation, but consider from the better viewpoint of erosion resistance of gained tunicle, with respect to the total solid composition in treatment agent, be preferably 0.01～40 quality %, more preferably 0.1～30 quality %.
< water (E) >
In surface treating agent for metallic materials of the present invention, contain water (E).
To the content of the water in surface treating agent for metallic materials, there is no particular limitation, but consider from the easier viewpoint of processing for the treatment of agent, with respect to treatment agent total amount, is preferably 30～99 quality %, more preferably 40～95 quality %.
< alcohol (F) >
In surface treating agent for metallic materials of the present invention, contain the alcohol (F) by the hydrolysis generation of above-mentioned organoalkoxysilane (B).By thering is the hydrolysis reaction of the organoalkoxysilane (B) of alkoxyl group, generate alcohol.
As the kind of alcohol, depend on the kind of alkoxyl group of the organoalkoxysilane of use, for example, can enumerate: methyl alcohol, ethanol, propyl alcohol etc.
Adjust volumetric molar concentration (the mol/L) (C of the alcohol (F) containing in surface treating agent for metallic materials of the present invention f1), volumetric molar concentration (the mol/L) (C of the alcohol in the treatment agent that the alkoxyl group that makes to contain in itself and organoalkoxysilane obtains while being all hydrolyzed f2) relation meet C f1/ C f2=0.05～0.9, preferably meet 0.1～0.8.
Above-mentioned molar concentration rate (C f1/ C f2) during less than 0.05, because silicate compound (A) and organoalkoxysilane (B) are combined the effect of necessary reactive functional groups and are disappeared from organoalkoxysilane (B) forming siloxanes, so the reduction of the adhesivity of the erosion resistance of tunicle, outer coating, formed tunicle and metal material surface.In addition, molar concentration rate (C f1/ C f2) surpass at 0.9 o'clock, because the effect of reactive functional groups is high, so form siloxanes combination between organoalkoxysilane (B), the composition that the corrosion inhibitor as metallic substance is played a role can not immobilization in tunicle.
To adjusting volumetric molar concentration (the mol/L) (C of the alcohol of the alkoxyl group that derives from organoalkoxysilane (B) f1) method there is no particular limitation, for example, can enumerate: in organoalkoxysilane, mixed in the solution of silanol condensation catalyst and water, controlled the method that the alcohol amount generating as by product is adjusted concentration; And remove the method etc. that the alcohol and water generating as by product is adjusted concentration.
In addition, the measuring method of determining alcohol is not particularly limited, can enumerates: vapor-phase chromatography or ion chromatography isochrome spectrometry, and nucleus magnetic resonance optical spectroscopy etc.
In addition, the above-mentioned metallic compound (C) in surface treating agent for metallic materials of the present invention preferably meets 0.01～50 with the mass ratio (C/F) of alcohol (F), more preferably meets 0.1～40.If in above-mentioned scope, the composition immobilization in tunicle that easily makes the corrosion inhibitor as metallic substance play a role, therefore from the viewpoint of the erosion resistance of gained tunicle, outer coating, better with the adhesivity of metal material surface, be preferred.
And the compound in surface treating agent for metallic materials of the present invention (D) preferably meets 0.01～25 with the mass ratio (D/F) of alcohol (F), more preferably meets 0.1～20, further preferably meets 0.1～15.If in above-mentioned scope, the composition immobilization in tunicle that easily makes the corrosion inhibitor as metallic substance play a role, therefore from the viewpoint of the erosion resistance of gained tunicle, outer coating, better with the adhesivity of metal material surface, be preferred.
The mass ratio (A/B) of the silicate compound in surface treating agent for metallic materials of the present invention (A) and organoalkoxysilane (B), is preferably 0.01～3.0, and more preferably 0.05～2.5.During less than 0.01, the situation that has continuous processibility to reduce, surpasses at 3.0 o'clock, has the situation of the adhesivity reduction of formed tunicle and metal material surface.
The total quality (A+B) of the silicate compound in surface treating agent for metallic materials of the present invention (A) and organoalkoxysilane (B), the mass ratio of metallizing thing (C) (C/ (A+B)) is preferably 0.01～2.0, and more preferably 0.05～1.5.During less than 0.01, the situation that tunicate erosion resistance reduces, surpasses at 2.0 o'clock, when the erosion resistance of tunicle reduces, also has the situation of the adhesivity reduction of tunicle and metal material surface.
The total quality (A+B) of the silicate compound in surface treating agent for metallic materials of the present invention (A) and organoalkoxysilane (B), be preferably 0.01～1.5 with the mass ratio (D/ (A+B)) of compound (D), more preferably 0.05～1.0.During less than 0.01, the situation that tunicate erosion resistance reduces, over 1.5 o'clock, when the adhesivity of erosion resistance, ground connection property, tunicle and the metal material surface of tunicle reduces, make in addition the composition playing a role as the corrosion inhibitor in metallic substance in tunicle, be difficult to immobilized situation.
Other additive of < >
In surface treating agent for metallic materials of the present invention, as required, also can contain various additives.Below, the additive containing is described.
< water-soluble polymer and/or water system emulsifying resins >
In surface treating agent for metallic materials of the present invention, also can contain the compound of at least a kind (G) being selected from water-soluble polymer and/or water system emulsifying resins.By adding this compound (G), can improve anti-finger printing or the oilness of tunicle.
