CN102741454A - Metal surface treatment agent and metal surface treatment method - Google Patents

Metal surface treatment agent and metal surface treatment method Download PDF

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Publication number
CN102741454A
CN102741454A CN201180007778XA CN201180007778A CN102741454A CN 102741454 A CN102741454 A CN 102741454A CN 201180007778X A CN201180007778X A CN 201180007778XA CN 201180007778 A CN201180007778 A CN 201180007778A CN 102741454 A CN102741454 A CN 102741454A
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compound
metal
surface treatment
resin
acid
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CN102741454B (en
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齐藤贵延
石川贵
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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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
    • 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
    • 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
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
    • 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
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

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

Abstract

Even if a resin film is laminated onto a substrate surface made from aluminium or an aluminium alloy, and molding is subsequently carried out, the metal surface treatment agent for forming a surface treatment coating that is provided imparts a high adhesion so as to prevent peeling of the laminate film, and can maintain a stable adhesion over the long term, regardless of exposure to solvents and acids. The metal surface treatment agent for forming a metal surface treatment coating for a resin undercoat or laminate on a substrate surface made from aluminium or an aluminium alloy contains a Cr(III) compound (A), and at least one type of compound (B) selected from inorganic compounds and organic compounds having film-forming properties and organic compounds which can bond to compound (A) to form a film. If the metal Cr equivalent mass of compound Cr(III) compound (A) is set to M, and the mass of compound (B) is set to N, the ratio N/M is set to fall within the range of 0.005 to 1.

Description

Metal conditioner and metal surface treating method
Technical field
The present invention relates to laminated film or resin coating film substrate with metal conditioner and the metal surface treating method that uses this metal conditioner; Said metal conditioner is used to form surface treatment capsule, and this surface treatment capsule can make the substrate material surface processed by aluminum or aluminum alloy and the adaptation between laminated film or the resin coating film be improved.
More specifically; Laminated film or the resin coating film substrate that the present invention relates to be used to form the excellent surface treatment capsule of resistance to chemical reagents is with metal conditioner etc.; Said surface treatment capsule forms resin coating film, implements under the situation that the shaping of harshnesses such as deep-draw processing, attenuate processing (processing of ご I) or stretch-draw processing processes then at the substrate material surface that resin film layer is pressed in the substrate material surface processed by aluminum or aluminum alloy or processed by aluminum or aluminum alloy; Also can give the high adaptation that this laminated film or resin coating film are peeled off, and then also can keep high adaptation in being exposed to acid, solvent etc. for a long time the time.
Background technology
Lamination process is the working method that resin system film (below be called resin molding or laminated film) heating is pressed on metal material surface, is to be one of metal material surface method for coating of purpose to protect the surface or to give designability, has been applied to various fields.With through comparing at metal material surface coating resin compsn and the method that makes its drying form resin coating film, the solvent that this lamination process produces when drying is few, and the generation of waste gas such as carbonic acid gas or greenhouse gases is also less.Therefore; Consider preferred the use from the environment protection aspect; Its purposes enlarges, and has been used to for example be main body or cover materials, containers for food use or the drying battery container etc. of raw-material food with jar with aluminium sheet material, steel sheet material, Packaging Aluminum Foil or stainless steel foil etc.
Particularly nearest; As the exterior material of such as the portable equipment that uses in mobile phone, electronic notebook, notebook computer or the pick up camera etc. with lithium-ion secondary cell; Tinsels such as preferred aluminium foil that functional quality is light and barrier is high or stainless steel foil have been used lamination process to the surface of such tinsel.In addition, study, and, also the tinsel through lamination process is studied as the exterior material of this lithium-ion secondary cell to lithium-ion secondary cell as the drive energy of electromobile or hybrid vehicle.
For for the laminated film that uses in the above-mentioned lamination process, after directly fitting on the metallic substance, add hot pressing.Therefore, with the coating resin compsn and make it dry and general resin coating film that form is compared, it has can suppress raw-material waste, pin hole (defective part) less and advantage such as excellent in workability.As the material of laminated film, use polyamide-based resins such as polyolefine such as polyester resins such as polyethylene terephthalate and PEN, Vilaterm and Vestolen PP 7052, nylon usually.
With the laminated film lamination process when metal material surface (following also abbreviate as " metallic surface "); For the adaptation that improves laminated film and metallic surface and the erosion resistance of metallic surface; After the metallic surface being carried out degreasing washing, to implement chemical conversion processing such as Plessy's green hydrochlorate etc. usually.But such chemical conversion processing need be used to remove the washing procedure of unnecessary treatment solution after processing, need expend cost and the washing water of discharging from this washing procedure are carried out wastewater treatment.Particularly chemical conversion processing such as Plessy's green hydrochlorate etc. comprises chromic treatment solution owing to will use, and therefore, in recent years from the consideration to environment, has tended to painstakingly avoid such processing.
On the other hand, the metallic surface is not implemented processings such as chemical conversion processing and when carrying out lamination process, have the problem that laminated film is peeled off from the metallic surface or metallic substance takes place to corrode and so on.For example; For containers for food use or wrapping material, in content being packed into through container after the lamination process or wrapping material after, implement with the sterilization is the heat treated of purpose; But when carrying out this heat treated, may cause laminated film to be peeled off from the metallic surface.In addition, for exterior material of lithium-ion secondary cell etc., in its manufacturing process, to stand the high processing of degree of finish.What the ionogen of lithium-ion secondary cell used is organic solvent and fluorine class lithium complex salts such as lithium hexafluoro phosphate or LiBF4 such as ethyl-carbonate or diethyl carbonate.Therefore; Such exterior material is behind the process life-time service; Can produce following problem: just as electrolytical organic solvent, the moisture in the atmosphere is not immersed in the container yet, generates hydrofluoric acid with the ionogen reaction; This hydrofluoric acid causes peeling off between metallic surface and the laminated film seeing through laminated film, can cause corrosion to the metallic surface simultaneously.In addition, also there is following problems: before lamination, will preheat (200 ~ 300 ℃) to metallic substance sometimes, and the effect of heat can cause that tunicle deterioration, adaptation reduce.
In order to tackle the problems referred to above, proposed before the lamination process the metallic surface form in order to improve and laminated film between method, and the treatment agent etc. of tunicle of adaptation.For example, a kind of water-soluble zirconium compound of specified quantitative, the water-soluble or water dispersible vinyl resin and substrate treating agent water-soluble or water dispersible thermohardening type linking agent of ad hoc structure of containing disclosed in the patent documentation 1.In addition, a kind of water-soluble zirconium compound of specified quantitative and/or chromium-free metal surface treatment agent of water-soluble titanium compound, organic phospho acid compound and tannin of containing proposed in the patent documentation 2.In addition, disclose the metal finishing medicament of a kind of pH in 1.5 ~ 6.0 scopes in the patent documentation 3, it contains the compound of amination phenol polymer and special metals such as Ti and Zr.In addition, a kind of amination phenol polymer, acrylic polymers, metallic compound and as required and the resin molding of the phosphorus compound (C) that uses of containing disclosed in the patent documentation 4.
