CN102877055B - Metal conditioner and utilize this inorganic agent to process and the metal material that obtains - Google Patents
Metal conditioner and utilize this inorganic agent to process and the metal material that obtains Download PDFInfo
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- CN102877055B CN102877055B CN201210245900.3A CN201210245900A CN102877055B CN 102877055 B CN102877055 B CN 102877055B CN 201210245900 A CN201210245900 A CN 201210245900A CN 102877055 B CN102877055 B CN 102877055B
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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
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Abstract
The present invention relates to be used to form the metal conditioner of surface treatment capsule, described surface treatment capsule, resin film layer being pressed in to metal material surface or forming resin coating film at metal material surface, then implement the shaping of harshness such as deep-draw processing and add man-hour, also can be given the high adhesion that can not make laminated film or resin coating film peel off. For this reason, the invention provides a kind of metal conditioner, it contains to be selected from emits zirconium acyl ion (ZrO in the aqueous solution2+) Zr compound and in the aqueous solution, emit titanium acyl ion (TiO2+) Ti compound in the 4th one kind or two or more group transition metal compound (a) and in same a part, there are 2 organic compounds (b) that are selected from above hydroxyl, carboxyl, phosphonate group, phosphate and sulfonic one kind or two or more functional group. The molecular weight that preferably has organic compounds (b) is 100 ~ 1000, and organic compound (b) has functional group with the ratio of 1 in every 30 ~ 300 molecular weight.
Description
Technical field
The present invention relates to metal conditioner and utilize this metal conditioner to process and obtainThe metal material arriving, described metal conditioner is used to form and can prevents metal material and laminated film or treeFat film is peeled off and the surface treatment capsule of adaptation and the closely sealed retentivity excellence of drug-resistant. Specifically, the present invention relates to the metal watch of the surface treatment capsule that is used to form the closely sealed retentivity excellence of drug-resistantFace inorganic agents etc., even if described surface treatment capsule is being pressed in resin film layer on metal material or at metalOn material, form resin coating film, then implement deep-draw processing, attenuate processing (processing of ご I) or stretch-draw and addIn the situation of the harsh shaping processing such as work, also can give can not make laminated film etc. peel off highly denseClosing property, and in the time being exposed in acid, organic solvent etc., also can keep high adhesion.
Background technology
Lamination process is that resinous film (following, to be called " resin molding " or " laminated film ") heating is pressed together onThe processing method on the surface (following, referred to as " metal surface ") of metal material is to protect metal surfaceOr to give design be one of metal surface method for coating of object, can be in various fields. With generalResin combination dissolves or is dispersed in the coating fluid obtaining in solvent and is coated on metal surface and is dried shapeThe method of resin film is compared, and the solvent that described lamination process produces when dry is few, carbon dioxide etc.The generation of waste gas or greenhouse gases is also few. Therefore,, from environmental protection aspect, preferably useLamination process, its purposes expands, and has been used to for example use with aluminium sheet material, steel sheet material, packagingAluminium foil or stainless steel foil etc. are main body or cover material, containers for food use or the dry cell of tank for the food of raw materialContainer etc.
Particularly nearest, as what use in mobile phone, electronic notebook, notebook computer or video camera etc.The exterior material of portable lithium rechargeable battery and lug (tablead) material, the preferably light and resistance of service property (quality)Every the high metal forming such as aluminium foil or stainless steel foil of property, adopt lamination to add to the surface of such metal formingWork. In addition, studying the lithium ion secondary as the drive energy of electric automobile or hybrid vehicleBattery, as its exterior material, is also studied the metal forming through lamination process.
Laminated film for such lamination process is directly fitted with metal material, then adds hot pressingClose. Therefore,, compared with coating resin composition the dry common resin coating film forming, having canSuppress raw-material waste, pin hole (defective part) less and the advantage such as excellent in workability. As the material of laminated filmMaterial, conventionally use the polyester resin such as PETG and PEN,The polyolefin such as polyethylene and polypropylene.
If metal surface is not implemented the processing such as chemical conversion processing while carrying out lamination process, has layerPress mold is peeled off from metal surface or the problem of corroding occurs metal material. For example,, for containers for food useOr packaging material, in the container after lamination process or packaging material, add after content, implement withSterilization is the heat treated of object, but laminated film is peeled off from metal surface sometimes in the time of this heat treated.In addition, for exterior material of lithium rechargeable battery etc., in its manufacturing process, to be subject to processing,Spend high processing. In addition, in the time of long-term use, there is following problems: the moisture in atmosphere can immerse appearanceIn device, itself and electrolyte react and generate hydrofluoric acid, and this hydrofluoric acid transmission layer press mold makes metal surfacePeel off with laminated film, and can erode metallic surfaces.
For the problems referred to above, by laminated film lamination process on metal surface time, in order to improve laminated filmAnd the adaptation between metal surface and the corrosion resistance of metal surface, carry out degreasing to metal surface clearWash, then conventionally implement the chemical conversion processing such as chromium phosphate hydrochlorate etc. But, such chemical conversion placeReason need to be implemented matting after processing, to remove remaining treatment fluid, for being arranged by this mattingThe rinse water going out is carried out wastewater treatment needs Expenses Cost. Especially the chemical conversion processing such as chromium phosphate hydrochlorateDeng owing to having used chromyl treatment fluid, therefore in recent years for the worry to environment, have and stop makingWith tendency.
For example, a kind of substrate treating agent is proposed in patent documentation 1, the water-soluble zirconium that it contains specified quantitativeWater-soluble or water dispersible acrylic resin and the water-soluble or water dispersible of compound, ad hoc structureThermoset cross-linked dose. In addition, a kind of chromium-free metal surface treatment agent has been proposed, its bag in patent documentation 2Draw together water-soluble zirconium compound and/or water-soluble titanium compound, organic phospho acid compound and the list of specified quantitativeRather. In addition, proposed a kind of Treatment of Metal Surface medicament in patent documentation 3, it is poly-that it contains amination phenolThe special metal compound of compound, Ti and Zr etc., and the pH of this Treatment of Metal Surface medicament is 1.5 ~ 6.0Scope. In addition, a kind of resin molding has been proposed in patent documentation 4, its contain amination phenol polymer,Acrylic polymer, metallic compound and phosphorus compound as required.
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 a kind of metal conditioner that is used to form surface treatment capsule,And utilize this metal conditioner to process and the metal material that obtains, described surface treatment capsuleEven resin film layer is pressed in to the surface of metal material or form on the surface of metal material resin coating film,Then implement, in the situation of the harsh shaping processing such as deep-draw processing, attenuate processing or stretch-draw processing, alsoEnough give the high adhesion that can not make this laminated film or resin coating film peel off.
The method of dealing with problems
Be characterised in that for the metal conditioner of the present invention addressing the above problem, it contains a kindOr two or more the 4th group transition metal compound (a) and organic compound (b), described the 4th family's transition goldGenus compound (a) is selected from emits zirconium acyl ion (ZrO in the aqueous solution2+) Zr compound and in the aqueous solutionEmit titanium acyl ion (TiO2+) Ti compound, described organic compound (b) has 2 in same a partIndividual above be selected from hydroxyl, carboxyl, phosphonate group (phosphonategroup), phosphate (phosphategroup)And one kind or two or more functional group in sulfonic group (sulfonategroup).
According to this invention, in the time that metal conditioner is coated metal surface, in metal conditionerThe 4th contained group transition metal compound (a) is because of zirconium acyl ion (ZrO2+), titanium acyl ion (TiO2+) etc. metalOxygen acyl ion (オ キ シ metal イ オ Application) and metal surface react and strong adsorption in metal surface.So, subsequently by carrying out heat drying etc. while removing moisture, can be because of zirconium acyl ion (ZrO2+) betweenCondensation reaction forms key, because of titanium acyl ion (TiO2+) between condensation reaction form key or because of zirconium acyl ion(ZrO2+) and titanium acyl ion (TiO2+) between condensation reaction form key. Its result, the application of the inventionMetal conditioner, can form the tough surface treatment quilt that brings high adhesion to metal surfaceFilm.
