CN102257178A - Surface treating agent for metallic materials - Google Patents
Surface treating agent for metallic materials Download PDFInfo
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- CN102257178A CN102257178A CN2008801324532A CN200880132453A CN102257178A CN 102257178 A CN102257178 A CN 102257178A CN 2008801324532 A CN2008801324532 A CN 2008801324532A CN 200880132453 A CN200880132453 A CN 200880132453A CN 102257178 A CN102257178 A CN 102257178A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—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
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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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
Technical field
The present invention relates to metallic substance with surface treatment agent, use this metallic substance with the surface treatment method of surface treatment agent and surface-treated metal material with tunicle.
Background technology
In order to obtain erosion resistance or coating, can implement surface treatment to the metal species material.That is, by surface treatment, it is important obtaining following effect: even 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 take place when applying.In the past, as the surface treatment of metal species material, the chromate treating that carried out making phosphatizing that the crystallization of the metal-salt of phosphoric acid separates out or formation to contain chromic tunicle.
In phosphatizing, at 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 can't moltenly deposit is separated out on the surface of metallic substance, forms phosphate coating.Because it is phosphate coating is separated out after the dissolving of metal material surface, therefore very good with the adhesivity of metallic substance.And, because by trickle crystalline set formation tunicle, therefore by anchor effect (anchor effect), also good with the coated adhesivity of filming by trickle concavo-convex generation.So, be still be widely used so far as the base treatment that applies, surface of good handles.
But, so that contacting with the acidic aqueous solution that contains phosphoric acid, metal produces solubilizing reaction owing to being 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 of the metallic substance kind is different.In addition, because the phosphoric acid salt that can't separate out on the surface of metallic substance can swim in treatment solution as sludge (sludge), therefore be necessary to be removed.In addition, also be necessary suitably to change the contact conditions (temperature, time etc.) of the aqueous solution and metallic substance, and, also exist in the problem that needs to carry out washing step (generation waste water) after the surface treatment.In addition, also inapplicable to lacking reactive material as stainless steel and so on.
In chromate treating, also exist and the same reaction type of phosphoric acid salt, behind painting solution, only carry out exsiccant application type chromate treating and be widely known by the people.The application type chromate treating is only to carry out the easy method of exsiccant with containing after the chromic aqueous solution is coated on metal material surface.Therefore, owing to after surface treatment, do not need washing step, form and do not produce the closed system of waste water, so in the surface treatment of coiled sheet (sheet coil), be widely adopted.In addition, application type chromic salt tunicle has the form of the sexavalent chrome (chromic acid) that has kept solubility in the tunicle skeleton based on chromic high molecular, because the oxygenizement (passivation, self-repair function) that the tunicle screen effect on trivalent chromium basis and sexavalent chrome produce can be given the metallic substance good anti-corrosion.In addition, when using, be well-known by Ni being carried out micro-displacement plating tunicle is become is difficult to peel off as its pre-treatment as the base treatment that applies.One of its reason can be enumerated: 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, by film component is the material of high molecular, and, in this tunicle, there is the corrosion inhibitor of solubility, formation can be with the tunicle of its prolonged preservation.In the application type chromate treating, can form tunicle with aforesaid characteristic.
But the tunicle that forms by the application type chromate treating contains sexavalent chrome, and therefore this sexavalent chrome considers to have the tendency of keeping someone at a respectful distance from the viewpoint of environment aspect, security by the stripping with contacting of moisture.So, carried out the various research and development that can suppress sexavalent chrome from the stripping of chromic salt tunicle.
Just, recently, chromic existence itself becomes and is out of favour, thereby has carried out the exploitation that more not chromyl non-chromate is handled.
Handle as non-chromate, disclose in the patent documentation 1 and used P-compound, Si compound and quaternary vanadium compound to form the steel plate of tunicle.But, use this technology, the adhesivity with metal material surface can not be fully guaranteed, and also sufficient erosion resistance can't be obtained.
In the patent documentation 2, disclose that to contain silane coupling agent, specific resin, F be the metal complex more than 4, 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 can't be obtained.
In the patent documentation 3, disclose by colloidal silicon-dioxide, organoalkoxysilane and vinyl monomer with ethene unsaturated group being carried out the water dispersible thing of core/shelly composite particles that the polymeric operation obtains.But in this particle is colloidal silicon-dioxide more than 80%.This technology is the technology that is used for this is blended in particle-stabilisedly resin, even also can't form tunicle with the direct use of this state, and also can't obtain erosion resistance.
In the 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 simultaneously and the effect of metal material surface bonded.But, in this technology, because metal ion is carried out chelating, form the form of easy dissolved metal ions, so the result can not fully suppress their stripping, can't obtain long-term erosion resistance.
In the patent documentation 5, disclose contain silane coupling agent 0.01～100g/L, silicon-dioxide 0.05～100g/L, Zr 0.01～50g/L and/or Ti 0.01～50g/L, contain the compound 0.01～100g/L of thiocarbonyl, the treatment solution of acrylic resin 0.1～100g/L.This technology has good adhesivity, so coating is good, but the erosion resistance of not having when applying is insufficient.And, gelation can take place through aftertreatment fluid after a while, therefore can't be in industrial use.