In addition; As the chemical conversion surface treatment agent that does not contain 6 valency chromium that has used 3 valency chromium cpds; A kind of chromium cpd that comprises phosphoric acid salt, 3 valencys, fluorine cpd, and the chemical conversion surface treatment agent of metallic compounds such as Zn, Ni have for example been proposed in patent documentation 5; Wherein point out, can form the excellent Plessy's green hydrochlorate tunicle of erosion resistance and adaptation.In addition; A kind of chromium cpd, Zr compound and/or Ti compound that contains 3 valencys, nitrate compound, Al compound, and the chemical conversion surface treatment agent of fluorine cpd are disclosed in the patent documentation 6; Wherein point out, can form the excellent chemical conversion of erosion resistance and adaptation and handle film.In addition, a kind of metallic surface coating composition that contains water, fluorine metal hydrochlorate (Off Le オ ロ メ タ レ one ト) anionic component and water soluble fluoridized chromium component is disclosed in the patent documentation 7.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-265821 communique
Patent documentation 2: TOHKEMY 2003-313680 communique
Patent documentation 3: TOHKEMY 2003-138382 communique
Patent documentation 4: TOHKEMY 2004-262143 communique
Patent documentation 5: japanese kokai publication hei 7-126859 communique
Patent documentation 6: TOHKEMY 2006-328501 communique
Patent documentation 7: Japan special table 2009-536692 communique
Summary of the invention
The problem that invention will solve
Disclosed treatment agent all is the surface treatment agents that contain chromium in the patent documentation 5 ~ 7, and formed surface treatment capsule all has the advantage of erosion resistance and excellent heat resistance.But when increasing the chromium content in the tunicle, there is the tendency that causes shaping processability to reduce in order further to improve erosion resistance.Particularly, under the situation of implementing harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, possibly cause tunicle to peel off or chap, there is the hidden danger of the erosion resistance decline that causes metallic substance in its result.
In addition; Disclosed surface treatment agent is called as so-called response type treatment agent in the patent documentation 5 ~ 7; Free hydrogen fluoride in the treatment solution can promote the dissolving on metal matrix material surface, and can be because of form the surface treatment capsule that comprises chromium etc. based on this dissolved surface reaction.When using such response type treatment agent; Existence possibly cause on metal matrix material such as above-mentioned aluminium sheet material or Packaging Aluminum Foil, being suitable for the difficulty that becomes because of the existence of etching compositions such as free hydrogen fluoride causes the metal matrix material surface that the hidden danger of over etching takes place.Particularly, for metal matrix material as thin as a wafer such as aluminium foil, not preferred over-drastic etching.In addition, when utilizing the response type treatment agent to handle,, therefore when wastewater treatment, also need spend in order to handle the cost of contained heavy metal in the treatment agent owing to after processing, will wash.
The object of the present invention is to provide a kind of laminated film or resin coating film substrate that is used to form surface treatment capsule to use metal conditioner; Said surface treatment capsule forms resin coating film, implements under the situation that harsh shapings such as deep-draw processing, attenuate processing or stretch-draw processing process then at the substrate material surface that resin film layer is pressed in the substrate material surface processed by aluminum or aluminum alloy or processed by aluminum or aluminum alloy; Also can give the high adaptation that this laminated film or resin coating film are peeled off, and then adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.In addition, another object of the present invention is to provide the metal surface treating method that uses this metal conditioner, the metallic substance that utilizes the metal finishing tunicle of this metal surface treating method formation and have the surface treatment capsule that utilizes this metal surface treating method formation.
The method of dealing with problems
The metal conditioner of the present invention that is used to address the above problem is to be used at the substrate material surface form layers press mold of being processed by aluminum or aluminum alloy or the resin coating film substrate metal conditioner with the metal finishing tunicle; Wherein, This metal conditioner contains Cr (III) compound (A) and compound (B); Said compound (B) for be selected from organic cpds with film-forming properties and mineral compound and can with the organic cpds of above-claimed cpd (A) be combined into film at least a kind; With the Metal Cr reduced mass of above-mentioned Cr (III) compound (A) be made as M, when the quality of above-claimed cpd (B) is made as N, N/M is 0.005 ~ 1.
According to this invention; Because be made as M at Metal Cr reduced mass with Cr (III) compound (A), when the quality of compound (B) is made as N; Make N/M in above-mentioned scope; And the content that makes Cr (III) compound in the metal conditioner reaches the state of high density (rich), therefore can make the surface treatment capsule that forms at the substrate material surface of being processed by aluminum or aluminum alloy also become the surface treatment capsule that is rich in Cr of erosion resistance and excellent heat resistance.And; Since contain in this metal conditioner be selected from organic cpds with film-forming properties and mineral compound and can with at least a kind the compound (B) in the organic cpds of above-claimed cpd (A) be combined into film; Therefore can improve adhesive capacity through crosslinked, chelating effect, form the excellent surface treatment capsule of shaping excellent in workability and adaptation for Cr (III).Its result; According to metal conditioner of the present invention; Can form following surface treatment capsule; Even it also can realize being difficult on surface treatment capsule, producing the high adaptation of peeling off or chapping under the situation of having implemented harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, and then adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.
In metal conditioner of the present invention; Above-claimed cpd (B) is for being selected from least a kind in organic cpds (b1), mineral compound (b2) and the organic chelate compound (b3); Said organic cpds (b1) for be selected from urethane resin, epoxy resin, polyolefin resin, vinyl resin, Vinylite, resol and the natural polymer more than a kind or 2 kinds; Said mineral compound (b2) be selected from silicate compound, zirconium compounds, titanium compound and the phosphate compounds more than a kind or 2 kinds, each intramolecularly of said organic chelate compound (b3) has at least a kind of functional group that is selected from more than 2 in hydroxyl, carboxyl, phosphonate group, phosphate, amino and the carboxamido-group.
According to this invention; Because the compound (B) with film-forming properties is for being selected from least a kind in above-mentioned organic cpds (b1), above-mentioned mineral compound (b2) and the above-mentioned organic chelate compound (b3); Therefore; Such compound (B) can improve adhesive capacity through crosslinked, the chelating effect for Cr (III), makes to have the adhesive capacity that can bring high shaping processability and adaptation in the surface treatment capsule that is rich in Cr.Its result; Can form following surface treatment capsule; Even it is under the situation of the shaping processing of having implemented harshnesses such as deep-draw processing, attenuate processing or stretch-draw processing; Also can realize being difficult on surface treatment capsule, producing the high adaptation of peeling off or chapping, and then adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.
With regard to metal conditioner of the present invention, above-mentioned metal conditioner is used for after this metal conditioner is coated above-mentioned metal matrix material surface, carrying out drying and forms above-mentioned metal finishing tunicle.
The metal conditioner of this invention is to be used for that this metal conditioner is coated the metal matrix material surface to carry out the so-called application type treatment agent that drying forms the metal finishing tunicle afterwards.Therefore; When using metal conditioner of the present invention; Do not exist existence to cause the metal matrix material surface that the hidden danger of over etching takes place, can be suitable for without a doubt yet for aluminium sheet material or the thin metal matrix material of Packaging Aluminum Foil equal thickness because of etching compositions such as free hydrogen fluoride in the treatment solution.In addition, therefore the metal conditioner of the present invention that the application type method relates to not only can reduce processing cost owing to need as the situation of using the response type treatment agent, after processing, not wash, saving that can also the implementation space.
The metal surface treating method of the present invention that is used to address the above problem is characterised in that; The metal conditioner of the invention described above is coated on the substrate material surface of being processed by aluminum or aluminum alloy, carries out heat drying in 60 ~ 250 ℃ temperature then and form surface treatment capsule.
According to this invention, as stated, can form and can realize being difficult on surface treatment capsule, producing the high adaptation of peeling off or chapping, and then the surface treatment capsule of adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.In addition, owing to be the application type method that need as the situation of using the response type treatment agent, after processing, not wash, therefore can reduce processing cost.
The metal finishing tunicle of the present invention that is used to address the above problem is characterised in that it is to utilize the metal treatment surface method of the invention described above to form.