Kind as water-soluble polymer and/or water system emulsifying resins, there is no particular limitation, for example, can enumerate: the water-soluble polymers such as polyacrylic acid, polymethyl acrylic acid, polyacrylamide, polyvinyl alcohol, the acrylic resin of the form being dispersed in water, polyurethane resin, epoxy resin, vibrin, polyamide resin, polyolefin resin, ethylene-propylene acid resin, poly-butyral resin, poly-acetal resin, fluoro-resin etc.
To the content of the compound in surface treating agent for metallic materials (G), there is no particular limitation.
Wherein, the total quality (A+B) of the silicate compound in treatment agent (A) and organoalkoxysilane (B) and the mass ratio of compound (G) (G/ (A+B)), be preferably 0.01～0.3, and more preferably 0.05～0.25.During less than 0.01, the situation that tunicate anti-finger printing or oilness do not improve, surpasses at 0.3 o'clock, the situation that tunicate erosion resistance and thermotolerance reduce.
In surface treating agent for metallic materials of the present invention, also can contain silanol condensation catalyst.As silanol condensation catalyst, there is no particular limitation, for example, can enumerate: formic acid, acetic acid, butyric acid, oxalic acid, succsinic acid, lactic acid, L-AA, tartrate, Citric Acid, DL-oxysuccinic acid, propanedioic acid, toxilic acid, phthalic acid, cyano group trimethylene phosphonic, cyano group Sanya propyl phosphonous acid, cyano group diethyl methylene phosphonic acid, cyanopropyl dimethylene phosphonic acids methane, methane-1-hydroxyl-1, 1-di 2 ethylhexyl phosphonic acid, ethane-1-hydroxyl-1, 1-di 2 ethylhexyl phosphonic acid, propane-1-hydroxyl-1, 1-di 2 ethylhexyl phosphonic acid, sulfonic acid, Phenylsulfonic acid, ketimine compound, aldimine compound, enamine compound,
Figure GDA00003265479900161
oxazolidine compound, aminoalkyl group organoalkoxysilane etc.
In surface treating agent for metallic materials of the present invention, also can contain the rust-inhibiting additive containing N.As their example, can enumerate: quadrol, triethylamine, urea, guanidine etc.
In surface treating agent for metallic materials of the present invention, as required, also can be containing being useful on the additive (lubricant) that improves oilness.By improving the oilness of tunicle, to preventing that tunicle from producing flaw, reducing the damage that adds tunicle in man-hour and play effective effect.
As additive, can enumerate: the solid lubricants such as polyethylene wax, oxidized polyethlene wax, its chlorinated polypropylene wax, carnauba wax, paraffin, montanin wax, rice wax, TEFLON (registered trademark) wax, dithiocarbonic anhydride, graphite.Can use one kind or two or more in these solid lubricants.
In surface treating agent for metallic materials of the present invention, as required, also can add water-soluble solvent, tensio-active agent, defoamer, flow agent (leveling agent), fungi-proofing rust-preventive agent, tinting material of alcohol, ketone, cellosolve class etc.Thus, can improve drying property, coating outward appearance, operability, Storage, the aesthetic property for the treatment of agent.But it is important adding in the degree of the quality obtaining in they do not damage the present invention, accounts at the most several quality % in treatment solution.
The pH of surface treating agent for metallic materials of the present invention, if can make stable treatment solution, can be that acidity can be also alkalescence.But, during pH less than 0.5, there is reactivity with metallic substance to uprise and the situation of degraded appearance, surpass at 14 o'clock, the stability of metallic compound reduces, and the stability for the treatment of agent self reduces, and is not therefore preferred.
In surface treating agent for metallic materials of the present invention, as required, can also contain solvent beyond above-mentioned water (for example, alcohol etc.).
To the preparation method of surface treating agent for metallic materials of the present invention, there is no particular limitation.For example, can use the stirrers such as mixing agitator by silicate compound (A), organoalkoxysilane (B), metallic compound (C), phosphate cpd and/or fluorine cpd (D) and water (E) are carried out fully mixing and manufacturing.
< surface treatment method >
To using the surface treatment method of surface treating agent for metallic materials of the present invention, there is no particular limitation, but preferred following surface treatment method: above-mentioned surface treating agent for metallic materials is coated on metal material surface, heat drying forms tunicle amount and counts 2～1000mg/m with Si adhesion amount on metal material surface 2tunicle.
Below, this surface treatment method is described.
Before coating, as required, for reaching the oil content removed on metal material surface or the object of spot, also can implement pre-treatment to metallic substance.Metallic substance, take that antirust to be coated with antirust oil condition more as object.In addition, even be coated with oil condition without slushing oil, in operation, also have the oil content that adheres to or spot etc.By implementing pre-treatment, will on metal material surface, clean, use surface treating agent for metallic materials of the present invention easily that metal material surface is wetting equably.In addition,, when there is no oil content or spot etc., with surface treating agent for metallic materials of the present invention, material surface being soaked equably, pretreatment procedure is not special needs.
In addition, as the method for pre-treatment, there is no particular limitation, can enumerate: the methods such as hot water cleaning, solvent cleaning, alkali degreasing cleaning.
As the metallic substance using, there is no particular limitation, can enumerate: hot-dip galvanized steel sheet (GI), make alloy galvanized steel plate (GA), molten zinc plating Zn-5%Al alloy steel plate (GF), molten zinc plating-55% aluminium alloy steel plate (GL), electrogalvanizing steel plate (EG), electro-galvanizing-Ni alloy steel plate (Zn-Ni) after its alloying, aluminize, aluminium sheet.In addition, also can use the iron plate of not implementing plating.
Method as surface treating agent for metallic materials to the coating of metallic substance, can, according to the selections such as the shape of processed metallic substance the suitableeest suitable method, can enumerate: rolling method, pickling process, spraying coating method etc.