In the 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 the patent documentation 7, the technology of using polyurethane resin, silane coupling agent and silicon-dioxide is disclosed.Disclosed technology in the patent documentation 6 and 7 can't fully be guaranteed the adhesivity with metal material surface.In addition, owing to can't make silicon-dioxide fully immobilization in tunicle, therefore can't obtain sufficient erosion resistance.
In the patent documentation 8, disclose lower floor's formation and contained the tunicle of organic resin and silane coupling agent, the organic resin tunicle that thiocarbonyl is contained on the upper strata.This technology relates to 2 layers of lower floor in the processing, by with the combination on upper strata, reached purpose first.Therefore as independent tunicle, still can't obtain adhesivity and erosion resistance with metallic substance.
In the 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 can't suppress the stripping of metallic compound.
In the patent documentation 10, the technology of using silane coupling agent, silica dioxide gel and water-based organic resin is disclosed.Silane coupling agent is combined with silica sphere, therefore can make the silica composition immobilization, but can't suppress the stripping of metallic compound.
As mentioned above, all methods all can't obtain replacing the surface treated steel plate of chromic salt tunicle, strongly need a kind of surface treatment agent of exploitation: can comprehensively satisfy all characteristics such as erosion resistance and outer coating, particularly can improve formed tunicle and metallic substance adhesivity, can make the surface treated steel plate that can suppress Corrosion of Metallic Materials.
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 metallic substance with surface treatment agent and use this metallic substance surface treatment method with treatment agent, described metallic substance uses surface treatment agent in the tunicle that the surface treatment of using application type forms, have all characteristics such as erosion resistance, outer coating, the good adhesion of particularly formed tunicle and metal material surface can make the composition immobilization in tunicle that plays a role as the Corrosion of Metallic Materials inhibitor.
Solve the means of problem
People of the present invention are based on the character of organoalkoxysilane, and the result who studies deeply finds to contain the compound of regulation and controlled the treatment agent of the amount of the alcohol that the hydrolysis by organoalkoxysilane generates by use, can solve above-mentioned problem.
That is, the invention provides following (1)～(9).
(1) metallic substance surface treatment agent, it is the metallic substance surface treatment agent that contains following (A)～(F):
Silicate compound (A);
Organoalkoxysilane (B);
Contain the metallic compound (C) that is selected from least a kind of metallic element among Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and the Zn;
Be selected from least a kind the compound (D) in phosphate cpd and the fluorine cpd;
Water (E); With
The alcohol (F) that generates 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 whole alkoxyl group hydrolysis the time volumetric molar concentration (the mol/L) (C of alcohol in treatment agent that generate
F2) ratio (C
F1/ C
F2) be adjusted into 0.05～0.9 scope.
(2) the metallic substance surface treatment agent described in (1), the mass ratio (C/F) of wherein above-mentioned alcohol (F) and above-mentioned metallic compound (C) are 0.01～50 scope.
(3) the metallic substance surface treatment agent 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) the metallic substance surface treatment agent described in each 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) the metallic substance surface treatment agent described in each of (1)～(4), wherein above-mentioned organoalkoxysilane (B) has amino and/or epoxy group(ing).
(6) the metallic substance surface treatment agent described in each of (1)～(5) wherein further contains at least a kind the compound (G) that is selected from water-soluble polymer and the water system emulsifying resins.
(7) the metallic substance surface treatment agent described in (6), wherein the total quality (A+B) of above-mentioned silicate compound (A) in the treatment agent and above-mentioned organoalkoxysilane (B) is 0.01～0.3 with the mass ratio (G/ (A+B)) of above-claimed cpd (G).
(8) surface treatment method of metallic substance, its be on metal material surface the coating (1)～(7) each described in the metallic substance surface treatment agent, heat drying forms the tunicle amount and counts 2～1000mg/m with the Si adhesion amount on above-mentioned metal material surface
2Tunicle.
(9) surface-treated metal material, its be to use that the surface treatment method of the metallic substance described in (8) obtains and the surface on have tunicle.
The invention effect
The invention provides metallic substance with surface treatment agent and use this metallic substance surface treatment method with surface treatment agent, described metallic substance uses surface treatment agent in the tunicle that the surface treatment of using application type forms, have all characteristics such as superior corrosion resistance, outer coating, the good adhesion of particularly formed tunicle and metal material surface can make the composition immobilization in tunicle that plays a role as the Corrosion of Metallic Materials inhibitor.
Embodiment
Below, to metallic substance of the present invention with surface treatment agent and use this metallic substance to describe with the surface treatment method of surface treatment agent.
At first, metallic substance is elaborated with surface treatment agent.