The metal finishing tunicle of this invention utilizes the related metal surface treating method of application type method that above-mentioned metal conditioner is handled and forms.The surface treatment capsule that forms can realize being difficult for the high adaptation peeling off or chap, and then adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.In addition, owing to be to utilize the application type method that need as the situation of using the response type treatment agent, after processing, not wash to form, therefore can form as handling film cheaply.
The metallic substance of the present invention that is used to address the above problem is characterised in that its surface treatment capsule that forms through the metal surface treating method that will utilize the invention described above is arranged at the substrate material surface of being processed by aluminum or aluminum alloy and obtains.
The effect of invention
According to metal conditioner of the present invention; Can form following surface treatment capsule; Even it is under the situation of the shaping processing of having implemented harshnesses such as deep-draw processing, attenuate processing or stretch-draw processing; Also can realize being difficult on surface treatment capsule, producing the high adaptation of peeling off or chapping, and then adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.
According to metal surface treating method of the present invention; Because this method carries out heat drying metal conditioner of the present invention is coated the substrate material surface of being processed by aluminum or aluminum alloy after, therefore can be, force the surface treatment capsule of worker's adaptation and drug-resistant excellent in stability in this substrate material surface formation erosion resistance, thermotolerance.Owing to the coating metal surfaces treatment agent after, carry out heat drying and do not wash, so need not follow the wastewater treatment of washing, not only can reduce processing cost, saving that can also the implementation space.
According to metal finishing tunicle of the present invention, can realize be difficult for producing the high adaptation of peeling off or chapping, and then adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.In addition, because this metal finishing tunicle is to utilize the application type method that need as the situation of using the response type treatment agent, after processing, not wash to form, therefore can becomes and handle film cheaply.
According to metallic substance of the present invention; Because it contains the metal finishing tunicle with above-mentioned characteristic at the substrate material surface of being processed by aluminum or aluminum alloy; Therefore at this surface treatment capsule laminated resin molding or after forming resin coating film; Even under the situation of having implemented harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, this laminated film or resin coating film also are difficult for peeling off, and adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.
Description of drawings
[Fig. 1] Fig. 1 is a schematic cross sectional view, shows an example of using metal conditioner of the present invention to form the metallic substance of surface treatment capsule.
Nomenclature
1 aluminum or aluminum alloy body material
2 surface treatment capsules
3 resin moldings (laminated film) or resin coating film
10 metallic substance
Embodiment
Below, describe to metal conditioner of the present invention, metal surface treating method, metal finishing tunicle and metallic substance.
[metal conditioner]
Metal conditioner of the present invention is to be used for forming the treatment agent of the substrate of laminating material 3 (resin molding or laminated film) with metal finishing tunicle 2 on the surface of the body material of being processed by aluminum or aluminum alloy 1 shown in Figure 1.And; It is characterized in that; Metal conditioner contains Cr (III) compound (A) and compound (B); Said compound (B) for be selected from organic cpds with film-forming properties and mineral compound and can with the organic cpds of above-claimed cpd (A) be combined into film at least a kind, with the Metal Cr reduced mass of above-mentioned Cr (III) compound (A) be made as M, when the quality of above-claimed cpd (B) is made as N, N/M is 0.005 ~ 1.
Below, formation of the present invention is elaborated.
(compound (A))
Cr (III) compound (A) is the chromium cpd that does not contain 3 valencys of 6 valency chromium.When utilization comprised the metal conditioner formation surface treatment capsule of this Cr (III) compound, Metal Cr can make the driving fit securely of substrate material surface and surface treatment capsule with the metal matrix material reaction.Though can utilize Cr (III) compound self to form the Cr compound layer; But through further containing compound (B); Metal conditioner can show excellent film-forming properties; Its result utilizes the water tolerance and the resistance to chemical reagents of the surface treatment capsule of this metal conditioner formation to improve, and particularly erosion resistance obtains tremendous raising.
As Cr (III) compound, can enumerate chromic salts, complex compound or coordination compound, specifically can enumerate: chromium sulphate, chromium nitrate, chromium fluoride, Plessy's green, chromium+oxalic acid, chromium acetate, biphosphate chromium, chromium acetylacetonate (Cr (C 5H 7O 2) 3) wait 3 valency chromium cpds.In addition, also can use reductive agent to generate Cr (III) by Cr (VI) reduction.
Be made as M at Metal Cr reduced mass with Cr (III) compound (A), when the quality of compound (B) is made as N, the content of Cr (III) compound makes N/M in 0.005 ~ 1 scope.High through making in the Cr concentration of Metal Cr reduced mass; Make the ratio of contained Cr (III) compound in the metal conditioner in above-mentioned scope; As stated; Metal Cr can make the driving fit securely of substrate material surface and surface treatment capsule with the metal matrix material reaction, and can form the Cr compound layer by Cr (III) compound self.Its result; Can improve adaptation between metal matrix material surface and the gained surface treatment capsule simultaneously, reach the adaptation between laminated film or resin coating film and the gained surface treatment capsule, and water tolerance, resistance to chemical reagents and erosion resistance are improved.
In addition, for utilizing N/M for the surface treatment capsule that the metal conditioner in the above-mentioned scope forms, the ratio (Q/P) of the quality P of the Metal Cr that contains in this surface treatment capsule and the quality Q except Metal Cr is in 0.005 ~ 1 scope.The surface treatment capsule that is rich in Cr so not only has excellent erosion resistance and thermotolerance because of Cr concentration is high, and, although Cr concentration is high, but still have excellent shaping processability and adaptation.Usually think simply that the surface treatment capsule that is rich in Cr is more crisp, but in the present invention, can think, formed the surface treatment capsule with firm tridimensional network, its result also is difficult for peeling off or chapping even stand intensive processing.Here, the surface treatment capsule with firm tridimensional network is to be brought by the compound with film-forming properties (B), and it is based on the adhesive capacity (bridging property) of this compound (B) for Cr.
N/M is lower than at 0.005 o'clock, and the Q/P of the surface treatment capsule of formation also is lower than 0.005, and containing of Metal Cr proportionally relatively obviously increased, and easy generation is peeled off, chapped.N/M was greater than 1 o'clock; The Q/P of the surface treatment capsule that forms also surpasses 1; Exist proportionally reduce relatively containing of Metal Cr, tendency that erosion resistance reduces; Its result, adaptation between metallic surface and the gained surface treatment capsule reduces, and possibly cause corrosive medium to enter into the metallic surface and causes erosion resistance to reduce.No matter be which kind of situation, when N/M departs from above-mentioned scope, all possibly can't guarantee the stable adaptation when particularly long-term exposure is in solvent, acid.
From improving adaptation, the even more ideal viewpoint of water tolerance, resistance to chemical reagents and erosion resistance being considered, preferred N/M is 0.01 ~ 0.5.More preferably 0.05 ~ 0.25.The Q/P of the surface treatment capsule of this moment is also preferably about 0.01 ~ 0.5 scope.More preferably 0.05 ~ 0.25.
In this application, said " solids component " of compound (B), be meant in compound (B) composition that constitutes metal conditioner except after state solvent etc. and evaporate into the solids component grading.Therefore; Said N/M is that 0.005 ~ 1 metal conditioner is equal to: with respect to Cr (III) compound (A) that constitutes metal conditioner and the total amount (all solids composition) of compound (B), the content of Cr (III) compound (A) is counted 50 ~ 99.5 quality % with metal conversion amount.Need to prove that the quality of Metal Cr can be used the x-ray fluorescence analysis device " 3270E " of electrical industry of science Co., Ltd., under the condition of pipe ball: Rh, voltage-to-current: 50KV-50mA, measure.