More specifically, for example, if tabular, use rolling method, or by treatment solution to metallic substance spray then carry out roll-in or under high pressure blowing adjust glue spread.If products formed can be set forth in dipping in treatment solution and take out, according to circumstances with pressurized air, blow away remaining treatment solution and adjust glue spread etc.
Heating temperature as when being formed on filming on metal material surface and being dried, is preferably 40～250 ℃, more preferably 60～200 ℃, is particularly preferably 60～180 ℃.If 40 ℃ of less thaies, moisture that can the residual main solvent as treatment agent of the present invention, metallic compound cannot be fixed, or the erosion resistance of tunicle can reduce.If surpass 250 ℃, in tunicle, easily there is crack, the situation that has erosion resistance to reduce.To heating and drying method, there is no particular limitation, uses hot blast, induction heater, infrared rays, near infrared ray etc. to heat, and treatment agent is dry.
In addition, heat-up time, can be according to the selections such as the kind of the compound in the surface treating agent for metallic materials using the suitableeest suitable condition.Wherein, from the viewpoint of productivity etc., preferably 0.1～60 second, more preferably 1～30 second.
The tunicle amount of adjusting the tunicle forming on metal material surface, makes it in Si adhesion amount, is 2～1000mg/m 2, be preferably 10～800mg/m 2, more preferably 20～500mg/m 2.Not enough 2mg/m 2time, there is the situation that cannot obtain sufficient effect of the present invention, surpass 1000mg/m 2time, can be saturated except effect, unfavorable economically, sometimes also can cause because of situation the reduction of erosion resistance.
On the tunicle that the surface treatment method stated in the use forms, being formed with organic polymeric membrane, to make dried thickness be 0.1～3.0 μ m, can give higher erosion resistance or anti-finger printing, oilness.This organic high molecular layer, can be used the resin emulsion such as known vinylformic acid, urethanum, epoxy, or use after adding therein silicon-dioxide, rust-preventive agent, lubricant, UV light absorber, pigment.
By using above-mentioned surface treating agent for metallic materials to carry out the surface treatment of metallic substance, can form there is erosion resistance, outer coating, thermotolerance, weldability, processibility, ground connection property, anti-finger printing continuously, the good adhesion of formed tunicle and metal material surface particularly, composition immobilized surface treatment capsule in tunicle that can make the corrosion inhibitor as metallic substance play a role.
The surface-treated metal material that uses surface treating agent for metallic materials of the present invention to obtain, goes for various uses.For example, can enumerate: the material using in the various fields such as building, electric, automobile etc.
Embodiment
Below, by embodiment and comparative example, effect of the present invention is described, the present embodiment only illustrates an example of the present invention, does not limit the present invention.
1. the making method of test board
(1) for examination material (material)
Use following commercially available material as supplying examination material.
(i) electrogalvanizing steel plate (EG): thickness of slab 0.8mm, weight per unit area=20/20 (g/m 2)
(ii) hot-dip galvanized steel sheet (GI): thickness of slab 0.8mm, weight per unit area=60/60 (g/m 2)
(iii) alloy galvanized steel plate (GA): thickness of slab 0.8mm, weight per unit area=40/40 (g/m 2)
In addition, weight per unit area represents the weight per unit area on the interarea of each steel plate.For example, the situation of electrogalvanizing steel plate, is 20/20 (g/m 2), refer on the two sides of steel plate and there is respectively 20g/m 2plating.
(2) pre-treatment (cleaning)
As the making method of test film, first use Japanese PARKERIZING to manufacture パ Le Network リ mono-Application N364S and process the above-mentioned surface for examination material, remove lip-deep oil content or spot.Then with tap water, wash, after confirming that metal material surface is soaked by water 100%, and then flow through pure water, as test board, use remove moisture in the baking oven of 100 ℃ of atmosphere after.
(3) adjustment for the treatment of solution of the present invention
According to the composition (solid composition quality ratio) that is illustrated in each composition in table 1, in water, mix, obtain treatment solution.
In addition, the composition in table 1 (A), (B), (C), (D) and use level (G), be illustrated in the amount coordinating in surface treatment liquid 1kg for metallic substance (g).In addition, the content of alcohol composition (F), is used vapor-phase chromatography to measure, by the cubage C of organoalkoxysilane f2, as following molar concentration rate (C f1)/(C f2) represent.
Figure GDA00003265479900211
Figure GDA00003265479900221
Figure GDA00003265479900231
Below, the compound using in his-and-hers watches 1 describes.
< silicate compound (A) >
A1:SnowtexC (daily output chemical industrial company manufactures)
A2:SnowtexO (daily output chemical industrial company manufactures)
< organoalkoxysilane (B) >
B1: γ-glycidoxy triethoxyl silane
B2: aminopropyltriethoxywerene werene
B3: vinyltriethoxysilane
B4: tetraethoxysilane
< metallic compound (C) >
C1: zirconium carbonate ammonium
C2: vanadium acetylacetonate
C3: magnesium nitrate
C4: aluminum nitrate
C5: zinc oxide
< compound (D) >
D1: phosphoric acid
D2:1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid
D3: hydrofluotitanic acid
D4: fluorine zirconic acid
< determining alcohol (molar concentration rate) (C f1)/(C f2) >
< compound (G) >
G1: acrylic resin (clear and polymer (strain) is manufactured, Polyzole AM-2386)
(4) treatment process
Use above-mentioned metallic substance surface treatment liquid, according to following coating method, on each test board, apply, afterwards, do not wash, directly put into baking oven, under the drying temperature shown in table 2, be dried, form the tunicle of the tunicle amount shown in table 2.
