CN102741454B - Metal surface treatment agent and metal surface treatment method - Google Patents
Metal surface treatment agent and metal surface treatment method Download PDFInfo
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- CN102741454B CN102741454B CN201180007778.XA CN201180007778A CN102741454B CN 102741454 B CN102741454 B CN 102741454B CN 201180007778 A CN201180007778 A CN 201180007778A CN 102741454 B CN102741454 B CN 102741454B
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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
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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
- C23C22/24—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
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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
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (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
Technical field
The present invention relates to laminated film or resin coating film substrate metal conditioner and use the metal surface treating method of this metal conditioner, described metal conditioner is for the formation of surface treatment capsule, and this surface treatment capsule can make the adaptation between the substrate material surface be made up of aluminum or aluminum alloy and laminated film or resin coating film be improved.
More specifically, the present invention relates to the laminated film or resin coating film substrate metal conditioner etc. for the formation of the surface treatment capsule of resistance to chemical reagents excellence, resin film layer is being pressed in the substrate material surface be made up of aluminum or aluminum alloy or is forming resin coating film at the substrate material surface be made up of aluminum or aluminum alloy by described surface treatment capsule, then deep-draw processing is implemented, when the harsh formed machining such as thinning processing (processing of ご I) or stretch-draw processing, also can give and can not make this laminated film or resin coating film that the high adhesion peeled off occurs, and then be exposed to acid for a long time, also high adhesion can be kept time in solvent etc.
Background technology
Lamination process is working method resin masking (hereinafter referred to as resin molding or laminated film) heating being pressed on metal material surface; to protect surface or to give one of metal material surface method for coating for the purpose of designability, to be applied to various field.With by making its drying be formed compared with the method for resin coating film at metal material surface coating resin composition, the solvent that this lamination process produces when drying is few, and the generation of the waste gas such as carbonic acid gas or greenhouse gases is also less.Therefore; preferably use from the viewpoint of environment protection; its purposes expands, and has been used to such as with main body or cover materials, containers for food use or drying battery container etc. that aluminium sheet material, steel sheet material, Packaging Aluminum Foil or stainless steel foil etc. are raw-material food tank.
Particularly nearest, as the exterior material of the portable equipment lithium-ion secondary cell used in mobile phone, electronic notebook, notebook computer or pick up camera etc., light and the tinsel such as the aluminium foil that barrier is high or stainless steel foil of preferred functional quality, employs lamination process to the surface of such tinsel.In addition, the lithium-ion secondary cell for the drive energy as electromobile or hybrid vehicle is studied, and as the exterior material of this lithium-ion secondary cell, is also studied the tinsel through lamination process.
For the laminated film used in above-mentioned lamination process, carry out adding hot pressing after directly fitting on metallic substance.Therefore, with coating resin composition and compared with the general resin coating film making it dry and formed, it has and can suppress raw-material waste, pin hole (defective part) less and the advantage such as excellent in workability.As the material of laminated film, usually use the polyamide-based resins such as polyolefine, nylon such as the polyester resin such as polyethylene terephthalate and PEN, polyethylene and polypropylene.
When laminated film lamination being machined in metal material surface (hereinafter also referred to as " metallic surface "), in order to the erosion resistance of the adaptation and metallic surface that improve laminated film and metallic surface, after degreasing washing is carried out to metallic surface, usually to implement the chemical conversion treatment etc. such as Plessy's green hydrochlorate.But such chemical conversion treatment needs the washing procedure carried out after treatment for removing unnecessary treatment solution, and wastewater treatment is carried out to the washing water of discharging from this washing procedure need Expenses Cost.Particularly the chemical conversion treatment etc. such as Plessy's green hydrochlorate, comprises chromic treatment solution owing to using, therefore, in recent years for the consideration to environment, has tended to deliberately avoid such process.
On the other hand, when the process such as chemical conversion treatment not implemented to metallic surface and carry out lamination process, there is the problem that corrosion and so on occurs from metallic surface stripping or metallic substance laminated film.Such as, for containers for food use or wrapping material, after loading in the container after lamination process or wrapping material by content, the heat treated for the purpose of sterilization be implemented, but when carrying out this heat treated, laminated film may be caused to peel off from metallic surface.In addition, for the exterior material etc. of lithium-ion secondary cell, the high processing of degree of finish to be stood in its manufacturing process.The ionogen of lithium-ion secondary cell uses the organic solvent such as ethyl-carbonate or diethyl carbonate and the fluorine such as lithium hexafluoro phosphate or LiBF4 class lithium complex salt.Therefore, such exterior material is after life-time service, following problem can be produced: not just as electrolytical organic solvent, moisture in air is also immersed in container, react with ionogen and generate hydrofluoric acid, the stripping that this hydrofluoric acid causes between metallic surface and laminated film at transmission layer press mold, can cause corrosion to metallic surface simultaneously.In addition, also there is following problems: sometimes will preheat metallic substance (200 ~ 300 DEG C) before being laminated, and the effect of heat can cause tunicle deterioration, adaptation reduces.
In order to tackle the problems referred to above, propose the method for tunicle that to be formed in metallic surface before lamination process in order to improve the adaptation between laminated film and treatment agent etc.For example, Patent Document 1 discloses a kind of containing the water-soluble zirconium compound of specified quantitative, the water-soluble of ad hoc structure or water-dispersible acrylic's resin and substrate treating agent that is water-soluble or water dispersible thermohardening type linking agent.In addition, propose in patent documentation 2 a kind of containing the water-soluble zirconium compound of specified quantitative and/or the chromium-free metal surface treatment agent of water-soluble titanium compound, organic phosphonic compound and tannin.In addition, Patent Document 3 discloses the metal finishing medicament of a kind of pH in 1.5 ~ 6.0 scopes, it contains the compound of the special metals such as amination phenol polymer and Ti and Zr.In addition, disclose in patent documentation 4 a kind of containing amination phenol polymer, acrylic polymers, metallic compound and the resin molding of phosphorus compound (C) used as required.
In addition, as the chemical conversion surface treatment agent not containing 6 valency chromium employing 3 valency chromium cpds, such as propose in patent documentation 5 and a kind ofly comprise phosphoric acid salt, the chromium cpd of 3 valencys, the chemical conversion surface treatment agent of the metallic compound such as fluorine cpd and Zn, Ni, wherein point out, the Plessy's green hydrochlorate tunicle of erosion resistance and excellent adhesion can be formed.In addition, Patent Document 6 discloses a kind of contain 3 valencys chromium cpd, Zr compound and/or Ti compound, nitrate compound, Al compound and fluorine cpd chemical conversion surface treatment agent, wherein point out, the chemical conversion treatment film of erosion resistance and excellent adhesion can be formed.In addition, Patent Document 7 discloses a kind of metallic surface coating composition containing water, fluorine metal hydrochlorate (Off Le オ ロ メ タ レ mono-ト) anionic component and water soluble fluoridized chromium component.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-265821 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-313680 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-138382 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2004-262143 publication
Patent documentation 5: Japanese Unexamined Patent Publication 7-126859 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2006-328501 publication
Patent documentation 7: Japanese Unexamined Patent Application Publication 2009-536692 publication
Summary of the invention
The problem that invention will solve
Disclosed in patent documentation 5 ~ 7, treatment agent is all the surface treatment agents containing chromium, and the surface treatment capsule formed all has the advantage of erosion resistance and excellent heat resistance.But when increasing the chromium content in tunicle to improve erosion resistance further, there is the tendency causing shaping processability to reduce.Particularly, when implementing the formed machining of the harshnesses such as deep-draw processing, thinning processing or stretch-draw processing, tunicle may be caused to occur to peel off or be full of cracks, its result, there is the hidden danger causing the erosion resistance of metallic substance to decline.