(compound (B))
Compound (B) be selected from organic cpds with film-forming properties and mineral compound and can with at least a kind of compound in the organic cpds of above-claimed cpd (A) be combined into film.Compound (B) with film-forming properties is undertaken the tackiness agent function in the surface treatment capsule that is rich in Cr (III), have to make the surface treatment capsule tolerance of being rich in Cr (III) force worker's effect.In addition, utilize the surface treatment capsule of the metal conditioner formation of inclusion compound (B) to pass through to improve film-forming properties, can make barrier be able to keep, and erosion resistance, water tolerance, solvent resistance and resistance to chemical reagents are improved.
As the compound with film-forming properties (B) or can with the compound (B) of above-claimed cpd (A) be combined into film, can enumerate: be selected from the organic cpds more than a kind or 2 kinds (b1) in urethane resin, epoxy resin, polyolefin resin, vinyl resin, Vinylite, resol and the natural polymer; Be selected from the mineral compound more than a kind or 2 kinds (b2) in silicate compound, zirconium compounds, titanium compound and the phosphate compounds; Each intramolecularly has the organic chelate compound (b3) that is selected from least a kind of functional group in hydroxyl, carboxyl, phosphonate group, phosphate, amino and the carboxamido-group more than 2.This organic chelate compound (b3) be can with the compound of above-claimed cpd (A) be combined into film.Be combined with in the metal conditioner and be selected from 1 in the above-claimed cpd (b1) ~ (b3) or compound more than 2 kind.
At first, the example of organic cpds (b1) is as follows.Organic cpds (b1) so long as can be in metal conditioner of the present invention the compound of the effect expected of stable existence and can obtaining get final product, but do not receive the qualification of the kind of organic cpds.With regard to the water-solubleization form of organic cpds, can be water-soluble or water dispersible (emulsion, dispersion liquid) in any form.In addition, with regard to ionic, can be ionic arbitrarily in anionic property, nonionic, the cationic.
As urethane resin; The urethane that obtains etc. can be listed below: the polycondensate being formed by alcohol such as polyester polyols (particularly binary) alcohol, polyethers polynary (particularly binary) alcohol, polycarbonate polynary (particularly binary) alcohol polynary (particularly binary) and aliphatics many (particularly two) isocyanic ester, alicyclic many (particularly two) isocyanic ester and/or aromatic series many (particularly two) isocyanate compound is in the urethane resin; Use N, N-dimethylamino dihydroxy methylpropane etc. to have the urethane that the such polyvalent alcohol with polyoxyethylene chain of amino polyvalent alcohol or polyoxyethylene glycol obtains as the part of above-mentioned polyvalent alcohol.
In these urethane, through to N, the part or all of amino that N-dimethylamino dihydroxy methylpropane etc. has amino polyvalent alcohol carries out quaternized its cationization that makes, and can make its water-solubleization.In addition, through improving the importing ratio of polyoxyethylene chain, can realize water-solubleization or water-dispersionization with non-ionic form.In addition, can obtain the urethane resin of anionic property through following method, promptly; Make the carbamate prepolymer that two ends have NCO by POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol; Make this prepolymer and carboxylic acid with 2 hydroxyls or the reaction of its reactive derivatives, must arrive the verivate that two ends have NCO, then; Adding trolamines etc. are to form ionomer (triethanolamine salt); And then add entry and form emulsion or dispersion liquid, and then add diamines as required to carry out chain extension, obtain the urethane resin of anionic property thus.
Carboxylic acid that uses when manufacturing has the water-dispersible polyurethane resin of anionic property and reactive derivatives are used for importing acidic-group and making urethane resin be water dispersible at urethane resin.As employed carboxylic acid, can enumerate dimethylolalkanoic acids such as dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid.In addition, as reactive derivatives, can enumerate the such hydrolyzable ester of acid anhydrides.Like this, through making water-dispersible polyurethane resin (A), durable adaptation, acidproof adaptation are improved for from water dispersible and do not use or do not use as far as possible emulsifying agent.
As epoxy resin, can enumerate: epoxy compounds with 2 above glycidyls; Have dihydroxyphenyl propane or Bisphenol F as the unitary epoxy compounds in the skeleton; Or make diamines effects such as epoxy compounds with 2 above glycidyls and quadrol, cationization take place and the epoxy resin that obtains; Make the nonionic epoxy resin that has dihydroxyphenyl propane or the Bisphenol F polyoxyethylene glycol that had addition on the side chain of epoxy compounds of 2 above glycidyls as the unitary epoxy compounds in the skeleton or other and obtain; Or the like.
As epoxy resin, can use to have dihydroxyphenyl propane or Bisphenol F as the unitary epoxy resin in the skeleton, also can use the silane modified or phosphoric acid modification of the part or all of glycidyl of this epoxy resin and the epoxy resin that obtains.
As having dihydroxyphenyl propane or Bisphenol F, can enumerate: the resin that obtains through repeatedly dehydrochlorination and addition reaction by epoxy chloropropane and dihydroxyphenyl propane or Bisphenol F as the unitary epoxy resin in the skeleton; And by the resin that obtains through repeatedly addition reaction between epoxy compounds with the glycidyl that (is preferably 2) more than 2 and the bis-phenol (A, F).
Kind as epoxy compounds; Can specifically be listed below: the diglycidyl ether of bis-phenol (A, F), o-phthalic acid diglycidyl ester, m-phthalic acid 2-glycidyl ester, terephthalic acid diglycidyl ester, PHB 2-glycidyl ester, tetrahydrochysene phthalic acid 2-glycidyl ester, hexahydrobenzene dioctyl phthalate 2-glycidyl ester, succsinic acid 2-glycidyl ester, hexanodioic acid 2-glycidyl ester, sebacic acid 2-glycidyl ester, ethylene glycol bisthioglycolate glycidyl ether, Ucar 35 diglycidyl ether, 1; 4-butanediol diglycidyl ether, 1; 6-pinakon diglycidyl ether, the many glycidyl ethers of Sorbitol Powder, polyalkylene glycol diglycidyl ether class, trimellitic acid three-glycidyl ester, triglycidyl isocyanurate, 1, the triglycidyl group ether of the olefin oxide affixture of 4-glycidoxy benzene, diglycidyl propylidene urea, USP Kosher triglycidyl group ether, trimethylolethane trimethacrylate glycidyl ether, trimethylolpropane tris glycidyl ether, tetramethylolmethane four glycidyl group ether, USP Kosher etc.Can above-mentioned epoxy compounds be used separately respectively or the combination use.
For silane-modified degree, so long as get final product more than the degree of the effect that can confirm to bring, do not have particular restriction by these modifications, can use known silane coupling agent.
Vinyl resin can use unsaturated Acrylic Acid Monomer to carry out addition polymerization and obtain.Vinyl resin can be the homopolymer of Acrylic Acid Monomer or any resin in the multipolymer, but so long as can in surface treatment agent, get final product by stable existence, its polymeric species is not had particular restriction.
As Acrylic Acid Monomer, for example can enumerate: the just own ester of methyl acrylate, TEB 3K, ethyl propenoate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methylacrylic acid, 2-EHA, vinylformic acid, methylacrylic acid, vinylformic acid 2-hydroxy methacrylate, vinylformic acid hydroxy propyl ester, 2-hydroxyethyl methacrylate, methylacrylic acid hydroxyl propyl ester, toxilic acid, methylene-succinic acid, acrylic amide, N hydroxymethyl acrylamide, diacetone-acryloamide(DAA), glycidyl acrylate, SY-Monomer G, vinylbenzene, acrylic amide, vinyl cyanide, polyethylene glycol methacrylate-styrene polymer etc.