＜metallic substance surface treatment agent 〉
Metallic substance surface treatment agent of the present invention is the metallic substance surface treatment agent that contains following (A)～(F): silicate compound (A); Organoalkoxysilane (B); Contain the metallic compound (C) that is selected from least a kind of metallic element among Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and the Zn; Be selected from the compound (D) in phosphate cpd and the fluorine cpd; Water (E) and the alcohol (F) that generates 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 whole alkoxyl group hydrolysis the time volumetric molar concentration (the mol/L) (C of alcohol in treatment agent that generate
F2) ratio (C
F1/ C
F2) be adjusted into 0.05～0.9 scope.
At first, the various compositions of formation metallic substance with surface treatment agent are described.
＜silicate compound (A) 〉
Metallic substance of the present invention is with containing silicate compound (A) in the surface treatment agent.By using silicate compound, can form all well behaved tunicles such as erosion resistance, outer coating, thermotolerance, weldability, continuous processibility.
Silicate compound is that there is no particular limitation to its kind with silicon and the oxygen material as the main composition composition.For example, can enumerate: alkaline silicates such as water glass, potassium silicate, lithium silicate, the colloid silica or the liquid phase silica that use ion exchange method from these silicate, to remove sodium, potassium or lithium and use method such as gelation to obtain, with silicon chlorides combustion oxidation and the aerosil made is dispersed in the dispersion that forms in the water in air, and the hydrolyzate of organoalkoxysilane etc.Wherein, consider preferred colloid silica and liquid phase silica from the better aspect of the performance of gained tunicle.
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, Snowtex 20, Snowtex 30, Snowtex 40, ア デ ラ イ ト AT-20N, ア デ ラ イ ト AT-20A, ア デ ラ イ ト AT-20Q etc. can enumerate: the Snowtex UP that is processed into special chain shape in addition, 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: AEROSIL 50, AEROSIL 130, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL TT600, AEROSIL MOX80, AEROSILMOX170 etc. also can be dispersed in them in the water and use.
There is no particular limitation with the content of the silicate compound (A) in the surface treatment agent to metallic substance, but from better viewpoint considerations such as the erosion resistance of gained tunicle, outer coating, thermotolerance, weldability, continuous processibilities, divide with respect to total solid formation the in the treatment agent, be preferably 0.1～70 quality %, more preferably 1～50 quality %.In addition, total solid formation the in the treatment agent divided, and is meant the solid formation branch that constitutes tunicle described later, do not comprise solvent etc.
＜organoalkoxysilane (B) 〉
Metallic substance of the present invention is with containing organoalkoxysilane (B) in the surface treatment agent.By with organoalkoxysilane (B) and above-mentioned silicate compound (A) and usefulness, can form and have the tunicle that combines the three-dimensional structure of generation by silicate compound (A) with the siloxanes of organoalkoxysilane (B).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.
There is no particular limitation to the organoalkoxysilane that uses among the present invention, for example, can enumerate: tetramethoxy-silicane, tetraethoxysilane, the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, Union carbide A-162, Union carbide A-162, cyclohexyl methyl dimethoxy silane, the n-hexyl Trimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, the decyl Trimethoxy silane, the octadecyl Trimethoxy silane, octadecyltriethoxy silane, the 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, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, γ-sulfydryl propyl group methyl dimethoxysilane, to the 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, consider preferably have the trialkoxy silane of the active alkoxyl group of 3mol from the aspect of easy adjustment determining alcohol.
In addition, organoalkoxysilane (B) preferably has at least a kind the functional group that is selected from amino and the epoxy group(ing).Infer that organoalkoxysilane (B) by having these functional groups, further promotes above-mentioned silicon compound (A) to combine with the siloxanes of above-mentioned organoalkoxysilane (B), and then form three-dimensional cross-linked tunicle with densification.Thus, tunicle can be more fixing with the composition that plays a role as the Corrosion of Metallic Materials inhibitor, further improves erosion resistance.
A kind of as the suitable embodiment of organoalkoxysilane can enumerate the following compound with general formula (I) expression.
[changing 1]
General formula (I)
In the 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 the vinyl.L represents divalent linking group or singly-bound.R represents alkyl or hydrogen atom.N represents 1～3 integer.
In the 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 the vinyl.Wherein, preferred epoxy group(ing), amino.In addition, n is 2 when above, and X can be the same or different.
In the general formula (I), L represents divalent linking group or singly-bound.
As the linking group that L represents, for example, can enumerate: alkylidene group (preferred carbonatoms 1～20) ,-O-,-S-, arylidene ,-CO-,-NH-,-SO
2-,-COO-,-CONH-or with their the combination group.Wherein, preferred alkylidene group.When L represents singly-bound, be meant that the X of general formula (I) directly is connected with Si (Siliciumatom).In addition, n is 2 when above, and L can be the same or different.
In the general formula (I), R represents alkyl (preferred carbonatoms 1～4) or hydrogen atom respectively independently.
In the general formula (I), n represents 1～3 integer.Wherein preferred 1.
In addition, organoalkoxysilane (B) also can be the hydrolyzate after a part of hydrolysis of alkoxyl group.