In addition, surface treatment agent disclosed in patent documentation 5 ~ 7 is called as so-called response type treatment agent, free hydrogen fluoride in treatment solution can promote the dissolving on metal matrix material surface, and can form the surface treatment capsule comprising chromium etc. because of the surface reaction based on this dissolving.When using such response type treatment agent, exist and cause metal matrix material surface that the hidden danger of over etching occurs because of the existence of the etching compositions such as free hydrogen fluoride, may cause being suitable in the metal matrix material such as above-mentioned aluminium sheet material or Packaging Aluminum Foil becoming difficulty.Particularly, for the metal matrix material that aluminium foil etc. is very thin, preferably inexcessive etching.In addition, when utilizing response type treatment agent to process, owing to will wash after treatment, therefore also need the cost spent in order to process contained heavy metal in treatment agent when wastewater treatment.
The object of the present invention is to provide a kind of laminated film for the formation of surface treatment capsule or resin coating film substrate metal conditioner, resin film layer is being pressed in the substrate material surface be made up of aluminum or aluminum alloy or is forming resin coating film at the substrate material surface be made up of aluminum or aluminum alloy by described surface treatment capsule, then deep-draw processing is implemented, when the harsh formed machining such as thinning processing or stretch-draw processing, also can give and not make this laminated film or resin coating film that the high adhesion peeled off occurs, and then be exposed to solvent, also can the adaptation of stable for extended periods of time time in acid.In addition, another object of the present invention is to provide the metallic substance using the metal surface treating method of this metal conditioner, the metal finishing tunicle utilizing this metal surface treating method to be formed and there is the surface treatment capsule utilizing this metal surface treating method to be formed.
The method of dealing with problems
Metal conditioner of the present invention for solving the problem is for the metal conditioner at the substrate material surface form layers press mold be made up of aluminum or aluminum alloy or resin coating film substrate metal finishing tunicle, wherein, this metal conditioner contains Cr (III) compound (A) and compound (B), described compound (B) is for being selected from the organic compound and mineral compound with film-forming properties, and at least a kind that can be combined into above-claimed cpd (A) in the organic compound of film, the Metal Cr reduced mass of above-mentioned Cr (III) compound (A) is set to M, when the quality of above-claimed cpd (B) is set to N, N/M is 0.005 ~ 1.
According to this invention, due to when the Metal Cr reduced mass of Cr (III) compound (A) being set to M, the quality of compound (B) being set to N, make N/M in above-mentioned scope, and make the content of the Cr in metal conditioner (III) compound reach the state of high density (rich), the surface treatment capsule formed at the substrate material surface be made up of aluminum or aluminum alloy therefore can be made also to become the surface treatment capsule being rich in Cr of erosion resistance and excellent heat resistance.And, due in this metal conditioner containing being selected from the organic compound and mineral compound with film-forming properties and the compound (B) of at least a kind that can be combined into above-claimed cpd (A) in the organic compound of film, therefore, it is possible to improve adhesive capacity by crosslinked, the chelate effect for Cr (III), forming shaped excellent in workability and the surface treatment capsule of excellent adhesion.Its result, according to metal conditioner of the present invention, following surface treatment capsule can be formed, even if it is when implementing the formed machining of the harshnesses such as deep-draw processing, thinning processing or stretch-draw processing, also the high adhesion being not easily peeling on surface treatment capsule or chapping can be realized, and then also can the adaptation of stable for extended periods of time when being exposed in solvent, acid.
In metal conditioner of the present invention, above-claimed cpd (B) is for being selected from organic compound (b1), at least a kind in mineral compound (b2) and organic chelate compound (b3), described organic compound (b1) is for being selected from urethane resin, epoxy resin, polyolefin resin, acrylic resin, Vinylite, one kind or two or more in resol and natural polymer, described mineral compound (b2) is selected from silicate compound, zirconium compounds, one kind or two or more in titanium compound and phosphate compounds, in every a part of described organic chelate compound (b3), there are more than 2 and be selected from hydroxyl, carboxyl, phosphonate group, phosphate, at least a kind of functional group in amino and amide group.
According to this invention, owing to there is the compound (B) of film-forming properties for being selected from least a kind in above-mentioned organic compound (b1), above-mentioned mineral compound (b2) and above-mentioned organic chelate compound (b3), therefore, such compound (B) can improve adhesive capacity by crosslinked, the chelate effect for Cr (III), makes to be rich in the surface treatment capsule of Cr to have the adhesive capacity can bringing high shaping processability and adaptation.Its result, following surface treatment capsule can be formed, even if it is when implementing the formed machining of the harshnesses such as deep-draw processing, thinning processing or stretch-draw processing, also the high adhesion being not easily peeling on surface treatment capsule or chapping can be realized, and then also can the adaptation of stable for extended periods of time when being exposed in solvent, acid.
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 to form above-mentioned metal finishing tunicle.
The metal conditioner of this invention carries out drying to form the so-called application type treatment agent of metal finishing tunicle after this metal conditioner is coated metal matrix material surface.Therefore, when using metal conditioner of the present invention, do not exist and cause metal matrix material surface that the hidden danger of over etching occurs because of the existence of the etching compositions such as hydrogen fluoride free in treatment solution, can be suitable for without any problems for aluminium sheet material or the thinner metal matrix material of Packaging Aluminum Foil equal thickness yet.In addition, the metal conditioner of the present invention that application type method relates to, owing to not needing to wash after treatment as using the situation of response type treatment agent, therefore not only can reduce processing cost, can also the saving of implementation space.
Feature for the metal surface treating method of the present invention solved the problem is, the metal conditioner of the invention described above is coated on the substrate material surface be made up of aluminum or aluminum alloy, then carries out heat drying to form surface treatment capsule in the temperature of 60 ~ 250 DEG C.
According to this invention, as mentioned above, the high adhesion that can realize not easily being peeling on surface treatment capsule or chapping can be formed, and then also can the surface treatment capsule of adaptation of stable for extended periods of time when being exposed in solvent, acid.In addition, owing to being the application type method not needing to carry out after treatment washing as using the situation of response type treatment agent, therefore processing cost can be reduced.
Feature for the metal finishing tunicle of the present invention solved the problem is, it utilizes the metal treatment surface method of the invention described above to be formed.
The metal finishing tunicle of this invention utilizes the metal surface treating method involved by application type method to process above-mentioned metal conditioner and is formed.The surface treatment capsule formed can realize the high adhesion not easily peeling off or chap, and then also can the adaptation of stable for extended periods of time when being exposed in solvent, acid.In addition, owing to being utilize not need the application type method of carrying out after treatment washing as using the situation of response type treatment agent to be formed, therefore, it is possible to as low cost process film and formed.