Drying temperature, by the envrionment temperature in baking oven with regulate the storage period in baking oven.In addition, drying temperature represents the arrival temperature on test board surface.The concrete method that blade coating (bar coat) applies and roller coat (roll coat) applies is as described below.
Blade coating applies: treatment solution is added drop-wise on test board, with #3～5 scraping strip coating machine (bar coater), applies.The tunicle amount that is adjusted to regulation by the model (kind hand) of scraping strip coating machine used and the concentration for the treatment of solution.
Roller coat applies: at room temperature test board is flooded in treatment solution about 1 second, after taking-up, with roller, remove unnecessary liquid, adjust glue spread.The dehydrating amount producing by roller and the concentration for the treatment of solution are adjusted to the tunicle amount of regulation.
[table 4]
One of table 2 ()
Figure GDA00003265479900251
[table 5]
Table 2 (two)
Figure GDA00003265479900261
[table 6]
Table 2 (three)
Figure GDA00003265479900262
(5) method of evaluation test
(5-1) erosion resistance evaluation
Surface-treated test board is cut into 70 * 150mm, by the inside and polyvinyl chloride sealing tape sealing for end, carries out following test.Evaluation is to evaluate rust area rate by visual judgement.
Salt spray testing (based on SST:JIS-Z-2371):
By visual, according to following determinating reference, evaluate the white rust generation area occupation ratio of SST120 after the time.
Round-robin test (CCT (JASO): M609-91 (materials used in auto manufacturing corrosion test method)):
By visual, according to following determinating reference, evaluate the white rust generation area occupation ratio after CCT30 circulation.
Determinating reference:
◎: rust area rate less than 10%
Zero: rust area rate is more than 10%～less than 20%
△: rust area rate is more than 20%～less than 40%
*: rust area rate is more than 40%
* *: all got rusty
(5-2) with the adhesivity evaluation of metallic substance
A method: make stainless steel round bar that diameter 40mm and surface be ground into mirror-like loading 50kg and on the surface of surface-treated test board reciprocal 10 times, carrying out sealing tape peels off, with copper sulfate solution (3% aqueous solution, room temperature, dipping 5 seconds), carry out displacement plating, evaluate the situation of peeling off of tunicle.
B method: with Sven-Gan Eriksson (エ リ Network セ Application, Eriksen) forcing machine is extruded 7mm through surface-treated test board, with Cellotape (registered trademark), peel off and all extrude processing part, with copper sulfate solution (3% aqueous solution, room temperature, dipping 5 seconds), carry out displacement plating, evaluate the situation of peeling off of tunicle.
Determinating reference:
◎: do not peel off
Zero: have few point-like to peel off
△: have slight peeling off
*: have significantly and peel off
(5-3) the stripping property evaluation of metallic compound
Test board through surface-treated is flooded 2 hours in the boiling water of pure water, with fluorescent x-ray analyzer, measure the remaining quantity of metallic compound.Adhesion amount by the metallic compound of measuring before test is calculated the fixed rate of metal.
Fixed rate (%)=remaining quantity (mg/m 2adhesion amount (mg/m before)/test 2) * 100
Determinating reference:
◎: more than 95%～100%
Zero: 90% above～less than 95%
△: more than 60%～less than 90%
*: more than 20%～less than 60%
* *: less than 20%
(5-4) evaluation of outer coating
On the test board through surface-treated, apply commercially available trimeric cyanamide alkydpaints, making the coating thickness after 160 ℃ of sintering is 20 μ m.Afterwards, in boiling water, flood after 2 hours, with NT cutting machine, be cut into 100 chessboard grid that 1mm is square, a part is wherein extruded to 6mm with forcing machine, stick with glue band and peel off, the remaining situation of filming according to following Evaluation operation.
Determinating reference:
◎: less than 5% is peeled off～do not peeled off
Zero: peel off less than below 10%～5%
△: peel off less than more than 20%～below 10%
*: peel off less than below 60%～20%
* *: peeled off more than 60%
Corrosion resistance test: to arrive the degree X shape ground cutting test plate of material, carried out the situation of getting rusty after above-mentioned CCT (round-robin test) 80 circulations according to following determinating reference evaluation with NT cutting machine.
Determinating reference:
◎: apart from the not enough 1mm of otch
Zero: apart from otch 1mm above～not enough 2mm
△: apart from otch 2mm above～not enough 5mm
*: more than otch 5mm
* *: filmed and peeled off
Surface-treated metal material to using the surface treating agent for metallic materials recorded in embodiment 1～51 and comparative example 52～67 to obtain, the result of carry out above-mentioned (5-1)～evaluation (5-4) is illustrated in table 3.
In addition, viewpoint from practicality considers, do not have " * " and " * * " to be necessary in above-mentioned assessment item.
[table 7]
One of table 3 ()
Figure GDA00003265479900301
[table 8]
Table 3 (two)
Figure GDA00003265479900311
[table 9]
Table 3 (three)
Figure GDA00003265479900312
As shown in table 3, can confirm the compound that contains regulation and adjust alcohol molar concentration rate (C f1)/(C f2) treatment agent of the present invention, erosion resistance, outer coating are good, and the good adhesion of formed tunicle and metal material surface, can suppress the stripping of the composition that the corrosion inhibitor as metallic substance plays a role.
Wherein, by the comparison of embodiment 23～26, when known use has epoxy group(ing) or amino organoalkoxysilane as organoalkoxysilane (B), various characteristics is better.In addition, by the comparison of embodiment 16 and 17, known by two kinds of organoalkoxysilanes used time, various characteristics further improves.
On the other hand, in comparative example, cannot obtain comprehensively meeting the result of all characteristics.

