CN102877052A - Drainage system obtained by the treatment processing and metal surface treatment agent and metal material - Google Patents
Drainage system obtained by the treatment processing and metal surface treatment agent and metal material Download PDFInfo
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- CN102877052A CN102877052A CN2012102455464A CN201210245546A CN102877052A CN 102877052 A CN102877052 A CN 102877052A CN 2012102455464 A CN2012102455464 A CN 2012102455464A CN 201210245546 A CN201210245546 A CN 201210245546A CN 102877052 A CN102877052 A CN 102877052A
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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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Abstract
The present invention provide drainage metal surface treatment agent and using the metal surface treatment processing of metal materials, the drainage metal surface treatment agent is used for forming can prevent metal materials and laminated film or a resin film stripping, and closed sex and drug resistance and retention excellent surface treatment by membrane. Drainage metal surface treatment agent of the present invention contains: polyvinyl alcohol compounds (A) and one or more than two crosslinking compounds (B), in the crosslinking compounds (B) has with polyvinyl alcohol compounds (A) crosslinking reaction of functional groups (B1), and contain vocs can react with polyvinyl alcohol compounds (A) the elements of the crosslinking of inorganic compounds (B2).
Description
Technical field
The present invention relates to water-based metal-surface-treating agent and utilize this metal conditioner to process and the metallic substance that obtains, this water-based metal-surface-treating agent is used to form and can prevents that metallic substance and laminated film or resin coating film from peeling off and the surface treatment capsule of adaptation and drug-resistant driving fit retentivity excellence.Specifically, the present invention relates to be used to form the water-based metal-surface-treating agent etc. of the surface treatment capsule of non-hexavalent chromium, even this surface treatment capsule forms resin coating film resin film layer is pressed on the metallic substance or at metallic substance, then implemented deep-draw processing, in the situation of the shaping processing that attenuate processing or stretch-draw (stretch draw) processing etc. are harsh, also can give the high adaptation that above-mentioned laminated film etc. is peeled off, even and be exposed to acid, under the conditions such as organic solvent, also have excellent drug-resistant driving fit retentivity, thereby can keep high adaptation.
Background technology
Lamination process be with resinous film (below; be called " resin molding " or " laminated film ") heating be pressed together on metallic substance the surface (below; referred to as " metallic surface ") working method; be that to protect the metallic surface or give designability be one of metallic surface method for coating of purpose, can be used for various fields.With with resin combination dissolving or be dispersed in that the coating liquid that obtains in the solvent is coated in the metallic surface and the dry method that forms resin coating film is compared, the generation of the waste gas such as the solvent that described lamination process produces when drying is few, carbonic acid gas or greenhouse gases is also few.Therefore; aspect environment protection; the preferred lamination process of using, its purposes enlarges, and has been used to such as main body or cover material, containers for food use or the drying battery container etc. of the food take aluminium sheet material, steel sheet material, Packaging Aluminum Foil or stainless steel foil etc. as raw material with tank.
Particularly nearest, exterior material and lug (tab lead) material as the portable lithium-ion secondary cell that uses in mobile phone, electronic notebook, notebook computer or the pick up camera etc., the tinsels such as the aluminium foil that preferred use lightweight and barrier are high or stainless steel foil have suitably been carried out lamination process to the surface of such tinsel.In addition, studying the lithium-ion secondary cell as the drive energy of electromobile or hybrid vehicle, as its exterior material, also the tinsel through lamination process is being studied.
Then direct and metallic substance applying adds hot pressing for the laminated film of such lamination process.Therefore, compare with application of resin composition and the dry common resin coating film that forms, have can suppress raw-material waste, pin hole (defective part) reaches the advantages such as excellent in workability less.As the material of laminated film, usually use the polyolefine such as the polyester resins such as polyethylene terephthalate and PEN, polyethylene and polypropylene.
If the metallic surface is not implemented the processing such as chemical conversion processing when carrying out lamination process, then exist laminated film to peel off from the metallic surface or the problem of the easy corrosion of metallic substance.For example, for containers for food use or wrapping material, behind the interpolation content, implement the heat treated take sterilization as purpose, but laminated film is peeled off from the metallic surface sometimes when this heat treated in the container after lamination process or the wrapping material.In addition, for exterior material of lithium-ion secondary cell etc., will the high processing of degree of being subject to processing in its manufacturing process.In addition, when life-time service, have following problems: the moisture in the atmosphere can immerse in the container, and itself and ionogen react and generate hydrofluoric acid, and this hydrofluoric acid sees through laminated film peels off metallic surface and laminated film, and can erode metallic surfaces.
For the problems referred to above, with the laminated film lamination process on the metallic surface time, in order to improve adaptation between laminated film and the metallic surface and the erosion resistance of metallic surface, carry out cleaning by degreasing to the metallic surface, then usually implement chemical conversion processing of Plessy's green hydrochlorate etc. etc.But such chemical conversion is processed need to implement matting after processing, to remove remaining treatment solution, carries out wastewater treatment for the rinse water of being discharged by this matting and will spend cost.Especially the chemical conversion processing of Plessy's green hydrochlorate etc. etc. has been owing to having used chromyl treatment solution, therefore in recent years to the worry of environment, the withdraw from service tendency is arranged.
For example, proposed a kind of primer in the patent documentation 1, it contains the water-soluble zirconium compound of specified quantitative, water-soluble or water dispersible acrylic resin and the water-soluble or water dispersible thermohardening type linking agent of ad hoc structure.In addition, proposed a kind of chromium-free metal surface treatment agent in the patent documentation 2, it comprises the water-soluble zirconium compound of specified quantitative and/or water-soluble titanium compound, organic phospho acid compound, and tannin.In addition, proposed a kind of metal finishing medicament in the patent documentation 3, it contains the special metal compounds such as amination phenol polymer, Ti and Zr, and the pH of this metal finishing medicament is 1.5 ~ 6.0 scope.In addition, proposed a kind of resin molding in the patent documentation 4, it contains amination phenol polymer, acrylic polymers, metallic compound and phosphorus compound as required.
The prior art document
Patent documentation
The open WO2002/063703 communique of [patent documentation 1] international monopoly
[patent documentation 2] TOHKEMY 2002-265821 communique
[patent documentation 3] TOHKEMY 2003-313680 communique
[patent documentation 4] TOHKEMY 2004-262143 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind ofly to be used to form the water-based metal-surface-treating agent of surface treatment capsule and to utilize this metal conditioner to process and the metallic substance that obtains, described surface treatment capsule can prevent that metallic substance and laminated film or resin coating film from peeling off and adaptation and drug-resistant driving fit retentivity excellence.Specifically, the invention provides the metal conditioner that is used to form the non-hexavalent chromium surface treatment capsule and utilize this metal conditioner to process and the metallic substance that obtains, even this surface treatment capsule forms resin coating film resin film layer is pressed on the metallic substance or at metallic substance, then implemented deep-draw processing, in the situation of the shaping processing that attenuate processing or stretch-draw processing etc. are harsh, also has the high adaptation that this laminated film or resin coating film are peeled off, even and be exposed to acid etc. under the condition, also have excellent drug-resistant driving fit retentivity, thereby can keep high adaptation.
The method of dealing with problems
The water-based metal-surface-treating agent of the present invention that is used for addressing the above problem contains: polyvinyl alcohol compounds (A) and one kind or two or more cross-linked compound (B), described cross-linked compound (B) are selected to have and can and contain in the bridging property mineral compound (B2) of the element that can react with described polyvinyl alcohol compounds (A) with the bridging property organic compound (B1) of the functional group of described polyvinyl alcohol compounds (A) reaction.
According to this invention, owing to containing polyvinyl alcohol compounds (A) and above-mentioned cross-linked compound (B), can make and utilize this water-based metal-surface-treating agent to process and the surface treatment capsule that obtains has high adaptation, even and also can keep high adaptation being exposed under the condition such as acid.Its result, even laminating resin film or formation resin coating film on metallic substance, then implemented in the situation of the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, even and in the situation that further be exposed to acid or organic solvent etc., can prevent that also this laminated film or resin coating film from peeling off from metallic substance.
In water-based metal-surface-treating agent of the present invention, described bridging property organic compound (B1) has the functional group more than a kind that is selected from glycidyl ether, isocyanate group, methylol and the aldehyde radical.
According to this invention, because bridging property organic compound (B1) has above-mentioned functional group, the adaptation of the surface treatment capsule that therefore utilizes this water-based metal-surface-treating agent to process and obtain is more excellent, even and long-term exposure in organic solvent or acid, also can keep more stable adaptation.
In water-based metal-surface-treating agent of the present invention, described bridging property mineral compound (B2) contains the one kind or two or more element that is selected among Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and the La.
According to this invention, because bridging property organic compound (B2) contains above-mentioned element, the adaptation of the surface treatment capsule that therefore utilizes this water-based metal-surface-treating agent to process and obtain is more excellent, and, even long-term exposure also can keep more stable adaptation in organic solvent or acid.
The metallic substance of the present invention that is used for addressing the above problem is characterised in that, it has the surface treatment capsule that above-mentioned water-based metal-surface-treating agent is coated in metal material surface and forms.
According to this invention, owing to the surface treatment capsule that forms of water-based metal-surface-treating agent with coating the invention described above, therefore, even the metallic substance with this surface treatment capsule is being implemented lamination process, and then implemented in the situation of the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, and further be exposed in the situation in the condition such as acid, can prevent that also the laminated film or the resin coating film that are formed on metal material surface from peeling off.
The effect of invention
According to water-based metal-surface-treating agent of the present invention, can be provided for forming and to prevent that metallic substance and laminated film or resin coating film from peeling off and the water-based metal-surface-treating agent of the surface treatment capsule of adaptation and drug-resistant driving fit retentivity excellence.
According to metallic substance of the present invention, can provide the metallic substance with above-mentioned surface treatment capsule.
Description of drawings
[Fig. 1] is the schematic cross sectional view that an example of the metallic substance with the surface treatment capsule that applies water-based metal-surface-treating agent of the present invention and form is shown.
Nomenclature
1 body material metal
2 surface treatment capsules
3 resin moldings (laminated film) or resin coating film
10 have the metallic substance of surface treatment capsule
Embodiment
Below, to water-based metal-surface-treating agent of the present invention and the metallic substance with the surface treatment capsule that this metal conditioner is coated in metal material surface and forms describe.Need to prove, technical scope of the present invention is not limited by the embodiment of the following description and accompanying drawing.
[water-based metal-surface-treating agent]
As shown in Figure 1, water-based metal-surface-treating agent of the present invention is for being the primary coat of the surperficial form layers press mold of metallic substance 1 (below, be called " body material metal 1 ") or resin coating film 3 at body material with the treatment agent of surface treatment capsule 2.It is characterized in that, contain polyvinyl alcohol compounds (A) and one kind or two or more cross-linked compound (B), described cross-linked compound (B) is selected from bridging property organic compound (B1) and bridging property mineral compound (B2)." contain " compound that refers to contain in the water-based metal-surface-treating agent except polyvinyl alcohol compounds (A) and cross-linked compound (B).As such compound, can enumerate such as tensio-active agent, defoamer, flow agent, antibacterial mildew inhibitor, tinting material etc.Can not damage purport of the present invention and contained these compounds by the scope of film properties.
Below, formation of the present invention is elaborated.
(polyvinyl alcohol compounds (A))
Polyvinyl alcohol compounds (A) is the one kind or two or more compound that is selected from polyvinyl alcohol and the derivative thereof.By containing polyvinyl alcohol compounds (A) and cross-linked compound (B), can improve adaptation and the drug-resistant driving fit retentivity of the surface treatment capsule that utilizes this water-based metal-surface-treating agent processing and obtain.
As polyvinyl alcohol and derivative thereof, can use the saponified etc. of saponified, the vinyl-acetic ester of polyvinyl acetate and multipolymer that other monomers form.This is saponified can be partly-hydrolysed thing, also can be fully saponified thing.
As with other monomers of vinyl acetate copolymerization, can enumerate such as vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid and their the anionic property comonomers such as salt; The nonionic comonomers such as vinylbenzene, vinyl cyanide, vinyl ether, (methyl) acrylamide, N-methylol (methyl) acrylamide, (methyl) methyl acrylate, (methyl) Hydroxyethyl acrylate, vinyl pyrrolidone, acryloyl morpholine, vinyl-acetic ester; (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid N-hydroxypropyl amino ethyl ester, vinyl imidazole, N, the cationic comonomers such as N-dimethyl diallyl amine.
In addition, can by making the reaction of above-mentioned polyvinyl alcohol and derivative thereof and dicthenone, make its acetoacetylate.
With respect to all solids composition contained in the water-based metal-surface-treating agent, the content of polyvinyl alcohol compounds (A) is preferably 10 quality % ~ 90 quality %, and more preferably 10 quality % ~ 80 quality % especially are preferably 20 quality % ~ 80 quality %.Be 10 quality % ~ 90 quality % by making this content, can further improve adaptation and the drug-resistant driving fit retentivity of the surface treatment capsule that obtains.
Need to prove, " all solids composition " refers to consist of in the composition of water-based metal-surface-treating agent except solvent etc. and evaporates into solids component grading, specifically, be the total amount of polyvinyl alcohol compounds (A) and one kind or two or more cross-linked compound (B), described cross-linked compound (B) is selected from bridging property organic compound (B1) and bridging property mineral compound (B2).Therefore, total amount (all solids composition) with respect to polyvinyl alcohol compounds (A) and cross-linked compound (B), the content of polyvinyl alcohol compounds (A) is preferably 10 quality % ~ 90 quality %, more preferably 10 quality % ~ 80 quality % especially are preferably 20 quality % ~ 80 quality %.
(cross-linked compound (B))
Cross-linked compound (B) is the one kind or two or more compound that is selected from bridging property organic compound (B1) and the bridging property mineral compound (B2).Water-based metal-surface-treating agent can improve adaptation and the drug-resistant driving fit retentivity of the surface treatment capsule that obtains with this water-based metal-surface-treating agent processing by containing cross-linked compound (B).
(bridging property organic compound (B1))
Bridging property organic compound (B1) be have can with the compound of the functional group of polyvinyl alcohol (A) reaction." can react " and refer to the meaning that contacts with polyvinyl alcohol (A) and can react with it." have " other functional group that refers to contain except these structural units, the meaning of combining unit.
As bridging property organic compound (B1), can enumerate and for example have the one kind or two or more organic compound that is selected from glycidyl ether, isocyanate group, methylol and the aldehyde radical.
As the organic compound with glycidyl ether, can use in the past known polynary glycidyl ether compound.As polynary glycidyl ether compound, can enumerate such as ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, glycerol diglycidylether, glycerin triglycidyl ether, glycerol polyglycidyl ether, two glycerol triglycidyl ether, polyglycerol triglycidyl ether, tetramethylolmethane four glycidyl ethers, TriMethylolPropane(TMP) diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, Sorbitol Powder polyglycidyl ether etc.
As the organic compound with isocyanate group, for example can enumerate: the isomer class of tolylene diisocyanate; 4, the aromatic diisocyanates such as 4 '-diphenylmethanediisocyanate; The aromatic-aliphatic diisocyanates such as xylylene diisocyanate; The ester ring type such as isophorone diisocyanate, HMDI vulcabond; Hexamethylene diisocyanate, 2,2, the aliphatic diisocyanate classes such as 4-trimethyl hexamethylene diisocyanate etc.For these isocyanate compounds, limit especially, but from the stable this point of water-based metal-surface-treating agent, the preferred use utilizes various end-capping reagents to carry out the isocyanate compound of end-blocking.As end-capping reagent, can enumerate such as various end-capping reagents such as phenols, alcohols, oximes, active methylene group class, sour amides, Carbamates, sulfites.
As the organic compound with methylol, can enumerate the multipolymer that forms such as: the homopolymer of resole, melamine methylol and N hydroxymethyl acrylamide monomer, N hydroxymethyl acrylamide monomer and other monomers etc.
As the organic compound with aldehyde radical, can enumerate such as: oxalic dialdehyde, mda, suceinic aldehyde, glutaraldehyde, hexanedial, heptan the dialdehyde compounds such as dialdehyde, have the compound of three above aldehyde radicals etc.
(bridging property mineral compound (B2))
Bridging property organic compound (B2) be contain can with the compound of the element of polyvinyl alcohol (A) reaction." can react " and refer to contact with polyvinyl alcohol (A) and can react with it." contain " other element that refers to contain except these elements.
As bridging property mineral compound (B2), can example as: contain the mineral compound that is selected from the one kind or two or more element among Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and the La.Wherein, more preferably contain the mineral compound that is selected from the one kind or two or more element among Mg, Al, Ca, Mn, Cr (III), Zn, Fe, Zr, Ti, Si, Ce, Te and the Hf, further preferably contain the mineral compound that is selected from the one kind or two or more element among Cr (III), Zr, Ti, Si, Ce and the Te.
Specifically, can enumerate, contain the salt, complex compound or the hydrous oxide that are selected from the one kind or two or more element among Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and the La (below, be also referred to as " salt etc. ").
More particularly, can enumerate: the magnesium salts such as two (methyl ethyl diketones), two hydrous magnesiums (II), magnesium aluminate, magnesium benzoate, magnesium formiate, magnesium oxalate, magnesium wolframate, inclined to one side magnesium-niobate, magnesium borate, magnesium molybdate, magnesium iodide, biphosphate magnesium, magnesium nitrate, sal epsom, magnesiumcarbonate, magnesium hydroxide, magnesium fluoride, magnesium ammonium phosphate, secondary magnesium phosphate, magnesium oxide etc.;
The aluminium salt such as aluminum nitrate, Tai-Ace S 150, aluminum potassium sulfate, aluminum sodium sulfate, aluminium ammonium sulfate, aluminum phosphate, aluminium carbonate, aluminum oxide, aluminium hydroxide, aluminum oxide, aluminum fluoride, aluminum iodide, aluminum acetate, aluminum benzoate, Tiorco 677, glyconic acid aluminium, selenic acid aluminium, oxalic acid aluminium, tartrate aluminium, Aluctyl, aluminum palmitate etc.;
The calcium salts such as two (methyl ethyl diketones), two hydrated calciums (II), calcium benzoate, citrate of lime, metastannic acid calcium, calcium selenate, calcium wolframate, calcium carbonate, calcium tetraborate, calcium molybdate, calcium maleate, calcium malate, DI-CALCIUM PHOSPHATE, Calcium Fluoride (Fluorspan), phosphonic acids calcium, nitrocalcite, calcium hydroxide, calcium oxide, caoxalate, calcium oxide, lime acetate etc.;
Two (methyl ethyl diketones), two hydrated manganeses (II), trimanganese tetroxide, manganese oxide (II), manganese oxide (III), manganese oxide (IV), Manganese dibromide (II), manganous oxalate (II), permanganic acid (VII), potassium permanganate (VII), sodium permanganate (VII), phosphate dihydrogen manganese (II), manganous nitrate (II), manganous sulfate (II), manganous sulfate (III), manganous sulfate (IV), manganous fluoride (II), manganous fluoride (III), manganous carbonate (II), manganous acetate (II), manganous acetate (III), ammonium sulfate manganese (II), manganese iodide (II), the manganese salt such as manganous hydroxide (II) etc. or manganate etc.;
Two (methyl ethyl diketone) two hydration cobalts (II), tri acetylacetonato closes cobalt (III), thionamic acid cobalt (II), cobalt chloride (II), purpureo-cobaltichloride (III), chlorination six cobaltammines (III), the sour ammonium of tetranitro two cobaltammines (III), rose vitriol (II), cobaltous ammonium sulfate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (II), cobalt oxide two aluminium, cobaltous hydroxide (II), cobalt oxide (II), cobaltous phosphate, cobaltous acetate (II), cobaltous formate (II), tricobalt tetroxide, cobaltous bromide (II), cobalt oxalate (II), cobaltous selenate (II), cobaltous tungstate (II), the inferior cobalt (II) of hydroxyl carbonic acid, cobalt molybdate (II), cobaltous iodide (II), the cobalt salts such as cobaltous phosphate (II) etc.;
Diamino sulfonic acid nickel (II), nickel benzoate (II), nickelous nitrate (II), single nickel salt (II), nickelous carbonate (II), acetylacetonate nickel (II), nickelous chloride (II), hexaammine nickel chloride, nickel oxide, nickel hydroxide (II), nickel oxide (II), nickelous acetate, citric acid nickel (II), succsinic acid nickel (II), nickelous bromide (II), nickelous oxalate (II), tartrate nickel (II), nickelous selenate (II), hydroxyl nickelous carbonate (II), lactic acid nickel (II), nickel molybdate (II), nickelous iodide (II), the nickel salts such as bisphosphate nickel (II) etc.;
The chromic salts such as chromic formate (III), chromium fluoride (III), chromium nitrate (III), chromium sulphate (III), chromium+oxalic acid (III), chromium acetate (III), biphosphate chromium (III), chromium hydroxide (III), chromic oxide (III), chromic bromide (III), iodate chromium (III) etc.;
Two (methyl ethyl diketones) close zinc (II), Zinc dibenzoate (II), hydroxyl zinc chloride (II), zinc formate (II), zinc citrate (II), zinc bromide (II), zinc oxalate (II), zinc tartrate (II), zinc metastannate (II), zinc selenate (II), zinc tungstate (II), zinc fluoride (II), zinc molybdate (II), zinc butyrate (II), bisphosphate zinc (II), zinc sulfate (II), zinc carbonate (II), zinc chloride (II), zinc iodide (II), zinc hydroxide (II), the zinc salts such as zinc oxide (II) etc.;
Two (methyl ethyl diketones), two hydrated irons (II), tri acetylacetonato iron (III), three ironic oxalate tripotassiums, ironic formiate (II), four ferric vandate (III), iron bromide (III), tartrate iron (III), ironic lactate (II), ferric fluoride (II), ferric fluoride (III), iron(ic) chloride (II), iron(ic) chloride (III), ferric iodide (II), ferric iodide (III), ferric sulfate (II), ferric sulfate (III), iron nitrate (II), iron nitrate (III), ironic acetate (II), ironic acetate (III), ironic citrate (II), ironic citrate (III), ferrous glycine (II), ferrous glycine (III), ironic oxalate (II), ironic oxalate (III), 2-pyridine carboxylic acid iron (II), 2-pyridine carboxylic acid iron (III), L-Phe iron (II), L-Phe iron (III), propanedioic acid iron (II), propanedioic acid iron (III), ironic hydroxide (II), ironic hydroxide (III), ferric oxide (II), ferric oxide (III), the molysite such as Z 250 etc.;
The strontium salt such as two (methyl ethyl diketones), two strontium hydrates (II), strontium formate (II), strontium citrate (II), strontium wolframate, metastannic acid strontium, strontium oxide (IV), strontium oxide (II), strontium oxalate, inclined to one side niobic acid strontium, strontium molybdate, strontium iodide, strontium nitrate, Strontium Sulphate, Strontium carbonate powder, strontium acetate, strontium chloride, strontium phosphate, strontium lactate etc.;
Two oxalic acid oxidation metatitanic acid two ammoniums, two oxalic acid oxidation metatitanic acid dipotassiums, titanium oxide (II), titanium oxide (III), titanium oxide (IV), titanyl sulfate, alkali formula titanium phosphate, titanium bromide (IV), metatitanic acid, zinc metatitanate (II), aluminium titanates (III), Potassium titanate, metatitanic acid cobalt (II), zirconia titanate, the metatitanic acid strontium, metatitanic acid iron (III), metatitanic acid copper (II), sodium titanate, two metatitanic acid neodymiums (III), barium metatitanate, metatitanic acid bismuth (III), magnesium titanate, magnesium titanate, metatitanic acid manganese (II), two lanthanium titanates (III), the metatitanic acid lithium, the sour ammonium of hexafluoro titanium (IV), the sour potassium of hexafluoro titanium (IV), titanium iodide (IV), titanium sulfate (III), titanium sulfate (IV), titanium chloride, Titanium Nitrate, titanyl sulfate, titanium fluoride (III), titanium fluoride (IV), the hexafluoro metatitanic acid, the lactic acid titanium, pertitanic acid, the lauric acid titanium, titanium acetylacetone, the titanium salts such as titanium hydroxide (IV) etc. or titanate etc.;
Four (methyl ethyl diketones) close zirconium (IV), chloride oxidation zirconium (IV), zirconium chloride (IV), zirconium silicate, zirconyl acetate (jealous woman acid acidifying ジ Le コ ニ ゥ system) (IV), zirconium white (IV), Zircosol ZN (IV), inclined to one side zirconic acid caesium, lithium meta-zirconate, inclined to one side zirconic acid zinc (II), inclined to one side zirconic acid aluminium (III), calcium metazirconate, inclined to one side zirconic acid cobalt (II), inclined to one side strontium zirconate, inclined to one side zirconic acid copper (II), inclined to one side sodium zirconate, inclined to one side zirconic acid nickel (II), inclined to one side barium zirconate, inclined to one side zirconic acid bismuth (III), inclined to one side magnesium zirconate, zirconyl carbonate, the sour ammonium of hexafluoro zirconium (IV), the sour potassium of hexafluoro zirconium (IV), the iodate zirconium, biphosphate zirconium white (IV), zirconyl carbonate, zirconium carbonate ammonium, zirconium carbonate ammonium, zirconium nitrate, zirconium nitrate, zirconium sulfate (IV), zirconium sulfate, hexafluoro zirconate, zirconium phosphate oxygen, zirconium pyrophosphate, the biphosphate zirconium, zirconium oxychloride, Zirconium tetrafluoride, zirconium acetate, zirconium white, the zirconates such as zirconium hydroxide etc.;
The silicate such as hexafluorosilicic acid, silicon-dioxide etc.;
Tungsten chloride (VI), oxidation wolframic acid iron (III), tungsten chloride (VI), two tungsten oxychlorides, Tungsten oxide, tungstic oxide, metatungstic acid, ammonium metawolframate, metatungstic acid sodium, para-tungstic acid, ammonium paratungstate, sodium paratungstate, zinc tungstate (II), potassium wolframate, calcium wolframate, cobaltous tungstate (II), strontium wolframate, the wolframic acid caesium, cupric wolframate (II), wolframic acid nickel, barium wolframate, magnesium wolframate, wolframic acid manganese (II), lithium tungstate, phospho-wolframic acid, ammonium phosphowolframate, the tungsten salt such as Tungstophosphoric acid, sodium salt etc. or tungstate etc.;
Tri acetylacetonato closes cerium (III), Cerium II Chloride (III), cerium oxide (III), cerium oxide (IV), comprise cerium bromide (III), Sedemesis (III), cerous hydroxide (IV), ammonium cerous sulfate (IV), cerous sulfate ammonium (III), cerous carbonate (III), cerous sulfate, cerous acetate (III), cerous nitrate (III), cerous sulfate (IV), cerium fluoride (III), cerous iodide (III), the cerium salt such as Cerium monophosphate (III) etc.;
The molybdenum salt such as molybdenum chloride (V), molybdenum oxide (IV), molybdenum oxide (VI), zinc molybdate (II), potassium molybdate, calcium molybdate, cobalt molybdate (II), cesium molybdate, nickel molybdate (II), barium molybdate, bismuth molybdate (III), magnesium molybdate, lithium molybdate, para-molybdic acid lithium, strontium molybdate, phospho-molybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, molybdic acid, ammonium molybdate, ammonium paramolybdate, Sodium orthomolybdate etc. or molybdate etc.;
The vanadic salts such as vanadium oxydichloride, vanadylic chloride, vanadium trichloride, vanadium oxide, four ferric vandate (III), bromination vanadium (III), oxalic acid vanadyl, iodate vanadium (II), vanadium pentoxide, metavanadic acid, sodium pyrovanadate, vanadic acid sodium, ammonium meta-vanadate, sodium metavanadate, potassium metavanadate, vanadylic chloride, three vanadium oxides, vanadium dioxide, vanadylic sulfate, acetic oxide acetone vanadium, vanadium acetylacetonate, phosphovanadomolybdic acid etc. or vanadate etc.;
The pink salts such as tin chloride (II), tin acetate (II), tin oxalate (II), tartrate tin (II), stannic oxide (IV), nitric acid tin, tin sulphate, Tin tetrafluoride. (II), Tin tetraiodide (II), Tin tetraiodide (IV), stannous pyrophosphate (II), metastannic acid, zinc metastannate, metastannic acid calcium, metastannic acid strontium, metastannic acid barium, metastannic acid magnesium or stannate etc.;
Bismuth benzoate (III), Bismuth Oxychloride (III), bismuth citrate (III), acetic acid oxygen bismuth (III), oxidation Bismuth tartrate (III), bismuth oxide (III), sulfuric acid oxygen two bismuths, bismuth bromide (III), Bismuth tartrate (III), bismuth hydroxide (III), carbonic acid gas two bismuths, zirconic acid bismuth (III), bismuthyl nitrate, four bismuth titanates (III), three bismuth titanates (III), fluoridize bismuth (III), bismuth molybdate (III), bismuth iodide (III), Bismuth trinitrate (III), bismuth chloride (III), bismuth sulfate (III), bismuth acetate (III), the bismuth salt such as bismuth phosphate (III) etc.;
The tantalum salt such as tantalum chloride (V), tantalum oxide (V), tantalum bromide (V), tantalic acid, six potassium tantalates, inclined to one side tantalic acid strontium, sodium metatantalate, inclined to one side lithium tantalate, iodate tantalum (V), methyl ethyl diketone oxygen tantalum, inclined to one side tantalic acid, inclined to one side tantalic acid ammonium, potassium tantalifluoride etc. or tantalate etc.;
The tellurium salt such as telluric acid, inclined to one side ammonium tellurate, inclined to one side potassium tellurate, inclined to one side sodium tellurate, telluronium iodide (IV), potassium tellurate, sodium tellurate, tellurous acid, potassium tellurite, sodium tellurite, tellurous acid barium, tellurous acid lithium, tellurium chloride (IV), tellurium oxide (IV), tellurium bromide (IV), hydroxide nitric acid three oxidations two telluriums, tellurous acid zinc etc. or tellurate etc.;
Tri acetylacetonato closes the indium salt such as indium (III), thionamic acid indium (III), indium dichloride, indium chloride (I), indium chloride (III), indium acetate (III), indium bromide (III), indium iodide (III), indium nitrate (III), indium sulfate (III), indium (III), Indium sesquioxide (III), indium hydroxide (III) etc.;
The barium salts such as two (methyl ethyl diketone) two hydration barium (II), barium selenite, tellurous acid barium, Barium dibenzoate, barium aluminate, bariumchloride, barium formate, barium citrate, barium oxide, barium bromide, barium oxalate, barium tartrate, inclined to one side barium zirconate, hydrated barta, metastannic acid barium, barium wolframate, barium metatitanate, inclined to one side niobic acid barium, barium lactate, barium metaborate, barium molybdate, barium iodide, barium hydrogen phosphate, barium carbonate, barium fluoride etc.;
Four (methyl ethyl diketones) close hafnium salt such as hafnium (IV), hafnium chloride (IV), hafnia (IV), iodate hafnium (IV), hafnium sulfate (IV), hafnium nitrate (IV), oxalic acid oxygen hafnium (IV), the acid of fluorine hafnium, fluohafnate, hafnium fluoride etc. or hafnates etc.;
The selenium salt such as potassium selenite, potassium biselenite, selenous acid three hydrogen caesiums, sodium hydroselenite, hydrogen selenite lithium, selenous acid copper (II), Sodium Selenite, barium selenite, oxychlorination selenium, Selenium monochloride (I), Selenium monochloride (IV), selenium oxide (IV), selenic acid aluminium, selenic acid, zincium selenious acid, potassium selenate, ammonium selenate, calcium selenate, cesium selenate, cobaltous selenate, cupric selenate (II), nickelous selenate, sodium selenate, barium selenate, zinc selenate etc. or selenate etc.;
The scandium salts such as Scium trichloride (III), formic acid scandium (III), acetic acid scandium (III), Scium trinitrate (III), Scium trioxide (III), scandium fluoride (III), scandium iodide (III), scandium sulfate (III) etc.;
The niobium salt such as niobium oxides (II), niobium oxides (V), five (oxalic acid hydrogen) niobium, niobium hydroxide (V), methyl ethyl diketone oxygen niobium, inclined to one side niobic acid, inclined to one side calcium niobate, inclined to one side niobic acid strontium, inclined to one side niobic acid barium, inclined to one side magnesium-niobate, inclined to one side Lithium niobium trioxide, inclined to one side niobic acid ammonium, inclined to one side sodium columbate, columbium pentachloride etc. or niobate etc.;
Thionamic acid copper (II), cupric benzoate (II), nitric acid four ammino copper (II), Cuprocitrol (II), cupric oxide (I), cupric bromide (I), cupric oxalate (II), Tubercuprose (II), venus crystals (II), propionic acid copper (II), valeric acid copper (II), copper gluconate (II), cupric tartrate (II), cupric chloride (II), cupric bromide (II), copper hydroxide (II), venus crystals (II), cupric nitrate (II), copper sulfate (II), copper carbonate (II), cupric oxide (II), alkali formula cuprous nitrate, cupric wolframate (II), ventilation breather (II), cupric lactate (II), cupric fluoride (II), the mantoquitas such as cupric iodide (I) etc.;
Tri acetylacetonato closes the yttrium salt such as yttrium (III), Yttrium trichloride (III), formic acid yttrium (III), Yttrium Citrate (III), yttium acetate (III), yttrium oxide (III), yttrium oxalate (III), Yttrium trinitrate (III), yttrium carbonate (III), yttrium fluoride (III), yttrium iodide (III), yttrium sulfate (III), yttrium phosphate (III) etc.;
Tri acetylacetonato closes the lanthanum salt such as lanthanum (III), Lanthanum trichloride (III), formic acid lanthanum (III), lanthanum acetate (III), lanthanum trioxide (III), lanthanum oxalate (III), lanthanum nitrate (III), Phosbloc (III), lanthanum fluoride (III), two lanthanium titanates (III), lanthanum sulfat (III), lanthanum orthophosphate (III), lanthanum iodide (III) etc.;
Tri acetylacetonato closes the neodymium salt such as neodymium (III), Neodymium trichloride (III), formic acid neodymium (III), neodymium acetate (III), Neodymium trioxide (III), neodymium bromide (III), neodymium oxalate (III), neodymium nitrate (III), neodymium carbonate (III), two metatitanic acid neodymiums (III), neodymium fluoride (III), neodymium iodide (III), Neodymium sulfate (III), neodymium phosphate (III) etc.Above-claimed cpd also can be for anhydride, also can be hydrate.In addition, can use separately, also can make up more than 2 kinds and use.In addition, can be dissolved in the water-based metal-surface-treating agent solvent, also can be dispersed in the water-based metal-surface-treating agent solvent.
With respect to all solids composition contained in the water-based metal-surface-treating agent, the total content (B=B1+B2) that is selected from the one kind or two or more cross-linked compound (B) in bridging property organic compound (B1) and the bridging property mineral compound (B2) is preferably 10 quality %～90 quality %, more preferably 20 quality %～90 quality % especially are preferably 30 quality %～85 quality %.Cross-linked compound (B) if content in the scope of 10 quality %～90 quality %, then can further improve through this water system metal conditioner and process and adaptation and the drug-resistant driving fit retentivity of the surface treatment capsule that obtains.
(solvent)
Operability when making water-based metal-surface-treating agent of the present invention be coated in metal material surface is good, can contain all kinds of SOLVENTS as required.
As solvent, for example can enumerate: water; The alkane solvents such as hexane, pentane; The aromatic series such as benzene, toluene kind solvent; The alcoholic solvents such as ethanol, n-butyl alcohol, ethyl cellosolve; Tetrahydrofuran (THF), two
The ether solvents such as alkane; The esters solvents such as ethyl acetate, butyl glycol ether acetic ester; The amide solvent such as dimethyl formamide, N-Methyl pyrrolidone; The sulfone kind solvents such as methyl-sulphoxide; The phosphoamide kind solvents such as hexamethyl phosphoric triamide etc. can use a kind in these solvents, also can use mixing more than 2 kinds in addition.In these solvents, reach favourable economically reason, preferably water from environment.
(other additive)
Do not damage purport of the present invention and by the scope of film properties in, water-based metal-surface-treating agent of the present invention can contain tensio-active agent, defoamer, flow agent, antibacterial mildew inhibitor, tinting material etc.
(preparation method of water-based metal-surface-treating agent)
Preparation method for water-based metal-surface-treating agent of the present invention is not particularly limited.For example, can be prepared as follows: with polyvinyl alcohol compounds (A) and cross-linked compound (B), the optional additive that contains and the optional mixing such as solvent that contain, and use the stirrer such as mixing tank to mix fully.
[metallic substance]
As shown in Figure 1, the metallic substance 10 of the present invention surface treatment capsule 2 that has body material metal 1 and form at its surface coating water-based metal-surface-treating agent of the present invention." coating " refers to according to the surface coated water-based metal-surface-treating agent of following working procedure of coating at body material metal 1." has " other formation that represents to have except body material metal 1 and surface treatment capsule 2.For example, can have the resin molding 3 that forms at surface treatment capsule 2 by lamination process.Owing to surface treatment capsule 2 is that water-based metal-surface-treating agent with the invention described above is coated on the body material metal 1 and forms, so adaptation and drug-resistant driving fit retentivity are excellent.
Because metallic substance 10 has above-mentioned such surface treatment capsule 2, therefore resin moldings 3 or resin coating film 3 are rear have been implemented the harsh shapings such as deep-draw processing, attenuate processing or stretch-draw processing and has added man-hour even form at surface treatment capsule 2, and further be exposed to condition lower time such as acid, can prevent that also resin molding 3 or resin coating film 3 from peeling off from metallic substance 10.
Need to prove, in Fig. 1, enumerated the example that has formed surface treatment capsule 2 and resin molding 3 or resin coating film 3 at a side surface of body material metal 1, but can also be in the both sides of body material metal 1, namely on the opposite side surface, also form surface treatment capsule 2, and resin molding 3 or resin coating film 3 further are set.
Kind for body material metal 1 is not particularly limited, and can use various materials.For example can enumerate, can be applicable to food with the metallic substance of the wrapping material of the material of main part of tank or cover material, containers for food use, drying battery container, secondary cell etc., but be not limited to above-mentioned materials, can also use the metallic substance that can be applied to extensive use.Particularly, can enumerate can be as the metallic substance of the exterior material of following lithium-ion secondary cell, and the exterior material of described lithium-ion secondary cell is the portable exterior material with lithium-ion secondary cell for mobile phone, electronic notebook, notebook computer or pick up camera etc., the exterior material of the lithium-ion secondary cell that uses as the drive energy of electromobile or hybrid vehicle.In these metallic substance, can preferably use can form on its surface surface treatment capsule, and can be further on surface treatment capsule laminating resin film etc., then can implement the metallic substance of the harsh shapings processing such as deep-draw processing, attenuate processing or stretch-draw processing.
As such metallic substance, can enumerate such as copper products such as fine copper, copper alloys; The aluminum such as fine aluminium, aluminium alloy; The iron material such as ordinary steel, steel alloy; The nickel material such as pure nickel, nickelalloy etc.
As copper alloy, preferably use the above copper alloy of cupric 50 quality %, for example, can use brass etc.As the alloying constituent beyond the copper removal in the copper alloy, can enumerate such as Zn, P, Al, Fe, Ni etc.As aluminium alloy, the preferred use contains the above aluminium alloy of aluminium 50 quality %, for example, can use Al-Mg to be associated gold etc.As the alloying constituent except aluminium in the aluminium alloy, can enumerate such as Si, Fe, Cu, Mn, Cr, Zn, Ti etc.As steel alloy, preferably use the above steel alloy of iron content 50 quality %, for example, can use stainless steel etc.As the alloying constituent beyond the deironing in the steel alloy, can enumerate such as C, Si, Mn, P, S, Ni, Cr, Mo etc.As nickelalloy, preferably use the above nickelalloy of nickeliferous 50 quality %, for example, can use Ni-P alloy etc.As the alloying constituent except nickel in the nickelalloy, can enumerate such as Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, P etc.
As mentioned above, adopt water-based metal-surface-treating agent of the present invention, owing to containing above-mentioned polyvinyl alcohol compounds (A) and being selected from one kind or two or more cross-linked compound (B) in above-mentioned bridging property organic compound (B 1) and the above-mentioned bridging property mineral compound (B2), therefore can make and utilize this water-based metal-surface-treating agent to process and the surface treatment capsule that obtains has high adaptation, even and be exposed under the condition such as acid and also can keep high adaptation.Its result, even be formed with laminating resin film or formation resin coating film on the metallic substance of surface treatment capsule, then implement the harsh shapings such as deep-draw processing, attenuate processing or stretch-draw processing and added man-hour, and further be exposed to the condition such as acid, organic solvent lower time, can prevent that also this laminated film or resin coating film from peeling off from metallic substance.
[surface treatment method]
Used the metal surface treating method of water-based metal-surface-treating agent to form by following operation: with water-based metal-surface-treating agent be coated on the body material metallic surface working procedure of coating and behind working procedure of coating, do not wash and drying, thus the drying process of formation surface treatment capsule.
(working procedure of coating)
Working procedure of coating is the operation that water-based metal-surface-treating agent is coated in the body material metallic surface.Be not particularly limited for the method that applies, can example as: spraying, dip-coating, roller coat, curtain are coated with, spin coating or method that these Combination of Methods are obtained.Working conditions for water-based metal-surface-treating agent is not particularly limited.For example, the water-based metal-surface-treating agent during coating and the temperature of metallic substance are preferably 10 ℃ ~ 90 ℃, more preferably 20 ℃ ~ 60 ℃.If temperature is below 60 ℃, then can suppress the use of excess energy.In addition, the time that applies and the amount of coating can suitably be set according to the desired thickness of the surface treatment capsule that obtains.
(drying process)
Drying process is behind working procedure of coating, and is dry and do not wash, thereby forms the operation of surface treatment capsule.Drying temperature can be set as the temperature that adapts to employed solvent phase.For example, in the situation that make water as solvent, be preferably 50 ℃ ~ 260 ℃ scope.Be not particularly limited for drying installation, can use intermittent type, continous way or heated air circulation type drying oven, Conveyorized hot-air drying stove or use electromagnetic induction heating furnace of IH well heater etc., its air quantity and wind speed etc. can Set arbitrarilies.
For the surface treatment capsule that obtains like this, add man-hour even further form harsh shapings such as having implemented deep-draw processing, attenuate processing or stretch-draw processing behind resin molding (laminated film) or the resin coating film thereon, and further be exposed to acid etc. in the condition time, also can prevent peeling off of the resin coating that consisted of by laminated film or resin coating film.
Need to prove, the thickness of the surface treatment capsule that obtains is preferably 0.01 μ m ~ 1 μ m, more preferably 0.02 μ m ~ 0.05 μ m.If thickness is this scope, then can further improve adaptation and the drug-resistant driving fit retentivity of surface treatment capsule.
[embodiment]
Below, the present invention will be described in more detail by embodiment and comparative example.The present invention is not subjected to the restriction of following examples.Need to prove, hereinafter, " part " is " mass parts ", and " quality % " and " % by weight " synonym, also are expressed as " % " sometimes if be not particularly limited hereinafter." ppm " and " mg/L " synonym.
[polyvinyl alcohol compounds (A)]
The polyvinyl alcohol compounds (A) that uses is as follows.
Aa: the polyvinyl alcohol of saponification deg 96%, viscosity 25mPaS
Ab: the acetoacetylate polyvinyl alcohol of saponification deg 99%, viscosity 12mPaS, acetoacetylate degree 9.8%
[cross-linked compound (B)]
(bridging property organic compound (B1))
As the organic compound with glycidyl ether (B1a), use glycerine polyglycidyl ether (3 functional groups, epoxy equivalent (weight) 144, viscosity 170mPaS).In addition, as the organic compound with isocyanate group (B1b), used hexamethylene diisocyanate-methyl aceto acetate block polymer.In addition, as the organic compound with methylol (symbol B1c), used melamine methylol.As the organic compound with aldehyde radical (B1d), used oxalic dialdehyde.
(bridging property mineral compound (B2))
The bridging property mineral compound (B2) that uses is as follows.
B2a: hydrofluotitanic acid (concentration 40.0 quality %)
B2b: fluorine zirconic acid (concentration 40.0 quality %)
B2c: silicon dioxide gel (surface charge positively charged ion, particle diameter 10 ~ 20nm, 19.0 quality %, pH=4.7)
B2d: lactic acid titanium (concentration 44.0 quality %)
B2e: noncrystal zirconia sol (nonvolatile component concentration 10.0 quality %, particle diameter 10 ~ 30nm, pH=2.8)
B2f: silicofluoric acid (concentration 40.0 quality %)
B2g: chromium fluoride (III) (Cr concentration 1.0 quality %)
B2h: ferric fluoride (III) (Fe concentration 2.5 quality %)
B2i: selenium oxide (IV)
B2j: cerium oxide sol (nonvolatile component concentration 15%, pH=3.5)
B2k: chromium acetate (III)
[water-based metal-surface-treating agent]
With given content combination polyvinyl alcohol compd A a and/or Ab and be selected from bridging property organic compound B1a ~ B1d and bridging property mineral compound B2a ~ B2g in one kind or two or more, as solvent, prepared the water-based metal-surface-treating agent of the embodiment 1 ~ 41 shown in table 1 ~ table 3 and comparative example 1 ~ 18 with water.Need to prove the nonvolatile component concentration (quality %) of each compound that " concentration " expression water-based metal-surface-treating agent in table 1 ~ table 3 is contained.In addition, " A concentration " expression is with respect to the total solids composition in the water-based metal-surface-treating agent, the total content (quality %) of polyvinyl alcohol compounds (A), " B1+B2 concentration " expression is with respect to the total solids composition in the water-based metal-surface-treating agent, the content of cross-linked compound (B) is the total content (quality %) of bridging property organic compound B1 and bridging property mineral compound B2.
[metallic substance]
As follows as the metallic substance that body material uses.
Al:A1100P, thickness 0.3mm
Cu:C1020P, thickness 0.3mm
Ni: pure nickel plate (more than the purity 99 quality %), thickness 0.3mm
SUS:SUS304 plate, thickness 0.3mm
Nickel-clad copper: the copper coin of electronickelling (thickness 0.3mm, nickel plating thickness 2 μ m)
From these metallic substance, the metallic substance shown in " body material " hurdle of option table 1 ~ table 3 has been prepared the body material of embodiment 1 ~ 41 and comparative example 1 ~ 22.
[making of test materials]
(surface treatment)
Body material metal for the embodiment 1 ~ 41 shown in table 1 ~ table 3 and comparative example 1 ~ 18, utilize 3% aqueous solution of Fine cleaner359E (alkali cleaner that Japanese PARKERIZING Co., Ltd. makes) to carry out degreasing in 1 minute 65 ℃ of sprayings, then wash the clean surface.Then, in order to make the moisture evaporation of metal material surface, in 80 ℃ of heat dryings 1 minute.Use the #3SUS wheat to strangle rod and be coated with the respectively water-based metal-surface-treating agent (working procedure of coating) of the embodiment shown in coating table 1 ~ table 31 ~ 41 and comparative example 1 ~ 18 through the surface of the metal matrix material of cleaning by degreasing by rod, in the heated air circulation type drying oven, in 200 ℃ of dryings 1 minute (drying process), obtained having the metallic substance of surface treatment capsule.Need to prove, prepare respectively two and utilize water-based metal-surface-treating agent of the same race to carry out the surface-treated metallic substance, as follows, utilize respectively diverse ways to implement lamination process at surface treatment capsule.
In addition, prepared the metallic substance shown in the comparative example 19 ~ 22, do not applied water-based metal-surface-treating agent, similarly carried out degreasing, washing with above-mentioned, heat drying has then obtained not having the metallic substance of surface treatment capsule.Need to prove, prepared respectively two metallic substance of the same race, as follows, utilize respectively the diverse ways effects on surface to implement lamination process.
(lamination process)
For in two that prepare the respectively metallic substance with surface treatment capsule one utilizes heated lamination to implement lamination process at its surface treatment capsule.Surface treatment capsule at another utilizes dry lamination to implement lamination process.For the metallic substance that does not have surface treatment capsule, implement heated lamination on the side surface one of therein, implemented dry lamination at another a side surface.
Utilize following the carrying out of lamination process of heated lamination.Use the #8SUS wheat to strangle rod, be coated with the dispersion liquid (Mitsui Chemicals, Inc's manufacturing, " R120K ", nonvolatile component concentration 20 quality %) of spreading acid modified polypropene by rod, then in the heated air circulation type drying oven in 200 ℃ of dryings 1 minute, thereby form bond layer.Then, the polypropylene screen of this bond layer and thickness 30 μ m (Tohcello Co., Ltd. makes, " CPPS ") is carried out 10 minutes hot pressings under 190 ℃, 2MPa condition, carry out utilizing the lamination process of heated lamination, thereby obtained the metallic substance that lamination has polypropylene screen.
Utilize following the carrying out of lamination process of dry lamination.Utilize the #8SUS wheat to strangle rod, (Toyomorton Co., Ltd. makes to have applied polyurethanes dry lamination caking agent by rod, " AD-503/CAT10 ", nonvolatile component concentration 25 quality %), then in the heated air circulation type drying oven in 80 ℃ of dryings 1 minute, then, with this bond layer and (the two village chemical industry Co., Ltd. manufacturing of 30 μ m un-stretched polypropylene films, " FCZX ") the Corona discharge Treatment face at 100 ℃, under the 1MPa after the pressing, placed 4 days in 40 ℃, carry out utilizing the lamination process of dry lamination, thereby obtained the metallic substance that lamination has polypropylene screen.
(processing is shaped)
The polypropylene screen laminated metal material that will obtain by heated lamination and the polypropylene screen laminated metal material that obtains by dry lamination are respectively in the processing of deep-draw attenuate processing (Twisted り ご I) carried out deep-draw processing in the test.The clad metal plate that is stamped into diameter 160mm is carried out pull and stretch processing (for the first time), made the cup of diameter 100mm.Then, this cup is carried out pull and stretch processing (for the second time) again to diameter 75mm, the step of going forward side by side is carried out pull and stretch processing (for the third time) to diameter 65mm, has made the tank as test materials.Need to prove, attenuate (thin-walled property part) rate in for the first time pull and stretch processing, for the second time pull and stretch processing, for the third time pull and stretch processing is respectively 5%, 15%, 15%.
[performance evaluation]
(adaptation)
For the tank after the processing that is shaped, estimated and had or not the peeling off of polypropylene screen (below, be called " initial stage adaptation ").Can be made into tank, be 3 minutes without the sample scoring of the peeling off of film, initial stage adaptation excellence, the sample scoring that the part of film is peeled off is 2 minutes, and it is 1 minute that the sample that whole of film is peeled off is marked.The result of evaluation test is shown in table 4 and table 5.
(drug-resistant driving fit retentivity)
At this, estimate for the driving fit retentivity for electrolytic solution in drug-resistant driving fit retentivity (below, be called " electrolyte resistance driving fit retentivity ").Specifically, as follows, the tank for after further being immersed in the electrolytic solution after the processing that is shaped has carried out having or not the evaluation of peeling off of polypropylene screen.
Tank after deep-draw processing be impregnated in the electrolyte solution for lithium ion secondary battery (LiPF of ionogen: 1mol/L that is filled in the encloses container and has added ion exchanged water 1000ppm
6, solvent: EC:DMC:DEC=1:1:1 (volume %)) in, then in 60 ℃ of thermostatic baths, placed 7 days.Need to prove, " EC " is ethylene carbonate, and " DMC " is methylcarbonate, and " DEC " is diethyl carbonate.
Then, take out test materials, be immersed in the ion exchanged water 1 minute, clean by shaking, then in the heated air circulation type drying oven in 100 ℃ of dryings 10 minutes.Then utilize the front end of pincet that face is scratched, the sample scoring that will not cause the peeling off of film, electrolyte resistance driving fit retentivity excellence is 3 minutes, the sample scoring that the part of film is peeled off is 2 minutes, and the sample scoring that whole of film is peeled off is 1 minute.The result of evaluation test is shown in table 4 and table 5.
Shown in table 4 and table 5, confirmed to have the water-based metal-surface-treating agent that coating embodiment 1 ~ 41 puts down in writing and the metallic substance of the surface treatment capsule that forms, initial stage adaptation and electrolyte resistance driving fit retentivity are all very excellent.
[table 4]
[table 5]
Claims (4)
1. water-based metal-surface-treating agent, it contains:
Polyvinyl alcohol compounds (A), and
One kind or two or more cross-linked compound (B), this cross-linked compound (B) be selected from have can with the bridging property organic compound (B1) of the functional group of described polyvinyl alcohol compounds (A) reaction and contain can with the bridging property mineral compound (B2) of the element of described polyvinyl alcohol compounds (A) reaction.
2. water-based metal-surface-treating agent according to claim 1, wherein, described bridging property organic compound (B1) has the functional group more than a kind that is selected from glycidyl ether, isocyanate group, methylol and the aldehyde radical.
3. claim 1 or 2 described water-based metal-surface-treating agents, wherein, described bridging property mineral compound (B2) contains the one kind or two or more element that is selected among Mg, Al, Ca, Mn, Co, Ni, Cr (III), Zn, Fe, Zr, Ti, Si, Sr, W, Ce, Mo, V, Sn, Bi, Ta, Te, In, Ba, Hf, Se, Sc, Nb, Cu, Y, Nd and the La.
4. metallic substance, it has each described water-based metal-surface-treating agent in the surface of metallic substance coating claim 1 ~ 3 and the surface treatment capsule that forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011157013A JP5827053B2 (en) | 2011-07-15 | 2011-07-15 | Water-based metal surface treatment agent and metal material treated with the treatment agent |
| JP2011-157013 | 2011-07-15 |
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| JP (1) | JP5827053B2 (en) |
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Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104404493A (en) * | 2014-10-31 | 2015-03-11 | 田琳琳 | Modified alloy surface conditioning agent |
| CN104789952A (en) * | 2015-04-08 | 2015-07-22 | 安徽豪鼎金属制品有限公司 | Thickening metal surface treatment agent comprising sericin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330729A (en) * | 1998-10-15 | 2002-01-09 | 日本帕卡濑精株式会社 | Hydrophilizing agent for metalic material, hydrophilizing fluid, method of hydrophilizing, metallic material and heat exchanger |
| CN1353776A (en) * | 1999-06-04 | 2002-06-12 | 卡森尼可关精株式会社 | Heat exchanger made of aluminium alloy |
| CN1377928A (en) * | 2001-03-27 | 2002-11-06 | 日本油漆株式会社 | Hydrophilic modifier, hydrophilic modifying method and hydrophilic modified aluminium or aluminium alloy materials therefrom |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW506996B (en) * | 2000-05-11 | 2002-10-21 | Nihon Parkerizing | Treating agents for metal surface, process of treating metal material and surface treated metal materials |
| JP2002285140A (en) * | 2001-03-27 | 2002-10-03 | Nippon Paint Co Ltd | Hydrophilizing agent, method for hydrophilizing and aluminum or aluminum alloy material subjected to hydrophilizing |
| CN1386901A (en) * | 2001-05-01 | 2002-12-25 | 日本巴卡莱近估股份有限公司 | Metal surface treating agent and method, and surface treatment of metal material |
| TW201129717A (en) * | 2009-12-04 | 2011-09-01 | Kansai Paint Co Ltd | Composition for treating metal surface and metal substrate with surface treatment film |
-
2011
- 2011-07-15 JP JP2011157013A patent/JP5827053B2/en active Active
-
2012
- 2012-07-13 TW TW101125350A patent/TWI554647B/en active
- 2012-07-13 KR KR1020120076485A patent/KR20130009680A/en active Application Filing
- 2012-07-16 CN CN201210245546.4A patent/CN102877052B/en active Active
-
2016
- 2016-09-22 KR KR1020160121640A patent/KR101708155B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330729A (en) * | 1998-10-15 | 2002-01-09 | 日本帕卡濑精株式会社 | Hydrophilizing agent for metalic material, hydrophilizing fluid, method of hydrophilizing, metallic material and heat exchanger |
| CN1353776A (en) * | 1999-06-04 | 2002-06-12 | 卡森尼可关精株式会社 | Heat exchanger made of aluminium alloy |
| CN1377928A (en) * | 2001-03-27 | 2002-11-06 | 日本油漆株式会社 | Hydrophilic modifier, hydrophilic modifying method and hydrophilic modified aluminium or aluminium alloy materials therefrom |
| CN1389524A (en) * | 2001-03-27 | 2003-01-08 | 日本油漆株式会社 | Hydrophilic modifier, hydropilic modifying method and modifying gydrophilic aluminium material or aluminium alloy material by using the same |
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| CN104404493A (en) * | 2014-10-31 | 2015-03-11 | 田琳琳 | Modified alloy surface conditioning agent |
| CN104862707A (en) * | 2015-04-08 | 2015-08-26 | 安徽豪鼎金属制品有限公司 | Stable metal surface treatment agent |
| CN104789952A (en) * | 2015-04-08 | 2015-07-22 | 安徽豪鼎金属制品有限公司 | Thickening metal surface treatment agent comprising sericin |
| CN104789953A (en) * | 2015-04-08 | 2015-07-22 | 安徽豪鼎金属制品有限公司 | Anti-corrosion metal surface treatment agent comprising sericin |
| CN104862681A (en) * | 2015-04-08 | 2015-08-26 | 安徽豪鼎金属制品有限公司 | Sericin emulsified metal surface treating agent |
| CN104862680A (en) * | 2015-04-08 | 2015-08-26 | 安徽豪鼎金属制品有限公司 | Anti-oxidation metal surface treatment agent |
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| US11591707B2 (en) | 2015-10-12 | 2023-02-28 | Ppg Industries Ohio, Inc. | Methods for electrolytically depositing pretreatment compositions |
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| CN105860696A (en) * | 2016-05-31 | 2016-08-17 | 合肥正浩机械科技有限公司 | Metal conditioner for cold-roll steel sheet surfaces |
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| CN105860693A (en) * | 2016-05-31 | 2016-08-17 | 合肥正浩机械科技有限公司 | Silicon-dioxide-added treating agent for metals |
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| CN106065236A (en) * | 2016-05-31 | 2016-11-02 | 合肥正浩机械科技有限公司 | A kind of radiator Al-alloy heat exchanger metal conditioner |
| CN105860695A (en) * | 2016-05-31 | 2016-08-17 | 合肥正浩机械科技有限公司 | Super-water-resistance peelable rust inhibitor for metal surfaces |
| CN105860694A (en) * | 2016-05-31 | 2016-08-17 | 合肥正浩机械科技有限公司 | High heat-resistant strippable metal preservative |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2013023703A (en) | 2013-02-04 |
| KR20160114560A (en) | 2016-10-05 |
| TW201317393A (en) | 2013-05-01 |
| KR20130009680A (en) | 2013-01-23 |
| KR101708155B1 (en) | 2017-02-17 |
| JP5827053B2 (en) | 2015-12-02 |
| TWI554647B (en) | 2016-10-21 |
| CN102877052B (en) | 2016-08-03 |
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