Feature for the metallic substance of the present invention solved the problem is, it obtains by the surface treatment capsule utilizing the metal surface treating method of the invention described above to be formed being arranged at the substrate material surface be made up of aluminum or aluminum alloy.
The effect of invention
According to metal conditioner of the present invention, following surface treatment capsule can be formed, even if it is when implementing the formed machining of the harshnesses such as deep-draw processing, thinning processing or stretch-draw processing, also the high adhesion being not easily peeling on surface treatment capsule or chapping can be realized, and then also can the adaptation of stable for extended periods of time when being exposed in solvent, acid.
According to metal surface treating method of the present invention, because the method carries out heat drying after metal conditioner of the present invention being coated the substrate material surface be made up of aluminum or aluminum alloy, therefore, it is possible to form erosion resistance, thermotolerance at this substrate material surface, force the surface treatment capsule of work adaptation and drug-resistant excellent in stability.Do not wash owing to carrying out heat drying after coating metal surfaces treatment agent, therefore do not need to carry out, with the wastewater treatment of washing, not only can reduce processing cost, can also the saving of implementation space.
According to metal finishing tunicle of the present invention, the high adhesion being not easily peeling or chapping can be realized, and then also can the adaptation of stable for extended periods of time when being exposed in solvent, acid.In addition, because this metal finishing tunicle utilizes not need the application type method of carrying out after treatment washing as using the situation of response type treatment agent to be formed, therefore, it is possible to become the process film of low cost.
According to metallic substance of the present invention, because it contains the metal finishing tunicle with above-mentioned characteristic at the substrate material surface be made up of aluminum or aluminum alloy, therefore laminating resin film or formed after resin coating film on this surface treatment capsule, even if when implementing the formed machining of the harshnesses such as deep-draw processing, thinning processing or stretch-draw processing, this laminated film or resin coating film are also not easily peeled off, and also can the adaptation of stable for extended periods of time when being exposed in solvent, acid.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is schematic cross sectional view, shows and uses metal conditioner of the present invention to form an example of 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, be described for 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 the treatment agent forming the substrate metal finishing tunicle 2 of laminating material 3 (resin molding or laminated film) for the surface of the body material 1 be made up of aluminum or aluminum alloy shown in Fig. 1.And, it is characterized in that, metal conditioner contains Cr (III) compound (A) and compound (B), described compound (B) is for being selected from the organic compound and mineral compound with film-forming properties and at least a kind that can be combined into above-claimed cpd (A) in the organic compound of film, the Metal Cr reduced mass of above-mentioned Cr (III) compound (A) is set to M, when the quality of above-claimed cpd (B) is set to N, N/M is 0.005 ~ 1.
Below, formation of the present invention is described in detail.
(compound (A))
Cr (III) compound (A) is not containing the chromium cpd of 3 valencys of 6 valency chromium.When the metal conditioner that utilization comprises this Cr (III) compound forms surface treatment capsule, Metal Cr can be reacted with metal matrix material and make substrate material surface and surface treatment capsule closely sealed securely.Although Cr (III) compound self can be utilized to form Cr compound layer, but by containing compound (B) further, metal conditioner can show excellent film-forming properties, its result, the water tolerance of the surface treatment capsule utilizing this metal conditioner to be formed and resistance to chemical reagents improve, and particularly erosion resistance obtains tremendous raising.
As Cr (III) compound, chromic salts, complex compound or coordination compound can be enumerated, 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) etc. 3 valency chromium cpds.In addition, reductive agent also can be used to be reduced by Cr (VI) and generate Cr (III).
When the Metal Cr reduced mass of Cr (III) compound (A) being set to M, the quality of compound (B) being set to N, the content of Cr (III) compound makes N/M in the scope of 0.005 ~ 1.High by making in the Cr concentration of Metal Cr reduced mass, make the ratio of Cr (III) compound contained in metal conditioner in above-mentioned scope, as mentioned above, Metal Cr can be reacted with metal matrix material and make substrate material surface and surface treatment capsule closely sealed securely, and can form Cr compound layer by Cr (III) compound self.Its result, the adaptation between metal matrix material surface and gained surface treatment capsule and laminated film or the adaptation between resin coating film and gained surface treatment capsule can be improved simultaneously, and water tolerance, resistance to chemical reagents and erosion resistance can be made to be improved.
In addition, for utilizing N/M for the surface treatment capsule that the metal conditioner in above-mentioned scope is formed, the ratio (Q/P) of the quality P of the Metal Cr contained in this surface treatment capsule and the quality Q except Metal Cr is in the scope of 0.005 ~ 1.The surface treatment capsule being rich in Cr so not only has excellent erosion resistance and thermotolerance because Cr concentration is high, and, although Cr concentration is high, but still there is excellent shaping processability and adaptation.Usually think simply, the surface treatment capsule being rich in Cr is more crisp, but in the present invention, can think, defines the surface treatment capsule with firmly tridimensional network, its result, also not easily occurs to peel off or be full of cracks even if stand strong processing.Here, the surface treatment capsule with firmly tridimensional network is 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 lower than 0.005 time, the Q/P of the surface treatment capsule of formation is also lower than 0.005, and relatively obviously increasing containing proportional of Metal Cr, is easily peeling, chaps.When N/M is greater than 1, the Q/P of the surface treatment capsule formed is also more than 1, there is the tendency reduced containing proportional relative reduction, erosion resistance of Metal Cr, its result, adaptation between metallic surface and gained surface treatment capsule reduces, and corrosive medium may be caused to enter into metallic surface and cause erosion resistance to reduce.No matter be which kind of situation, when N/M departs from above-mentioned scope, all possibly cannot guarantee stable adaptation when particularly long-term exposure is in solvent, acid.
From raising adaptation, make the more preferably viewpoint consideration of water tolerance, resistance to chemical reagents and erosion resistance, preferred N/M is 0.01 ~ 0.5.Be more preferably 0.05 ~ 0.25.The Q/P of surface treatment capsule now also preferred about 0.01 ~ 0.5 scope.Be more preferably 0.05 ~ 0.25.
In this application, described " solids component " of compound (B), refers in compound (B) composition forming metal conditioner except aftermentioned solvent etc. evaporates into the solids component except grading.Therefore, described N/M be 0.005 ~ 1 metal conditioner be equal to: relative to formation Cr (III) compound (A) of metal conditioner and the total amount (all solids composition) of compound (B), the content of Cr (III) compound (A) is 50 ~ 99.5 quality % with metal conversion gauge.It should be noted that, the quality of Metal Cr can use the x-ray fluorescence analysis device " 3270E " of electrical industry Co., Ltd. of science, measures under the condition of pipe ball: Rh, voltage-to-current: 50KV-50mA.