Claims (1)

1. surface treating agent for metallic materials, it is the surface treating agent for metallic materials that contains following (A) ~ (F):
Silicate compound (A);
Organoalkoxysilane (B);
Containing the metallic compound (C) that is selected from least a kind of metallic element in Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and Zn;
Be selected from the compound of at least a kind (D) in phosphate cpd and fluorine cpd;
Water (E); With
The alcohol (F) being generated by the hydrolysis of above-mentioned organoalkoxysilane (B),
And make the volumetric molar concentration (C of above-mentioned alcohol (F) in treatment agent f1), with above-mentioned organoalkoxysilane (B) in contain the hydrolysis of whole alkoxyl group time the alcohol that the generates volumetric molar concentration (C in treatment agent f2) ratio (C f1/ C f2) being adjusted into 0.05 ~ 0.9 scope, the unit of described volumetric molar concentration is mol/L.
2. surface treating agent for metallic materials claimed in claim 1, wherein above-mentioned alcohol (F) is 0.01 ~ 50 with the mass ratio (C/F) of above-mentioned metallic compound (C).
3. surface treating agent for metallic materials claimed in claim 1, the scope that wherein mass ratio (D/F) of above-mentioned alcohol (F) and above-claimed cpd (D) is 0.01 ~ 25.
4. surface treating agent for metallic materials claimed in claim 1, wherein above-mentioned silicate compound (A) is 0.01 ~ 3.0 with the mass ratio (A/B) of above-mentioned organoalkoxysilane (B);
The total quality (A+B) of above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B) is 0.01 ~ 2.0 with the mass ratio of above-mentioned metallic compound (C) (C/ (A+B));
The total quality (A+B) of above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B) is 0.01 ~ 1.5 with the mass ratio of above-claimed cpd (D) (D/ (A+B)).
5. surface treating agent for metallic materials claimed in claim 1, wherein above-mentioned organoalkoxysilane (B) has amino and/or epoxy group(ing).
6. the surface treating agent for metallic materials described in any one of claim 1 ~ 5, wherein further contains the compound of at least a kind (G) being selected from water-soluble polymer and water system emulsifying resins.
7. surface treating agent for metallic materials claimed in claim 6, wherein the total quality (A+B) of above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B) and the mass ratio of above-claimed cpd (G) (G/ (A+B)) are 0.01 ~ 0.3.
8. the surface treatment method of metallic substance, it is on metal material surface, to be coated with the surface treating agent for metallic materials described in any one of claim 1 ~ 7, heat drying forms tunicle amount and counts 2 ~ 1000mg/m with Si adhesion amount on above-mentioned metal material surface 2tunicle.
9. surface-treated metal material, it is that right to use requires to have tunicle on that the surface treatment method of the metallic substance described in 8 obtains and surface.
CN200880132453.2A 2008-12-16 2008-12-16 Surface treating agent for metallic materials Active CN102257178B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2008/072839 WO2010070728A1 (en) 2008-12-16 2008-12-16 Surface treating agent for metallic materials