To the content of metallic substance with the organoalkoxysilane (B) in the surface treatment agent, 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 the adhesivity of metal material surface, divide with respect to total solid formation the in the treatment agent, be preferably 0.1～70 quality %, more preferably 1～50 quality %.
＜metallic compound (C) 〉
Metallic substance of the present invention is with containing metallic compound (C) in the surface treatment agent, described metallic compound (C) contains at least a kind of metallic element that is selected among Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and the Zn.By with metallic compound (C) and phosphate cpd described later and/or fluorine cpd and usefulness, can in tunicle, form the salt of insoluble.The salt of inferring this insoluble is by promoting the crosslinking reaction of above-mentioned silicon compound (A) and above-mentioned organoalkoxysilane (B), and then form cancellated tunicle with densification, make metallic compound (C) immobilization easily in tunicle that plays a role as the Corrosion of Metallic Materials inhibitor.
Metallic compound (C) is if contain above-mentioned metallic element, and then there is no particular limitation, for example, can enumerate: contain nitrate, acetate, phosphoric acid salt, vitriol, ammonium salt, fluorochemical of above-mentioned metal etc.
As the object lesson of metallic compound (C), as the metallic compound that contains 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, can enumerate also that the aqueous solution with water-soluble zirconates carries out ion-exchange or alkali neutralization and zirconic acid and the salt thereof made.
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, the four different third oxygen titaniums, titanium acetylacetone, di-isopropyl titanium bis-acetylacetonate etc.In addition, can enumerate also that the aqueous solution with titanyl sulfate carries out metatitanic acid that thermal hydrolysis obtains, the titanic hydroxide that obtains with the alkali neutralization and their salt.
As the metallic compound that contains Co, for example, can enumerate: rose vitriol, Xiao Suangu, 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: sal epsom, 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 tervalent chromium, 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 generates by basic side chain (ア Le カ リ サ イ De, alkali side), potassium zincate etc.
Wherein, consider, more preferably contain and be selected from the metallic compound that contains Zr, V, Al or Zn from the effective aspect that improves erosion resistance, and in their salt more than at least a kind.
To the content of metallic substance with the metallic compound (C) in the surface treatment agent, there is no particular limitation, but consider from the better viewpoint of erosion resistance, the ground connection property of gained tunicle, divides with respect to total solid formation the in the treatment agent, be preferably 0.05～50 quality %, more preferably 0.1～30 quality %.
＜phosphate cpd and/or fluorine cpd 〉
Metallic substance of the present invention is with containing at least a kind the compound (D) that is selected from phosphate cpd and the fluorine cpd in the surface treatment agent.As mentioned above, phosphate cpd and/or fluorine cpd by metallizing thing (C) and usefulness, can promote the crosslinking reaction of above-mentioned silicon compound (A) and above-mentioned organoalkoxysilane (B).And, phosphate cpd and/or fluorine cpd, can etching as the metal of body material, form and substrate material surface bonded tunicle, therefore infer the erosion resistance that can further improve tunicle, with the adhesivity of metal material surface.
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.); Condensed phosphoric acids such as tetra-sodium; Phytic acid, has 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, cyano group propyl group dimethylene phosphonic acids methane, 1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid etc.
Phosphate cpd can separately or will be used in combination more than 2 kinds.
As fluorine cpd, for example, can enumerate: hydrofluoric acid, its ammonium salt, its an alkali metal salt; 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 suitable use has the material that is selected from least a element among Ti, Zr, Hf, Si, Al and the B, particularly, for example, can enumerate: to (TiF
6)
2-, (ZrF
6)
2-, (HfF
6)
2-, (SiF
6)
2-, (AlF
6)
3-, (BF
4OH)
-Carry out the complex compound that hydrogen atom is 1～3 atom addition, these anionic ammonium salts, these anionic metal-salts etc. Deng negatively charged ion.More specifically, can enumerate: hydrofluotitanic acid, fluorine zirconic acid, silicofluoric acid etc.
Fluorine cpd can separately or will be used in combination more than 2 kinds.
To the total content of metallic substance with the compound (D) in the surface treatment agent, there is no particular limitation, but consider from the better viewpoint of the erosion resistance of gained tunicle, divides with respect to total solid formation the in the treatment agent, be preferably 0.01～40 quality %, more preferably 0.1～30 quality %.
＜water (E) 〉
Metallic substance of the present invention is with containing water (E) in the surface treatment agent.
To the content of metallic substance with the water in the surface treatment agent, there is no particular limitation, but consider from the easier viewpoint of the processing of treatment agent, with respect to the treatment agent total amount, is preferably 30～99 quality %, more preferably 40～95 quality %.
＜alcohol (F) 〉
Metallic substance of the present invention is with containing the alcohol (F) that is generated by the hydrolysis of above-mentioned organoalkoxysilane (B) in the surface treatment agent.The hydrolysis reaction of the organoalkoxysilane (B) by having alkoxyl group generates 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 metallic substance of the present invention with the alcohol that contains in the surface treatment agent (F)
F1), volumetric molar concentration (the mol/L) (C of the alcohol in the treatment agent that obtains when making the whole hydrolysis of the alkoxyl group that contains in itself and the organoalkoxysilane
F2) relation satisfy C
F1/ C
F2=0.05～0.9, preferably satisfy 0.1～0.8.
