CN103339210A - Metal surface treatment composition - Google Patents

Metal surface treatment composition Download PDF

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Publication number
CN103339210A
CN103339210A CN2012800076086A CN201280007608A CN103339210A CN 103339210 A CN103339210 A CN 103339210A CN 2012800076086 A CN2012800076086 A CN 2012800076086A CN 201280007608 A CN201280007608 A CN 201280007608A CN 103339210 A CN103339210 A CN 103339210A
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resin
metal
weight
compound
composition
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CN103339210B (en
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和智大介
屋部幸诚
原真纯
冈田荣作
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
    • C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Wood Science & Technology (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Paints Or Removers (AREA)

Abstract

[Problem] To provide a means for forming on a metal material a film for imparting sufficient corrosion resistance without pretreatment such as zinc phosphate-based conversion coatings. [Solution] A metal surface treatment composition which is used in an energization method having multiple stages in the same bath and which contains Bi ions and a resin emulsion in which at least one type of cationic resin is dispersed in water, wherein the zeta potential of the aforementioned resin emulsion in a pH5-pH9 aqueous medium is +40mV to +100mV.

Description

The metal finishing composition
Technical field
The present invention relates to a kind ofly can form the metal surface treating composition of the epithelium that can give excellent erosion resistance and appearance of film and use its metal surface treating method metallic substance, particularly complex-shaped metal constituting body.
Background technology
In the past, as giving the method that excellent erosion resistance is used to various metallic substance, particularly complex-shaped metal constituting body, the galvanic deposit that has high covering power usually applied.But, only applying the electrodeposition coating get by galvanic deposit, majority can not obtain desirable erosion resistance, so the zinc phosphate of application standard system changes into the coated surface processing of the chemical conversion type of processing etc. before galvanic deposit applies.
Galvanic deposit applies and can roughly be divided into: by in the water-borne coatings that contains the anionic property resin emulsion coated thing being carried out anode electrolysis the anionic electrodeposition deposition of separating out of filming is applied, by in the water-borne coatings that contains the resin cation (R.C.) emulsion, coated thing being carried out catholyte the cationic electrodeposition of separating out of filming is applied, but need not in electrolysis treatment to worry that base metal cationic electrodeposition of stripping in coating is coated with the erosion resistance that is beneficial to the Ferrious material material and improves, for the body of a motor car of conduct based on the metal constituting body of ferrous material, trolley part, family's electrical article, material of construction etc. are being extensive use of cationic electrodeposition and are applying
The history that cationic electrodeposition is coated on the market is long, once by cooperating chromium cpd, lead compound to guarantee rust-preventing characteristic.But, even it is also insufficient to do rust-preventing characteristic like this, so must carry out the substrate processing that zinc phosphate system changes into processing etc.Now, according to environmental standard, particularly the ELV standard in Europe can not be used chromium cpd, lead compound in fact, so studying the replacement composition, has found this rust-preventing characteristic effect in bismuth compound, particularly, discloses the patent documentation that lists below.
In patent documentation 1 (Japanese kokai publication hei 5-32919), a kind of electrocoating paint resin combination is disclosed, it is characterized in that, contain at least a kind with the bismuth compound coating and pigment.
In patent documentation 2 (WO99/31187), a kind of cation electric deposition paint composition is disclosed, it is characterized in that it comprises the water-based that the aqueous liquid dispersion that cooperated the modified with organic acids bismuth compound to exist with non-water-soluble form forms and disperses paste.
In patent documentation 3 (TOHKEMY 2004-137367), a kind of cation electrodeposition coating is disclosed, it is characterized in that the resin combination that it comprises gluey bismuth metal and has sulfonium base and propargyl.
In patent documentation 4 (TOHKEMY 2007-197688), a kind of electrocoating paint is disclosed, it is characterized in that it contains the electrocoating paint of the particle that is selected from least a kind of metallic compound in bismuth hydroxide, zirconium compounds and the tungsten compound, this metallic compound is 1～1000nm.
In patent documentation 5 (Japanese kokai publication hei 11-80621), a kind of cation electric deposition paint composition is disclosed, it is characterized in that it contains aliphatics alkoxyl group bismuth carboxylate salt brine solution.