Publications (2)

Publication Number Publication Date
CN102257178A CN102257178A (en) 2011-11-23
CN102257178B true CN102257178B (en) 2014-05-07

Family

ID=42268419

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200880132453.2A Active CN102257178B (en) 2008-12-16 2008-12-16 Surface treating agent for metallic materials

Country Status (5)

Country Link
JP (1) JP5555177B2 (en)
KR (1) KR101278311B1 (en)
CN (1) CN102257178B (en)
TW (1) TWI447264B (en)
WO (1) WO2010070728A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104099017A (en) * 2014-06-19 2014-10-15 锐展(铜陵)科技有限公司 Rustless aluminium alloy surface treating agent

Families Citing this family (75)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG187123A1 (en) * 2010-09-29 2013-02-28 Jfe Steel Corp Method for manufacturing zinc or zinc alloy coated steel sheet and zinc or zinc alloy coated steel sheet manufactured by the m,ethod
US9127366B2 (en) * 2010-09-29 2015-09-08 Jfe Steel Corporation Zinc-based metal coated steel sheet
KR101176480B1 (en) 2010-12-30 2012-08-28 주식회사 흥아포밍 Trivalent Chromate Solution, Chromated Metal, And Manufacturing Method Of Chromated Metal
JP5595305B2 (en) * 2011-02-25 2014-09-24 日新製鋼株式会社 Welded steel pipe
JP5889561B2 (en) * 2011-07-15 2016-03-22 日本パーカライジング株式会社 Water-based metal surface treatment agent and metal material with surface coating
JP2013074121A (en) * 2011-09-28 2013-04-22 Fujifilm Corp Substrate for photoelectric conversion element and photoelectric conversion element
JP5478588B2 (en) * 2011-11-18 2014-04-23 株式会社神戸製鋼所 Surface-treated metal plate with excellent corrosion resistance and conductivity
CN102424963B (en) * 2011-12-23 2013-09-18 无锡鸿海龙船机有限公司 Phosphate treatment technology for deformation-free scuffing-resistant inner sleeve
CN103360808B (en) * 2012-03-31 2016-01-20 攀钢集团攀枝花钢铁研究院有限公司 A kind of metal protection coating and uses thereof and hot-dip metal plated material
CN102747356B (en) * 2012-07-30 2014-08-20 长沙学院 Normal temperature calcium-manganese phosphorizing liquid
JP6003507B2 (en) * 2012-10-05 2016-10-05 Ｊｆｅスチール株式会社 Electrical steel sheet with insulation coating
JP6151907B2 (en) * 2012-10-12 2017-06-21 日本パーカライジング株式会社 Water-based metal surface treatment agent, metal surface treatment film, and metal material with metal surface treatment film
TWI555881B (en) * 2012-11-16 2016-11-01 China Steel Corp A water-based metal surface treatment agent and a metal surface treatment method using the same
CN103059722B (en) * 2012-12-18 2016-01-20 安徽翔艺达机械有限公司 A kind of Metal surface silane treatment agent containing carboxymethyl cellulose and preparation method thereof
WO2014122900A1 (en) * 2013-02-08 2014-08-14 Ｊｆｅスチール株式会社 Surface treatment liquid for galvanized steel sheet, galvanized steel sheet with surface treatment film and method for producing same
KR101534765B1 (en) * 2013-02-19 2015-07-06 주식회사 노루코일코팅 Surface Treating Composition of Magnesium and Magnesium Alloy and Surface Treating Method Using The Same
JP6043663B2 (en) 2013-03-21 2016-12-14 日本パーカライジング株式会社 Water-based hydrophilic coating composition that forms a film excellent in self-cleaning ability against adhering dirt and surface treatment material that forms a film excellent in self-cleaning ability against adhering dirt
EP2990504B1 (en) * 2013-04-26 2020-04-29 Nihon Parkerizing Co., Ltd. Aqueous hydrophilizing surface treatment agent, hydrophilic coating film and hydrophilizing surface treatment method
CN104059489B (en) * 2013-05-03 2016-05-25 攀钢集团攀枝花钢铁研究院有限公司 A kind of metal surface chemical pretreatment solution and its production and use and hot-dip metal plated material
JP6315750B2 (en) * 2013-06-10 2018-04-25 関西ペイント株式会社 Aqueous metal surface treatment agent
DE102013215441A1 (en) * 2013-08-06 2015-02-12 Henkel Ag & Co. Kgaa Metal pretreatment compositions comprising silanes and organophosphonic acids
DE102013215440A1 (en) * 2013-08-06 2015-02-12 Henkel Ag & Co. Kgaa Metal pretreatment with acidic hydrous compositions comprising silanes
CN104073074B (en) * 2013-09-05 2016-08-24 攀钢集团攀枝花钢铁研究院有限公司 A kind of metal surface chromium inorganic agent and preparation method thereof and hot-dip metal plated material
CN103540917B (en) * 2013-09-27 2016-06-22 宁波英科特精工机械股份有限公司 A kind of metal conditioner and preparation method thereof
JP2015074743A (en) * 2013-10-10 2015-04-20 共栄社化学株式会社 Aqueous rust-removing paint
KR101781771B1 (en) 2013-11-29 2017-09-25 제이에프이 스틸 가부시키가이샤 Zinc or zinc alloy coated steel sheet with surface treatment film, and method of producing same
JP6203291B2 (en) * 2013-12-24 2017-09-27 日本パーカライジング株式会社 Surface treatment agent for metal materials
CN103820794B (en) * 2014-02-24 2018-04-03 深圳市宝骏环保涂料有限公司 Water-based band embroiders rust-removing and-preventing agent and production method
CN103966590B (en) * 2014-04-02 2016-06-29 上海大学 The method of single silane coupler compound chromium-free passivation liquid and passivation zinc-coated wire overlay coating
CN106164335B (en) * 2014-04-04 2018-12-04 日涂表面处理化工有限公司 Metal conditioner, coating method and the coating steel of galvanized steel
CN104060257A (en) * 2014-05-26 2014-09-24 安徽红桥金属制造有限公司 Chromium-free passivator for zinc coating and preparation method of chromium-free passivator
CN104018147A (en) * 2014-06-13 2014-09-03 苏州汉力新材料有限公司 Alloy metal-base preservative
CN104005012B (en) * 2014-06-13 2016-09-14 上海兴赛尔表面材料有限公司 Corrosion-resistance treatment compositions and using method thereof for aluminum and aluminium alloy
CN104195536B (en) * 2014-07-01 2017-01-04 国家电网公司 Promote rust inactivation transforming agent
JP2016030777A (en) * 2014-07-28 2016-03-07 奥野製薬工業株式会社 Process liquid for siliceous film formation
JP6441655B2 (en) * 2014-12-09 2018-12-19 新日鐵住金株式会社 Ground treatment liquid, method for producing organic coated galvanized steel pipe using ground treatment liquid, and organic coated galvanized steel pipe