Above-mentioned molar concentration rate (C
F1/ C
F2) during less than 0.05, because silicate compound (A) disappears from organoalkoxysilane (B) to the effect that the formation siloxanes combines the reactive functional groups of necessity with organoalkoxysilane (B), so the adhesivity of the erosion resistance of tunicle, outer coating, formed tunicle and metal material surface reduces.In addition, molar concentration rate (C
F1/ C
F2) surpass at 0.9 o'clock, because the effect height of reactive functional groups, so form the siloxanes combination between the organoalkoxysilane (B), make the composition that plays a role as the Corrosion of Metallic Materials inhibitor can not immobilization in tunicle.
Adjustment is derived from volumetric molar concentration (the mol/L) (C of alcohol of the alkoxyl group of organoalkoxysilane (B)
F1) method there is no particular limitation, for example, can enumerate: mixed in organoalkoxysilane in the solution of silanol condensation catalyst and water, the alcohol amount that control generates as by product is adjusted the method for concentration; And remove the method etc. that the alcohol and water that generates as by product is adjusted concentration.
In addition,, can enumerate the qualification especially of measuring method of determining alcohol: vapor-phase chromatography or ion chromatography isochrome spectrometry, and the nucleus magnetic resonance optical spectroscopy etc.
In addition, metallic substance of the present invention preferably satisfies 0.01～50 with the mass ratio (C/F) of above-mentioned metallic compound (C) in the surface treatment agent and alcohol (F), more preferably satisfies 0.1～40.If in above-mentioned scope, then make the composition immobilization in tunicle that plays a role as the Corrosion of Metallic Materials inhibitor easily, therefore from the erosion resistance of gained tunicle, outer coating, consider, be preferred with the better aspect of the adhesivity of metal material surface.
And metallic substance of the present invention preferably satisfies 0.01～25 with the mass ratio (D/F) of compound (D) in the surface treatment agent and alcohol (F), more preferably satisfies 0.1～20, further preferably satisfies 0.1～15.If in above-mentioned scope, then make the composition immobilization in tunicle that plays a role as the Corrosion of Metallic Materials inhibitor easily, therefore from the erosion resistance of gained tunicle, outer coating, consider, be preferred with the better aspect of the adhesivity of metal material surface.
Metallic substance of the present invention is preferably 0.01～3.0 with the mass ratio (A/B) of the silicate compound (A) in the surface treatment agent with organoalkoxysilane (B), 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, and the situation of the adhesivity reduction of formed tunicle and metal material surface is arranged.
Metallic substance of the present invention is with the silicate compound (A) in the surface treatment agent and the total quality (A+B) of organoalkoxysilane (B), and 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.
Metallic substance of the present invention is with the silicate compound (A) in the surface treatment agent and the total quality (A+B) of organoalkoxysilane (B), is preferably 0.01～1.5 with the mass ratio (D/ (A+B)) of compound (D), and more preferably 0.05～1.0.During less than 0.01, the situation that tunicate erosion resistance reduces, above 1.5 o'clock, when the adhesivity of erosion resistance, ground connection property, tunicle and the metal material surface of tunicle reduces, make the composition that plays a role as the corrosion inhibitor in the metallic substance in tunicle, be difficult to immobilized situation in addition.
＜other additive 〉
Metallic substance of the present invention as required, also can contain various additives with in the surface treatment agent.Below, the additive that contains is described.
＜water-soluble polymer and/or water system emulsifying resins 〉
Metallic substance of the present invention is with also containing at least a kind the compound (G) that is selected from water-soluble polymer and/or the water system emulsifying resins in the surface treatment agent.By adding this compound (G), can improve the 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: water-soluble polymers such as polyacrylic acid, polymethyl acrylic acid, polyacrylamide, polyvinyl alcohol are dispersed in the acrylic resin, polyurethane resin, Resins, epoxy, vibrin, polyamide resin, polyolefin resin, ethylene-propylene acid resin of the form in the water, poly-butyral resin, poly-acetal resin, fluoro-resin etc.
There is no particular limitation with the content of the compound (G) in the surface treatment agent to metallic substance.
Wherein, the total quality (A+B) of silicate compound in the treatment agent (A) and organoalkoxysilane (B) and the mass ratio of compound (G) (G/ (A+B)) are 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.