Vinyl resin can use the acid mono of vinylformic acid, methylacrylic acid separately.In addition, also can use above-mentioned monomer and these acid mono combination and utilize carboxylic acid to carry out Water-borne modification and the anionic property vinyl resin that obtains.In addition; Can also use vinylformic acid N, (methyl) acrylic acid alkyl amino ester such as N-dimethylamino propyl ester, methylacrylic acid N-methylamino ethyl ester are such have amino by cationic monomer and the combination of aforesaid propylene acid mono, and pass through Water-borne modification and the cationic vinyl resin that obtains.
As Vinylite, can enumerate Mannich amine modifier, polyvinyl imidazol, polyvinylpyridine, polymine, Yodo Sol VC 400 and Yodo Sol VC 400 partially or completely saponified etc. of polyvinylphenol.
In addition, about vinyl-acetic ester, can be the resin that obtains through saponification with the polymkeric substance that can obtain with the monomer copolymerization of vinyl acetate copolymerization.In addition, can also be for example to import anionic groups such as carboxylic acid, sulfonic acid, phosphoric acid in the polymkeric substance after polymerization, comprise the cation group of quaternary ammonium group and the resin that obtains through ionize.In addition, can also be to import diacetone-acryloamide(DAA) base, acetoacetyl, sulfydryl, silanol group etc. and carried out modified resins.
Need to prove, as can with the monomer of vinyl acetate copolymerization, for example can enumerate: unsaturated carboxylic acid and ester classes thereof such as toxilic acid, fumaric acid, Ba Dousuan, methylene-succinic acid, (methyl) vinylformic acid; Terminal olefin such as ethene, propylene; Alkene sulfonic acids such as (methyl) propene sulfonic acid, ethionic acid, sulfonic acid malate; Alkene sulfonic acid an alkali metal salts such as (methyl) sodium allyl sulfonate, ethylene sulfonate, sodium sulfonate (methyl) propenoate, sodium sulfonate (oxysuccinic acid mono alkyl ester), sodium disulfonate oxysuccinic acid alkyl ester; N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid an alkali metal salt etc. contain the monomer of carboxamido-group; And N-vinyl pyrrolidone, N-vinyl pyrrolidone verivate etc.
As resol, can be set forth in the polycondensate that forms by phenols (phenol, naphthols, bis-phenol etc.) and formaldehyde that bonding on the ring of phenols has (replacement) amino methyl.In addition, can also enumerate the resole that contains methylol that has from condensation property.
As natural polymer, can enumerate natural polysaecharides such as chitin, chitosan, Mierocrystalline cellulose, starch, dextrin, inulin, tannin.Also can be that part of hydroxyl, the amino that has in the structure to natural polysaecharides carries out hydroxypropylization, hydroxyethylization, methylates, glycerylization and the verivate that obtains.
As polyolefin resin, can enumerate Vestolen PP 7052; Vilaterm; The polyolefine such as multipolymer that propylene, ethene and terminal olefin formed with unsaturated carboxylic acid (for example vinylformic acid, methylacrylic acid) carry out modification and the modified polyolefin that obtains; The multipolymer that ethene and vinylformic acid (methylacrylic acid) form; Or the like.In addition, can also be the multipolymer that obtains with a small amount of other ethylene unsaturated monomer copolymerization.As the method for Water-borne modification, can also utilize ammonia, amine that the carboxylic acid that imports on the polyolefin resin is neutralized.
Can think that the film-forming properties that these organic cpds (b1) have through itself plays the effect that formation can tolerate the surface treatment capsule of forcing the worker of undertaking; Perhaps, when these organic cpds (b1) are when having the organic cpds of functional group, through playing the effect that formation can tolerate the surface treatment capsule of forcing the worker of undertaking with Cr (III) compound crosslink; Perhaps, when these organic cpds (b1) are when having the compound of above-mentioned two kinds of effects, play the effect that formation can tolerate the surface treatment capsule of forcing the worker of undertaking through this synergy.
As these organic cpds (b1), can enumerate water soluble resin, passed through self-emulsifying or utilize emulsifying agent to carry out forced emulsification and water-based crosslinkable resin or aqueous high molecular resin such as the water-based emulsion that forms, aqueous liquid dispersion.Wherein, preferably adopt the effect of heat, ultraviolet ray or electron beam etc. that number-average molecular weight can apply when forming tunicle less than 1000 monomer or oligopolymer to issue to be conigenous crosslinked and the crosslinkable resin of high molecular takes place or the crosslinkable resin of high molecular can take place with other linking agent reaction.In addition, can also to adopt number-average molecular weight be 1000 ~ 1000000 and can issue the macromolecule resin of produced film in the effect of heat etc.In addition, only otherwise destroy effect of the present invention, these macromolecule resins can be the resins with crosslinking reaction property functional group.
Below, the example of mineral compound (b2) is shown.
As silicate compound, can use silicate base metal-salt, polymeric silica, water-dispersible silica etc.For example, as the silicate base metal-salt, can enumerate sodium salt, sylvite, lithium salts.As water-dispersible silica, comprise from liquid phase synthetic liquid phase silica, from gas phase synthetic aerosil, can use wherein any in the present invention.As liquid phase silica, can enumerate colloid silica, chain silicon-dioxide, branching (ペ Application ダ Application ト shape) silicon-dioxide, tabular silicon-dioxide, hollow silica etc.Need to prove, do not have particular determination for the form of silicon-dioxide and their particle diameter.But when considering the thickness of surface treatment capsule of the present invention, the particle diameter of preferred silicon-dioxide is below 100nm.In addition, can be pure silicon dioxide colloid, also can be the silicon-dioxide that has passed through various stabilization treatment, can also be the silicon-dioxide that applies processing has been passed through on the surface.Silicate compound can be distinguished independent use or multiple combination is used.
As zirconium compounds, can use carbonate, oxide compound, oxyhydroxide, nitrate salt, vitriol, phosphoric acid salt, fluorochemical, fluoric-containing acid (salt), organic acid salt, organic complex of Zr etc.Specifically can enumerate: zirconyl carbonate, zirconyl carbonate, zirconium carbonate ammonium, zirconium carbonate ammonium (NH 4) 2[Zr (CO 3) 2(OH) 2], zirconium white (IV) (ZIRCONIUM DIOXIDE 99.5), zirconium nitrate, Zircosol ZN ZrO (NO 3) 2, zirconium sulfate (IV), zirconyl sulfate, titanium sulfate (IV), titanyl sulfate TiOSO 4, zirconium phosphate oxygen, zirconium pyrophosphate, di(2-ethylhexyl)phosphate hydrogen-oxygen zirconium, Zirconium tetrafluoride, hexafluoro zirconate H 2ZrF 6, ammonium hexafluorozirconate [(NH 4) 2ZrF 6], zirconyl acetate, methyl ethyl diketone zirconium Zr (OC (=CH 2) CH 2COCH 3) 4Deng.These zirconium compoundss can be anhydrides, also can be hydrates.
As titanium compound, can use carbonate, oxide compound, oxyhydroxide, nitrate salt, vitriol, phosphoric acid salt, fluorochemical, fluoric-containing acid (salt), organic acid salt, organic complex of Ti etc.Specifically can enumerate titanium oxide (IV) (titanium oxide), Titanium Nitrate, titanium sulfate (III), titanium sulfate (IV), titanyl sulfate TiOSO 4, titanium fluoride (III), titanium fluoride (IV), hexafluoro metatitanic acid H 2TiF 6, ammonium hexa-fluorotitanate [(NH 4) 2TiF 6], LAURIC ACID 99 MIN titanium, diisopropoxy diacetone titanium (C 5H 7O 2) 2Ti [OCH (CH 3) 2] 2, titanium acetylacetone Ti (OC (=CH 2) CH 2COCH 3) 3Deng.These titanium compounds can be anhydrides, also can be hydrates.