KR101736557B1 (en) * 2014-12-26 2017-05-17 주식회사 포스코 Composition for Cr-free coating material and surface treated steel sheet with superior blackening-resistance and corrosion-resistance
CN104593789A (en) * 2015-01-12 2015-05-06 国家电网公司 Four-in-one chemical treating reagent for high-voltage power transmission line tower
CN104911573A (en) * 2015-07-02 2015-09-16 常熟风范电力设备股份有限公司 Method for preparing hot galvanizing chrome-free passivant in batches
CN105463428B (en) * 2015-12-07 2019-01-11 乐凯胶片股份有限公司 A kind of aluminium foil surface passivating solution and aluminum plastic film
CN105483681B (en) * 2015-12-10 2018-02-09 广东志远环保设备有限公司 A kind of preparation method of zinc system metal treatment fluid
CN107620057B (en) * 2015-12-10 2019-01-25 吴联凯 A kind of application method of the phosphating solution for metal processing
CN108884573A (en) * 2016-03-22 2018-11-23 奥野制药工业株式会社 The processing method of epithelium formation composition and metal material
CN105839085A (en) * 2016-06-06 2016-08-10 无锡伊佩克科技有限公司 Rapidly solidified metal passivator and preparation method thereof
CN105951080B (en) * 2016-06-27 2018-11-20 力同铝业（广东）有限公司 Aluminum alloy surface composite passivant and preparation method thereof
CN105951081B (en) * 2016-06-27 2018-12-14 重庆新美鱼博洋铝业有限公司 Environment-friendly type aluminium alloy non-chromium passivator and preparation method thereof
JP6757220B2 (en) * 2016-09-27 2020-09-16 日本パーカライジング株式会社 Surface treatment agent for metal materials and its manufacturing method, and metal materials with surface treatment coating and its manufacturing method
KR101786392B1 (en) * 2016-10-10 2017-10-17 주식회사 포스코 Solution composition for surface treating of steel sheet, zinc-based metal plated steel sheet using the same, and manufacturing method of the same
KR101742066B1 (en) 2017-04-18 2017-06-01 주식회사 삼성씨앤엠 Steel coating composition with good non-flammability and durability and protection coating method for steel structures therewith
CN110832114A (en) * 2017-07-03 2020-02-21 深圳市宏昌发科技有限公司 Passivating agent, metal workpiece and surface treatment method thereof
WO2019006612A1 (en) * 2017-07-03 2019-01-10 深圳市宏昌发科技有限公司 Passivator, passivation process for metal-plated part and metal workpiece
JP7142498B2 (en) * 2018-06-28 2022-09-27 日本パーカライジング株式会社 Surface treatment agent for metal material, metal material with surface treatment film, and method for producing the same
JP7090507B2 (en) * 2018-08-17 2022-06-24 日本製鉄株式会社 Painted steel material with chemical conversion coating, and its manufacturing method
CN109304287B (en) * 2018-11-30 2021-09-28 沈阳帕卡濑精有限总公司 Pretreatment process suitable for high-aluminum hybrid vehicle body of whole vehicle factory
WO2020165035A1 (en) * 2019-02-14 2020-08-20 Chemetall Gmbh Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor
CN113631743B (en) * 2019-03-19 2022-08-26 日本制铁株式会社 Surface-treated metal material
CN109943834A (en) * 2019-03-28 2019-06-28 江苏鑫露化工新材料有限公司 It is a kind of for enhancing zirconium, the additive of titanium compound inactivating performance and its application
JP7266459B2 (en) * 2019-05-16 2023-04-28 Ｊｆｅ鋼板株式会社 Method for manufacturing surface-treated steel sheet
CN111978864A (en) * 2019-05-24 2020-11-24 电子科技大学 Surface modifier, preparation method and application thereof
CN110760916B (en) * 2019-11-18 2022-04-05 和县科嘉阀门铸造有限公司 Method for improving corrosion resistance of magnesium alloy valve
KR102329418B1 (en) * 2019-12-03 2021-11-22 주식회사 포스코 Composition for surface treating of steel sheet, steel sheet using the same, and manufacturing method of the same
KR102357081B1 (en) * 2019-12-12 2022-01-28 주식회사 포스코 Electro-galvanized steel sheet having excellent heat-resistant and tape adhesive, steel sheet using the same, and manufacturing method of the same
CN111005013B (en) * 2019-12-23 2021-11-23 三达奥克化学股份有限公司 Steel-aluminum universal environment-friendly rare earth metal chemical conversion film treating agent
US20210198522A1 (en) * 2019-12-31 2021-07-01 Industrial Technology Research Institute Water-based coating material and method for manufacturing the same
CN111218679B (en) * 2020-01-23 2022-07-05 广东省建筑科学研究院集团股份有限公司 Metal-organic framework membrane preparation liquid and membrane and preparation method thereof
CN111560203B (en) * 2020-04-23 2022-02-15 乐凯胶片股份有限公司 Aluminum foil treatment fluid and application thereof
CN111850532B (en) * 2020-07-16 2021-10-29 武汉迪赛环保新材料股份有限公司 Chromium-free surface treatment liquid for electro-galvanized steel plate and preparation method thereof
CN112663036A (en) * 2020-11-27 2021-04-16 华帝股份有限公司 Metal surface pretreatment agent, preparation method and application
CN112853336A (en) * 2020-12-31 2021-05-28 广州和力表面处理技术有限公司 Chromium-free surface treating agent for aluminum can cover packaging material, and preparation method and passivation process thereof
CN113584424A (en) * 2021-07-27 2021-11-02 张艳芳 Stainless steel surface treatment method
KR20230081132A (en) * 2021-11-30 2023-06-07 주식회사 포스코 Coating composition for hot dip galvanized steel sheet having excellent corrosion resistant and anti-blackening, hot dip galvanized steel sheet prepared by using thereof, and manufacturing method the same
KR20230093920A (en) * 2021-12-20 2023-06-27 주식회사 포스코 Composition for surface treating of steel sheet, steel sheet using thereof, and manufacturing method of the same
TWI820931B (en) * 2022-03-03 2023-11-01 日商日本製鐵股份有限公司 Surface treated steel plate
JP2023153668A (en) * 2022-04-05 2023-10-18 日本パーカライジング株式会社 Surface treating agent for fibers, method for treating surface of fiber, and surface-treated fiber
CN117820883B (en) * 2024-03-05 2024-05-03 苏州群鹰防腐材料有限公司 Composite ceramic anti-corrosion material applied to ocean engineering and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1381532A (en) * 2001-04-19 2002-11-27 日本油漆株式会社 Nonchromate metal surface finishing agent, surface handling and method and processed steel products