Metallic substance of the present invention is with also containing silanol condensation catalyst in the surface treatment agent.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, the L-xitix, tartrate, Citric Acid, the DL-oxysuccinic acid, propanedioic acid, toxilic acid, phthalic acid, the cyano group trimethylene phosphonic, cyano group Sanya propyl phosphonous acid, cyano group diethyl methylene phosphonic acid, cyano group propyl group dimethylene phosphonic acids methane, methane-1-hydroxyl-1, the 1-di 2 ethylhexyl phosphonic acid, ethane-1-hydroxyl-1, the 1-di 2 ethylhexyl phosphonic acid, propane-1-hydroxyl-1, the 1-di 2 ethylhexyl phosphonic acid, sulfonic acid, Phenylsulfonic acid, ketimine compound, the aldimine compound, enamine compound;
Oxazolidine compound, aminoalkyl group organoalkoxysilane etc.
Metallic substance of the present invention is with the rust-inhibiting additive that also can contain N in the surface treatment agent.As their example, can enumerate: quadrol, triethylamine, urea, guanidine etc.
Metallic substance of the present invention as required, also can contain the additive (lubricant) that is useful on the raising oilness with in the surface treatment agent.By improving the oilness of tunicle, produce flaw, reduce the damage that adds the tunicle in man-hour and play effective function preventing tunicle.
As additive, can enumerate: 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 in these solid lubricants more than a kind or 2 kinds.
Metallic substance of the present invention is with in the surface treatment agent, as required, also can add the 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 of treatment agent.But it is important adding in they do not damage the degree of the quality that obtains among the present invention, accounts for several quality % at the most in treatment solution.
Metallic substance of the present invention if can make stable treated liquid, then can be that acidity also can be alkalescence with the pH of surface treatment agent.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 of treatment agent self reduces, and is not preferred therefore.
Metallic substance of the present invention is with in the surface treatment agent, as required, can also contain solvent beyond the above-mentioned water (for example, alcohol etc.).
There is no particular limitation with the preparation method of surface treatment agent to metallic substance of the present invention.For example, can use stirrers such as mixing agitator to make by silicate compound (A), organoalkoxysilane (B), metallic compound (C), phosphate cpd and/or fluorine cpd (D) and water (E) are carried out thorough mixing.
＜surface treatment method 〉
There is no particular limitation with the surface treatment method of surface treatment agent to using metallic substance of the present invention, but preferred following surface treatment method: above-mentioned metallic substance is coated on the metal material surface with surface treatment agent, heat drying forms the tunicle amount and counts 2～1000mg/m with the Si adhesion amount on metal material surface
2Tunicle.
Below, this surface treatment method is described.
Before coating, as required,, also can implement pre-treatment to metallic substance for reaching the oil content removed on the metal material surface or the purpose of spot.Metallic substance, it is more with antirust to be that purpose is coated with antirust oil condition.In addition, even without slushing oil oiled situation, also have the oil content that adheres to or spot etc. in the operation.By implementing pre-treatment,, use metallic substance of the present invention easily that metal material surface is wetting equably with surface treatment agent with cleaning on the metal material surface.In addition, do not have oil content or spot etc., with metallic substance of the present invention with surface treatment agent with material surface when wetting equably, pretreatment procedure is not special needs.
In addition, as the method for pre-treatment, there is no particular limitation, can enumerate: methods such as hot water cleaning, solvent cleaning, alkali degreasing cleaning.
As the metallic substance that uses, 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 and do not implement galvanized iron plate.
, can enumerate: rolling method, pickling process, spraying coating method etc. with the method for surface treatment agent as metallic substance according to selections such as the shape the suitableeest suitable method of processed metallic substance to the coating of metallic substance.
More specifically, for example,, then use rolling method, perhaps treatment solution is sprayed to metallic substance and carry out roll-in then or the body of under high pressure blowing is adjusted glue spread if tabular.If the moulding product then can be set forth in dipping taking-up in the treatment solution, according to circumstances blow away remaining treatment solution and adjust glue spread etc. with pressurized air.
Heating temperature as will be formed on filming on the metal material surface and carry out drying the time is preferably 40～250 ℃, more preferably 60～200 ℃, is preferably 60～180 ℃ especially.If 40 ℃ of less thaies, then can be residual as the moisture of the main solvent of treatment agent of the present invention, metallic compound can't be fixed, perhaps the erosion resistance of tunicle can reduce.If surpass 250 ℃, the situation that has erosion resistance to reduce the crack then appears easily, in the tunicle.There is no particular limitation to heating and drying method, uses hot blast, induction heater, infrared rays, near infrared ray etc. to heat, and the treatment agent drying is got final product.
In addition, heat-up time, can be according to selections such as the kind suitable the suitableeest condition of the metallic substance that uses with the compound in the surface treatment agent.Wherein, consider from aspects such as productivitys, preferred 0.1～60 second, more preferably 1～30 second.
Adjusting the tunicle amount of the tunicle that forms on the metal material surface, make it in the Si adhesion amount, is 2～1000mg/m
2, be preferably 10～800mg/m
2, more preferably 20～500mg/m
2Not enough 2mg/m
2The time, the situation that can't obtain sufficient effect of the present invention is arranged, surpass 1000mg/m
2The time, can be saturated except effect, unfavorable economically, also can cause the reduction of erosion resistance sometimes because of situation.