In addition, with regard to organic compound contained in metal conditioner (b), due to its can with by theThe zirconium acyl ion (ZrO that 4 group transition metal compounds (a) are emitted2+) or titanium acyl ion (TiO2+) etc. metal oxygen acylIon forms water soluble salt or complex salt, therefore, has the effect of the stability that improves these metal oxygen acyl ionsReally. In addition, after metal conditioner is coated to metal surface by carrying out heat drying etc.While removing moisture, organic compound (b) and Zr or the combination of strong ground of Ti, have the film forming that improves tunicleEffect.
With regard to metal conditioner of the present invention, the molecular weight of preferred above-mentioned organic compound (b) isMore than 100 and below 1000, and this organic compound (b) is with in every 30 ~ 300 molecular weight 1Ratio has the compound of above-mentioned functional group, thus, can realize excellent adaptation.
With regard to metal conditioner of the present invention, the quality (Mb) of preferred above-mentioned organic compound (b)With the ratio [Mb/Ma] of the quality (Ma) of the metal in above-mentioned the 4th group transition metal compound (a) be0.05 ~ 0.6, thus, can realize excellent adaptation.
In metal conditioner of the present invention, preferably contain be selected from polyurethane resin, epoxy resin,In acrylic resin, phenolic resins, polyester resin, polyvinyl resin and polyolefin resinThe water-base resin (c) of one kind or two or more nonionic or anionic property, thus, can give gained surfaceProcess tunicle with flexibility and more excellent film forming.
In metal conditioner of the present invention, preferably contain there is the Zr of being selected from, Ti, V, Mo, W,The metallic compound (d) of the one kind or two or more metallic element in Ce and Nb, thus, it can be used asCorrosion inhibiter and given play to more excellent corrosion resistance and improved effect.
Be characterised in that for the metal material of the present invention addressing the above problem, it has sends out above-mentionedBright surface conditioning agent is coated metal surface and the surface treatment capsule that forms.
According to this invention, because the metal conditioner having the invention described above is coated metal materialSurface and the surface treatment capsule that forms, therefore, even on this surface treatment capsule further lamination treeAdipose membrane or form resin coating film, then implement the harsh one-tenth such as the processing of deep-draw processing, attenuate or stretch-draw processingIn the situation of shape processing, also can preventing layer press mold or resin coating film peel off from metal material. And,Even be further exposed to acid etc. in the situation that, also can prevent that this laminated film or resin coating film are from goldBelong on material and peeling off.
The effect of invention
According to metal conditioner of the present invention and utilize this inorganic agent to process the metal material obtaining,By above-mentioned effect, can improve closely sealed between metal material surface and gained surface treatment capsule simultaneouslyProperty and laminated film and gained surface treatment capsule between adaptation, and be exposed to acid etc. in time alsoCan keep high adhesion. Its result, though on the metal material that is formed with surface treatment capsule laminationResin molding or form resin coating film, then implements the processing of deep-draw processing, attenuate or stretch-draw processing etc. harshIn the situation of processing of being shaped, even and in being further exposed to acid, organic solvent etc. in the situation that,Also can prevent that this laminated film or resin coating film from peeling off from metal material. Particularly, even in distillation placeIn the corrosive environment of reason, electrolyte impregnating, also can keep excellent adaptation.
Brief description of the drawings
Fig. 1 is the schematic cross sectional view that the embodiment of surface treatment capsule of the present invention is shown.
Symbol description
1 metal material
2 surface treatment capsules
3 laminated films or resin coating film
10 have the metal material of surface treatment capsule
Detailed description of the invention
Below, for metal conditioner of the present invention and utilize this inorganic agent process and obtainMetal material describe. It should be noted that, technical scope of the present invention be not subject to following explanation andThe restriction of the embodiment of accompanying drawing.
[metal conditioner]
As shown in Figure 1, metal conditioner of the present invention is for the metal material as matrix materialThe surface of material 1 (hereinafter referred to as " matrix material metal 1 ") forms the table for substrate of laminated film or resin coating film 3Face is processed the inorganic agent of tunicle 2. This metal conditioner is characterised in that, it contains the 4th family's transitionMetallic compound (a) and organic compound (b), described the 4th group transition metal compound (a) is selected from waterIn solution, emit zirconium acyl ion (ZrO2+) Zr compound and in the aqueous solution, emit titanium acyl ion(TiO2+) Ti compound in one kind or two or more, described organic compound (b) is in same a partHave 2 be selected from above in hydroxyl, carboxyl, phosphonate group, phosphate and sulfonic group a kind or 2 kinds withUpper functional group.
Described " containing " refers to, in metal conditioner, also can contain except above-mentioned the 4th family's mistakeCross metallic compound (a) and above-mentioned organic compound (b) other compound in addition. As such chemical combinationThing, for example can enumerate, surfactant, defoamer, levelling agent, antibacterial mildew inhibitor, colouring agent etc.Can not destroy purport of the present invention and contained these compounds by the scope of film properties. Need explanation, as the matrix material metal 1 of surface treatment object as described later.
Below, be elaborated for each inscape.
(the 4th group transition metal compound)
The 4th group transition metal compound (a) is to be selected from the aqueous solution, to emit zirconium acyl ion (ZrO2+) ZrCompound and emit titanium acyl ion (TiO in the aqueous solution2+) Ti compound in a kind or 2 kinds withUpper compound. The surface that metal conditioner is coated to matrix material metal 1 is (also referred to as " metal watchFace ") time, the 4th group transition metal compound (a) is because of zirconium acyl ion (ZrO2+), titanium acyl ion (TiO2+) etc.Metal oxygen acyl ion react with metal surface and strong adsorption in metal surface. Dry in the heating by subsequentlyWhen dry grade is removed moisture, the metal oxygen acyl ion of absorption can pass through zirconium acyl ion (ZrO2+) between condensation anti-Should form key, pass through titanium acyl ion (TiO2+) between condensation reaction form key or by zirconium acyl ion(ZrO2+) and titanium acyl ion (TiO2+) between condensation reaction form key. Its result, by this one-tenth key, canBe formed as metal surface and bring the tough surface treatment capsule of high adhesion.
Zirconium compounds as long as emitting zirconium acyl ion (ZrO in the time being dissolved in the water2+) compoundCan, there is no particular restriction. As such zirconium compounds, for example can enumerate: basic carbonate oxygen zirconium(Zr2(CO3)(OH)2O2), zirconyl hydroxychloride (ZrO (OH) Cl), ammonium zirconyl carbonate((NH4)2ZrO(CO3)2), zirconyl carbonate potassium (K2ZrO(CO3)2K2), zirconyl carbonate sodium(Na2ZrO(CO3)2K2), zirconyl nitrate (ZrO (NO3)2), zirconyl acetate (ZrO (CH3COO)2), sulfuric acidOxygen zirconium (ZrOSO4), di(2-ethylhexyl)phosphate hydrogen-oxygen zirconium (ZrO (H2PO4)2), zirconium stearate (ZrO (C18H35O2)2) etc.
Titanium compound as long as emitting titanium acyl ion (TiO in the aqueous solution2+) compound, andWithout particular restriction. As such titanium compound, for example can enumerate: dioxalic acid oxygen titanium two ammoniums((NH4)2[Ti(C2O4)2O]·nH2O), titanyl sulfate (TiOSO4), diisopropoxy bis-acetylacetonate titanium(Ti(O-i-C3H7)2(C5H7O2)2) and hydroxyl lactyl-lactic acid close titanium (Ti (OH)2[OCH(CH3)COOH]2) etc.
In metal conditioner, can contain respectively independent zirconium compounds and titanium compound, also canTo comprise the two. Contain separately in the situation of one of zirconium compounds and titanium compound Treatment of Metal SurfaceIn agent, the content of contained compound is preferably 0.001 quality % ~ 70 quality %, more preferably 0.01 quality% ~ 50 quality %. Be 0.001 quality % ~ 70 quality % by making content, can further improve gainedThe closely sealed retentivity of the adaptation of surface treatment capsule and drug-resistant.