In patent documentation 6 (Japanese kokai publication hei 11-80622), a kind of cation electric deposition paint composition is disclosed, it is characterized in that it is the aqueous solution of the bismuth salt that formed by the organic acid more than 2 kinds, at least a kind of organic acid bismuth salt brine solution that contains as the aliphatic hydroxyl carboxylic acid of this organic acid.
In patent documentation 7 (Japanese kokai publication hei 11-100533), a kind of cation electric deposition paint composition is disclosed, it is characterized in that it contains use L body in optical isomer and accounts for the bismuth lactate that the lactic acid more than 80% forms.
In patent documentation 8 (Japanese kokai publication hei 11-106687), a kind of cation electric deposition paint composition is disclosed, it is characterized in that, it is the aqueous solution of the bismuth salt that formed by the organic acid more than 2 kinds, at least a kind of organic acid bismuth salt brine solution that contains as aliphatics alkoxyl group carboxylic acid of this organic acid.
These patent documentations can roughly be divided into patent documentation 1～4 and patent documentation 5～8.Namely, be characterised in that, patent documentation 1～4th makes water-borne coatings to be insoluble bismuth compound or bismuth metal compound disperse to form, and patent documentation 5～8th is dissolved to till the solid state component noresidue bismuth compound at least, and the state that just is made into the Bi ion adds in the coating then.
But the material that the bismuth compound in these patent documentations after all just is used as the replacement of chromium cpd, lead compound then can not obtain sufficient erosion resistance if do not carry out the substrate processing that zinc phosphate system changes into processing etc.In fact, in these patent documentations, only disclose to change into the embodiment that is combined as prerequisite of processing with zinc phosphate system.
On the other hand, recently, study: by the method except bismuth compound erosion resistance further being improved, is the substrate processing that changes into processing etc. even do not implement zinc phosphate, and 1 layer of coating also can be guaranteed the technology of sufficient erosion resistance.
For example, in patent documentation 9 (TOHKEMY 2008-274392), a kind of formation method of surface treatment epithelium is disclosed, it is characterized in that, it is that thereby the multistep step mode by at least 2 steps applies the method that the epithelium binder forms epithelium on metal base, (i) the epithelium binder comprises with total amount of metal (mass conversion) and counts 30～20, the following compound of 000ppm and 1～40 quality % resinous principle, described compound contains zirconium compounds and is selected from titanium as required, cobalt, vanadium, tungsten, molybdenum, copper, zinc, indium, aluminium, bismuth, yttrium, lanthanide series metal, at least a kind of metal (a) in the alkalies and alkaline earth, (ii) with metal base as negative electrode, carry out the coating of the 1st step 10～360 seconds by switching on down at the voltage (V1) of 1～50V, then, with metal base as negative electrode, by the voltage (V2) of 50～400V down energising carry out the later coating of the 2nd step 60～600 seconds, and (iii) the difference of voltage (V2) and voltage (V1) is at least 10V.
In addition, in patent documentation 10 (TOHKEMY 2008-538383), disclose a kind of multilayer film formation method that dipping operation, pretreatment procedure and galvanic deposit apply operation that comprises, wherein, described dipping operation is the coated thing of dipping in water-based paint compositions.Described water-based paint compositions has the matrix resin of cation group and (C) water-based paint compositions of solidifying agent for containing (A) rare earth compound, (B), the amount of (A) rare earth compound that this water-based paint compositions is contained, being converted into rare earth metal with respect to the coating solid state component is 0.05～10 weight %; Described pretreatment procedure is: in this water-based paint compositions, coated thing as negative electrode, is applied the voltage that is lower than 50V; Described galvanic deposit applies operation: in this water-based paint compositions, coated thing is applied the voltage of 50～450V as negative electrode.