As phosphate cpd, can use phosphoric acid salt, condensed phosphate etc.Can enumerate generation phosphoric acid for example, two generation phosphoric acid, three generations's phosphoric acid, tetra-sodium, tripolyphosphate etc. metal-salt.As the kind of metal, can enumerate sodium, potassium, zirconium, titanium, vanadium, manganese, cobalt, nickel etc.
Below, the example of organic chelate compound (b3) is shown.
Organic chelate compound (b3) is the compound that each intramolecularly has at least a kind of functional group in the group of being selected from down more than 2: hydroxyl, carboxyl, phosphonate group, phosphate, amino, the carboxamido-group that can form tunicle with 3 valency chromium chelatings.
As organic chelate compound, can use poly-basic organic acid, organic phospho acid, polyamine compound, amide compound etc.Specifically can enumerate: tartrate, oxysuccinic acid, Hydrocerol A, xitix, quadrol, N, dinethylformamide, 1,3-diamino--2-propyl alcohol-N, N; N ', N '-tetraacethyl, amino three (methylene phosphonic acids), 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid, quadrol-N; N, N ', N '-four (methylene phosphonic acid), hexamethylene-diamine-N, N; N ', N '-four (methylene phosphonic acid), NSC 446-N, N, N '; N ", N " and-five (methylene phosphonic acids), 2-phosphonic acids butane-1,2,4-tricarboxylic acid etc.These have chelate compound also can be the alkali metal salts or ammonium salt of part.
As stated, with the Metal Cr reduced mass of Cr (III) compound (A) be made as M, when the quality of compound (B) is made as N, the content of the compound of the above explanation in the metal conditioner (B) makes N/M in 0.005 ~ 1 scope.Ratio through processing compound (B) is at the metal conditioner of above-mentioned scope; As illustrated in the explanation hurdle of above-claimed cpd (A); Can form surface treatment capsule with firm tridimensional network; Its result forces the also difficult surface treatment capsule of peeling off and chapping of worker even can form to apply.Surface treatment capsule with firm tridimensional network is brought by the compound with film-forming properties (B), and it is based on the adhesive capacity (crosslinked, chelating effect) of this compound (B) for Cr.
(solvent)
The solvent that constitutes metal conditioner is main body with water, but according to the needs of the drying property of improving tunicle etc., also can make up the water-miscible organic solvent that uses alcohols, ketone or cellosolve class.
(other composition)
In addition, do not destroy purport of the present invention and by the scope of film properties in, can add tensio-active agent, skimmer, flow agent, antibacterial mildew inhibitor, tinting material, and solidifying agent etc.In addition; In the scope of not destroying effect of the present invention, can add methylolation trimeric cyanamide, carbodiimide, and the organic crosslinking agent such as isocyanic ester and of the erosion resistance that is used to improve tunicle in order to improve γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl-triethoxysilicane, γ-An Jibingjisanyiyangjiguiwan and the N-beta-aminoethyl-silane coupling agents such as gamma-amino propyl trimethoxy silicane of adaptation.
(metal matrix material)
The process object of metal conditioner of the present invention is the body material of being processed by aluminum or aluminum alloy.Metal conditioner of the present invention is coated the surface as this metal matrix material of object being treated, thereby forms surface treatment capsule on its surface.As the metal matrix material of processing by aluminum or aluminum alloy 1, for example can enumerate: the thin plate material of processing by aluminum or aluminum alloy, packaging paper tinsel etc.
More than; According to metal conditioner of the present invention; Be made as M at Metal Cr reduced mass with Cr (III) compound (A), when the quality of compound (B) is made as N; Owing to make N/M in above-mentioned scope, and make the content of Cr (III) compound in the metal conditioner reach the high density state, therefore can make the surface treatment capsule that forms at the substrate material surface of processing by aluminum or aluminum alloy become the surface treatment capsule that is rich in Cr of erosion resistance and excellent heat resistance.And, owing to contain compound (B) in this metal conditioner, therefore can form the surface treatment capsule that adhesive capacity is high, shaping processability is excellent and adaptation is also excellent for Cr with film-forming properties.Its result; Can form following surface treatment capsule: even it is under the situation of the shaping processing of having implemented harshnesses such as deep-draw processing, attenuate processing or stretch-draw processing; Also can realize being difficult on surface treatment capsule, producing the high adaptation of peeling off or chapping, and then adaptation that also can stable for extended periods of time in being exposed to solvent, acid the time.
[metal surface treating method]
Metal surface treating method of the present invention is after the metal conditioner of the invention described above is coated the surface of the body material of being processed by aluminum or aluminum alloy, under 60 ~ 250 ℃ temperature, carries out the method for heat drying.The liquid temperature of metal conditioner is usually in 10 ~ 50 ℃ scope.Coating process for metal conditioner does not have particular restriction, preferably adopts spray method, pickling process etc.Be generally about 0.5 ~ 180 second the duration of contact of metal conditioner and metallic surface.
For formed surface treatment capsule, under 60 ~ 250 ℃ temperature, carry out heat drying.This TR can be in above-mentioned scope changes arbitrarily according to the kind of resinous principle, but more preferably 80 ~ 200 ℃.
The method of heat drying does not have particular restriction, can adopt the electromagnetic induction heating furnace of intermittent type or continous way heated air circulation type drying oven, conveyor type hot-air drying stove or use IH well heater etc., and its air quantity and wind speed etc. can be set arbitrarily.
[metallic substance]
As shown in Figure 1, metallic substance 10 of the present invention has the surface treatment capsule 2 that utilizes above-mentioned metal surface treating method processing and obtain.For example; As shown in Figure 1; On the metal matrix material that constitutes by aluminum or aluminum alloy 1, be formed with and utilize above-mentioned metal surface treating method to handle and the surface treatment capsule 2 that obtains as object being treated, and at this surface treatment capsule 2 laminated resin moldings 3, or on this surface treatment capsule 2, be formed with resin coating film 3.For the metallic substance 10 of such formation, implement harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing then.Need to prove; Shown in Fig. 1 is the example that a side surface in metal matrix material 1 is formed with surface treatment capsule 2 and resin molding or resin coating film (3), but also can be on the two sides of metal matrix material 1, promptly also form surface treatment capsule and then resin molding is set or resin coating film on the opposite side surface.
For the surface treatment capsule 2 that on metal matrix material 1, forms, as stated, the ratio (Q/P) of the quality P of the Metal Cr that contains in this surface treatment capsule 2 and the quality Q except Metal Cr is in 0.005 ~ 1 scope.The surface treatment capsule that is rich in Cr 2 so not only has excellent erosion resistance and thermotolerance because of being rich in Cr, and, although Cr concentration is high, but still have excellent shaping processability and adaptation.Need to prove that from adaptation height, water tolerance, resistance to chemical reagents and the even more ideal viewpoint of erosion resistance, preferred surface is handled the Q/P of tunicle 2 in 0.01 ~ 0.5 scope.More preferably 0.05 ~ 0.25.
In addition, the thickness of surface treatment capsule is preferably 1 ~ 100nm.When surpassing 100nm, can't tolerate and force the worker, during less than 1nm, can't guarantee that sufficient erosion resistance, adaptation etc. are by film properties.