(compound (B))
Compound (B) is selected from the organic compound and mineral compound with film-forming properties and at least a kind of compound that can be combined into above-claimed cpd (A) in the organic compound of film.The compound (B) with film-forming properties undertakes tackiness agent function in the surface treatment capsule being rich in Cr (III), has the effect that work is forced in the surface treatment capsule tolerance making to be rich in Cr (III).In addition, the surface treatment capsule utilizing the metal conditioner of inclusion compound (B) to be formed, by improving film-forming properties, barrier can be made to be kept, and erosion resistance, water tolerance, solvent resistance and resistance to chemical reagents is improved.
As there is the compound (B) of film-forming properties or the compound (B) of film can being combined into above-claimed cpd (A), can enumerate: be selected from the one kind or two or more organic compound (b1) in urethane resin, epoxy resin, polyolefin resin, acrylic resin, Vinylite, resol and natural polymer; Be selected from the one kind or two or more mineral compound (b2) in silicate compound, zirconium compounds, titanium compound and phosphate compounds; There is in every a part organic chelate compound (b3) that more than 2 are selected from least a kind of functional group in hydroxyl, carboxyl, phosphonate group, phosphate, amino and amide group.This organic chelate compound (b3) can be combined into the compound of film with above-claimed cpd (A).1 or two or more compound of being selected from above-claimed cpd (b1) ~ (b3) is combined with in metal conditioner.
First, the example of organic compound (b1) is as follows.Organic compound (b1) as long as can in metal conditioner of the present invention stable existence and the compound of expected effect can be obtained, but not by the restriction of the kind of organic compound.With regard to the water-solubleization form of organic compound, it can be water-soluble or any form in water dispersible (emulsion, dispersion liquid).In addition, with regard to ionic, can be ionic arbitrarily in anionic property, nonionic, cationic.
As urethane resin, the urethane etc. obtained can be listed below: by polyester polyols (particularly binary) alcohol, polyether polyols (particularly binary) alcohol, polynary (particularly binary) alcohol and aliphatics many (particularly two) isocyanic ester such as polycarbonate polyol (particularly binary) alcohol, in the polycondensate that alicyclic many (particularly two) isocyanic ester and/or aromatic series many (particularly two) isocyanate compound are formed and urethane resin, use N, N-dimethylamino dihydroxy methylpropane etc. has amino polyvalent alcohol, or the such polyvalent alcohol with polyoxyethylene chain of polyoxyethylene glycol is as the part of above-mentioned polyvalent alcohol and the urethane obtained.
In these urethane, carry out quaternized its cationization that makes by part or all of amino N, N-dimethylamino dihydroxy methylpropane etc. to amino polyvalent alcohol, can its water-solubleization be made.In addition, by improving the importing ratio of polyoxyethylene chain, water-solubleization or moisture dispersion can be realized with non-ionic form.In addition, the urethane resin of anionic property is obtained by following method, namely, the carbamate prepolymer that two ends have isocyanate group is manufactured by polyisocyanates and polyvalent alcohol, this prepolymer is reacted with the carboxylic acid or its reactive derivatives with 2 hydroxyls, the derivative that two ends have isocyanate group must be arrived, then, add trolamine etc. to form ionomer (triethanolamine salt), and then add water to form emulsion or dispersion liquid, and then add diamines as required to carry out chain extension, obtain the urethane resin of anionic property thus.
The carboxylic acid that manufacture uses when having the water-dispersible polyurethane resin of anionic property and reactive derivatives for importing acidic-group and making urethane resin be water dispersible in urethane resin.As used carboxylic acid, the dimethylolalkanoic acids such as dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid can be enumerated.In addition, as reactive derivatives, the hydrolyzable ester that acid anhydrides is such can be enumerated.Like this, by making water-dispersible polyurethane resin (A) for not using or do not use as far as possible emulsifying agent from water dispersible, durable adaptation, acidproof adaptation can be made to improve.
As epoxy resin, can enumerate: the epoxy compounds with more than 2 glycidyls; There is dihydroxyphenyl propane or the Bisphenol F epoxy compounds as the unit in skeleton; Or make to have more than 2 glycidyls the diamines effect such as epoxy compounds and quadrol, there is cationization and the epoxy resin obtained; To make to have on dihydroxyphenyl propane or Bisphenol F have an epoxy compounds of more than 2 glycidyls side chain as the epoxy compounds of the unit in skeleton or other addition polyoxyethylene glycol and the nonionic epoxy resin obtained; Etc..
As epoxy resin, can use and there is dihydroxyphenyl propane or the Bisphenol F epoxy resin as the unit in 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 obtained.
As there is dihydroxyphenyl propane or Bisphenol F as the epoxy resin of the unit in skeleton, can enumerate: the resin obtained through dehydrochlorination repeatedly and addition reaction by epoxy chloropropane and dihydroxyphenyl propane or Bisphenol F; And by having the resin obtained through addition reaction repeatedly between the epoxy compounds of more than 2 (being preferably 2) glycidyls and bis-phenol (A, F).
As the kind of epoxy compounds, can specifically be listed below: bis-phenol (A, F) diglycidyl ether, o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, P-hydroxybenzoic acid 2-glycidyl ester, four hydrogen phthalate 2-glycidyl esters, hexahydrobenzene dioctyl phthalate 2-glycidyl ester, succsinic acid 2-glycidyl ester, hexanodioic acid 2-glycidyl ester, Diglycidyl Sebacate, ethylene glycol diglycidyl base ether, propylene glycol diglycidyl ether, BDO diglycidyl ether, 1,6-hexylene glycol diglycidyl ether, sorbitol polyglycidyl base ether, polyalkylene glycol diglycidyl ether class, trimellitic acid three-glycidyl ester, triglycidyl isocyanurate, Isosorbide-5-Nitrae-glycidoxy benzene, diglycidyl propylidene urea, glycerol triglycidyl group ether, trimethylolethane trimethacrylate glycidyl ether, trimethylolpropane tris glycidyl ether, tetramethylolmethane four glycidyl group ether, the triglycidyl group ether etc. of the olefin oxide affixture of glycerol.Above-mentioned epoxy compounds individually can be used or combinationally use.
For silane-modified degree, as long as more than the degree of the effect brought by these modifications can be confirmed, there is no particular restriction, known silane coupling agent can be used.
Acrylic resin can use unsaturated Acrylic Acid Monomer carry out addition polymerization and obtain.Acrylic resin can be any resin in the homopolymer of Acrylic Acid Monomer or multipolymer, as long as but can in surface treatment agent stable existence, particular restriction be there is no to its polymeric species.
As Acrylic Acid Monomer, can enumerate such as: methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the just own ester of methacrylic acid, 2-EHA, vinylformic acid, methacrylic acid, vinylformic acid 2-hydroxy methacrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxy propyl methacrylate, toxilic acid, methylene-succinic acid, acrylamide, N hydroxymethyl acrylamide, diacetone-acryloamide(DAA), glycidyl acrylate, glycidyl methacrylate, vinylbenzene, acrylamide, vinyl cyanide, polyethylene glycol methacrylate-styrene polymer etc.