In patent documentation 11 (TOHKEMY 2010-24471), a kind of multilayer film formation method is disclosed, it is impregnating metal base material in the aqueous solution of the organic acid salt that contains bismuth or inorganic acid salt, first operation is for to form the bismuth compound overlay film by this metal base is carried out electrolysis as negative electrode, and second operation is for to apply to form electrodeposition coating by cationic electrodeposition on this overlay film.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 5-32919 communique
Patent documentation 2: Japanese WO99/31187 communique
Patent documentation 3: TOHKEMY 2004-137367 communique
Patent documentation 4: TOHKEMY 2007-197688 communique
Patent documentation 5: Japanese kokai publication hei 11-80621 communique
Patent documentation 6: Japanese kokai publication hei 11-80622 communique
Patent documentation 7: Japanese kokai publication hei 11-100533 communique
Patent documentation 8: Japanese kokai publication hei 11-106687 communique
Patent documentation 9: TOHKEMY 2008-274392 communique
Patent documentation 10: TOHKEMY 2008-538383 communique
Patent documentation 11: TOHKEMY 2010-24471 communique
Summary of the invention
The problem that invention will solve
The inventor etc. carry out all research to these technology in the past, the result has drawn following conclusion: for the epithelium of giving sufficient erosion resistance under the situation of not carrying out the pre-treatment that zinc phosphate system changes into epithelium etc. on the metallic substance forms, or the application of Bi is the most effective.And the action effect to Bi is studied again.
And, action effect as Bi, in the past, attracted attention as the function of the curing catalysts of resin and the corrosion-resisting function of base metal, but in the technology in the past, though can expect the function as curing catalysts, the corrosion-resisting function of metal is extremely insufficient, will farthest bring into play this just and be used as and be related to the key of dealing with problems and study.
The corrosion-resisting function of base metal is on contacted of Bi and metal, namely on the interface of base metal surfaces and epithelium, do not exist harmless yet, but in technology in the past, Bi becomes branch evenly to disperse in epithelium, infers the sufficient Bi that does not exist on base metal surfaces for the performance erosion resistance.
As previously mentioned, patent documentation 1～4th makes water-borne coatings is insoluble bismuth compound or bismuth metal disperses to form, and the same with other pigment when by such composition epithelium being separated out, Bi can evenly disperse in epithelium.
Patent documentation 5～8 is characterised in that, bismuth compound is dissolved to till the solid state component noresidue, the state that just is made into the Bi ion is added in the coating then, organic acid sequestering power as the stabilization agent of Bi is faint, so when it is dropped into composition, Bi is hydrolysis slowly, can become oxide compound or oxyhydroxide, thereby can not expect the long stabilization as the Bi ion.Thus, Bi still is dispersed in the epithelium.In these patent documentations, zinc phosphate system is changed into processing proved above-mentioned deduction again as surface treatment.
On the other hand, patent documentation 9 and patent documentation 10 are that making inorganic at base metal is the technology that makes resin involucra stacked after epithelium is separated out, favourable aspect the protection against corrosion of base metal, but because of inorganic be that epithelium and resin involucra all are the mechanism that the pH by the base metal surfaces that formed by catholyte rises and separates out, so be difficult for forming stacked epithelium.
Though patent documentation 11 separates out Bi by electrolysis treatment, in same operation, resin is separated out.With regard to separating out with regard to the mechanism of resin, it results from the electrolysis of the water in the electrolysis treatment usually, its cause the raw material near interface pH rising and lose the stability of resin emulsion, cohesion is separated out thus.Therefore, attempt when same in-process desires to make Bi and resin to separate out, separating out simultaneously of Bi and resin takes place, and can not obtain separating out for the sufficient Bi that brings into play erosion resistance.
The method of dealing with problems
Discoveries such as the inventor: in same bath, by the low voltage catholyte Bi reduction is separated out, then the diffusion of Bi ion was become in the inadequate stage, the reaction mechanism that rises resin is separated out by such pH.
Confirm then: the epithelium that obtains thus from needless to say, by the Bi that exists with high density in base metal surfaces, also can fully improve the erosion resistance of base metal as the ability of the curing catalysis of the resin with Bi.
But following problems also occurred: the Z-electromotive force of resin reduces when the low voltage catholyte, finally arrives iso-electric point and cohesion takes place separates out, and causes the minimizing that the reduction of Bi is separated out thus.
The inventor etc. are in order to solve the problem of above-mentioned technology in the past, application has the cationic resin emulsion of specific skeleton, the Z-electromotive force that the resin emulsion of separating out that controlling influences resin has, the resin that suppresses in the low voltage catholyte is separated out, and consequently successfully makes the property the separated out raising of Bi.That is, the present invention is (1)～(9) shown in following.