As the purposes of metallic substance 10, can enumerate can be used in food with jar the metallic substance of main body or cover materials, containers for food use, drying battery container, the exterior material of secondary cell etc., but be not limited to these purposes, can be applicable to purposes widely.Particularly; Can enumerate to be the metallic substance of object being treated as the exterior material of following lithium-ion secondary cell and with the metal matrix material 1 processed by aluminum or aluminum alloy, and the exterior material of said lithium-ion secondary cell is to be used for the portable equipment of mobile phone, electronic notebook, laptop or pick up camera etc. recently with the exterior material of lithium-ion secondary cell, as the exterior material of the lithium-ion secondary cell of the drive energy use of electromobile or hybrid vehicle.
Embodiment
Below, in conjunction with embodiment and comparative example the present invention is carried out more detailed explanation.The present invention does not receive the restriction of following embodiment.Need to prove that following " part " refers to " mass parts ".
< Cr (III) compound (A) >
A1: chromium sulphate
A2: chromium nitrate
A3: chromium fluoride
A4: biphosphate chromium
< organic compound resin (b1) >
(urethane resin: symbol b1I)
Set of monomers is become: polyhydroxy reactant " by m-phthalic acid and 1, the polyester polyol that the 6-pinakon forms (number-average molecular weight: 2000) 200 parts, TriMethylolPropane(TMP) (molecular weight: 32 parts of 134) 5 parts, N methyldiethanol amine ", isocyanate prepolymer composition " 118 parts of isophorone diisocyanates ", chainextender " 5 parts of quadrols ".
Urethane resin a synthetic as follows: above-mentioned polyhydroxy reactant and above-mentioned isocyanate prepolymer composition are reacted in methyl ethyl ketone solvent, in 80 ℃, obtain carbamate prepolymer.In methyl-sulfate (30 parts) aqueous solution, after the emulsification, they are reacted in 10% aqueous solution of chainextender this carbamate prepolymer, remove then and desolvate, obtain urethane resin I.
(epoxy resin: symbol b1II)
Composition 1 " dihydroxyphenyl propane based epoxy resin (Yuka Shell Epoxy Co., Ltd. system, EPYCOTE828) (epoxy equivalent (weight): 187g) 235.7 parts ", composition 2 " 59.4 parts of dihydroxyphenyl propanes ", composition 3 " 0.1 part of catalysts (lithium chloride) ", composition 4 " 14 parts of diethylolamine ".
Epoxy resin b1 synthetic as follows: have in the four neck flasks of 125 parts of mentioned component 1 ~ 3 and propylene glycol monomethyl ether in adding, the limit import the nitrogen limit in stir, 140 ℃ make its reaction, obtain reaction product solution.Then, add 343.3 parts of propylene glycol monomethyl ether, 8.2 parts of hexamethylene diisocyanates, in stir down, 65 ℃ make its reaction, obtain the modified high-molecular epoxy resin solution.Then, add 92.7 parts of propylene glycol monomethyl ether and mentioned component 4, in stir down, 65 ℃ make its reaction, after reaction finishes, add 154.7 parts of propylene glycol monomethyl ether, obtain the aqueous solution of amine-modified epoxy resin II.
(vinyl resin: symbol b1III)
Adopted following monomer to form: " 20 parts of TEB 3Ks, 40 parts of Bing Xisuandingzhis, 10 parts of methylacrylic acid 2-hydroxy propyl esters, 10 parts of vinylbenzene, methylacrylic acid N, 20 parts of N-dimethylamino propyl ester ".
Compound method is following: in mixed 100 parts of the 10 quality % emulsifier aqueous solutions that obtain with 6:4 by reactive emulsifier " Adeka Reasoap NE-20 " (Asahi Denka Co., Ltd.'s system) and non-ionic emulsifier " Emulgen 840S " (Kao Corp's system), mix above-mentioned monomer; Utilize homogenizer to carry out emulsification in 10 minutes, obtain the monomer emulsion with 5000rpm.Then; Take into account and add 150 parts of above-mentioned emulsifier aqueous solutions in the four neck flasks of monomer supply pump to possessing stirrer, reflux exchanger, temperature, remain in 40 ~ 50 ℃, join the 5 quality % aqueous solution (50 parts) and the above-mentioned monomer emulsion of ammonium persulphate in the tap funnel respectively; And this tap funnel is installed on other mouthful neck of flask; Drip with about 2 hours, and temperature is warming up to 60 ℃, carried out stirring in about 1 hour.Be cooled to room temperature while stirring, obtain the emulsified soln of vinyl resin b1III.
(resol: symbol b1IV)
Used the cation-modified resol b1IV of the bisphenol type shown in the following structural formula.In the following structural formula, the polymerization degree (m+n) is 10 ~ 15, and n/m is 40/60.
[Chemical formula 1]
(Vinylite: symbol b1V)
Used the multipolymer (molecular-weight average: 20000) that forms by vinyl alcohol (80 quality %) and methylacrylic acid (20 quality %).Compound method is following: vinyl-acetic ester and methylacrylic acid are mixed, obtain the polymkeric substance of vinyl-acetic ester and methylacrylic acid.Then, through vinyl-acetic ester is fully saponified, obtain Vinylite b1V.
(natural polysaecharides: symbol b1VI)
Used the glyceryl chitosan shown in the following structural formula (number-average molecular weight: 100,000, R represents glycerylization, glyceryl degree: 1.1).
[Chemical formula 2]
Figure BDA00001951333100191
(natural polysaecharides: symbol b1VII)
Used CMC 99.5 (molecular-weight average: 50000).
(polyolefin resin: symbol b1VIII)
Used the multipolymer that forms by ethene (80 quality %) and vinylformic acid (20 quality %) (molecular-weight average: 100000, in the ammonia and article).
(Vinylite: symbol b1IX)
Used the partly-hydrolysed thing (molecular-weight average: 50000,5 quality % acetoacetylation) of Yodo Sol VC 400.Compound method is following: make the vinyl acetate polyisocyanate polyaddition, and it is 90% partly-hydrolysed that it is taken place, then, with respect to copolymer 1 00 quality %, make 5 quality % that acetoacetylation take place.
(Vinylite: symbol b1X)
Used Z 150PH (molecular-weight average: 10000).Compound method is following: make the vinyl acetate polyisocyanate polyaddition and obtain Yodo Sol VC 400, carry out fully saponified then.
(resol: symbol b1XI)
Used resole (dimer) with methylol.
(epoxy resin: symbol b1XII)
The many glycidyl ethers of Sorbitol Powder have been used.
(epoxy resin: symbol b1XIII)
Mix with the ethylene oxide adduct of dihydroxyphenyl propane 324 parts (0.2 mole), T 46155 polyoxytrimethylene block polymer 2680 parts (0.4 mole) and as the hydrogenation diphenylmethanediisocyanate 50 parts (0.4 moles) of polyisocyanate compound; And then adding is as the dibutyl tin dilaurate 3g (0.1 quality %) of catalyzer; Reacted 2 hours down in 80 ℃, obtain emulsified soln.
(urethane resin: symbol b1XIV)
Make polyester polyol (hexanodioic acid/3-methyl isophthalic acid; Several 2.0, the hydroxyl value 112.2 of 5-pentanediol, number-average molecular weight 1000, functional group) 100 parts, 3 parts of TriMethylolPropane(TMP)s, 25 parts of dimethylol propionic acids, isophorone diisocyanate react in MEK for 85 parts, obtain carbamate prepolymer.Mix 9.4 parts of triethylamines therein, and drop in the water, above-mentioned carbamate prepolymer is scattered in the water, utilize quadrol to make this prepolymer elongation, thus the dispersion-s of obtaining.Methylethylketone is removed in distillation, obtains containing the urethane resin water-based dispersion-s of 30 quality % nonvolatile component.The acid number that is scattered in the urethane that contains carboxyl in the gained aqueous dispersion is 49 (KOHmg/g).