Acrylic resin can be used alone the acid mono of vinylformic acid, methacrylic acid.In addition, above-mentioned monomer and these acid mono also can be used to combine and the anionic property acrylic resin utilizing carboxylic acid to carry out Water-borne modification and obtain.In addition, can also use vinylformic acid N, what (methyl) acrylic acid alkyl amino ester such as N-dimethylamino propyl ester, methacrylic acid N-methylamino ethyl ester were such has amino being combined and the cationic acrylic resin obtained through Water-borne modification by cationic monomer and aforesaid propylene acid mono.
As Vinylite, the partially or completely saponified etc. of the Mannich amine modifier of polyvinylphenol, polyvinyl imidazol, polyvinylpyridine, polymine, polyvinyl acetate and polyvinyl acetate can be enumerated.
In addition, about vinyl-acetic ester, it can be the resin obtained through saponification with the polymkeric substance that can obtain with the monomer copolymerization of vinyl acetate copolymerization.In addition, can also be import in polymkeric substance after polymerisation the anionic groups such as such as carboxylic acid, sulfonic acid, phosphoric acid, comprise quaternary ammonium group cation group and the resin obtained through ionization.In addition, can also be import diacetone-acryloamide(DAA) base, acetoacetyl, sulfydryl, silanol group etc. and carried out the resin of modification.
It should be noted that, as can with the monomer of vinyl acetate copolymerization, can enumerate such as: unsaturated carboxylic acid and the ester classes thereof such as toxilic acid, fumaric acid, β-crotonic acid, methylene-succinic acid, (methyl) vinylformic acid; The alpha-olefin such as ethene, propylene; The alkene sulfonic acids such as (methyl) propene sulfonic acid, ethionic acid, sulfonic acid malate; The alkene sulfonic acid an alkali metal salts such as (methyl) sodium allyl sulfonate, ethylene sulfonate, sodium sulfonate (methyl) acrylate, sodium sulfonate (oxysuccinic acid mono alkyl ester), sodium disulfonate oxysuccinic acid alkyl ester; The monomer containing amide group such as N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid an alkali metal salt; And NVP, NVP derivative etc.
As resol, the ring that can be set forth in phenols is bonded with the polycondensate formed by phenols (phenol, naphthols, bis-phenol etc.) and formaldehyde of (replacement) amino methyl.In addition, the resole containing methylol had from condensation can also be enumerated.
As natural polymer, the natural polysaecharides such as chitin, chitosan, Mierocrystalline cellulose, starch, dextrin, inulin, tannin can be enumerated.Also can be part of hydroxyl, the amino had in the structure to natural polysaecharides carry out hydroxypropylated, hydroxyethylated, methylate, glyceryl and the derivative obtained.
As polyolefin resin, polypropylene can be enumerated; Polyethylene; With unsaturated carboxylic acid (such as vinylformic acid, methacrylic acid), modification is carried out to polyolefine such as the multipolymers that propylene, ethene and alpha-olefin are formed and the modified polyolefin obtained; The multipolymer that ethene and vinylformic acid (methacrylic acid) are formed; Etc..In addition, can also be and other ethylene unsaturated monomer copolymerization a small amount of and the multipolymer that obtains.As the method for Water-borne modification, ammonia, amine can also be utilized to neutralize the carboxylic acid imported on polyolefin resin.
Can think, the film-forming properties that these organic compound (b1) are had by itself and playing undertakes the effect being formed and can tolerate the surface treatment capsule forcing work; Or, when these organic compound (b1) are the organic compound with functional group, by playing the effect of undertaking and being formed and can tolerate the surface treatment capsule forcing work with Cr (III) compound crosslink; Or, when these organic compound (b1) are the compounds with above-mentioned two kinds of effects, played the effect of undertaking and being formed and can tolerate the surface treatment capsule forcing work by this synergy.
As these organic compound (b1), water-based crosslinkable resin or the aqueous high molecular resin such as water-based emulsion, aqueous liquid dispersion that water soluble resin can be enumerated, have passed through self-emulsifying or utilize emulsifying agent to carry out forced emulsification and formed.Wherein, preferably adopt number-average molecular weight be less than 1000 monomer or the oligopolymer effect of heat, ultraviolet or electron beam etc. that can apply when forming tunicle issue and be conigenous crosslinked and the crosslinkable resin of high molecular occur or can react with other linking agent and the crosslinkable resin of high molecular occurs.In addition, number-average molecular weight can also be adopted to be 1000 ~ 1000000 and the macromolecule resin of produced film can be issued 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 functional group.
Below, the example of mineral compound (b2) is shown.
As silicate compound, silicate base metal-salt, polymeric silica, water-dispersible silica etc. can be used.Such as, as silicate base metal-salt, sodium salt, sylvite, lithium salts can be enumerated.As water-dispersible silica, comprise the liquid phase silica from liquid phase synthesis, the aerosil from vapor-phase synthesis, can be used wherein any one in the present invention.As liquid phase silica, colloid silica, chain silicon-dioxide, branching (ペ Application ダ Application ト shape) silicon-dioxide, tabular silicon-dioxide, hollow silica etc. can be enumerated.It should be noted that, particular determination be there is no 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 at below 100nm.In addition, can be pure silicon dioxide colloid, also can be through the silicon-dioxide of various stabilization treatment, can also be the silicon-dioxide that surface have passed through coating process.Silicate compound individually can use or is used by multiple combination.
As zirconium compounds, the carbonate of Zr, oxide compound, oxyhydroxide, nitrate, vitriol, phosphoric acid salt, fluorochemical, fluoric-containing acid (salt), organic acid salt, organic complex etc. can be used.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), 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, the carbonate of Ti, oxide compound, oxyhydroxide, nitrate, vitriol, phosphoric acid salt, fluorochemical, fluoric-containing acid (salt), organic acid salt, organic complex etc. can be used.Specifically can enumerate titanium oxide (IV) (titanium dioxide), Titanium Nitrate, titanium sulfate (III), titanium sulfate (IV), titanyl sulfate TiOSO
4, titanium fluoride (III), titanium fluoride (IV), hexafluorotitanic acid H
2tiF
6, ammonium hexa-fluorotitanate [(NH
4)
2tiF
6], lauric acid 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, phosphoric acid salt, condensed phosphate etc. can be used.Can enumerate such as generation phosphoric acid, two generation phosphoric acid, three generations's phosphoric acid, tetra-sodium, tripolyphosphate etc. metal-salt.As the kind of metal, sodium, potassium, zirconium, titanium, vanadium, manganese, cobalt, nickel etc. can be enumerated.
Below, the example of organic chelate compound (b3) is shown.
Organic chelate compound (b3) has the compound that more than 2 are selected from least a kind of functional group in lower group in every a part: hydroxyl, carboxyl, phosphonate group, phosphate, amino, the amide group that can form tunicle with 3 valency chromium chelatings.
As organic chelate compound, poly-basic organic acid, organic phospho acid, polyhydric amine compounds, amide compound etc. can be used.Specifically can enumerate: tartrate, oxysuccinic acid, citric acid, xitix, quadrol, N, dinethylformamide, DAP-N, N, N ', N '-tetraacethyl, amino three (methylene phosphonic acids), 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, quadrol-N, N, N ', N '-four (methylene phosphonic acid), hexamethylene-diamine-N, N, N ', N '-four (methylene phosphonic acid), diethylenetriamine-N, N, N '; N "; N "-five (methylene phosphonic acids), 2-phosphonobutane-1,2,4-tricarboxylic acid etc.These have chelate compound also can be alkali metal salts or ammonium salt partly.