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 use resin emulsions such as known vinylformic acid, urethanum, epoxy, uses after perhaps adding silicon-dioxide, rust-preventive agent, lubricant, UV light absorber, pigment therein.
By using above-mentioned metallic substance to carry out the surface treatment of metallic substance with surface treatment agent, can form have erosion resistance, outer coating, thermotolerance, weldability, processibility, ground connection property, anti-finger printing continuously, the good adhesion of particularly formed tunicle and metal material surface can make the composition immobilized surface treatment capsule in tunicle that plays a role as the Corrosion of Metallic Materials inhibitor.
Use metallic substance of the present invention with the surface-treated metal material that surface treatment agent obtains, go for various uses.For example, can enumerate: the material that in various fields such as building, electric, automobile, uses etc.
Embodiment
Below, by embodiment and comparative example effect of the present invention being described, 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 the 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 is represented 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), be meant on the two sides of steel plate to have 20g/m respectively
2Plating.
(2) pre-treatment (cleaning)
As the making method of test film, at first use Japanese PARKERIZING to make パ Le Network リ-Application N364S and handle above-mentioned surface, remove lip-deep oil content or spot for the examination material.Wash with tap water then, confirm that metal material surface is soaked by water 100% after, and then flow through pure water, use as test board after in the baking oven of 100 ℃ of atmosphere, removing moisture.
(3) adjustment of treatment solution of the present invention
Mix in water according to the composition that is illustrated in each composition in the table 1 (dividing mass ratio), obtain treatment solution Gu form.
In addition, the composition in the table 1 (A), (B), (C), (D) and use level (G) are illustrated in metallic substance with the amount that cooperates among the surface treatment liquid 1kg (g).In addition, the content of pure composition (F) uses vapor-phase chromatography to measure, by the cubage C of organoalkoxysilane
F2, as following molar concentration rate (C
F1)/(C
F2) expression.
Below, the compound that uses in the his-and-hers watches 1 describes.
＜silicon compound (A) 〉
A1:SnowtexC (daily output chemical industrial company makes)
A2:SnowtexO (daily output chemical industrial company makes)
＜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, the 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 made, Polyzole AM-2386)
(4) treatment process
Use above-mentioned metallic substance surface treatment liquid, on each test board, apply, afterwards, do not wash, directly put into baking oven, under the drying temperature shown in the table 2, carry out drying, form the tunicle of the tunicle amount shown in the table 2 according to following coating method.
Drying temperature is by the envrionment temperature in the baking oven with regulate the storage period in the baking oven.In addition, drying temperature is represented 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 the test board, and (bar coater) applies with #3～5 scraping strip coating machines.The model (kind hand) by the scraping strip coating machine that uses and the concentration of treatment solution are adjusted to the tunicle amount of regulation.
Roller coat applies: at room temperature test board was flooded in treatment solution about 1 second, after the taking-up, remove excess liquid with roller, adjust glue spread.The dehydrating amount that produces by roller and the concentration of treatment solution are adjusted to the tunicle amount of regulation.
[table 4]
One of table 2 ()
[table 5]
Table 2 (two)
[table 6]
Table 2 (three)
(5) method of evaluation test
(5-1) erosion resistance evaluation
Surface-treated test board is cut into 70 * 150mm, the inside and end are sealed with the polyvinyl chloride sealing tape, carry out following test.Evaluation is to estimate the rust area rate by visual judgement.
Salt spray testing (based on SST:JIS-Z-2371):
Estimate the white rust generation area occupation ratio of SST120 after the time by visual according to following determinating reference.
Round-robin test (CCT (JASO): M609-91 (materials used in auto manufacturing corrosion test method)):
Estimate white rust generation area occupation ratio after the CCT30 circulation by visual according to following determinating reference.
Determinating reference:
◎: rust area rate less than 10%
Zero: the rust area rate is more than 10%～less than 20%
△: the rust area rate is more than 20%～less than 40%
*: the 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, carry out displacement plating with copper sulfate solution (3% aqueous solution, room temperature, dipping 5 seconds), estimate 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, peel off with Cellotape (registered trademark) and all to extrude the processing part, carry out displacement plating with copper sulfate solution (3% aqueous solution, room temperature, dipping 5 seconds), estimate the situation of peeling off of tunicle.
Determinating reference:
◎: do not peel off
Zero: have few point-like to peel off
△: slight peeling off arranged
*: have significantly and peel off
(5-3) the stripping property evaluation of metallic compound
To in the boiling water of surface-treated test board, flood 2 hours, measure the remaining quantity of metallic compound with fluorescent x-ray analyzer at pure water.Adhesion amount by the metallic compound of measuring before the test is calculated the fixed rate of metal.
Fixed rate (%)=remaining quantity (mg/m
2Adhesion amount (mg/m before the)/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
Applying commercially available trimeric cyanamide alkydpaints on surface-treated test board, making the coating thickness behind 160 ℃ of sintering is 20 μ m.Afterwards, dipping was cut into 100 chessboard grid that 1mm is square with the NT cutting machine after 2 hours in boiling water, and a part is wherein extruded 6mm with forcing machine, sticked with glue band and peeled off, and implemented the remaining situation of filming according to following evaluation.