< mineral compound (b2) >
B2I: colloid silica, median size 20nm
B2II: zirconium carbonate ammonium
B2III: titanium acetylacetone
B2IV: tripolyphosphate
< chelate compound (b3) >
B3I: tartrate
B3II: xitix
B3III:1-hydroxy ethylidene-1, the 1-di 2 ethylhexyl phosphonic acid
B3IV:1,3-diamino--2-propyl alcohol-N, N, N ', N '-tetraacethyl
[metal conditioner]
With above-mentioned water-base resin and water soluble metallic compound combination, the metal conditioner of the embodiment 1 ~ 40 shown in the table 1 and the metal conditioner of comparative example 1 ~ 10 have been prepared.
[table 1]
Figure BDA00001951333100211
[test is with the making of material]
For aluminium alloy plate (JIS A 3004, thickness of slab 0.26mm), 2% aqueous solution that uses Fine cleaner 4377K (alkali cleaner that Nihon Parkerizing Co., Ltd. makes) in 50 ℃ carry out spraying for 10 seconds degreasing after, wash the cleaner surface.Then, in order to make the moisture evaporation on aluminium alloy plate surface, carried out 1 minute heat drying in 80 ℃.Utilize rod to be coated with device the metal conditioner of embodiment shown in the table 11 ~ 40 and comparative example 1 ~ 10 is coated the surface through the aluminium alloy plate of degreasing washing; And in the heated air circulation type drying oven in 200 ℃ of dryings 1 minute, thereby formed the surface treatment capsule of given thickness on the surface of aluminium alloy plate.Be formed with on the aluminium alloy plate of surface treatment capsule, in 250 ℃ with 5 seconds of polyester film (thickness 16 μ m) heat lamination (arriving the plate temperature is 180 ℃), and face is pressed reach 50kg/cm 2, made " clad metal plate ".
[comparative example 11 ~ 13]
As comparative example 11; Commercially available Plessy's green hydrochlorate treatment agent (AM-K702:Nihon Parkerizing Co., Ltd. system) is carried out spraying in 5 seconds in 50 ℃ to be handled; And wash and remove unreacted medicament; Carry out 1 minute heat drying in 80 ℃, (the Cr adhesion amount is 20mg/m to have obtained test film 2).In addition; As comparative example 12; Commercially available zirconium phosphate treatment agent (AL-404:Nihon Parkerizing Co., Ltd. system) is carried out spraying in 20 seconds in 40 ℃ to be handled; And wash and remove unreacted medicament, carry out 1 minute heat drying in 80 ℃, (the Zr adhesion amount is 15mg/m to have obtained test film 2).In addition, as comparative example 13, also made the test film that only passes through degreasing.
The clad metal plate that utilizes drawing attenuated processing experiment that the laminating resin film is obtained has carried out deep-draw processing.The clad metal plate that is die-cut into diameter 160mm is carried out pull and stretch processing (the 1st time), made the cup of diameter 100mm.Then, once more with this glass pull and stretch processing (the 2nd time) diameter 75mm, and then pull and stretch processing (the 3rd time) has been made as the jar of test with material to diameter 65mm.Attenuate (thin-walled property) rate of wherein, the 1st pull and stretch processing, the 2nd pull and stretch processing, the 3rd pull and stretch processing is respectively 5%, 15%, 15%.
[performance evaluation]
Estimate for initial stage adaptation, durable adaptation and the acidproof adaptation of clad metal plate being carried out after deep-draw is processed as described below.Its result is as shown in table 2.
(initial stage adaptation)
To having carried out the evaluation of initial stage adaptation with material through the test after the deep-draw processing.Situation about the peeling off note of can manufacturing tank, film not taking place is done " zero "; Can manufacturing tank but have the situation note that the part film has taken place to peel off to make " △ "; Fail the situation note of manufacturing tank with fracture has taken place and do " * ".In addition, the situation note that in " zero ", do not peel off observing fully, especially outward appearance is excellent is made " ◎ ".
(durable adaptation)
To using material, in the atmosphere of heating and pressurizing steam, implemented distillation test through the test after the deep-draw processing.Distillation test is used commercially available sterilising plant (autoclave), under 125 ℃, has carried out 1 hour.Material is used in test for after the test, and situation about the peeling off note that film does not take place is done " zero "; To there be the situation note that the part film has taken place to peel off to make " △ "; The situation note that film has taken place to peel off on whole is done " * ".In addition, the situation note that in " zero ", do not peel off observing fully, especially outward appearance is excellent is made " ◎ ".
(acidproof adaptation)
To using material, estimate for the adaptation of dipping after 16 hours in 50 ℃ the 0.5%HF aqueous solution through the test after the deep-draw processing.Situation about the peeling off note that film does not take place is done " zero "; To there be the situation note that the part film has taken place to peel off to make " △ "; The situation note that film has taken place to peel off on whole is done " * ".In addition, the situation note that in " zero ", do not peel off observing fully, especially outward appearance is excellent is made " ◎ ".
[table 2]
Figure BDA00001951333100241
As shown in table 2, utilize the metal conditioner of embodiment 1 ~ 40 to carry out all excellences of the initial stage adaptation of surface-treated metallic substance, durable adaptation and acidproof adaptation.
On the other hand; Contain Cr (III) compound (A) and be selected from organic cpds with film-forming properties and at least a kind of compound (B) in the mineral compound and be made as M at Metal Cr reduced mass with Cr (III) compound (A), the high comparative example 3,4,5,6,7 of N/M when the quality of compound (B) is made as N; And the comparative example 1 that only contains Cr (III) compound; The comparative example 2 that compound (B) is few does not contain the comparative example 8 of Cr (III) compound, has all obtained the bad result of adaptation.Particularly, durable adaptation and acidproof adaptation are significantly bad.

Claims (6)

1. metal conditioner, it is used for using the metal finishing tunicle at substrate material surface form layers press mold of being processed by aluminum or aluminum alloy or resin coating film substrate, wherein,
This metal conditioner contains Cr (III) compound (A) and compound (B); Said compound (B) for be selected from organic cpds with film-forming properties and mineral compound and can with the organic cpds of said compound (A) be combined into film at least a kind
With the Metal Cr reduced mass of said Cr (III) compound (A) be made as M, when the quality of said compound (B) is made as N, N/M is 0.005 ~ 1.
2. metal conditioner according to claim 1; Wherein, Said compound (B) is for being selected from least a kind in organic cpds (b1), mineral compound (b2) and the organic chelate compound (b3); Said organic cpds (b1) for be selected from urethane resin, epoxy resin, polyolefin resin, vinyl resin, Vinylite, resol and the natural polymer more than a kind or 2 kinds; Said mineral compound (b2) for be selected from silicate compound, zirconium compounds, titanium compound and the phosphate compounds more than a kind or 2 kinds, each intramolecularly of said organic chelate compound (b3) has at least a kind of functional group that is selected from more than 2 in hydroxyl, carboxyl, phosphonate group, phosphate, amino and the carboxamido-group.
3. metal conditioner according to claim 1 and 2, wherein, said metal conditioner is used for after this metal conditioner is coated said metal matrix material surface, carrying out drying and forms said metal finishing tunicle.
4. metal surface treating method; It comprises: each described metal conditioner in the claim 1 ~ 3 is coated on the surface of the body material of being processed by aluminum or aluminum alloy, carries out heat drying in 60 ~ 250 ℃ temperature then and form surface treatment capsule.
5. metal finishing tunicle, it utilizes the described metal surface treating method of claim 4 to form.
6. metallic substance, it is arranged at the substrate material surface of being processed by aluminum or aluminum alloy through the surface treatment capsule that will utilize the described metal surface treating method of claim 4 to form and obtains.
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