As mentioned above, the Metal Cr reduced mass of Cr (III) compound (A) is set to M, when the quality of compound (B) is set to N, the content of the compound described above (B) in metal conditioner makes N/M in the scope of 0.005 ~ 1.By making the metal conditioner of ratio in above-mentioned scope of compound (B), as illustrated in the explanation hurdle of above-claimed cpd (A), the surface treatment capsule with firmly tridimensional network can be formed, its result, applies to force the surface treatment capsule that stripping and be full of cracks also not easily occur work even if can be formed.The surface treatment capsule with firmly tridimensional network is brought by the compound (B) with film-forming properties, and it is based on the adhesive capacity (crosslinked, chelate effect) of this compound (B) for Cr.
(solvent)
Form the solvent of metal conditioner based on water, but according to improving the needs of drying property etc. of tunicle, also can combinationally use the water-miscible organic solvent of alcohols, ketone or cellosolve class.
(other composition)
In addition, not destroying purport of the present invention and by the scope of film properties, tensio-active agent, defoamer, flow agent, antibacterial mildew inhibitor, tinting material and solidifying agent etc. can be added.In addition, in the scope not destroying effect of the present invention, the organic crosslinking agents such as the methylolated melamine of the erosion resistance for improving tunicle, carbodiimide and isocyanic ester and the silane coupling agent such as γ-glycidoxypropyl group triethoxyl silane, γ-glycidoxypropyl group triethoxyl silane, γ aminopropyltriethoxy silane and N-beta-aminoethyl-gamma-amino propyl trimethoxy silicane in order to improve adaptation can be added.
(metal matrix material)
The handling object of metal conditioner of the present invention is the body material be made up of aluminum or aluminum alloy.Metal conditioner of the present invention coats the surface of this metal matrix material as treated object, thus forms surface treatment capsule on its surface.As the metal matrix material 1 be made up of aluminum or aluminum alloy, can enumerate such as: the thin plate material be made up of aluminum or aluminum alloy, packaging paper tinsel etc.
Above, according to metal conditioner of the present invention, when the Metal Cr reduced mass of Cr (III) compound (A) being set to M, the quality of compound (B) being set to N, owing to making N/M in above-mentioned scope, and make the content of the Cr in metal conditioner (III) compound reach high density state, the surface treatment capsule formed at the substrate material surface be made up of aluminum or aluminum alloy therefore can be made to become the surface treatment capsule being rich in Cr of erosion resistance and excellent heat resistance.And, due in this metal conditioner containing the compound (B) with film-forming properties, therefore, it is possible to formed high for the adhesive capacity of Cr, shaping processability is excellent and the surface treatment capsule that adaptation is also excellent.Its result, following surface treatment capsule can be formed: even if it is when implementing the formed machining of the harshnesses such as deep-draw processing, thinning processing or stretch-draw processing, also the high adhesion being not easily peeling on surface treatment capsule or chapping can be realized, and then also can the adaptation of stable for extended periods of time when being exposed in solvent, acid.
[metal surface treating method]
Metal surface treating method of the present invention is after the surface metal conditioner of the invention described above being coated the body material be made up of aluminum or aluminum alloy, carries out the method for heat drying at the temperature of 60 ~ 250 DEG C.The liquid temperature of metal conditioner is usually in the scope of 10 ~ 50 DEG C.Coating process for metal conditioner there is no particular restriction, preferably adopts spray method, pickling process etc.The duration of contact of metal conditioner and metallic surface is generally about 0.5 ~ 180 second.
For formed surface treatment capsule, at the temperature of 60 ~ 250 DEG C, carry out heat drying.This temperature range can change arbitrarily according to the kind of resinous principle in above-mentioned scope, but is more preferably 80 ~ 200 DEG C.
The method of heat drying is not particularly limited, and can adopt the electromagnetic induction heating furnace etc. of intermittent type or continous way heated air circulation type drying oven, conveyor type hot-air drying stove or use IH well heater, its air quantity and wind speed etc. can set arbitrarily.
[metallic substance]
As shown in Figure 1, metallic substance 10 of the present invention has and utilizes above-mentioned metal surface treating method process and the surface treatment capsule 2 obtained.Such as, as shown in Figure 1, utilizing above-mentioned metal surface treating method process and the surface treatment capsule 2 obtained as the metal matrix material 1 be made up of aluminum or aluminum alloy of treated object is formed with, and on this surface treatment capsule 2 laminating resin film 3 or be formed with resin coating film 3 on this surface treatment capsule 2.For the metallic substance 10 formed like this, then implement the formed machining that deep-draw processing, thinning processing or stretch-draw processing etc. are harsh.It should be noted that, shown in Fig. 1 is the example being formed with surface treatment capsule 2 and resin molding or resin coating film (3) at a side surface of metal matrix material 1, but also can also form surface treatment capsule on the two sides of metal matrix material 1, namely on opposite side surface and then arrange resin molding or resin coating film.
For the surface treatment capsule 2 formed in metal matrix material 1, as mentioned above, the quality P of Metal Cr contained in this surface treatment capsule 2 and the ratio (Q/P) of the quality Q except Metal Cr are in the scope of 0.005 ~ 1.The surface treatment capsule 2 being rich in Cr so not only has excellent erosion resistance and thermotolerance because being rich in Cr, and, although Cr concentration is high, but still there is excellent shaping processability and adaptation.It should be noted that, water tolerance, resistance to chemical reagents and erosion resistance more preferably viewpoint high from adaptation, the Q/P of preferred surface process tunicle 2 is in the scope of 0.01 ~ 0.5.Be more preferably 0.05 ~ 0.25.
In addition, the thickness of surface treatment capsule is preferably 1 ~ 100nm.During more than 100nm, cannot tolerate and force work, when being less than 1nm, cannot guarantee that sufficient erosion resistance, adaptation etc. are by film properties.
As the purposes of metallic substance 10, the metallic substance of exterior material etc. of the main body that can be used in food tank or cover materials, containers for food use, drying battery container, secondary cell can be enumerated, but be not limited to these purposes, can be applicable to purposes widely.Particularly, can enumerate and can be used as the exterior material of following lithium-ion secondary cell and the metallic substance being treated object with the metal matrix material 1 be made up of aluminum or aluminum alloy, the exterior material of described lithium-ion secondary cell is recently for the exterior material of the portable equipment lithium-ion secondary cell in mobile phone, electronic notebook, laptop or pick up camera etc., the exterior material of lithium-ion secondary cell that uses as the drive energy of electromobile or hybrid vehicle.
Embodiment
Below, in conjunction with the embodiments and comparative example the present invention is described in more detail.The present invention is not by the restriction of following embodiment.It should be noted 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 " polyester polyol that formed by m-phthalic acid and 1,6-hexylene glycol (and number-average molecular weight: 2000) 200 parts, TriMethylolPropane(TMP) (molecular weight: 134) 5 parts, N methyldiethanol amine 32 parts ", isocyanate prepolymer composition " isophorone diisocyanate 118 parts ", chainextender " quadrol 5 parts ".
The synthesis of urethane resin a is as follows: above-mentioned polyhydroxy reactant and above-mentioned isocyanate prepolymer composition are reacted in methyl ethyl ketone solvent, in 80 DEG C, obtains carbamate prepolymer.In methyl-sulfate (30 parts) aqueous solution, after emulsification, make them react in 10% aqueous solution of chainextender this carbamate prepolymer, then except desolventizing, obtain urethane resin I.
(epoxy resin: symbol b1II)
Composition 1 " bisphenol A type epoxy resin (Yuka Shell Epoxy Co., Ltd. system, EPYCOTE828) (epoxy equivalent (weight): 187g) 235.7 parts ", composition 2 " dihydroxyphenyl propane 59.4 parts ", composition 3 " catalysts (lithium chloride) 0.1 part ", composition 4 " diethanolamine 14 parts ".
The synthesis of epoxy resin b1 is as follows: adding in the four neck flasks having mentioned component 1 ~ 3 and propylene glycol monomethyl ether 125 parts, limit import nitrogen limit in stirring under, 140 DEG C make it react, obtain reaction product solution.Then, add propylene glycol monomethyl ether 343.3 parts, hexamethylene diisocyanate 8.2 parts, in stirring under, 65 DEG C make it react, obtain modified high-molecular epoxy resin solution.Then, add propylene glycol monomethyl ether 92.7 parts and mentioned component 4, under stirring, 65 DEG C make it react, after reaction terminates, add propylene glycol monomethyl ether 154.7 parts, obtain the aqueous solution of amine-modified epoxy resin II.
(acrylic resin: symbol b1III)
Have employed following monomer composition: " methyl methacrylate 20 parts, butyl acrylate 40 parts, methacrylic acid 2-hydroxy propyl ester 10 parts, vinylbenzene 10 parts, methacrylic acid N, N-dimethylamino propyl ester 20 parts ".
Synthetic method is as follows: in the 10 quality % emulsifier aqueous solution 100 parts be mixed to get 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 with 5000rpm, obtain monomer emulsion.Then, to possessing stirrer, reflux exchanger, temperature take into account in four neck flasks of monomer supply pump and add above-mentioned emulsifier aqueous solution 150 parts, be held in 40 ~ 50 DEG C, the 5 quality % aqueous solution (50 parts) of ammonium persulphate and above-mentioned monomer emulsion are joined in dropping funnel respectively, and this dropping funnel is installed on other mouthful of neck of flask, dripped with about 2 hours, and by temperature to 60 DEG C, carried out stirring for about 1 hour.Be cooled to room temperature while stirring, obtain the emulsified soln of acrylic resin b1III.
(resol: symbol b1IV)
Employ the cation-modified resol b1IV of bisphenol type shown in following structural formula.In following structural formula, the polymerization degree (m+n) is 10 ~ 15, n/m is 40/60.
[chemical formula 1]
(Vinylite: symbol b1V)
Employ the multipolymer (molecular-weight average: 20000) formed by vinyl alcohol (80 quality %) and methacrylic acid (20 quality %).Synthetic method is as follows: by vinyl-acetic ester and methacrylic acid mixing, obtain the polymkeric substance of vinyl-acetic ester and methacrylic acid.Then, by vinyl-acetic ester is fully saponified, obtain Vinylite b1V.
(natural polysaecharides: symbol b1VI)
Employ glyceryl chitosan (number-average molecular weight: 100,000, R represents glyceryl, the glyceryl degree: 1.1) shown in following structural formula.
[chemical formula 2]
(natural polysaecharides: symbol b1VII)
Employ carboxymethyl cellulose (molecular-weight average: 50000).
(polyolefin resin: symbol b1VIII)
Employ formed by ethene (80 quality %) and vinylformic acid (20 quality %) multipolymer (molecular-weight average: 100000, in ammonia and product).
(Vinylite: symbol b1IX)
Employ the partly-hydrolysed thing (molecular-weight average: 50000,5 quality % acetoacetylation) of polyvinyl acetate.Synthetic method is as follows: make vinyl acetate polyisocyanate polyaddition, and it is 90% partly-hydrolysed to make it occur, and then, relative to copolymer 1 00 quality %, makes 5 quality % that acetoacetylation occur.
(Vinylite: symbol b1X)
Employ polyvinyl alcohol (molecular-weight average: 10000).Synthetic method is as follows: make vinyl acetate polyisocyanate polyaddition and obtain polyvinyl acetate, then carries out fully saponified.
(resol: symbol b1XI)
Employ the resole (dimer) with methylol.
(epoxy resin: symbol b1XII)
Employ sorbitol polyglycidyl base ether.
(epoxy resin: symbol b1XIII)
The ethylene oxide adduct 324 parts (0.2 mole) of dihydroxyphenyl propane, polyoxyethylene polyoxypropylene block polymer 2680 parts (0.4 mole) and the hydrogenation diphenylmethanediisocyanate 50 parts (0.4 mole) as polyisocyanate compound are mixed, and then the dibutyl tin dilaurate 3g (0.1 quality %) added as catalyzer, react 2 hours at 80 DEG C, obtain emulsified soln.
(urethane resin: symbol b1XIV)
Make polyester polyol (hexanodioic acid/3-methyl isophthalic acid, 5-pentanediol, number-average molecular weight 1000, functional group number 2.0, hydroxyl value 112.2) 100 parts, TriMethylolPropane(TMP) 3 parts, dimethylol propionic acid 25 parts, isophorone diisocyanate 85 parts react in MEK, obtains carbamate prepolymer.Mix triethylamine 9.4 parts wherein, and drop in water, make above-mentioned carbamate prepolymer be scattered in water, utilize quadrol that this prepolymer is extended, thus obtain dispersion.Distillation removing methylethylketone, obtains the polyurethane resin aqueous dispersion containing 30 quality % nonvolatile component.The acid number being scattered in the urethane containing carboxyl in 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-1,1-di 2 ethylhexyl phosphonic acid
B3IV:1,3-diamino-2-propyl alcohol-N, N, N ', N '-tetraacethyl
[metal conditioner]
By above-mentioned water-base resin and water soluble metallic compound combination, the metal conditioner of the embodiment 1 ~ 40 shown in table 1 and the metal conditioner of comparative example 1 ~ 10 are prepared.
[table 1]
[making of test material]
For aluminium alloy plate (JIS A 3004, thickness of slab 0.26mm), use 2% aqueous solution of Fine cleaner 4377K (alkali cleaner that Nihon Parkerizing Co., Ltd. manufactures) after 50 DEG C of degreasings of carrying out spraying for 10 seconds, carry out washing and come clean surface.Then, in order to make the moisture on aluminium alloy plate surface evaporate, 1 minute heat drying has been carried out in 80 DEG C.Rod coaters is utilized the metal conditioner of the embodiment 1 ~ 40 shown in table 1 and comparative example 1 ~ 10 to be coated the surface of the aluminium alloy plate through degreasing washing, and in 200 DEG C of dryings 1 minute in heated air circulation type drying oven, thus define the surface treatment capsule of given thickness on the surface of aluminium alloy plate.On the aluminium alloy plate being formed with surface treatment capsule, in 250 DEG C by polyester film (thickness 16 μm) heat lamination 5 second (arriving plate temperature is 180 DEG C), and face pressure is made to reach 50kg/cm
2, made " clad metal plate ".
[comparative example 11 ~ 13]
As comparative example 11, in 50 DEG C, spraying process in 5 seconds is carried out to commercially available Plessy's green hydrochlorate treatment agent (AM-K702:Nihon Parkerizing Co., Ltd. system), and carry out washing to remove unreacted medicament, carry out 1 minute heat drying in 80 DEG C, (Cr adhesion amount is 20mg/m to obtain test film
2).In addition, as comparative example 12, in 40 DEG C, spraying process in 20 seconds is carried out to commercially available zirconium phosphate treatment agent (AL-404:Nihon Parkerizing Co., Ltd. system), and carry out washing to remove unreacted medicament, carry out 1 minute heat drying in 80 DEG C, (Zr adhesion amount is 15mg/m to obtain test film
2).In addition, as comparative example 13, the test film merely through degreasing has also been made.
The clad metal plate utilizing drawing attenuated processing experiment to obtain laminating resin film has carried out deep-draw processing.Drawing processing (the 1st time) is carried out to the clad metal plate being die-cut into diameter 160mm, has made the cup of diameter 100mm.Then, again by this glass of drawing processing (the 2nd time) diameter 75mm, and then drawing processing (the 3rd time), to diameter 65mm, has made the tank as test material.Wherein, thinning (thin-walled property) rate of the 1st drawing processing, the 2nd drawing processing, the 3rd drawing processing is respectively 5%, 15%, 15%.
[performance evaluation]
As described below initial stage adaptation, durable adaptation and acidproof adaptation after carrying out deep-draw processing to clad metal plate are evaluated.Its result is as shown in table 2.
(initial stage adaptation)
The evaluation of initial stage adaptation has been carried out for the test material after deep-draw processing.Tank can be made, the situation of the stripping of film does not occur be denoted as "○"; Tank can be made but the situation having part film to there occurs stripping is denoted as " △ "; The situation failing to make tank by there occurs fracture is denoted as "×".In addition, in "○", the situation not observing stripping, especially excellent appearance is completely denoted as " ◎ ".
(durable adaptation)
For the test material after deep-draw processing, in the atmosphere of heating and pressurizing steam, implement distillation test.Distillation test uses commercially available sterilising plant (autoclave), at 125 DEG C, carried out 1 hour.For the test material after test, the situation of the stripping that film does not occur is denoted as "○"; The situation having part film to there occurs stripping is denoted as " △ "; The situation that film be there occurs on whole stripping is denoted as "×".In addition, in "○", the situation not observing stripping, especially excellent appearance is completely denoted as " ◎ ".
(acidproof adaptation)
For the test material after deep-draw processing, the adaptation flood 16 hours in the 0.5%HF aqueous solution of 50 DEG C after is evaluated.The situation of the stripping that film does not occur is denoted as "○"; The situation having part film to there occurs stripping is denoted as " △ "; The situation that film be there occurs on whole stripping is denoted as "×".In addition, in "○", the situation not observing stripping, especially excellent appearance is completely denoted as " ◎ ".
[table 2]
As shown in table 2, utilize the metal conditioner of embodiment 1 ~ 40 to carry out the initial stage adaptation of surface-treated metallic substance, durable adaptation and acidproof adaptation all excellent.
On the other hand, containing Cr (III) compound (A) and be selected from there is film-forming properties organic compound and mineral compound at least a kind of compound (B) and the Metal Cr reduced mass of Cr (III) compound (A) being set to M, the quality of compound (B) is set to N time N/M high comparative example 3,4,5,6,7, and the comparative example 1 only containing Cr (III) compound, the comparative example 2 that compound (B) is few, not containing the comparative example 8 of Cr (III) compound, all obtain the result that adaptation is bad.Particularly, durable adaptation and acidproof adaptation significantly bad.
Claims (6)
1. a metal conditioner, it is for the substrate metal finishing tunicle at the substrate material surface form layers press mold be made up of aluminum or aluminum alloy or resin coating film, wherein,
This metal conditioner contains Cr (III) compound (A) and compound (B), described compound (B) is for being selected from the organic compound and mineral compound with film-forming properties and at least a kind that can be combined into described compound (A) in the organic compound of film
The Metal Cr reduced mass of described Cr (III) compound (A) is set to M, when the quality of described compound (B) is set to N, N/M is 0.005 ~ 1.
2. metal conditioner according to claim 1, wherein, described compound (B) is for being selected from organic compound (b1), at least a kind in mineral compound (b2) and organic chelate compound (b3), described organic compound (b1) is for being selected from urethane resin, epoxy resin, polyolefin resin, acrylic resin, Vinylite, one kind or two or more in resol and natural polymer, described mineral compound (b2) is for being selected from silicate compound, zirconium compounds, one kind or two or more in titanium compound and phosphate compounds, in every a part of described organic chelate compound (b3), there are more than 2 and be selected from hydroxyl, carboxyl, phosphonate group, phosphate, at least a kind of functional group in amino and amide group.
3. metal conditioner according to claim 1 and 2, wherein, described metal conditioner is used for after this metal conditioner is coated described substrate material surface, carrying out drying to form described metal finishing tunicle.
4. a metal surface treating method, it comprises following operation: the surface metal conditioner according to any one of claims 1 to 3 being coated on the body material be made up of aluminum or aluminum alloy, then heat drying is carried out to form surface treatment capsule in the temperature of 60 ~ 250 DEG C
Wherein, the thickness of surface treatment capsule is in the scope of 1 ~ 100nm.
5. a metal finishing tunicle, it utilizes the metal surface treating method described in claim 4 to be formed.
6. a metallic substance, it obtains by the surface treatment capsule that the metal surface treating method utilized described in claim 4 is formed being arranged at the substrate material surface be made up of aluminum or aluminum alloy.
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| JP2010019604 | 2010-01-29 | ||
| JP2010-019604 | 2010-01-29 | ||
| PCT/JP2011/051554 WO2011093359A1 (en) | 2010-01-29 | 2011-01-27 | Metal surface treatment agent and metal surface treatment method |
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| KR (1) | KR101444569B1 (en) |
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| CN105649745A (en) * | 2015-12-31 | 2016-06-08 | 芜湖恒耀汽车零部件有限公司 | Exhaust pipe lifting hook assembly |
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| KR102500400B1 (en) * | 2018-03-29 | 2023-02-15 | 니혼 파커라이징 가부시키가이샤 | Surface treatment agent, aluminum or aluminum alloy material having surface treatment film, and manufacturing method thereof |
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| WO2011093359A1 (en) | 2011-08-04 |
| JP5854505B2 (en) | 2016-02-09 |
| TWI510674B (en) | 2015-12-01 |
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| KR101444569B1 (en) | 2014-09-24 |
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