Although reason is still not clear, known, utilize in the inorganic agent taking zirconium compounds as basic ingredient and joinThe surface treatment capsule that the metal conditioner that closes titanium compound and obtain forms can bring higher closeClosing property. Being combined with in the two metal conditioner of zirconium compounds and titanium compound, the two joinComposition and division in a proportion example with the metal quality in compound than [the titanium quality in titanium compound: Mat]/[in zirconium compoundsZirconium quality: Maz] meter, be preferably 0.005 ~ 1, more preferably 0.01 ~ 0.43. With the gold of such scopeBelong to mass ratio [Mat/Maz] and coordinate the metal conditioner forming to form to show high adhesion moreSurface treatment capsule.
(organic compound)
Organic compound (b) be in same a part, have 2 be selected from above hydroxyl, carboxyl, phosphonate group,The compound of the one kind or two or more functional group in phosphate and sulfonic group. This organic compound (b) with byThe zirconium acyl ion (ZrO that above-mentioned the 4th group transition metal compound (a) is emitted2+) and/or titanium acyl ion (TiO2+)Deng the ionization of metal oxygen acyl, form water miscible salt or complex salt. The water miscible salt or the complex salt tool that formBe improved the effect of the stability of these metal oxygen acyl ions, therefore can make metal oxygen acyl ion playAbove-mentioned effect stablized continue, thereby can stably form can for metal surface bring height closely sealedThe tough surface treatment capsule of property. In addition, after metal conditioner is coated to metal surfaceBy carrying out heat drying etc. while removing moisture, organic compound (b) with form metal oxygen acyl ionZr and/or the combination of strong ground of Ti, have the effect that the film forming of formed surface treatment capsule is improved.
The functional group that organic compound (b) has is hydroxyl, carboxyl, phosphonate group, phosphate and sulfonic groupIn any group, in same a part of this organic compound (b), there are 2 above above-mentioned functional groups. ToolWhile having 2 above above-mentioned functional groups, can be 3 and can be also 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, 2Individual above functional group is selected from same in above-mentioned hydroxyl, carboxyl, phosphonate group, phosphate and sulfonic groupPlanting functional group, can be also different types of functional group.
The molecular weight of organic compound (b) is preferably more than 100 and below 1000, more preferably 100 withUpper and 900 below. The organic compound (b) of molecular weight within the scope of this is with in every 30 ~ 300 molecular weightThe ratio of 1 has functional group. It should be noted that, for other chemical constitution of organic compound (b)There is no particular determination.
As the concrete example of such organic compound (b), for example can enumerate: ethylene glycol, propane diols, fourMethylene glycol, diethylene glycol, dibutylene glycol, glycerine, pentaerythrite, catechol, 1,2,3-benzeneThe multivalence hydroxy compounds such as triphenol, catechin, glucose, amylopectin; Oxalic acid, malonic acid, amberThe polybasic carboxylic acids such as acid, adipic acid, maleic acid; Glycolic acid, lactic acid, glyceric acid, tartronic acid,Tartaric acid, malic acid, citric acid, pantoic acid, ascorbic acid, salicylic acid, protocatechuic acid, vanillic acid,The hydroxycarboxylic acid such as gallic acid, mandelic acid; 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxy ethylidene-1,1-bis-Phosphonic acids, ethylenediamine-N, N, N ', N '-tetra-(methylene phosphonic acid), hexamethylene diamine-N, N, N ', N '-tetra-(methyleneBase phosphonic acids), diethylenetriamines-N, N, N ', N ' ', N ' '-five (methylene phosphonic acid), 2-phosphonic acids butane-1,2,4-The organic phospho acids such as tricarboxylic acids; The organic phosphoric acids such as phytic acid, starch phosphate, glucose monophosphate.
Organic compound (b) has following effect: the zirconium acyl ion of emitting in the aqueous solution with zirconium compounds(ZrO2+) and/or the titanium acyl ion (TiO that emits in the aqueous solution of titanium compound2+) coordination, thereby improveStability in metal conditioner. In addition, utilize this metal conditioner to form surface treatment quiltWhen film, organic compound (b) thus also have with zirconium acyl ion and/or titanium acyl ion strong in conjunction with making intoThe effect that film improves. Its result, the corrosion resistance of surface treatment capsule and be arranged at this surfaceLaminated film on processing tunicle or the adaptation excellence between resin coating film.
In metal conditioner, the content of contained organic compound (b) is with the quality of organic compound (b)Ratio [the matter of the mass M a of the metallic element (Zr and/or Ti) in Mb and the 4th group transition metal compound (a)Amount ratio=Mb/Ma] count and be preferably 0.05 ~ 0.6, more preferably 0.1 ~ 0.4. By containing than scope with this qualityThere are organic compound (b) and the 4th group transition metal compound (a), can make the corrosion resistant of surface treatment capsuleErosion property and and the adaptation that is arranged between laminated film or the resin coating film on surface treatment capsule becomeWell. Mass ratio [Mb/Ma] is less than at 0.05 o'clock, may cause the film forming of surface treatment capsule to reduce,Mass ratio [Mb/Ma] is greater than at 0.6 o'clock, may cause surface treatment capsule and be arranged at this surface treatment quiltAdaptation between laminated film or resin coating film on film reduces.
(water-base resin)
Water-base resin (c) is to be selected from polyurethane resin, epoxy resin, acrylic resin, phenolic resins, poly-One kind or two or more nonionic in esters resin, polyvinyl resin and polyolefin resin orAnionic property organic compound. This organic compound is the chemical combination with anionic group or non-ionic groupThing, can stable existence in metal conditioner of the present invention, as long as obtaining desired effectThe compound of fruit, the kind to this organic compound indefinite. It should be noted that, just organicThe water-solubleization form of compound, this organic compound can be water miscible, can be also aqueous dispersionProperty (emulsion, dispersion liquid).
As polyurethane resin, can be listed below polyurethane obtaining etc.: by PEPA, polyethersThe polyalcohol such as polyalcohol, polycarbonate polyol and aliphatic polyisocyante, alicyclic isocyanateAnd/or the condensation polymer that aromatic polyisocyanate compound forms is in polyurethane resin, use poly-second twoThe such polyalcohol with polyoxyethylene chain of alcohol, polypropylene glycol is as the part of above-mentioned polyalcohol and obtainThe polyurethane arriving. For such polyurethane, by improving the importing ratio of above-mentioned polyoxyethylene chain, energyEnough realize water-solubleization or aqueous dispersion with non-ionic form.
In addition,, by following method, can obtain the water-dispersible polyurethane resin of anionic property: by how differentCyanate and polyalcohol manufacture two ends have the carbamate prepolymer of NCO, make this prepolymerReact with carboxylic acid or its reactive derivatives with more than 2 hydroxyl, must arrive two ends and there is isocyanatesThe derivative of base, then, adds triethanolamine etc. to form ionomer (triethanolamine salt),And then this ionomer is added to the water to form emulsion or dispersion liquid, and then as requiredAdd diamines to carry out chain extension.
The carboxylic acid and the reactivity that while manufacturing the above-mentioned water-dispersible polyurethane resin with anionic property, useDerivative is for importing acidic-group and make polyurethane resin be water dispersible at polyurethane resin.As used carboxylic acid, can enumerate dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid,The dimethylolalkanoic acids such as dihydroxymethyl caproic acid. In addition, as reactive derivatives, can enumerate acid anhydrides like thisHydrolyzable ester etc.
As epoxy resin, can enumerate: the epoxide with more than 2 glycidyl; HaveBisphenol-A or Bisphenol F are as the epoxide of the unit in skeleton; Or make to have 2 above shrinkThe diamines effects such as glyceryl epoxide and ethylenediamine, there is cationization and the epoxy tree that obtainsFat; Make to have bisphenol-A or Bisphenol F and have 2 as the epoxide of the unit in skeleton or otherAddition polyethylene glycol on the side chain of the epoxide of individual above glycidyl and the nonionic that obtainsEpoxy resin; Etc..
As epoxy resin, can use and there is bisphenol-A or the Bisphenol F epoxy as the unit in skeletonResin. It should be noted that, can be also that the part or all of glycidyl of this epoxy resin is through silaneModification or phosphoric acid modification and the epoxy resin that obtains.
As thering is bisphenol-A or the Bisphenol F epoxy resin as the unit in skeleton, can enumerate: byEpoxychloropropane and bisphenol-A or Bisphenol F obtain through dehydrochlorination reaction and addition reaction repeatedlyResin; By have 2 above, epoxides preferably with 2 glycidyls and bis-phenol (A,F) between through addition reaction repeatedly and the resin obtaining.