Determinating reference:
◎: less than 5% is peeled off～is 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: arriving the degree X shape ground cutting test plate of material, it is carried out the situation of getting rusty after above-mentioned CCT (round-robin test) 80 circulates according to following determinating reference evaluation with the NT cutting machine.
Determinating reference:
◎: apart from the not enough 1mm of otch
Zero: apart from more than the otch 1mm～not enough 2mm
△: apart from more than the otch 2mm～not enough 5mm
*: more than otch 5mm
* *: filmed and peeled off
To the surface-treated metal material that the metallic substance that uses record in embodiment 1～51 and the comparative example 52～67 obtains with surface treatment agent, the result who carries out the evaluation of above-mentioned (5-1)～(5-4) is illustrated in the table 3.
In addition, the viewpoint from the practicality considers, do not have " * " and " * * " to be necessary in the above-mentioned assessment item.
[table 7]
One of table 3 ()
[table 8]
Table 3 (two)
[table 9]
Table 3 (three)
As shown in table 3, can confirm to contain the compound of regulation and adjust pure 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 plays a role as the Corrosion of Metallic Materials inhibitor.
Wherein, by the comparison of embodiment 23～26, use as can be known when having epoxy group(ing) or amino organoalkoxysilane as organoalkoxysilane (B), various characteristics is better.In addition, by the comparison of embodiment 16 and 17, with two kinds of organoalkoxysilanes and time spent, various characteristics further improves as can be known.
On the other hand, in comparative example, can't comprehensively be satisfied the result of all characteristics.
Claims (9)
1. metallic substance surface treatment agent, it is the metallic substance surface treatment agent that contains following (A)～(F):
Silicate compound (A);
Organoalkoxysilane (B);
Contain the metallic compound (C) that is selected from least a kind of metallic element among Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr and the Zn;
Be selected from least a kind the compound (D) in phosphate cpd and the fluorine cpd;
Water (E); With
The alcohol (F) that generates 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 whole alkoxyl group hydrolysis the time volumetric molar concentration (the mol/L) (C of alcohol in treatment agent that generate
F2) ratio (C
F1/ C
F2) be adjusted into 0.05～0.9 scope.
2. the described metallic substance surface treatment agent of claim 1, wherein above-mentioned alcohol (F) is 0.01～50 with the mass ratio (C/F) of above-mentioned metallic compound (C).
3. claim 1 or 2 described metallic substance surface treatment agents, the mass ratio (D/F) of wherein above-mentioned alcohol (F) and above-claimed cpd (D) are 0.01～25 scope.
4. the metallic substance surface treatment agent described in each of claim 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. the metallic substance surface treatment agent described in each of claim 1～4, wherein above-mentioned organoalkoxysilane (B) has amino and/or epoxy group(ing).
6. the metallic substance surface treatment agent described in each of claim 1～5 wherein further contains at least a kind the compound (G) that is selected from water-soluble polymer and the water system emulsifying resins.
7. the described metallic substance surface treatment agent of claim 6, the total quality (A+B) of wherein above-mentioned silicate compound (A) and above-mentioned organoalkoxysilane (B) is 0.01～0.3 with the mass ratio of above-claimed cpd (G) (G/ (A+B)).
8. the surface treatment method of metallic substance, its be on metal material surface the coating claim 1～7 each described in the metallic substance surface treatment agent, heat drying forms the tunicle amount and counts 2～1000mg/m with the Si adhesion amount on above-mentioned metal material surface
2Tunicle.
9. surface-treated metal material, its be to use that the surface treatment method of the described metallic substance of claim 8 obtains and the surface on have tunicle.
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|---|---|---|---|
| PCT/JP2008/072839 WO2010070728A1 (en) | 2008-12-16 | 2008-12-16 | Surface treating agent for metallic materials |
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| Publication Number | Publication Date |
|---|---|
| CN102257178A true CN102257178A (en) | 2011-11-23 |
| CN102257178B CN102257178B (en) | 2014-05-07 |
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|---|---|
| JP (1) | JP5555177B2 (en) |
| KR (1) | KR101278311B1 (en) |
| CN (1) | CN102257178B (en) |
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Citations (2)
| 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 |
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP1847633B1 (en) * | 2005-02-02 | 2018-08-22 | Nihon Parkerizing Co., Ltd. | Aqueous surface treating agent for metal material, surface treating method and surface-treated metal material |
-
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| 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 |
| 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 |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101278311B1 (en) | 2013-07-05 |
| JP5555177B2 (en) | 2014-07-23 |
| TWI447264B (en) | 2014-08-01 |
| CN102257178B (en) | 2014-05-07 |
| JPWO2010070728A1 (en) | 2012-05-24 |
| TW201024460A (en) | 2010-07-01 |
| KR20110083744A (en) | 2011-07-20 |
| WO2010070728A1 (en) | 2010-06-24 |
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