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001059184A (en) * 1999-08-18 2001-03-06 Nisshin Steel Co Ltd Surface treating solution for plated steel sheet and treatment thereby
JP2001070728A (en) 1999-09-09 2001-03-21 Nitta Ind Corp Filter for removing gas and production of the same
JP3857866B2 (en) 2000-02-29 2006-12-13 日本ペイント株式会社 Non-chromate metal surface treatment agent, surface treatment method and treated painted steel
WO2006082951A1 (en) * 2005-02-02 2006-08-10 Nihon Parkerizing Co., Ltd. Aqueous surface treating agent for metal material, surface treating method and surface-treated metal material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1381532A (en) * 2001-04-19 2002-11-27 日本油漆株式会社 Nonchromate metal surface finishing agent, surface handling and method and processed steel products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开2001-59184A 2001.03.06

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104099017A (en) * 2014-06-19 2014-10-15 锐展(铜陵)科技有限公司 Rustless aluminium alloy surface treating agent

Also Published As

Publication number Publication date
JP5555177B2 (en) 2014-07-23
TWI447264B (en) 2014-08-01
WO2010070728A1 (en) 2010-06-24
JPWO2010070728A1 (en) 2012-05-24
TW201024460A (en) 2010-07-01
KR20110083744A (en) 2011-07-20
KR101278311B1 (en) 2013-07-05
CN102257178A (en) 2011-11-23

Similar Documents

Publication Publication Date Title
CN102257178B (en) Surface treating agent for metallic materials
TWI444504B (en) Surface-treating agent for galvanized steel plate
JP6806892B2 (en) A surface-treated solution composition containing trivalent chromium and an inorganic compound, a galvanized steel sheet surface-treated using the same, and a method for producing the same.
JP5144660B2 (en) Aqueous surface treatment solution for galvanized steel sheet and galvanized steel sheet
AU2011262860B2 (en) Inorganic chromium-free metal surface treatment agent
JP2005036261A (en) Metal surface treatment composition, metal surface treatment method, and galvanized steel sheet
EP3208274B1 (en) Organosilicon compound, method for producing same and metal surface treatment agent using same
JP2005194627A (en) Water based treatment chemical for metal surface
JP2004238638A (en) Surface treatment composition and surface-treated metal strip
JP2011068996A (en) Composition for surface treatment of metallic material, and treatment method
JP5661238B2 (en) Surface-treated galvanized steel sheet
JP6569194B2 (en) Surface-treated hot-dip galvanized steel sheet with excellent corrosion resistance
JP5638191B2 (en) Chemical conversion treated metal plate and manufacturing method thereof
JP3952198B2 (en) Metal surface treatment method and galvanized steel sheet
JPH11335864A (en) Production of surface treated steel plate having excellent corrosion resistance
JP5447218B2 (en) Surface-treated plated steel sheet and surface treatment liquid
JP6056792B2 (en) Surface treatment liquid for galvanized steel sheet, surface-treated galvanized steel sheet and method for producing the same
JPH11335863A (en) Production of surface treated steel plate having excellent corrosion resistance
JP5222491B2 (en) Surface-treated steel sheet
JP6323424B2 (en) Surface-treated hot-dip galvanized steel sheet with excellent corrosion resistance
KR100952613B1 (en) Cr-free Sealing Solution And Method of Fabricating PhosPhated Electro-galvanized Steel Sheet Using The Same
JP6098579B2 (en) Regular spangled galvanized steel sheet with surface treatment film
JP2013060646A (en) Composition for spray coating surface treatment, method for producing surface-treated hot-dip galvanized steel sheet, and the surface-treated hot-dip galvanized steel sheet
JP6112148B2 (en) Galvanized steel sheet with excellent corrosion resistance
JPH1161432A (en) Metal plate surface-treated with inorganic/organic composite

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant