CN102877055A - Metal surface treatment agent and metal material obtained through processing with same - Google Patents
Metal surface treatment agent and metal material obtained through processing with same Download PDFInfo
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- CN102877055A CN102877055A CN2012102459003A CN201210245900A CN102877055A CN 102877055 A CN102877055 A CN 102877055A CN 2012102459003 A CN2012102459003 A CN 2012102459003A CN 201210245900 A CN201210245900 A CN 201210245900A CN 102877055 A CN102877055 A CN 102877055A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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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
Abstract
The invention relates to a metal surface treatment agent for forming a surface treatment coating. Even if a resin film is laminated on the surface of metal material or a resin coating is formed on the surface of the metal material and rigor forming processing such as deep drawing processing is carried out, the surface treatment film imparts the laminated film or the resin coating high adhesion for preventing stripping. The metal surface treatment agent contains one or more than one kind of group-IV transition metal compounds (a) selected from a Zr compound emitting ZrO2+ in water solution and a Ti compound emitting TiO2+ in the water solution, and an organic compound (b) which is characterized in that the same molecule contains more than two functional groups which are one or more than one kind selected from hydroxyl group, carboxyl group, phosphonate group, phosphate group, and sulfonate group. Preferably, the molecular weight of the organic compound (b) is 100~1000 and the ratio of the functional groups in the organic compound is one in 30~300 molecular weight.
Description
Technical field
The present invention relates to metal conditioner and utilize this metal conditioner to process and the metallic substance that obtains, described metal conditioner 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.Particularly, the present invention relates to be used to form the metal conditioner etc. of the surface treatment capsule of drug-resistant driving fit retentivity excellence, even described surface treatment capsule is being pressed in resin film layer on the metallic substance or is forming resin coating film, then implements in the situation that the harsh shaping such as deep-draw processing, attenuate processing (processing of ご I) or stretch-draw processing processes at metallic substance, also can give the high adaptation that laminated film etc. is peeled off, and also can keep high adaptation in being exposed to acid, organic solvent etc. the time.
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 fluid that obtains in the solvent is coated on 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; from the environment protection aspect; 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 preferred aluminium foil that functional quality is light and barrier is high or stainless steel foil have adopted 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 coating 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 metallic substance corrosion.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 such as Plessy's green hydrochlorate etc.But such chemical conversion is processed need to implement matting after processing, and to remove remaining treatment solution, carrying out wastewater treatment for the rinse water of being discharged by this matting needs Expenses Cost.Especially the chemical conversion processing such as Plessy's green hydrochlorate etc. therefore in recent years for the worry to environment, has the withdraw from service tendency owing to having used chromyl treatment solution.
For example, proposed a kind of substrate treating agent 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 thermoset 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 compound of amination phenol polymer, Ti and Zr etc., 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
Patent documentation 1: TOHKEMY 2002-265821 communique
Patent documentation 2: TOHKEMY 2003-313680 communique
Patent documentation 3: TOHKEMY 2003-138382 communique
Patent documentation 4: TOHKEMY 2004-262143 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide and a kind ofly be used to form the metal conditioner of surface treatment capsule and utilize this metal conditioner to process and the metallic substance that obtains, even described surface treatment capsule forms resin coating film, then implements also can give the high adaptation that this laminated film or resin coating film are peeled off in the situation of the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing on the surface that resin film layer is pressed in metallic substance or on the surface of metallic substance.
The method of dealing with problems
The metal conditioner of the present invention that is used for addressing the above problem is characterised in that, it contains one kind or two or more the 4th group transition metal compound (a) and organic compound (b), and described the 4th group transition metal compound (a) is selected from and emits zirconium acyl ion (ZrO in the aqueous solution
2+) the Zr compound and in the aqueous solution, emit titanium acyl ion (TiO
2+) the Ti compound, described organic compound (b) has the one kind or two or more functional group that is selected from more than 2 in hydroxyl, carboxyl, phosphonate group (phosphonate group), phosphate (phosphate group) and the sulfonic group (sulfonate group) in a part.
According to this invention, when metal conditioner was coated the metallic surface, the 4th group transition metal compound (a) contained in the metal conditioner was because of zirconium acyl ion (ZrO
2+), titanium acyl ion (TiO
2+) etc. metal oxygen acyl ion (オ キ シ metal イ オ Application) and metallic surface react and strong adsorption in the metallic surface.So, subsequently by carrying out heat drying etc. when removing moisture, can be because of zirconium acyl ion (ZrO
2+) between condensation reaction form key, because of titanium acyl ion (TiO
2+) between condensation reaction form key or because of zirconium acyl ion (ZrO
2+) and titanium acyl ion (TiO
2+) between condensation reaction form key.Its result, the metal conditioner of the application of the invention can form the tough surface treatment capsule that brings high adaptation to the metallic surface.
In addition, with regard to organic compound contained in the metal conditioner (b), because its meeting and the zirconium acyl ion (ZrO that is emitted by the 4th group transition metal compound (a)
2+) or titanium acyl ion (TiO
2+) etc. metal oxygen acyl ion form water-soluble salt or complex salt, therefore, have the effect of the stability that improves these metal oxygen acyl ions.In addition, by carrying out heat drying etc. when removing moisture, organic compound (b) and Zr or the combination of strong ground of Ti have the effect of the film-forming properties that improves tunicle after metal conditioner is coated the metallic surface.
With regard to metal conditioner of the present invention, the molecular weight of preferred above-mentioned organic compound (b) is more than 100 and below 1000, and this organic compound (b) is the compound that has above-mentioned functional group with 1 ratio in per 30 ~ 300 the molecular weight, thus, can realize excellent adaptation.
With regard to metal conditioner of the present invention, the ratio [Mb/Ma] of the quality (Ma) of the metal in the quality (Mb) of preferred above-mentioned organic compound (b) and above-mentioned the 4th group transition metal compound (a) is 0.05 ~ 0.6, thus, can realize excellent adaptation.
In metal conditioner of the present invention, preferably contain the one kind or two or more nonionic that is selected from urethane resin, Resins, epoxy, acrylic resin, resol, polyester resin, polyvinyl resin and the polyolefin resin or the water-base resin (c) of anionic property, thus, can give the gained surface treatment capsule with flexibility and more excellent film-forming properties.
In metal conditioner of the present invention, preferably contain and have the metallic compound (d) that is selected from the one kind or two or more metallic element among Zr, Ti, V, Mo, W, Ce and the Nb, thus, it can be used as inhibiter and has given play to more excellent erosion resistance and improved effect.
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 of the surface treatment agent of the invention described above being coated the metallic surface and forming.
According to this invention, owing to having the metal conditioner of the invention described above is coated the surface treatment capsule that metal material surface forms, therefore, even at further laminating resin film or form resin coating film, then implement in the situation of the harsh shapings processing such as deep-draw processing, attenuate processing or stretch-draw processing on this surface treatment capsule, also can the preventing layer press mold or resin coating film peel off from metallic substance.And, even in the situation that further be exposed in the acid etc., can prevent that also this laminated film or resin coating film from peeling off from metallic substance.
The effect of invention
According to metal conditioner of the present invention and utilize this treatment agent to process the metallic substance that obtains, by above-mentioned effect, adaptation between metal material surface and the gained surface treatment capsule and the adaptation between laminated film and the gained surface treatment capsule can be improved simultaneously, and also high adaptation can be kept in being exposed to acid etc. the time.Its result, even be formed with laminating resin film or formation resin coating film on the metallic substance of surface treatment capsule, then implement 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 in acid, the organic solvent etc., can prevent that also this laminated film or resin coating film from peeling off from metallic substance.Particularly, even in the corrosive environment of distillation processing, electrolytic solution impregnating, also can keep excellent adaptation.
Description of drawings
Fig. 1 is the schematic cross sectional view that the embodiment of surface treatment capsule of the present invention is shown.
Nomenclature
1 metallic substance
2 surface treatment capsules
3 laminated films or resin coating film
10 have the metallic substance of surface treatment capsule
Embodiment
Below, for metal conditioner of the present invention and utilize this treatment agent to process and the metallic substance that obtains describes.Need to prove, technical scope of the present invention is not subjected to the restriction of the embodiment of following explanation and accompanying drawing.
[metal conditioner]
As shown in Figure 1, metal conditioner of the present invention is for as the substrate of the surperficial form layers press mold of the metallic substance 1 (hereinafter referred to as " body material metal 1 ") of body material or resin coating film 3 treatment agent with surface treatment capsule 2.This metal conditioner is characterised in that, it contains the 4th group transition metal compound (a) and organic compound (b), and described the 4th group transition metal compound (a) is to be selected to emit zirconium acyl ion (ZrO in the aqueous solution
2+) the Zr compound and in the aqueous solution, emit titanium acyl ion (TiO
2+) the Ti compound in one kind or two or more, described organic compound (b) has the one kind or two or more functional group that is selected from more than 2 in hydroxyl, carboxyl, phosphonate group, phosphate and the sulfonic group in a part.
Described " containing " refers to, in metal conditioner, also can contain other compound except above-mentioned the 4th group transition metal compound (a) and above-mentioned organic compound (b).As such compound, for example can enumerate tensio-active agent, defoamer, flow agent, antibacterial mildew inhibitor, tinting material etc.Can not destroy purport of the present invention and contained these compounds by the scope of film properties.Need to prove, as the body material metal 1 of surface treatment object as described later.
Below, be elaborated for each integrant.
(the 4th group transition metal compound)
The 4th group transition metal compound (a) is to be selected to emit zirconium acyl ion (ZrO in the aqueous solution
2+) the Zr compound and in the aqueous solution, emit titanium acyl ion (TiO
2+) the Ti compound in one kind or two or more compound.When metal conditioner was coated the surface (being also referred to as " metallic surface ") of body material metal 1, the 4th group transition metal compound (a) was because of zirconium acyl ion (ZrO
2+), titanium acyl ion (TiO
2+) etc. the reaction of metal oxygen acyl ion and metallic surface and strong adsorption in the metallic surface.When heat drying by subsequently etc. was removed moisture, the metal oxygen acyl ion of absorption can pass through zirconium acyl ion (ZrO
2+) between condensation reaction form key, by titanium acyl ion (TiO
2+) between condensation reaction form key or by zirconium acyl ion (ZrO
2+) and titanium acyl ion (TiO
2+) between condensation reaction form key.Its result becomes key by this, can form the tough surface treatment capsule that high adaptation is brought in the metallic surface.
Zirconium compounds is so long as can emit zirconium acyl ion (ZrO when being dissolved in the water
2+) compound get final product, there is no particular restriction.As such zirconium compounds, for example can enumerate: basic carbonate oxygen zirconium (Zr
2(CO
3) (OH)
2O
2), zirconyl hydroxychloride (ZrO (OH) Cl), ammonium zirconyl carbonate ((NH
4)
2ZrO (CO
3)
2), zirconyl carbonate potassium (K
2ZrO (CO
3)
2K
2), zirconyl carbonate sodium (Na
2ZrO (CO
3)
2K
2), Zircosol ZN (ZrO (NO
3)
2), zirconyl acetate (ZrO (CH
3COO)
2), zirconyl sulfate (ZrOSO
4), di(2-ethylhexyl)phosphate hydrogen-oxygen zirconium (ZrO (H
2PO
4)
2), zirconium stearate (ZrO (C
18H
35O
2)
2) etc.
Titanium compound is so long as can emit titanium acyl ion (TiO in the aqueous solution
2+) compound get final product, there is no particular restriction.As such titanium compound, for example can enumerate: dioxalic acid oxygen titanium two ammonium ((NH
4)
2[Ti (C
2O
4)
2O] nH
2O), titanyl sulfate (TiOSO
4), diisopropoxy bis-acetylacetonate titanium (Ti (O-i-C
3H
7)
2(C
5H
7O
2)
2), and the hydroxyl lactyl-lactic acid close titanium (Ti (OH)
2[OCH (CH
3) COOH]
2) etc.
In metal conditioner, can contain respectively independent zirconium compounds and titanium compound, also can comprise the two.Contain separately in the situation of one of zirconium compounds and titanium compound, the content of contained compound is preferably 0.001 quality % ~ 70 quality % in the metal conditioner, more preferably 0.01 quality % ~ 50 quality %.Be 0.001 quality % ~ 70 quality % by making content, can further improve adaptation and the drug-resistant driving fit retentivity of gained surface treatment capsule.
Although reason is still not clear, known, utilize the surface treatment capsule of the metal conditioner formation that the cooperation titanium compound obtains in the treatment agent take zirconium compounds as basic ingredient can bring higher adaptation.In being combined with the two metal conditioner of zirconium compounds and titanium compound, the mixing ratio of the two in the metal quality in the compound than [the titanium quality in the titanium compound: Mat]/[the zirconium quality in the zirconium compounds: Maz], be preferably 0.005 ~ 1, more preferably 0.01 ~ 0.43.Metal quality with such scope cooperates the metal conditioner that forms can form the surface treatment capsule of the higher adaptation of demonstration than [Mat/Maz].
(organic compound)
Organic compound (b) is to have the compound that is selected from the one kind or two or more functional group in hydroxyl, carboxyl, phosphonate group, phosphate and the sulfonic group more than 2 in a part.This organic compound (b) and the zirconium acyl ion (ZrO that is emitted by above-mentioned the 4th group transition metal compound (a)
2+) and/or titanium acyl ion (TiO
2+) etc. the ionization of metal oxygen acyl, form water miscible salt or complex salt.The water miscible salt that forms or complex salt have the effect of the stability that improves these metal oxygen acyl ions, the above-mentioned effect that therefore metal oxygen acyl ion is played is stablized to be continued, thereby can stably form the tough surface treatment capsule that can bring for the metallic surface high adaptation.In addition, after metal conditioner is coated the metallic surface by carrying out heat drying etc. when removing moisture, organic compound (b) and the Zr and/or the combination of strong ground of Ti that consist of metal oxygen acyl ion have the effect of the film-forming properties raising that makes formed surface treatment capsule.
The functional group that organic compound (b) has is any group in hydroxyl, carboxyl, phosphonate group, phosphate and the sulfonic group, has above-mentioned functional group more than 2 in same a part of this organic compound (b).When having more than 2 above-mentioned functional group, can be 3 and also can be 4, can also be more than 4.The upper limit for the number of above-mentioned functional group there is no particular determination, can be for example 10.In addition, 2 above functional groups can be the functional groups of the same race that is selected from above-mentioned hydroxyl, carboxyl, phosphonate group, phosphate and the sulfonic group, also can be different types of functional groups.
The molecular weight of organic compound (b) is preferably more than 100 and below 1000, more preferably more than 100 and below 900.The organic compound (b) of molecular weight in this scope has functional group with 1 ratio in per 30 ~ 300 the molecular weight.Need to prove, there is no particular determination for other chemical structure of organic compound (b).
Concrete example as such organic compound (b), for example can enumerate: ethylene glycol, propylene glycol, tetramethylene glycol, Diethylene Glycol, dibutylene glycol, glycerine, tetramethylolmethane, pyrocatechol, 1, the multivalence oxy-compound such as 2,3-benzenetriol, catechin, glucose, amylopectin; The polycarboxylic acids such as oxalic acid, propanedioic acid, succsinic acid, hexanodioic acid, toxilic acid; The hydroxycarboxylic acids such as oxyacetic acid, lactic acid, R-Glyceric acid, tartronic acid, tartrate, oxysuccinic acid, citric acid, pantoic acid, xitix, Whitfield's ointment, Protocatechuic Acid, vanillic acid, gallic acid, amygdalic acid; 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 acid), 2-phosphonic acids butane-1, the organic phospho acids such as 2,4-tricarboxylic acid; The organic phosphoric acids such as phytic acid, starch phosphates, glucose monophosphate.
Organic compound (b) has following effect: the zirconium acyl ion (ZrO that emits in the aqueous solution with zirconium compounds
2+) and/or the titanium acyl ion (TiO that in the aqueous solution, emits of titanium compound
2+) coordination, thereby the stability of raising in metal conditioner.In addition, when utilizing this metal conditioner to form surface treatment capsule, organic compound (b) thus also have with zirconium acyl ion and/or titanium acyl ion strongly in conjunction with the effect that film-forming properties is improved.Its result, the erosion resistance of surface treatment capsule and and be arranged at laminated film on this surface treatment capsule or the adaptation between the resin coating film is excellent.
The content of contained organic compound (b) is preferably 0.05 ~ 0.6 in the ratio [mass ratio=Mb/Ma] of the mass M a of the mass M b of organic compound (b) and the metallic element (Zr and/or Ti) in the 4th group transition metal compound (a) in the metal conditioner, and more preferably 0.1 ~ 0.4.By containing organic compound (b) and the 4th group transition metal compound (a) with this quality than scope, can make surface treatment capsule erosion resistance and and the laminated film or the adaptation between the resin coating film that are arranged on the surface treatment capsule become good.Mass ratio [Mb/Ma] was less than 0.05 o'clock, may cause the film-forming properties of surface treatment capsule to reduce, mass ratio [Mb/Ma] is greater than 0.6 o'clock, may cause surface treatment capsule and the laminated film or the adaptation between the resin coating film that are arranged on this surface treatment capsule reduce.
(water-base resin)
Water-base resin (c) is one kind or two or more nonionic or the anionic property organic compound that is selected from urethane resin, Resins, epoxy, acrylic resin, resol, polyester resin, polyvinyl resin and the polyolefin resin.This organic compound is the compound with anionic group or non-ionic group, but stable existence in metal conditioner of the present invention, get final product so long as can obtain the compound of desired effect, to kind and the indefinite of this organic compound.Need to prove, with regard to the water-solubleization form of organic compound, this organic compound can be water miscible, also can be water dispersible (emulsion, dispersion liquid).
As urethane resin, can be listed below the urethane that obtains etc.: be in the urethane resin at the polycondensate by the polyvalent alcohol such as polyester polyol, polyether glycol, polycarbonate polyol and aliphatic polyisocyante, alicyclic isocyanate and/or aromatic polyisocyanate compound formation, the urethane that uses the such polyvalent alcohol with polyoxyethylene chain of polyoxyethylene glycol, polypropylene glycol to obtain as the part of above-mentioned polyvalent alcohol.For such urethane, by improving the importing ratio of above-mentioned polyoxyethylene chain, can realize water-solubleization or water-dispersion with non-ionic form.
In addition, by following method, can obtain the water-dispersible polyurethane resin of anionic property: make the carbamate prepolymer that two ends have isocyanate group by polyisocyanates and polyvalent alcohol, make this prepolymer and the carboxylic acid with 2 above hydroxyls or the reaction of its reactive derivatives, must arrive the derivative that two ends have isocyanate group, then, adding trolamines etc. are to form ionomer (triethanolamine salt), and then this ionomer is added to the water to form emulsion or dispersion liquid, and then add as required diamines to carry out chain extension.
Making the above-mentioned carboxylic acid that uses when having the water-dispersible polyurethane resin of anionic property and reactive derivatives is used for importing acidic-group and making urethane resin be water dispersible at urethane resin.As employed carboxylic acid, can enumerate the dimethylolalkanoic acids such as dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid.In addition, as reactive derivatives, can enumerate the such hydrolyzable ester of acid anhydrides etc.
As Resins, epoxy, can enumerate: the epoxy compounds with 2 above glycidyls; Have dihydroxyphenyl propane or Bisphenol F as the epoxy compounds of the unit in the skeleton; Or make the diamines effects such as epoxy compounds with 2 above glycidyls and quadrol, cationization occur and the Resins, epoxy that obtains; Make and have dihydroxyphenyl propane or Bisphenol F as addition polyoxyethylene glycol on the side chain of the epoxy compounds of the unit in the skeleton or other epoxy compounds with 2 above glycidyls and the nonionic Resins, epoxy that obtains; Etc..
As Resins, epoxy, can use to have dihydroxyphenyl propane or Bisphenol F as the Resins, epoxy of the unit in the skeleton.Need to prove, also can be the silane modified or phosphoric acid modification of the part or all of glycidyl of this Resins, epoxy and the Resins, epoxy that obtains.
As having dihydroxyphenyl propane or the Bisphenol F Resins, epoxy as the unit in the skeleton, can enumerate: by epoxy chloropropane and dihydroxyphenyl propane or Bisphenol F through repeatedly dehydrochlorination reaction and addition reaction and the resin that obtains; By having between the epoxy compounds that more than 2, preferably has 2 glycidyls and the bis-phenol (A, F) through repeatedly addition reaction and the resin that obtains.
As epoxy compounds, for example can enumerate: bis-phenol (A, F) diglycidyl ether, o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, the P-hydroxybenzoic acid 2-glycidyl ester, tetrahydrochysene phthalic acid 2-glycidyl ester, hexahydrobenzene dioctyl phthalate 2-glycidyl ester, the succsinic acid 2-glycidyl ester, the hexanodioic acid 2-glycidyl ester, Diglycidyl Sebacate, the ethylene glycol bisthioglycolate glycidyl ether, the propylene glycol diglycidyl ether, 1, the 4-butanediol diglycidyl ether, 1,6-hexylene glycol diglycidyl ether, the many glycidyl ethers of Sorbitol Powder, polyalkylene glycol diglycidyl ether class, the trimellitic acid three-glycidyl ester, triglycidyl isocyanurate, Isosorbide-5-Nitrae-glycidoxy benzene, diglycidyl propylidene urea, glycerol triglycidyl group ether, the trimethylolethane trimethacrylate glycidyl ether, the trimethylolpropane tris glycidyl ether, tetramethylolmethane four glycidyl group ether, the triglycidyl group ether of the olefin oxide affixture of glycerol etc.Above-mentioned epoxy compounds can be used singly or in combination respectively.
Need to prove, with regard to the silane-modified degree of Resins, epoxy, so long as get final product more than can confirming the degree of the effect of being brought by these modifications, there is no particular restriction.Can use known silane coupling agent to carry out silane-modified.
As acrylic resin, can enumerate the homopolymer of Acrylic Acid Monomer or multipolymer and by these Acrylic Acid Monomers and the multipolymer that can form with the addition polymerization monomer of this Acrylic Acid Monomer copolymerization.As long as such acrylic resin can be in surface treatment agent stable existence, its polymerization methods be there is no particular determination.
As Acrylic Acid Monomer, can enumerate such as the just own ester of methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid, 2-EHA, vinylformic acid, methacrylic acid, vinylformic acid 2-hydroxy methacrylate, vinylformic acid hydroxy propyl ester, 2-hydroxyethyl methacrylate, methacrylic acid hydroxyl propyl ester, glycidyl acrylate, glycidyl methacrylate, vinylformic acid sulphur ethyl ester, polyethylene glycol methacrylate-styrene polymer etc.As can with the addition polymerization monomer of Acrylic Acid Monomer copolymerization, can enumerate toxilic acid, methylene-succinic acid, acrylamide, N hydroxymethyl acrylamide, diacetone-acryloamide(DAA), vinylbenzene, vinyl cyanide, vinyl sulfonic acid etc.
As Vinylite, can enumerate partly-hydrolysed thing or fully saponified thing, the Polyvinylpyrolidone (PVP) etc. of polyvinyl acetate, polyvinyl acetate.
About vinyl-acetic ester, it can be the resin that obtains through saponification with the polymkeric substance that can obtain with the monomer copolymerization of vinyl acetate copolymerization.In addition, can use import anionic groups such as carboxylic acid, sulfonic acid, phosphoric acid in the polymkeric substance after polymerization and obtain polymer-modified or import diacetone-acryloamide(DAA) base, acetoacetyl, sulfydryl, silanol group etc. have the functional group of crosslinking reaction and obtain polymer-modified.
Need to prove, as can with the monomer of vinyl acetate copolymerization, can enumerate such as unsaturated carboxylic acid and 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; N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid an alkali metal salt etc. contain the monomer of amide group; NVP, NVP derivative; Etc..
As resol, can enumerate low-molecular-weight water soluble resin or emulsion resin as the polycondensate that is formed by phenols (phenol, naphthols, bis-phenol etc.) and formaldehyde.Wherein, preferably has the resole that contains methylol from condensation.
As natural polymer, can enumerate Mierocrystalline cellulose, starch, dextrin, inulin, xanthan gum, tamarind seed gum, tannic acid, lignosulfonic acid etc.
As polyolefin resin, can enumerate: polypropylene, polyethylene, and the modified polyolefin that obtained by unsaturated carboxylic acid (for example vinylformic acid, methacrylic acid) modification of the polyolefine such as multipolymer that form of propylene or ethene and alpha-olefin or the multipolymer of ethene and vinylformic acid (methacrylic acid) formation.In addition, can also be the multipolymer that obtains with a small amount of other ethylene unsaturated monomer copolymerization.As the method for Water-borne modification, can enumerate the method for utilizing ammonia, amine that the carboxylic acid that imports on the polyolefin resin is neutralized.
For these nonionics or anionic property water-base resin (c), the adhesive effect that the film-forming properties that has as itself brings comprises: (1) can give flexibility to the surface treatment capsule that is formed by the 4th group transition metal compound (a) and organic compound (b); And, the reactive functional groups of (2) water-base resin (c) and the 4th group transition metal compound (a) or metallic compound (b) reaction, thus adhere to surface treatment capsule strongly.Therefore, by the above-mentioned effect that water-base resin (c) has, the metal conditioner that contains water-base resin (c) can form and can tolerate the more tough surface treatment capsule of forcing the worker.
As the water-base resin (c) of these nonionics or anionic property, can enumerate water soluble resin, passed through self-emulsifying or utilize water-based crosslinkable resin or the aqueous high molecular resin such as water-based emulsion, aqueous liquid dispersion of the forced emulsification that emulsifying agent carries out.Wherein, can preferably adopt the effect of heat, ultraviolet ray or electron beam etc. that number-average molecular weight applies when forming tunicle less than 1000 monomer or oligopolymer to issue to be conigenous crosslinked and then the crosslinkable resin of high molecular occurs; Or the crosslinkable resin of high molecular occurs in number-average molecular weight less than 1000 monomer or oligopolymer and the reaction of other linking agent.In addition, can also adopt number-average molecular weight be 1000 ~ 1000000 and can be under the effect of heat etc. the macromolecule resin of film forming.In addition, only otherwise destroy effect of the present invention, these macromolecule resins can be the resins with crosslinking reaction functional group.
The content of the water-base resin that contains in the metal conditioner (c) is preferably 0.05 ~ 1.5, more preferably 0.1 ~ 0.8 in the ratio [mass ratio=Mc/Ma] of the mass M a of the mass M c of water-base resin (c) and the metallic element (Zr and/or Ti) in the 4th group transition metal compound (a).By containing water-base resin (c) and the 4th group transition metal compound (a) with this quality than scope, can be when the gained surface treatment capsule being given flexibility and more excellent film-forming properties, formation can tolerate the more tough surface treatment capsule of forcing the worker.
(metallic compound)
Metallic compound (d) is to have the water-soluble cpds that is selected from the one kind or two or more metallic element among Zr, Ti, V, Mo, W, Ce and the Nb.
In this metallic compound (d), the metallic compound with the metallic element that is selected from Zr and Ti is not emit zirconium acyl ion (ZrO in the aqueous solution
2+) or titanium acyl ion (TiO
2+) metallic compound, it is different from above-mentioned the 4th group transition metal compound (a).As such metallic compound (d), can enumerate such as fluorine zirconic acid, ammonium fluozirconate, potassium fluozirconate, sodium fluozirconate, hydrofluotitanic acid, metatitanic acid hydrofluoric acid ammonium (the sour ア Application モ ニ ウ system of チ タ Application acid Off Star water element), potassium fluotitanate, titanium sodium fluoride etc.
Having the metallic compound that is selected from V, Mo, W, Ce, reaches the one kind or two or more metallic element among the Nb is salt, complex compound or the coordination compound of these metallic elements.Specifically can enumerate such as: vanadium pentoxide, metavanadic acid, ammonium meta-vanadate, sodium metavanadate, and the Oxidation Number such as vanadium oxytrichloride be the vanadium compound of 5 valencys; Three vanadium oxides, vanadium dioxide, vanadylic sulfate, methyl ethyl diketone vanadyl, vanadium acetylacetonate, vanadium trichloride, and the Oxidation Number of the vanadium such as phosphovanadomolybdic acid be the vanadium compound of 5 valencys, 4 valencys or 3 valencys; Molybdic acid, ammonium molybdate, Sodium orthomolybdate, and the molybdenum compound such as phospho-molybdic acid compound (for example, ammonium phosphomolybdate, sodium phosphomolybdate etc.); The tungsten compounds such as metatungstic acid, ammonium metawolframate, metatungstic acid sodium, para-tungstic acid, ammonium paratungstate and sodium paratungstate; Cerous acetate, cerous nitrate (III) or (IV), and the cerium compound such as Cerium II Chloride; Fluoridize the niobium compounds such as niobium and niobium phosphate; Etc..
The metallic compound that adds the specified rate in the metal conditioner to can be directed to by the 4th group transition metal compound (a) in conjunction with and in the surface treatment capsule that forms, thereby further improve erosion resistance and and laminated film between adaptation.Its result is even also can keep excellent adaptation in the corrosive environment of distillation processing, electrolytic solution impregnating.
With regard to the content of metallic compound contained in the metal conditioner (d), ratio [mass ratio=Md/Ma] in the mass M a of metallic element (Zr and/or Ti) in the mass M d of metallic compound (d) and the 4th group transition metal compound (a) is preferably 0.05 ~ 2.0, more preferably 0.1 ~ 1.5.By containing metallic compound (d) and the 4th group transition metal compound (a) with this quality than scope, can prevent that the adaptation between metallic surface and the gained surface treatment capsule from reducing, prevent that corrosive medium from immersing the metallic surface and causing erosion resistance to reduce.Especially has following advantage: can prevent from high humidity environment, occuring the reduction of the adaptation between metallic surface and the gained surface treatment capsule, and then prevent that the gained surface treatment capsule from becoming fragile, improve the flexibility of surface treatment capsule self, even make it that reduction of the adaptation between gained surface treatment capsule and the laminated film also can not occur in subsequently process processing.
(solvent)
Operability when in order to make metal conditioner of the present invention being coated metal material surface is good, can contain as required all kinds of SOLVENTS.Such solvent is take water as main body, but according to the needs such as drying property that improve surface treatment capsule, also can be used in combination the water-miscible organic solvent of alcohols, ketone or cellosolve class.
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; The ether solvents such as tetrahydrofuran (THF), diox; The esters solvent such as ethyl acetate, butoxy acetic acid ethyl ester; The amide solvent such as dimethyl formamide, N-Methyl pyrrolidone; The sulfone kind solvents such as dimethyl sulfoxide (DMSO); The phosphoamide kind solvents such as hexamethyl phosphoric triamide; Etc..Can use a kind in above-mentioned each solvent, also can use mixing more than 2 kinds.In these solvents, based on to environment aspect, the favourable reason of economic aspect, preferably water.
(other additive)
Do not destroy purport of the present invention and by the scope of film properties in, metal conditioner of the present invention can contain tensio-active agent, defoamer, flow agent, antibacterial mildew inhibitor, tinting material, solidifying agent etc.In addition, do not destroy purport of the present invention and by the scope of film properties in, the organic crosslinking agents such as methylolation trimeric cyanamide, carbodiimide and isocyanic ester of the erosion resistance of surface treatment capsule be can also add to improve, and the γ of adaptation-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl-triethoxysilicane, γ aminopropyltriethoxy silane, and N-beta-aminoethyl-silane coupling agents such as gamma-amino propyl trimethoxy silicane are used for improving.
(preparation method of metal conditioner)
The manufacture method of metal conditioner of the present invention there is no particular restriction.For example, can prepare as follows: the 4th group transition metal compound (a) and organic compound (b) are mixed with the optional water-base resin (c) that contains, metallic compound (d), other additive, solvent etc., utilize the stirrer such as mixing tank fully to mix, thus the preparation metal conditioner.
[metallic substance]
As shown in Figure 1, metallic substance 10 of the present invention has body material metal 1 and metal conditioner of the present invention is coated on the surface of this body material metal 1 and the surface treatment capsule 2 that forms.In this application, the metallic substance 1 that surface treatment capsule 2 is not set is called " body material metal 1 ", will be called at the metallic substance that this body material metal 1 is provided with surface treatment capsule 2 " metallic substance 10 ".Need to prove, shown in Fig. 1 is the example that is formed with surface treatment capsule 2 and resin molding 3 or resin coating film 3 at a side surface of body material metal 1, but also can be on the two sides of body material metal 1, namely also form surface treatment capsule 2 on the opposite side surface, and then resin molding 3 or resin coating film 3 are set.
Described " having " refers to also can have other formation except body material metal 1 and surface treatment capsule 2.For example, on surface treatment capsule 2, can have the resin molding 3 that obtains through lamination or the resin coating film 3 that forms through coating.Described " coating " refers to, by the surface coated metal conditioner of above-mentioned painting process at body material metal 1.Owing to surface treatment capsule 2 is that metal conditioner with the invention described above is coated on the body material metal 1 and forms, therefore have excellent adaptation and drug-resistant driving fit retentivity.
There is no particular restriction for the shape of body material metal 1 and structure etc., can enumerate such as tabular, paper tinsel shape etc.In addition, there is no particular restriction for the kind of body material metal 1, can adopt various metals.Can enumerate such as can being applicable to the metallic substance of food with the exterior material of the main body of tank or cover material, containers for food use, drying battery container, secondary cell etc., but be not limited to these materials, can 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, the exterior material of the lithium-ion secondary cell that the exterior material of described lithium-ion secondary cell is the portable exterior material with lithium-ion secondary cell that is used for recently mobile phone, electronic notebook, notebook computer or pick up camera etc., use as the drive energy of electromobile or hybrid vehicle.In these metallic substance, can preferably use can form on its surface surface treatment capsule 2, and can be on surface treatment capsule 2 laminating resin film 3 etc. and can implement subsequently 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 nickel materials such as the iron materials such as the aluminums such as the copper products such as fine copper, copper alloy, fine aluminium, aluminium alloy, ordinary steel, steel alloy, pure nickel, nickelalloy etc.
As copper alloy, preferred use contains the copper alloy of the above copper of 50 quality %, but example such as brass etc.As other alloying constituent beyond the copper removal in the copper alloy, can enumerate such as Zn, P, Al, Fe, Ni etc.As aluminium alloy, preferred use contains the aluminium alloy of the above aluminium of 50 quality %, but example such as Al-Mg are associated gold etc.As the alloying constituent of other except aluminium in the aluminium alloy, can enumerate such as Si, Fe, Cu, Mn, Cr, Zn, Ti etc.As steel alloy, preferred use contains the steel alloy of the above iron of 50 quality %, but example such as stainless steel etc.As other alloying constituent beyond the deironing in the steel alloy, can enumerate such as C, Si, Mn, P, S, Ni, Cr, Mo etc.As nickelalloy, preferred use contains the nickelalloy of the above nickel of 50 quality %, but example such as Ni-P alloy etc.As the alloying constituent of other except nickel in the nickelalloy, can enumerate such as Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, P etc.
Body material metal 1 also can form the tunicle that comprises above-mentioned metallic element on the surface of above-mentioned metallic substance metallic substance, stupalith or organic materials in addition.Such metal tunicle can form by methods such as plating, evaporation, coating (clad).In addition, there is no particular restriction for the shape of body material metal 1, structure etc., but example such as metallic substance tabular or the paper tinsel shape.
Above, according to metallic substance 10 of the present invention, because it has aforesaid surface treatment capsule 2, even therefore after surface treatment capsule 2 forms resin molding 3 or resin coating film 3, implement in the situation of the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, and in the situation that further be exposed in the acid etc., can prevent that also resin molding 3 or resin coating film 3 from peeling off from metallic substance 10.
[surface treatment method]
That to obtain adhesion amount be 10 ~ 3000mg/m by above-mentioned metal conditioner being coated the metallic surface and being carried out drying with the metal surface treating method of metal conditioner
2The method of tunicle, the method comprises following operation: the painting process of metal conditioner being coated the body material metallic surface; With behind painting process, carry out drying without washing, thereby form the drying process of surface treatment capsule.
Need to prove, for the surface of metallic substance, can carry out as required in advance degreasing, cleaning.Grease-removing agent can be selected from the various materials that are suitable for metal matrix material.In addition, scavenging solution makes water usually, but also can be water-soluble solvent or water phase surfactant mixture etc.In addition, there is no particular restriction for degreasing method, purging method, preferably adopt spray method or pickling process etc.
(painting process)
Painting process is the operation of metal conditioner being coated the body material metallic surface.Method for coating there is no particular restriction, can adopt that for example spraying, dip-coating, roller coat, curtain are coated with, spin coating or the method that obtained by these Combination of Methods.The working conditions of metal conditioner there is no particular restriction.For example, during coating the liquid temperature of metal conditioner preferably in 10 ℃ ~ 50 ℃ scope.Be generally 0.5 second the duration of contact of metal conditioner and metallic surface ~ about 180 seconds.Metal conditioner of the present invention is the treatment agent of application type, therefore, with after metal conditioner contacts, carries out drying described later without cleaning, thereby forms the metal finishing tunicle.
(drying process)
Drying process is behind painting process, carries out drying without washing, thereby forms the operation of surface treatment capsule.Drying temperature can be set as the temperature that adapts to employed solvent phase.For example, make in the situation of water as solvent, drying temperature is preferably 60 ℃ ~ 250 ℃ scope.This temperature range can be in above-mentioned scope changes arbitrarily according to the kind of resinous principle, but more preferably 80 ~ 200 ℃.Drying installation there is no particular determination, can adopt intermittent type, continous way or heated air circulation type drying oven, conveyor type hot-air drying stove or use electromagnetic induction heating furnace of IH well heater etc., and its air quantity and wind speed etc. can Set arbitrarilies.
For the surface treatment capsule that obtains thus, even implement in the situation of the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing after further forming resin molding (laminated film) or resin coating film thereon, and in the situation that further be exposed to acid etc. in, also can prevent from being peeled off by the resin coating that laminated film or resin coating film consist of.
The thickness of gained surface treatment capsule is preferably 0.01 μ m ~ 1 μ m, more preferably 0.02 μ m ~ 0.05 μ m.Thickness by making surface treatment capsule can further improve adaptation and the drug-resistant driving fit retentivity of surface treatment capsule in this scope.
Embodiment
Below, reach in conjunction with the embodiments comparative example the present invention is described in more detail.The present invention is not subjected to the restriction of following embodiment.Need to prove, following " part " refers to " mass parts ", and " quality % " and " % by weight " synonym are following in the situation that there is not particular determination sometimes also to be expressed as " % "." ppm " and " mg/L " synonym.
[metallic substance]
Metallic substance (body material metal) as body material is as follows.
Al:A1100P, thick 0.3mm
Cu:C1020P, thick 0.3mm
Ni: pure nickel plate (purity is more than 99 quality %), thick 0.3mm
SUS:SUS304 plate, thick 0.3mm
Nickel-clad copper: electronickelling copper coin (thick 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 4, the body material metal of preparation embodiment 1 ~ 98 and comparative example 1 ~ 18.
[metal conditioner]
With the 4th group transition metal compound (a) as follows and organic compound (b) and the water-base resin (c) that can optionally use and metallic compound (d) combination, as solvent, the metal conditioner of the embodiment 1 ~ 98 shown in table 1 ~ table 4 and the metal conditioner of comparative example 1 ~ 13 have been prepared with water.Need to prove the shared nonvolatile component amount concentration (quality %) of above-mentioned each compound in " concentration " expression metal conditioner in the table.For the 4th group transition metal compound (a) and metallic compound (d), be expressed as metal concentration (quality %).
[the 4th group transition metal compound (a)]
Az1: zirconium carbonate ammonium
Az2: zirconyl acetate
Az3: Zircosol ZN
At1: dioxalic acid oxygen titanium two ammoniums
At2: the hydroxyl lactyl-lactic acid closes titanium [organic compound (b)]
B1: (molecular weight: 106, functional group content: 53.1g solid/eq(g solid/eq is Diethylene Glycol
The unit of azoles quinoline equivalent))
B2: tetramethylolmethane (molecular weight: 136, functional group content: 34g solid/eq)
B3: pyrocatechol (molecular weight: 110, functional group content: 55.1g solid/eq)
B4: tartrate (molecular weight: 150, functional group content: 37.5g solid/eq)
B5:L-xitix (molecular weight: 175, functional group content: 43.8g solid/eq)
B6: oxyacetic acid (molecular weight: 78, functional group content: 38.0g solid/eq)
B7:1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid (molecular weight: 206, functional group content: 68.7g solid/eq)
B8: phytic acid ammonium (molecular weight: 738, functional group content: 123.0g solid/eq)
B9: polymaleic acid (molecular weight: 3000, functional group content: 58g solid/eq)
B10: polyoxyethylene glycol (molecular weight: 800, functional group content: 400g solid/eq)
[water-soluble polymer (c)]
(c1: urethane resin-anionic property)
Make polyester polyol (hexanodioic acid/3-methyl isophthalic acid, 5-pentanediol, number-average molecular weight: 1000, functional group's number: 2, hydroxyl value: 112.2) 100 parts, 3 parts of TriMethylolPropane(TMP)s, 25 parts of dimethylol propionic acids, and 85 parts of isophorone diisocyanates among MEK (methyl ethyl ketone), react, obtain carbamate prepolymer.In this carbamate prepolymer, mix 9.4 parts of triethylamines, and drop in the water, above-mentioned carbamate prepolymer is scattered in the water, utilize quadrol to make this prepolymer elongation, thus the dispersion of obtaining.Methyl ethyl ketone is removed in distillation, obtains containing the polyurethane resin aqueous dispersion of 30 quality % nonvolatile component.The acid number that is scattered in the urethane that contains carboxyl in the gained polyurethane resin aqueous dispersion is 49 (KOHmg/g).
(c2: Resins, epoxy-anionic property)
Add ortho-phosphoric acid 85g and propylene glycol monomethyl ether 140g, and slowly add the bisphenol A type epoxy resin 425g of epoxy equivalent (weight) 250, in 80 ℃ of reactions 2 hours.After reaction finishes, below 50 ℃, slowly add 29 quality % ammonia soln 150g, and then add water 1150g, obtain in the ammonia of phosphoric acid modification Resins, epoxy of acid number 35, solid component concentration 25 quality % and product.
(c3: acrylic resin-nonionic)
Adopted following monomer composition: " methyl methacrylate (molecular weight: 100) 20 parts, butyl acrylate (molecular weight: 128) 40 parts, methacrylic acid 2-hydroxy propyl ester (molecular weight: 144) 10 parts, vinylbenzene (molecular weight: 104) 10 parts, methacrylic acid N, N-dimethylamino propyl ester (molecular weight: 175) 20 parts ".Acrylic resin c's is synthetic as follows: in 100 parts of the 10 quality % emulsifier aqueous solutions (S-1) that mixed with 6:4 by reactive emulsifier " Adeka Reasoap NE-20 " (Asahi Denka Co., Ltd.'s system) and non-ionic emulsifier " Emulgen840S " (Kao Corp's system), mix above-mentioned monomer, and utilize homogenizer to carry out emulsification in 10 minutes with 5000rpm, obtain monomer emulsion (ER).Then, in the four neck flasks that are equipped with stirrer, reflux exchanger, temperature and take into account the monomer supply pump, add the mentioned emulsifier aqueous solution (S-1) 150 parts, remain in 40 ~ 50 ℃, join respectively the 5 quality % aqueous solution (50 parts) and the above-mentioned monomer emulsion (ER) of ammonium persulphate in the dropping funnel, and this dropping funnel is installed on other mouthful neck of flask, utilize approximately to drip in 2 hours, and temperature is warming up to 60 ℃, carried out approximately stirring in 1 hour.Be cooled to while stirring room temperature, obtain the emulsified soln of acrylic resin.
(c4: acrylic resin-nonionic)
Used the aqueous solution (nonvolatile component concentration 22.0 quality %, viscosity 90mPas) of acrylamide polymer.
(c5: resol-nonionic)
Used the resole (dimer) with methylol.
(c6: vibrin-anionic property)
Utilize following method to synthesize the vibrin (solids component (NVC.) 30%) of anionic property by the condensation reaction of following pure composition and following sour composition, described pure composition comprises ethylene glycol (90mol%) and TriMethylolPropane(TMP) (10mol%), and described sour composition comprises m-phthalic acid (40mol%), terephthalic acid (41mol%), Sodium Dimethyl Isophthalate-5-sulfonate (2mol%) and trimellitic acid 1,2-anhydride (17mol%).In being installed, the 1000mL round-bottomed flask of claisen pipe and atmospheric condenser adds the complete sour composition of 1mol, complete pure composition and catalyzer (lime acetate: 0.25g, the tetrabutyl titanate: 0.1g) of 2mol, to carrying out nitrogen replacement in the system, and be heated to 180 ℃, content is melted.Then, make and bathe temperature rise to 200 ℃, carry out approximately 2 hours heated and stirred, carried out esterification or transesterification reaction.Then, make and bathe temperature rise to 260 ℃, approximately make after 15 minutes and be decompressed to 0.5mmHg in the system, carried out approximately reaction (polycondensation) in 3 hours.After reaction finishes, in the situation that import the nitrogen naturally cooling, take out content.Add in the resin that takes out and to make final pH reach 6 ~ 7 an amount of ammoniacal liquor (about water, adopting to make solids component reach 25% amount), and in autoclave, under 100 ℃, carry out 2 hours heated and stirred, obtained the water-based emulsion resin.Need to prove, described " solids component " refers to except solvent etc. and evaporates into composition grading.
(c7: polyvinyl alcohol-nonionic)
Used saponification deg: 99%, viscosity: 12mPaS, acetoacetylation degree: 9.8%, molecular-weight average: 50000 acetoacetylation polyvinyl alcohol.
(c8: polyolefine-anionic property)
In four neck flasks, drop into propylene-ethylene-alpha-olefin copolymer (propylene composition: 68 % by mole, ethene composition: 8 % by mole, butylene composition: 24 % by mole, weight-average molecular weight: 60,000) 1 part of 100 parts, 10 parts of maleic anhydrides, 10 parts of methyl methacrylates and dicumyl peroxide, carry out stirring in 2 hours in 180 ℃, make its reaction.Obtained weight-average molecular weight and be 45,000, the graft weight of maleic anhydride is the modified polyolefin resin composition of 8.4 % by weight.Then, utilize stirring rake to make 100 parts of above-mentioned modified polyolefins, 10 parts of dimethylethanolamines and 10 parts of uniform stirrings in four neck flasks, under 100 ℃, 2 hours condition of polyethylene oxide alkyl ethers vitriol, after the melting, the 300 parts of continuation of ion exchanged water that add 90 ℃ were stirred 1 hour, had prepared the aqueous resin composition of pH8.0.
[metallic compound (d)]
(d) is as follows for employed water soluble metallic compound.
D1: fluorine zirconic acid
D2: ammonium molybdate
D3: vanadium acetylacetonate
[the test making of material]
For each body material shown in table 1 ~ table 4,3% aqueous solution that utilizes Fine cleaner359E (Nihon Parkerizing Co., Ltd. make alkali cleaner) in 65 ℃ carry out spraying degreasing in 1 minute after, wash the clean surface.Then, in order to make the moisture evaporation of substrate material surface, carried out 1 minute heat drying in 80 ℃.Use the #3SUS wheat to strangle rod, utilize rod to be coated with method the metal conditioner of the embodiment 1 ~ 98 shown in table 1 ~ table 4 and comparative example 1 ~ 13 is coated substrate material surface through cleaning by degreasing, and in the heated air circulation type drying oven in 180 ℃ of dryings 1 minute, thereby formed surface treatment capsule on the surface of body material.In addition, for the body material of the comparative example 14 ~ 18 shown in the table 4 through with above-mentioned same degreasing, washing after, carry out heat drying and the material that obtains, also test.
Need to prove, in table 1 ~ table 4, Maz represents the zirconium quality in the zirconium compounds, Mat represents the titanium quality in the titanium compound, Ma represents the quality of the metal (Zr and/or Ti) in the 4th group transition metal compound (a), Mb represents the quality of organic compound (b), and Mc represents the quality of water-base resin (c), and Md represents the quality of metallic compound (d).
The surface treatment capsule that forms for the metal conditioner that utilizes embodiment 1 ~ 98 and comparative example 1 ~ 13 and the body material of comparative example 14 ~ 18, the polypropylene screen that utilized heat lamination as follows or dry lamination lamination.
(heat lamination)
Then, use the #8SUS wheat to strangle rod, utilize rod to be coated with method with the dispersion liquid of sour modified polypropene (Mitsui Chemicals, Inc's system, " R120K ", nonvolatile component concentration: after 20%) coating on the face that is formed with surface treatment capsule of body material, in the heated air circulation type drying oven, in 200 ℃ of dryings 1 minute, formed thus bond layer.Then, with the PP film (Tohcello Co., Ltd. system, " CPPS ") of this bond layer and thick 30 μ m hot pressing 10 minutes under 190 ℃, 2MPa, made thus polypropylene screen lamination body material.
(dry lamination)
Use the #8SUS wheat to strangle rod, utilize rod to be coated with method and be coated with polyurethanes dry lamination caking agent (Toyomorton Co., Ltd. system, " AD-503/CAT10 ", nonvolatile component concentration: 25%), then in the heated air circulation type drying oven in 80 ℃ of dryings 1 minute, formed bond layer.Then, with the Corona discharge Treatment face of the un-stretched polypropylene film (two village chemical industry Co., Ltd. systems, " FCZX ") of this bond layer and 30 μ m after carrying out pressing under 100 ℃, 1MPa, in 40 ℃ of slakings 4 days, made thus polypropylene screen lamination body material.
Then, utilize drawing attenuated processing experiment that above-mentioned each the polypropylene screen lamination body material by heat lamination or dry lamination manufacturing has been carried out deep-draw processing.The above-mentioned lamination body material that is die-cut into diameter 160mm is carried out pull and stretch processing (the 1st time), made the cup of diameter 100mm.Then, again this glass pull and stretch is processed (the 2nd time) to diameter 75mm, and then pull and stretch processing (the 3rd time) one-tenth diameter 65mm, the tank of using material as test made.Need to prove, attenuate (thin-walled property part) rate of the 1st pull and stretch processing, the 2nd pull and stretch processing, the 3rd pull and stretch processing is respectively 5%, 15%, 15%.
[performance evaluation]
Estimate as described below for the initial stage adaptation, durable adaptation, the bonding retentivity of electrolyte resistance and the liquid stabilising that each polypropylene screen lamination body material are carried out after deep-draw is processed.Its result is shown in table 5 ~ table 8.
(initial stage adaptation)
For having carried out the evaluation of initial stage adaptation with material through the test after the deep-draw processing.Can make tank, the peeling off of film not occur, the situation of initial stage adaptation excellence is denoted as " 3 minutes ", the situation that will have part film to occur to peel off is denoted as " 2 minutes ", the situation that whole face peels off has been occured film be denoted as " 1 minute ".Situation about in 3 minutes, do not peel off observing fully in addition,, especially outward appearance is excellent, the initial stage adaptation is very excellent is denoted as " 4 minutes ".
(durable adaptation)
For through the test material after the deep-draw processing, carried out the evaluation of durable adaptation in the atmosphere of heating and pressurizing steam, having implemented the material after the distillation test.Distillation test is used commercially available sterilising plant (autoclave), has carried out processing in 1 hour in 125 ℃ heating and pressurizing vapor atmosphere.Then, tip with tweezers scratches face, the situation about peeling off that film does not occur fully is denoted as " 6 minutes ", peel off having occured but the very high situation of resistance is denoted as " 5 minutes ", peel off having occured but the high situation of resistance is denoted as " 4 minutes ", do not have situation so not high but that can reach realistic scale be denoted as " 3 minutes " resistance, will be denoted as with the situation that very weak power can be peeled off film " 2 minutes ", the situation about peeling off that film has occured is denoted as " 1 minute ".
(the bonding retentivity of electrolyte resistance)
For through the test material after the deep-draw processing, carried out the evaluation of the bonding retentivity of electrolyte resistance in electrolyte solution for lithium ion secondary battery, having passed through the material after the dip test.Specific as follows: with through the test after the deep-draw processing with the interpolation of material soaking in being filled in encloses container the electrolyte solution for lithium ion secondary battery (ionogen: 1M-LiPF of ion exchanged water 1000ppm
6, solvent: EC:DMC:DEC=1:1:1 (volume %)) in, then put in 60 ℃ the thermostatic bath 7 days.Need to prove, " EC " represents ethylene carbonate, and " DMC " represents methylcarbonate, and " DEC " represents diethyl carbonate.
Then, take out test and use material, in ion exchanged water, flooded 1 minute, clean by shaking, then in the heated air circulation type drying oven in 100 ℃ of dryings 10 minutes.Then, tip with tweezers scratches face, the situation about peeling off that film does not occur fully is denoted as " 6 minutes ", peel off having occured but the very high situation of resistance is denoted as " 5 minutes ", peel off having occured but the high situation of resistance is denoted as " 4 minutes ", do not have situation so not high but that can reach realistic scale be denoted as " 3 minutes " resistance, will be denoted as with the situation that very weak power can be peeled off film " 2 minutes ", the situation about peeling off that film has occured is denoted as " 1 minute ".
(medicament stability)
For medicament stability, the permanent stability of metal conditioner are estimated.Specific as follows: as each 200mL of metal conditioner of the embodiment 1 ~ 98 shown in table 1 ~ table 4 and comparative example 1 ~ 13 to be sealing into respectively in the plastic containers (Port リ container) of 300mL, to estimate for medicament (metal conditioner) state that in 20 ℃ atmosphere, leaves standstill after 2 weeks.The situation of not solidifying fully, separating and precipitating is denoted as " 3 minutes ", will only confirm precipitation but occur solidify and separate and the situation that can reach realistic scale is denoted as " 2 minutes ", be denoted as " 1 minute " with observing the situation of solidifying and separating.
[table 5]
[table 6]
[table 7]
[table 8]
Shown in table 5 ~ table 8, the belt surface that can confirm to use the metal conditioner of embodiment 1 ~ 98 and metal matrix material to process and obtain is processed the metallic substance of tunicle, no matter adopt heat lamination or dry lamination, all have very excellent initial stage cementability and the bonding retentivity of electrolyte resistance.
Claims (6)
1. metal conditioner, it contains:
One kind or two or more the 4th group transition metal compound (a) and
Organic compound (b),
Described the 4th group transition metal compound (a) is selected from and emits zirconium acyl ion (ZrO in the aqueous solution
2+) the Zr compound and in the aqueous solution, emit titanium acyl ion (TiO
2+) the Ti compound,
Described organic compound (b) has the one kind or two or more functional group that is selected from more than 2 in hydroxyl, carboxyl, phosphonate group, phosphate and the sulfonic group in a part.
2. metal conditioner according to claim 1, wherein, the molecular weight of described organic compound (b) is more than 100 and below 1000, and this organic compound (b) is the compound that has described functional group with 1 ratio in per 30 ~ 300 the molecular weight.
3. metal conditioner according to claim 1 and 2, wherein, the ratio [Mb/Ma] of the quality (Ma) of metal is 0.05 ~ 0.6 in the quality (Mb) of described organic compound (b) and described the 4th group transition metal compound (a).
4. each described metal conditioner according to claim 1 ~ 3 wherein contains the one kind or two or more nonionic that is selected from urethane resin, Resins, epoxy, acrylic resin, resol, polyester resin, polyvinyl resin and the polyolefin resin or the water-base resin (c) of anionic property.
5. each described metal conditioner according to claim 1 ~ 4 wherein contains and has the metallic compound (d) that is selected from the one kind or two or more metallic element among Zr, Ti, V, Mo, W, Ce and the Nb.
6. metallic substance, it has the surface treatment capsule of each described surface treatment agent in the claim 1 ~ 5 being coated the metallic surface and forming.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-157015 | 2011-07-15 | ||
| JP2011157015A JP5744654B2 (en) | 2011-07-15 | 2011-07-15 | Metal surface treatment agent and metal material treated with the treatment agent |
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| Publication Number | Publication Date |
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| CN102877055A true CN102877055A (en) | 2013-01-16 |
| CN102877055B CN102877055B (en) | 2016-05-04 |
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| Country | Link |
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| JP (1) | JP5744654B2 (en) |
| KR (1) | KR101610428B1 (en) |
| CN (1) | CN102877055B (en) |
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| CN103668144A (en) * | 2013-12-24 | 2014-03-26 | 淮南天力生物工程开发有限公司 | Environmentally friendly organic metal treating fluid and preparation method thereof |
| CN104031543A (en) * | 2014-06-13 | 2014-09-10 | 苏州汉力新材料有限公司 | Laminated metal protection coating and metal material |
| CN104073209A (en) * | 2014-06-17 | 2014-10-01 | 张家港市橡燊达机械有限公司 | Hot galvanizing metal material adhesion agent |
| CN104726855A (en) * | 2013-12-18 | 2015-06-24 | 日本帕卡濑精株式会社 | Aqueous metal surface treatment agent, metal surface treatment coating film and metal material having a metal surface treatment coating film |
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- 2012-07-13 KR KR1020120076841A patent/KR101610428B1/en active IP Right Grant
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| JPH09268376A (en) * | 1996-04-02 | 1997-10-14 | Nippon Steel Corp | Production of coated steel tube |
| 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 |
| JP2011032576A (en) * | 2009-07-06 | 2011-02-17 | Sumitomo Metal Ind Ltd | Surface-treated plated steel sheet and surface treatment solution |
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| CN103668144A (en) * | 2013-12-24 | 2014-03-26 | 淮南天力生物工程开发有限公司 | Environmentally friendly organic metal treating fluid and preparation method thereof |
| CN103668144B (en) * | 2013-12-24 | 2016-01-20 | 淮南天力生物工程开发有限公司 | A kind of environment-friendly type organo-metallic treatment solution and preparation method thereof |
| CN104031543A (en) * | 2014-06-13 | 2014-09-10 | 苏州汉力新材料有限公司 | Laminated metal protection coating and metal material |
| CN104073209A (en) * | 2014-06-17 | 2014-10-01 | 张家港市橡燊达机械有限公司 | Hot galvanizing metal material adhesion agent |
| CN108713072A (en) * | 2016-02-09 | 2018-10-26 | 日本帕卡濑精株式会社 | Surface conditioning agent, the manufacturing method for being surface-treated epithelium and aluminium or aluminium alloy material with surface treatment epithelium |
| CN110284163A (en) * | 2019-07-31 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN110284163B (en) * | 2019-07-31 | 2020-08-04 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN115216760A (en) * | 2022-06-23 | 2022-10-21 | 安徽舜邦精细化工有限公司 | Slag-free coating agent |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5744654B2 (en) | 2015-07-08 |
| CN102877055B (en) | 2016-05-04 |
| KR101610428B1 (en) | 2016-04-07 |
| TW201317395A (en) | 2013-05-01 |
| KR20130009702A (en) | 2013-01-23 |
| JP2013023705A (en) | 2013-02-04 |
| TWI521094B (en) | 2016-02-11 |
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