As epoxide, for example can enumerate: diglycidyl ether, the adjacent benzene two of bis-phenol (A, F)Formic acid 2-glycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester,P-hydroxybenzoic acid 2-glycidyl ester, tetrahydrochysene phthalic acid 2-glycidyl ester, hexahydrobenzene dioctyl phthalate twoEthylene oxidic ester, butanedioic acid 2-glycidyl ester, adipic acid 2-glycidyl ester, decanedioic acid two shrink sweetGrease, ethylene glycol bisthioglycolate glycidyl ether, propane diols diglycidyl ether, BDO two shrinkGlyceryl ether, 1,6-hexylene glycol diglycidyl ether, the many glycidyl ethers of D-sorbite, poly-alkyleneBase glycol diglycidyl ether class, trimellitic acid three-glycidyl ester, triglycidyl isocyanurate,Isosorbide-5-Nitrae-glycidoxy benzene, diglycidyl propylidene urea, glycerine triglycidyl group ether, three hydroxylsMethyl ethane triglycidyl group ether, trimethylolpropane tris glycidyl ether, pentaerythrite four shrinkThe triglycidyl group ether of the oxyalkylene addition product of glyceryl ether, glycerine etc. Above-mentioned epoxideCan be used singly or in combination respectively.
It should be noted that, with regard to the silane-modified degree of epoxy resin, as long as can confirm byThe degree of the effect that these modifications bring above, there is no particular restriction. Can use known silane evenConnection agent is carried out silane-modified.
As acrylic resin, can enumerate the homopolymers of acrylic monomers or copolymer and by these thirdAcrylic monomer and the copolymer that can form with the addition polymerization monomer of this acrylic monomers copolymerization. Like thisAs long as acrylic resin can be in surface conditioning agent stable existence, its polymerization methods be there is no to spyDifferent restriction.
As acrylic monomers, for example can enumerate: methyl acrylate, methyl methacrylate, acrylic acidEthyl ester, EMA, isopropyl methacrylate, n-BMA, metering systemAcid isobutyl ester, the just own ester of methacrylic acid, 2-EHA, acrylic acid, methacrylic acid,Acrylic acid 2-hydroxy methacrylate, acrylic acid hydroxy propyl ester, 2-hydroxyethyl methacrylate, methacrylic acidHydroxy propyl ester, glycidyl acrylate, GMA, acrylic acid sulphur ethyl ester, poly-Glycolmethacrylate etc. As can with the addition polymerization monomer of acrylic monomers copolymerization, canEnumerate maleic acid, itaconic acid, acrylamide, N hydroxymethyl acrylamide, DAAM, benzeneEthene, acrylonitrile, vinyl sulfonic acid etc.
As vinylite, can enumerate polyvinyl acetate, polyvinyl acetate partly-hydrolysed thing orFully saponified thing, PVP etc.
About vinyl acetate, can be with can with the monomer copolymerization of vinyl acetate copolymerization obtain poly-The resin that compound obtains through saponification. In addition, can use in the polymer after polymerization and for example importThe anionic groups such as carboxylic acid, sulfonic acid, phosphoric acid and obtain polymer-modified or import diacetone acryloylAmido, acetoacetyl, sulfydryl, silanol group etc. have the functional group of cross-linking reaction and changing of obtainingProperty polymer.
It should be noted that, as can with the monomer of vinyl acetate copolymerization, for example can enumerate: MalaysiaUnsaturated carboxylic acid and the ester classes thereof such as acid, fumaric acid, crotonic acid, itaconic acid, (methyl) acrylic acid; Ethene,The alpha-olefins such as propylene; The alkene sulfonic acids such as (methyl) propene sulfonic acid, ethionic acid, sulfonic acid malate; (firstBase) ALS, ethylene sulfonate, sodium sulfonate (methyl) acrylate, sodium sulfonate (malic acid listArrcostab), the alkene sulfonic acid alkali metal salt such as sodium disulfonate malic acid Arrcostab; N hydroxymethyl acrylamide,The monomer that acrylamide alkyl sulfonic acid alkali metal salt etc. contains amide groups; NVP, N-Vinyl pyrrolidone derivative; Etc..
As phenolic resins, can enumerate as being formed by phenols (phenol, naphthols, bis-phenol etc.) and formaldehydeLow-molecular-weight water-soluble resin or the emulsion resin of condensation polymer. Wherein, preferably there is containing from condensationThe resol of methylol.
As natural polymer, can enumerate cellulose, starch, dextrin, inulin, xanthans, tamarindGlue, tannic acid, lignin sulfonic acid etc.
As polyolefin resin, can enumerate: polypropylene, polyethylene and propylene or ethene and alpha-olefinThe polyolefin such as the copolymer forming for example, are obtained by unsaturated carboxylic acid (acrylic acid, methacrylic acid) modificationImproved polyalkene or the copolymer that forms of ethene and acrylic acid (methacrylic acid). In addition, all rightIt is the copolymer obtaining 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 to neutralize the carboxylic acid importing on polyolefin resin.
For these nonionics or anionic property water-base resin (c), the one-tenth having as itselfThe adhesive effect that film brings, comprising: (1) can be to by the 4th group transition metal compound (a) with haveThe surface treatment capsule that organic compounds (b) forms is given flexibility; And, the reaction of (2) water-base resin (c)Property functional group reacts with the 4th group transition metal compound (a) or metallic compound (b), thereby glues stronglyBe fixed in surface treatment capsule. Therefore, the above-mentioned effect having by water-base resin (c), contains water-based treeThe metal conditioner of fat (c) can form and can tolerate the more tough surface treatment capsule of forcing work.
As the water-base resin (c) of these nonionics or anionic property, can enumerate water-soluble resin, processSelf-emulsifying or utilize the water-based such as water-based emulsion, aqueous liquid dispersion of the forced emulsification that emulsifying agent carries out crosslinkedProperty resin or aqueous high molecular resin. Wherein, can preferably adopt number-average molecular weight to be less than 1000The effect of heat, ultraviolet ray or electron beam etc. that monomer or oligomer apply in the time forming tunicle issues is conigenous friendshipThe crosslinkable resin of connection and then generation producing high-molecular; Or number-average molecular weight is less than 1000 monomer or oligomericThing reacts with other crosslinking agent and the crosslinkable resin of producing high-molecular occurs. In addition, can also adopt number equalMolecular 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 have cross-linking reaction functional groupResin.
The content of the water-base resin (c) containing in metal conditioner is with the mass M c of water-base resin (c)Ratio [quality with the mass M a of the metallic element (Zr and/or Ti) in the 4th group transition metal compound (a)Ratio=Mc/Ma] meter be preferably 0.05 ~ 1.5, more preferably 0.1 ~ 0.8. By containing than scope with this qualityWater-base resin (c) and the 4th group transition metal compound (a), can give soft to gained surface treatment capsuleWhen soft and more excellent film forming, formation can tolerate the more tough surface of forcing workReason tunicle.
(metallic compound)
Metallic compound (d) is to have a kind or 2 that is selected from Zr, Ti, V, Mo, W, Ce and NbPlant the water soluble compound of above metallic element.
In this metallic compound (d), the metallic compound with the metallic element that is selected from Zr and Ti is at waterIn solution, can not emit zirconium acyl ion (ZrO2+) or titanium acyl ion (TiO2+) metallic compound, it is different fromAbove-mentioned the 4th group transition metal compound (a). As such metallic compound (d), can enumerate for example fluorineZirconic acid, ammonium fluozirconate, potassium fluorozirconate, sodium fluozirconate, fluotitanic acid, (the チ タ Application acid of metatitanic acid hydrofluoric acid ammoniumThe sour ア Application モ ニ ウ system of Off Star water element), potassium fluotitanate, titanium sodium fluoride etc.
There is the metal that is selected from the one kind or two or more metallic element in V, Mo, W, Ce and NbCompound is salt, complex compound or the complex of these metallic elements. Specifically for example can enumerate: five oxygenChanging the oxidation numbers such as vanadium, metavanadic acid, ammonium metavanadate, sodium metavanadate and vanadium oxytrichloride is the vanadium chemical combination of 5 valencysThing; Three vanadium oxides, vanadium dioxide, vanadic sulfate, acetylacetone,2,4-pentanedione vanadyl, vanadium acetylacetonate, tri-chlorinationThe oxidation number of the vanadium such as vanadium and phosphovanadomolybdic acid is the vfanadium compound of 5 valencys, 4 valencys or 3 valencys; Molybdic acid, molybdic acidThe molybdenum compounds such as ammonium, sodium molybdate and phosphomolybdic acid compound (for example, ammonium phosphomolybdate, sodium phosphomolybdate etc.);The tungsten compounds such as metatungstic acid, ammonium metatungstate, 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 chloride; Fluoridize the niobium such as niobium and niobium phosphateCompound; Etc..
The metallic compound that adds the specified rate in metal conditioner to can be directed to by the 4th familyTransistion metal compound (a) in conjunction with and form surface treatment capsule in, thereby further improve corrosion resistanceAnd and laminated film between adaptation. Its result, even in the corruption of distilling processing, electrolyte impregnatingIn erosion environment, also can keep excellent adaptation.
With regard to the content of metallic compound contained in metal conditioner (d), with metallic compound (d)Mass M d and the 4th group transition metal compound (a) in the mass M a of metallic element (Zr and/or Ti)Ratio [mass ratio=Md/Ma] meter, be preferably 0.05 ~ 2.0, more preferably 0.1 ~ 1.5. By with this matterAmount contains metallic compound (d) and the 4th group transition metal compound (a) than scope, can prevent metal watchAdaptation between face and gained surface treatment capsule reduces, and prevents that corrosive medium from immersing metal surface and leadingCausing corrosion resistance reduces. Especially there is following advantage: can prevent from occurring metal watch in high humidity environmentThe reduction of the adaptation between face and gained surface treatment capsule, and then prevent that gained surface treatment capsule from becomingCrisp, improve the flexibility of surface treatment capsule self, even if it also can not occurred through processing subsequentlyThe reduction of the adaptation between gained surface treatment capsule and laminated film.
(solvent)
Operability when making metal conditioner of the present invention coat metal material surface is goodGood, can contain as required various solvents. Such solvent is taking water as main body, but according to improving surfaceThe drying property of processing tunicle etc. needs, and also can be used in combination the water-soluble of alcohols, ketone or cellosolve classProperty organic solvent.
As solvent, for example can enumerate: water; The alkane solvents such as hexane, pentane; The virtue such as benzene, tolueneFragrant same clan solvent; The alcohols solvents such as ethanol, n-butyl alcohol, ethyl cellosolve; Oxolane, diox etc.Ether solvent; The esters solvent such as ethyl acetate, butoxy acetic acid ethyl ester; Dimethyl formamide, N-methylThe amide solvents such as pyrrolidones; The sulfone kind solvents such as dimethyl sulfoxide (DMSO); The phosphoric acid such as HPTAmide solvent; Etc.. Can use a kind in above-mentioned each solvent, also two or more can be mixedUse. In these solvents, based on to environment aspect, the favourable reason of economic aspect, preferred water.
(other additive)
Do not destroy purport of the present invention and by the scope of film properties in, metal conditioner of the present inventionCan contain surfactant, defoamer, levelling agent, antibacterial mildew inhibitor, colouring agent, curing agent etc. SeparatelyOutward, do not destroy purport of the present invention and by the scope of film properties in, can also add to improve surfaceProcess organic being cross-linked such as methylolation melamine, carbodiimide and isocyanates of the corrosion resistance of tunicleAgent, and for improving γ-glycidoxy propyl-triethoxysilicane, the γ-glycidoxy of adaptationPropyl-triethoxysilicane, γ aminopropyltriethoxy silane and N-beta-aminoethyl-gamma-amino propyl groupThe silane couplers such as trimethoxy silane.
(preparation method of metal conditioner)
The manufacture method of metal conditioner of the present invention there is no particular restriction. For example, can be as followsPreparation: by the 4th group transition metal compound (a) and organic compound (b) and the water-base resin optionally containing(c), the mixing such as metallic compound (d), other additive, solvent, utilize the mixers such as blender to carry outFully mix, thereby prepare metal conditioner.
[metal material]
As shown in Figure 1, metal material 10 of the present invention has matrix material metal 1 and by of the present inventionMetal conditioner is coated on the surface of this matrix material metal 1 and the surface treatment capsule 2 that forms.In this application, the metal material 1 that surface treatment capsule 2 is not set is called to " matrix material metal 1 ",The metal material that is provided with surface treatment capsule 2 on this matrix material metal 1 is called to " metal material10 ". It should be noted that, shown in Fig. 1 is to be formed with at a side surface of matrix material metal 1The example of surface treatment capsule 2 and resin molding 3 or resin coating film 3, but also can be at matrix materialThe two sides of metal 1, also form surface treatment capsule 2 on opposite side surface, and then resin molding 3 is setOr resin coating film 3.
Described " having " refers to also can have except matrix material metal 1 and surface treatment capsule 2Other formation. For example, on surface treatment capsule 2, can have the resin molding 3 that obtains through lamination orThe resin coating film 3 forming through coating. Described " coating " refer to, by above-mentioned painting process at matrix materialThe surface-coated metal conditioner of material metal 1. Because surface treatment capsule 2 is by the invention described aboveMetal conditioner be coated on matrix material metal 1 and form, therefore have excellent closely sealedProperty and the closely sealed retentivity of drug-resistant.
Shape and structure etc. for matrix material metal 1 there is no particular restriction, can enumerate for example tabular,Paper tinsel shape etc. In addition, there is no particular restriction for the kind of matrix material metal 1, can adopt various metals.Can enumerate for example can be applicable to the food main body of tank or cover material, containers for food use, dry cell container,The metal material of the exterior material of secondary cell etc., but be not limited to these materials, can use canBe applied to the metal material of extensive use. Particularly, can enumerate and can be used as following lithium rechargeable batteryThe metal material of exterior material, the exterior material of described lithium rechargeable battery be recently for mobile phone,The portable exterior material with lithium rechargeable battery in electronic notebook, notebook computer or video camera etc.Material, the lithium rechargeable battery that uses as the drive energy of electric automobile or hybrid vehicle exteriorMaterial. In these metal materials, can preferably use and can form surface treatment capsule 2 energy on its surfaceEnough on surface treatment capsule 2 laminated resin film 3 grades and can implement deep-draw processing subsequently, subtractThe metal material that the harsh shaping such as thin processing or stretch-draw processing is processed.
As such metal material, for example can enumerate: the copper products such as fine copper, copper alloy, fine aluminium, aluminiumThe nickel materials such as the iron materials such as the aluminums such as alloy, ordinary steel, steel alloy, pure nickel, nickel alloy etc.
As copper alloy, preferably use the copper alloy that contains the above copper of 50 quality %, can use for example yellowCopper etc. As other alloying component beyond copper removal in copper alloy, can enumerate for example Zn, P, Al, Fe,Ni etc. As aluminium alloy, preferably use the aluminium alloy that contains the above aluminium of 50 quality %, for example can useAl-Mg is associated gold etc. As the alloying component of other except aluminium in aluminium alloy, for example can enumerate Si,Fe, Cu, Mn, Cr, Zn, Ti etc. As steel alloy, preferably use and contain the above iron of 50 quality %Steel alloy, can use such as stainless steel etc. As other alloying component beyond deironing in steel alloy,Can enumerate such as C, Si, Mn, P, S, Ni, Cr, Mo etc. As nickel alloy, preferably use and containThere is the nickel alloy of the above nickel of 50 quality %, can use such as Ni-P alloy etc. As removing nickel in nickel alloyOther alloying component in addition, can enumerate for example Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo,P etc.
Matrix material metal 1 also can or have at metal material, ceramic material beyond above-mentioned metal materialThe surface of machine material forms the tunicle that comprises above-mentioned metallic element. Such metal tunicle can for example pass throughThe methods such as plating, evaporation, coated (clad) form. In addition, for the shape of matrix material metal 1,There is no particular restriction for structures etc., can use the metal material of for example tabular or paper tinsel shape.
Above, according to metal material 10 of the present invention, because it has surface treatment quilt as aboveFilm 2, even implement deeply therefore form resin molding 3 or resin coating film 3 on surface treatment capsule 2 afterDraw in the situation of the harsh shaping processing such as processing, attenuate processing or stretch-draw processing, and further sudden and violentBe exposed to acid etc. in situation under, also can prevent that resin molding 3 or resin coating film 3 are from metal material 10Peel off.
[surface treatment method]
Using the metal surface treating method of metal conditioner is by by above-mentioned Treatment of Metal SurfaceAgent is coated metal surface and is dried to obtain adhesion amount is 10 ~ 3000mg/m2The side of tunicleMethod, the method comprises following operation: metal conditioner is coated to the painting of matrix material metal surfaceCloth operation; With after painting process, be dried without washing, thereby form surface treatment capsuleDrying process.
It should be noted that, for the surface of metal material, can carry out as required in advance degreasing, clearWash. Degreasing agent can be selected from be suitable for the various materials of metal matrix material. In addition, cleaning fluid is commonMake water, but also can be water-soluble solvent or aqueous surfactant solution etc. In addition, for degreasing sideMethod, cleaning method there is no particular restriction, preferably adopt spray-on process or infusion process etc.
(painting process)
Painting process is the operation of metal conditioner being coated to matrix material metal surface. For paintingThe method of cloth there is no particular restriction, can adopt for example spraying, dip-coating, roller coat, curtain painting, spin coating or byThe method that these Combination of Methods obtain. The service condition of metal conditioner there is no particular restriction. For example,When coating, the liquid temperature of metal conditioner is preferably in the scope of 10 DEG C ~ 50 DEG C. Metal conditionerBe generally 0.5 second with the time of contact of metal surface ~ about 180 seconds. Metal conditioner of the present inventionFor the inorganic agent of application type, therefore, after contacting with metal conditioner, enter without cleaningRow is described later dry, thereby forms Treatment of Metal Surface tunicle.
(drying process)
Drying process is after painting process, is dried, thereby forms surface treatment without washingThe operation of tunicle. Baking temperature can be set as the temperature adapting to used solvent phase. For example, useIn the situation of water as solvent, baking temperature is preferably the scope of 60 DEG C ~ 250 DEG C. This temperature range canTo change arbitrarily according to the kind of resinous principle in above-mentioned scope, but more preferably 80 ~ 200 DEG C.Drying device there is no particular determination, can adopt batch (-type), continous way or heated air circulation type drying oven, transmissionBelt hot-air drying stove or used electromagnetic induction heating furnace of IH heater etc., its air quantity and wind speedDeng setting arbitrarily.
For the surface treatment capsule obtaining thus, even if further form resin molding (laminated film) thereonOr after resin coating film, implement the situation of the harsh shaping processing such as the processing of deep-draw processing, attenuate or stretch-draw processingUnder, and be further exposed to acid etc. in the situation that, also can prevent by laminated film or resin coating filmThe resin coating forming is peeled off.
The thickness of gained surface treatment capsule is preferably 0.01 μ m ~ 1 μ m, more preferably0.02 μ m ~ 0.05 μ m. By making the thickness of surface treatment capsule within the scope of this, can further improveThe closely sealed retentivity of the adaptation of surface treatment capsule and drug-resistant.
Embodiment
Below, in conjunction with the embodiments and comparative example the present invention is described in more detail. The present invention is notBe subject to the restriction of following embodiment. It should be noted that, following " part " refers to " mass parts ", " quality % "With " % by weight " synonym, following be sometimes also expressed as in the situation that being not particularly limited " % ". " ppm "With " mg/L " synonym.
[metal material]
Metal material (matrix material metal) as matrix 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: (thick 0.3mm, nickel plating thickness 2 μ are m) for electronickelling copper coin
From these metal materials, the metal material shown in " matrix material " hurdle of option table 1 ~ table 4, standardThe matrix material metal of standby embodiment 1 ~ 98 and comparative example 1 ~ 18.
[metal conditioner]
By the 4th group transition metal compound (a) and organic compound (b) and visual need as followsThe water-base resin (c) using and metallic compound (d) combination, using water as solvent, prepared table 1 ~ tableThe metal conditioner of embodiment 1 ~ 98 shown in 4 and the metal conditioner of comparative example 1 ~ 13.It should be noted that, " concentration " in table represents that in metal conditioner, above-mentioned each compound is sharedVolatile amount concentration (quality %). 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: zirconyl nitrate
At1: dioxalic acid oxygen titanium two ammoniums
At2: hydroxyl lactyl-lactic acid closes titanium [organic compound (b)]
B1: diethylene glycol (molecular weight: 106, functional group content: 53.1gsolid/eq(gsolid/eq isThe unit of azoles quinoline equivalent))
B2: pentaerythrite (molecular weight: 136, functional group content: 34gsolid/eq)
B3: catechol (molecular weight: 110, functional group content: 55.1gsolid/eq)
B4: tartaric acid (molecular weight: 150, functional group content: 37.5gsolid/eq)
B5:L-ascorbic acid (molecular weight: 175, functional group content: 43.8gsolid/eq)
B6: glycolic acid (molecular weight: 78, functional group content: 38.0gsolid/eq)
B7:1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid (molecular weight: 206, functional group content: 68.7gsolid/eq)
B8: phytic acid ammonium (molecular weight: 738, functional group content: 123.0gsolid/eq)
B9: poly (molecular weight: 3000, functional group content: 58gsolid/eq)
B10: polyethylene glycol (molecular weight: 800, functional group content: 400gsolid/eq)
[water soluble polymer (c)]
(c1: polyurethane resin-anionic property)
Make PEPA (adipic acid/3-methyl isophthalic acid, 5-pentanediol, number-average molecular weight: 1000, functional groupNumber: 2, hydroxyl value: 112.2) 100 parts, 3 parts of trimethylolpropanes, 25 parts of dihydromethyl propionic acids and85 parts of reactions in MEK (methyl ethyl ketone) of IPDI, obtain carbamate pre-Polymers. In this carbamate prepolymer, mix 9.4 parts of triethylamines, and drop in water, make above-mentioned ammoniaCarbamate prepolymer is scattered in water, utilizes ethylenediamine that this prepolymer is extended, thus the dispersion of obtaining.Methyl ethyl ketone is removed in distillation, and the polyurethane resin water-based that obtains containing 30 quality % nonvolatile component is dividedA prose style free from parallelism. The acid number that is scattered in the polyurethane that contains carboxyl in gained polyurethane resin aqueous dispersion is49(KOHmg/g)。
(c2: epoxy resin-anionic property)
Add orthophosphoric acid 85g and propylene glycol monomethyl ether 140g, and slowly add epoxide equivalent 250Bisphenol A type epoxy resin 425g, in 80 DEG C of reactions 2 hours. After reaction finishes, below 50 DEG C,Slowly add 29 quality % ammonia spirit 150g, and then add water 1150g, obtain acid number 35, solidIn the ammonia of the phosphoric acid modification epoxy resin of body constituent concentration 25 quality % and product.
(c3: acrylic resin-nonionic)
Adopt following monomer composition: " methyl methacrylate (molecular weight: 100) 20 parts, acrylic acidButyl ester (molecular weight: 128) 40 parts, methacrylic acid 2-hydroxy propyl ester (molecular weight: 144) 10 parts, benzene secondAlkene (molecular weight: 104) 10 parts, methacrylic acid N, N-dimethylamino propyl ester (molecular weight: 175) 20Part ". Acrylic resin c's is synthetic as follows: by reactive emulsifier " AdekaReasoapNE-20 " (strainThe ADEKA of formula commercial firm system) and non-ionic emulsifier " Emulgen840S " (Kao Corp's system) with 6:In 4 100 parts of the 10 quality % emulsifier aqueous solutions (S-1) that mix, mix above-mentioned monomer, and utilizeHomogenizer carries out emulsification in 10 minutes with 5000rpm, obtains monomer emulsion (ER). Then, to assemblingThere are mixer, reflux condenser, temperature to take into account in four neck flasks of monomer supply pump and add mentioned emulsifier150 parts of the aqueous solution (S-1), are held in 40 ~ 50 DEG C, by the 5 quality % aqueous solution (50 parts) of ammonium persulfateAnd above-mentioned monomer emulsion (ER) joins in dropping funel respectively, and this dropping funel is installed on to flaskOther mouthful of neck, utilize within approximately 2 hours, drip, and temperature be warming up to 60 DEG C, carried out approximately 1Hour stir. Be cooled to while stirring room temperature, obtain the emulsified solution of acrylic resin.
(c4: acrylic resin-nonionic)
The aqueous solution (nonvolatile component concentration 22.0 quality %, the viscosity of acrylamide polymer are used90mPa·s)。
(c5: phenolic resins-nonionic)
Use the resol (dimer) with methylol.
(c6: mylar-anionic property)
Utilize following method to synthesize anion by the condensation reaction of following alcohol composition and following sour compositionThe mylar (solid constituent (NVC.) 30%) of property, described alcohol composition comprises ethylene glycol (90mol%) and threeHydroxymethyl-propane (10mol%), described sour composition comprises M-phthalic acid (40mol%), terephthalic acid (TPA)(41mol%), Sodium Dimethyl Isophthalate-5-sulfonate (2mol%) and trimellitic anhydride (17mol%). ?Be provided with the complete sour composition that adds 1mol in the 1000mL round-bottomed flask of Clarkson pipe and aerial condenser,The full alcohol composition of 2mol and catalyst (calcium acetate: 0.25g, tetrabutyl titanate: 0.1g), to entering in systemRow nitrogen replacement, and be heated to 180 DEG C, content is melted. Then, make to bathe temperature rise to 200 DEG C,Carry out adding thermal agitation in approximately 2 hours, carried out esterification or ester exchange reaction. Then, make to bathe temperature rise to 260DEG C, after approximately 15 minutes, make to be decompressed to 0.5mmHg in system, carry out reaction (polycondensation reaction) in approximately 3 hours.After reaction finishes, naturally cooling in the situation that importing nitrogen, take out content. In the resin taking outAdd and can make final pH reach 6 ~ 7 appropriate ammoniacal liquor (about water, to adopt and make solid constituent reach 25%Amount), and carry out adding thermal agitation in 2 hours in autoclave, at 100 DEG C, obtained water-based emulsion resin.It should be noted that, described " solid constituent " refers to and evaporates into the composition grading except solvent etc.
(c7: polyvinyl alcohol-nonionic)
Use saponification degree: 99%, viscosity: 12mPaS, acetoacetylation degree: 9.8%, averageMolecular weight: 50000 acetoacetylation polyvinyl alcohol.
(c8: polyolefin-anionic property)
In four neck flasks, drop into propylene-ethylene-alpha olefin copolymer (propylene composition: 68 % by mole, etheneComposition: 8 % by mole, butylene composition: 24 % by mole, weight average molecular weight: 60,000) 100 parts, Malaysia1 part of 10 parts, acid anhydrides, 10 parts of methyl methacrylates and cumyl peroxide, carry out 2 in 180 DEG CHour stir, make its reaction. Obtained weight average molecular weight and be 45,000, the graft weight of maleic anhydride isThe modified polyolefin resin composition of 8.4 % by weight. Then, utilize paddle to make above-mentioned improved polyalkene10 parts, 100 parts, 10 parts of dimethylethanolamines and polyethylene oxide alkyl ethers sulfate in four neck flasks,Uniform stirring under the condition of 100 DEG C, 2 hours, after melting, adds the ion exchange water 300 of 90 DEG CPart continuation stirs 1 hour, has prepared the aqueous resin composition of pH8.0.
[metallic compound (d)]
The water soluble metallic compound (d) using is as follows.
D1: fluorine zirconic acid
D2: ammonium molybdate
D3: vanadium acetylacetonate
[making of material for test]
For the each matrix material shown in table 1 ~ table 4, utilize Finecleaner359E (NihonThe alkali cleaner that Parkerizing Co., Ltd. manufactures) 3% aqueous solution to carry out spraying in 1 minute in 65 DEG C de-After fat, wash clean surface. Then, in order to make the moisture evaporation of substrate material surface, in80 DEG C have been carried out 1 minute heat drying. Use #3SUS wheat to strangle rod, utilize excellent painting method by table 1 ~ table 4Shown embodiment 1 ~ 98 and the metal conditioner of comparative example 1 ~ 13 are coated through cleaning by degreasingSubstrate material surface, and in heated air circulation type drying oven in 180 DEG C dry 1 minute, thereby at matrixThe surface of material has formed surface treatment capsule. In addition, for the base of the comparative example 14 ~ 18 shown in table 4Body material after degreasing similar to the above, washing, carry out heat drying and the material that obtains, also enterGo test.
It should be noted that, in table 1 ~ table 4, Maz represents the zirconium quality in zirconium compounds, MatRepresent the titanium quality in titanium compound, Ma represents the metal (Zr in the 4th group transition metal compound (a)And/or Ti) quality, Mb represents the quality of organic compound (b), Mc represents the matter of water-base resin (c)Amount, Md represents the quality of metallic compound (d).
For the surface treatment that utilizes the metal conditioner of embodiment 1 ~ 98 and comparative example 1 ~ 13 to formThe matrix material of tunicle and comparative example 14 ~ 18, utilizes heat lamination as follows or dry lamination foldedLayer polypropylene screen.
(heat lamination)
Then, use #8SUS wheat to strangle rod, utilize excellent painting method by the dispersion liquid (Mitsui of sour modified polypropeneKCC's system, " R120K ", nonvolatile component concentration: 20%) coat the formation of matrix materialAfter having on the face of surface treatment capsule, in heated air circulation type drying oven in 200 DEG C dry 1 minute,Form thus bond layer. Then, by PP film (the Tohcello strain of this bond layer and thick 30 μ mFormula commercial firm system, " CPPS ") hot pressing 10 minutes under 190 DEG C, 2MPa, manufacture thus polypropyleneFilm lamination matrix material.
(dry lamination)
Use #8SUS wheat to strangle rod, utilize excellent painting method to be coated with polyurethanes dry lamination bonding agent(Toyomorton Co., Ltd. system, " AD-503/CAT10 ", nonvolatile component concentration: 25%), thenIn heated air circulation type drying oven in 80 DEG C dry 1 minute, formed bond layer. Then, shouldThe un-stretched polypropylene film (two chemical industry Co., Ltd. of village systems, " FCZX ") of bond layer and 30 μ mCorona discharge Treatment face under 100 DEG C, 1MPa, carry out after pressing, in 40 DEG C of slakings 4 days, thusManufacture polypropylene screen lamination matrix material.
Then, utilize drawing attenuated processing experiment above-mentioned each poly-to what manufacture by heat lamination or dry laminationPropylene film lamination matrix material has carried out deep-draw processing. To being die-cut into the above-mentioned lamination base of diameter 160mmBody material carries out drawing processing (the 1st time), has made the cup of diameter 100mm. Then, again by this cupDrawing processing (the 2nd time) is to diameter 75mm, and then drawing processing (the 3rd time) becomes diameter 65mm, systemMake the tank as test material. It should be noted that, the 1st drawing processing, the 2nd drawing addAttenuate (thin-walled property part) rate of work, the 3rd drawing processing is respectively 5%, 15%, 15%.
[performance evaluation]
For each polypropylene screen lamination matrix material being carried out to initial stage adaptation after deep-draw processing, durable closeClosing property, the bonding retentivity of electrolyte resistance and liquid stabilising are evaluated as described below.Its result is as shown in table 5 ~ table 8.
(initial stage adaptation)
Carry out the evaluation of initial stage adaptation with material for the test after deep-draw processing. Can makeMake tank, the peeling off of film do not occur, the situation of initial stage adaptation excellence is denoted as " 3 points ", will have part film to send outGive birth to situation about peeling off and be denoted as " 2 points ", the situation that whole face peels off has been occurred film to and be denoted as " 1 point ". In addition,In 3 points, peel off not observing completely, especially outward appearance excellence, initial stage adaptation are very excellentSituation is denoted as " 4 points ".
(durable adaptation)
For the test material after deep-draw processing, to real in the atmosphere of heating steam under pressureExecute the material after distillation test and carried out the evaluation of durable adaptation. Distillation test is used commercially available sterilizingDevice (autoclave) has carried out processing for 1 hour in the heating steam under pressure atmosphere of 125 DEG C. Then,Scratch face with the tip of tweezers, the situation about peeling off that film does not occur is completely denoted as to " 6 points ", will occurPeel off but the very high situation of resistance is denoted as " 5 points ", peel off having occurred but the high situation of resistanceBe denoted as " 4 points ", situation so not high resistance but that can reach realistic scale is denoted as to " 3 points ", will be with non-The situation that normal weak power can be peeled off film is denoted as " 2 points ", will situation about the peeling off note of film occurDo " 1 point ".
(the bonding retentivity of electrolyte resistance)
For the test material after deep-draw processing, to warp in electrolyte solution for lithium ion secondary batteryCross the material after immersion test and carried out the evaluation of the bonding retentivity of electrolyte resistance. Specific as follows: will be throughCross test material soaking after deep-draw processing at the ion exchange water that has been filled in interpolation in closed containerElectrolyte solution for lithium ion secondary battery (the electrolyte: 1M-LiPF of 1000ppm6, solvent: EC:DMC:DEC=1:1:1 (volume %)) in, then put in the thermostat of 60 DEG C 7 days. It should be noted that," EC " represents ethylene carbonate, and " DMC " represents dimethyl carbonate, and " DEC " represents diethyl carbonate.
Then, take out test material, in ion exchange water, flood 1 minute, undertaken by shakeClean, then in heated air circulation type drying oven, be dried 10 minutes in 100 DEG C. Then, with tweezersTip scratches face, and the situation about peeling off that film does not occur is completely denoted as to " 6 points ", by having occurred to peel off,But the situation that resistance is very high is denoted as " 5 points ", peel off having occurred but the high situation of resistance is denoted as " 4 points ",Situation so not high resistance but that can reach realistic scale is denoted as to " 3 points ", will be with very weak powerThe situation that film is peeled off is denoted as " 2 points ", and the situation about peeling off that film has occurred is denoted as to " 1 point ".
(medicament stability)
For medicament stability, the long-time stability of metal conditioner are evaluated. Concrete asUnder: by each the metal conditioner of the embodiment shown in table 1 ~ table 41 ~ 98 and comparative example 1 ~ 13200mL is sealing into respectively in the plastic containers (Port リ container) of 300mL, for the gas atmosphere at 20 DEG CEnclosing medicament (metal conditioner) state leaving standstill after 2 weeks evaluates. To not occur solid completelyChange, separate and precipitation situation be denoted as " 3 points ", will only confirm precipitation but do not occur solidify and separate,And the situation that can reach realistic scale is denoted as " 2 points ", be denoted as " 1 by observing the situation of solidifying and separatePoint ".
[table 5]
[table 6]
[table 7]
[table 8]
As shown in table 5 ~ table 8, can confirm to use metal conditioner and the Metal Substrate of embodiment 1 ~ 98Body material is processed and the belt surface that obtains is processed the metal material of tunicle, no matter adopts heat lamination stillDry lamination, all has very excellent initial stage cementability and the bonding retentivity of electrolyte resistance.
Claims (5)
1. a 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 in the aqueous solution, emits zirconium acyl ion ZrO2+ZrCompound and emit titanium acyl ion TiO in the aqueous solution2+Ti compound,
Described organic compound (b) in same a part, have 2 be selected from above hydroxyl, carboxyl, phosphonate group,One kind or two or more functional group in phosphate and sulfonic group,
The middle metal of the mass M b of described organic compound (b) and described the 4th group transition metal compound (a)The ratio Mb/Ma of mass M a is 0.05～0.6.
2. metal conditioner according to claim 1, wherein, described organic compound (b)Molecular weight be more than 100 and below 1000, this organic compound (b) is the molecular weight with every 30～300In the ratio of 1 there is the compound of described functional group.
3. metal conditioner according to claim 1 and 2, wherein contains and is selected from polyurethaneResin, epoxy resin, acrylic resin, phenolic resins, polyester resin, polyvinyl resin andThe water-base resin (c) of the one kind or two or more nonionic in polyolefin resin or anionic property.
4. metal conditioner according to claim 1 and 2, wherein contain there is the Zr of being selected from,The metallic compound (d) of the one kind or two or more metallic element in Ti, V, Mo, W, Ce and Nb.
5. a metal material, it has the surface conditioning agent described in any one in claim 1～4The surface treatment capsule of coating metal surface and form.
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| Application Number | Priority Date | Filing Date | Title |
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| 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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| JP (1) | JP5744654B2 (en) |
| KR (1) | KR101610428B1 (en) |
| CN (1) | CN102877055B (en) |
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| CA2931667C (en) | 2013-11-29 | 2020-03-24 | Nisshin Steel Co., Ltd. | Method for treating surface of zinc-aluminum-magnesium alloy-plated steel sheet |
| KR20150071648A (en) * | 2013-12-18 | 2015-06-26 | 니혼 파커라이징 가부시키가이샤 | Aqueous metal surface treatment agent, metal surface treatment coating film and metal material having a metal surface treatment coating film |
| JP6526950B2 (en) * | 2013-12-18 | 2019-06-05 | 日本パーカライジング株式会社 | Water-based metal surface treatment agent, metal surface treatment film and metal material with metal surface treatment film |
| 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 |
| JP6643808B2 (en) * | 2015-03-19 | 2020-02-12 | 大日製罐株式会社 | Metal can manufacturing method |
| JP2017141485A (en) * | 2016-02-09 | 2017-08-17 | 日本パーカライジング株式会社 | Surface treatment agent, surface treatment film manufacturing method, aluminum material or aluminum alloy material having surface treatment film |
| US11293104B2 (en) * | 2017-06-27 | 2022-04-05 | Bulk Chemicals, Inc. | Inorganic non-chrome aqueous treatment composition and process for coating metal surfaces |
| JP6574973B1 (en) * | 2018-10-09 | 2019-09-18 | サイデン化学株式会社 | RESIN EMULSION FOR METAL SURFACE TREATMENT, METAL SURFACE TREATING AGENT, SURFACE TREATED METAL MATERIAL AND ITS MANUFACTURING METHOD, AND RESIN EMULSION MANUFACTURING METHOD |
| KR102692287B1 (en) * | 2019-05-07 | 2024-08-05 | 현대자동차주식회사 | Method of improving adhestion strengths between the heterogeneous materials of metal and resin |
| JP7303048B2 (en) * | 2019-06-28 | 2023-07-04 | 日本パーカライジング株式会社 | copper clad laminate |
| 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 |
| JP7451118B2 (en) * | 2019-09-11 | 2024-03-18 | 日本製紙株式会社 | Modified polyolefin resin |
| EP4072853A4 (en) * | 2019-12-12 | 2024-05-22 | Nelumbo Inc. | Functionalized textile compositions and articles |
| EP4136174A4 (en) * | 2020-04-15 | 2023-12-20 | Henkel AG & Co. KGaA | Anti-blackening coating composition |
| CN115216760B (en) * | 2022-06-23 | 2024-01-16 | 安徽舜邦精细化工有限公司 | Slag-free coating agent |
| CN115613025B (en) * | 2022-10-28 | 2024-09-24 | 江苏胜达科技有限公司 | High-efficiency acid-free pretreatment process for bead wire |
| CN115874186B (en) * | 2022-12-05 | 2023-07-14 | 诺泰生物科技(合肥)有限公司 | Preparation method and application of water-based siloxane aluminum copper corrosion inhibitor |
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| 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 |
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| JPH09268376A (en) * | 1996-04-02 | 1997-10-14 | Nippon Steel Corp | Production of coated steel tube |
| JP3851106B2 (en) * | 2000-05-11 | 2006-11-29 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
| JP5447218B2 (en) * | 2009-07-06 | 2014-03-19 | 新日鐵住金株式会社 | Surface-treated plated steel sheet and surface treatment liquid |
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| 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 |
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| Publication number | Publication date |
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| CN102877055A (en) | 2013-01-16 |
| KR101610428B1 (en) | 2016-04-07 |
| TW201317395A (en) | 2013-05-01 |
| KR20130009702A (en) | 2013-01-23 |
| JP5744654B2 (en) | 2015-07-08 |
| JP2013023705A (en) | 2013-02-04 |
| TWI521094B (en) | 2016-02-11 |
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