The present invention (1) is a kind of metal finishing composition, it is characterized in that, it contains resin emulsion and Bi ion, described resin emulsion contains at least a kind in the cationic resin, the Z-electromotive force of described resin emulsion in the water medium of pH5～pH9 be+40mV～+ 100mV, described composition is used in the multistep current flow method in the same bath.Be to use Z-potential determination device (ZETASIZER Nano-Z:MALVERN system) and the measured value that obtains (is measured temperature: 25 ℃, measure medium: purified water) at claims of the application and the Z-electromotive force in the specification sheets herein.In addition, use ammoniacal liquor, utilize automatic titration device (MPT-2:MALVERN system) to carry out pH and adjust.Further, in order to begin to measure the Z-electromotive force, under being concentration more than the 20kcps, required least count rate measures.
The present invention (2) is according to the described metal finishing composition of foregoing invention (1), it is characterized in that, the Z-electromotive force of the described resin emulsion of in the water medium of pH5～pH9, measuring for+40mV～+ 100mV, and the Z-electromotive force of the described resin emulsion that is measured in the water medium more than pH11 is less than+10mV.
The present invention (3) is according to foregoing invention (1) or (2) described metal finishing composition, it is characterized in that, at least a kind cationization position of described cationic resin by more than the pH11, the amine compound modification of the 1mol/L aqueous solution forms.
The present invention (4) is according to the described metal finishing composition of foregoing invention (3), it is characterized in that, amine compound (E) is the compound that contains the NH base shown in the formula 1, R1, R2 independently of one another and respectively by-(R) m-shown in, R is alkylidene group, arylidene (for example phenylene), carbonyl, m is more than 0 or 1, X, Y independent of one another and be hydrogen, hydroxyl, alkyl, aryl, carboxyl, amino or imino-{ herein, R, X and Y are independent of one another, and more than one the group that can be selected from alkyl, aryl, hydroxyl, carboxyl, amino and the halogen radical further replaces }.
Figure BDA00003614182400061
The present invention (5) is according to the described metal finishing composition of foregoing invention (4), it is characterized in that, what contain at least a kind of X with following formula 1, Y one is the amine compound of hydroxyl only.
The present invention (6) is according to the described metal finishing composition of foregoing invention (5), it is characterized in that, gross weight with the raw material of described cationic resin is benchmark, by the only described cationic resins that form for the amine compound of hydroxyl (E) modification of X, Y more than at least a kind, formula 1, its be to use 5 weight %～described amine compound of 30 weight % and.Herein, " gross weight of the raw material of described cationic resin " refers to use under the situation of solvent the not gross weight of solvent-laden raw material when synthetic described cationic resin.
The present invention (7) is foregoing invention (5) or (6) described metal finishing composition, it is characterized in that, the raw material of described cationic resin be X, Y contained in the amine compound (E) of formula 1 only one for the amine compound of hydroxyl be 10～100 weight %.
The present invention (8) is a kind of metal surface treating method, it is characterized in that, dipping metal to be treated material in each described composition of described invention (1)～(7) is separated out in that the metal to be treated material is made to film at metallic substance in as the electrolysis treatment operation of negative electrode.
The present invention (9) is a kind of metal surface treating method, it is characterized in that, second operation in 30～300 seconds of electrolysis under voltage 50～400V that it has first operation and implements after described first operation, wherein, described first operation is after making the surface metallic substance of cleaningization impregnated in each described composition of foregoing invention 1～7, or while flooding with this metallic substance as negative electrode, in 10～120 seconds of the following electrolysis of voltage 15V, herein, described second operation and then described first operation in same bath, implement
Embodiment
" metal surface treating method "
(applicable object)
The metal finishing that the present invention relates to can be for preventing that the purpose that various metals are corroded from using with composition.Though metallic substance is not particularly limited, can list cold-rolled steel sheet, hot-rolled steel sheet, casting material, steel pipe etc. ferrous materials, on these ferrous materials, implemented zinc-plated processing and/or the aluminize material, aluminium alloy plate, the aluminium that form are that casting material, magnesium alloy plate, magnesium are casting material etc.Be specially adapted to complex-shaped metal constituting body, for example as based on the body of a motor car of the metal constituting body of ferrous material, trolley part, tame electrical article, material of construction etc.
(metal surface treating method)
The metal surface treating method that the present invention relates to comprises following operation: use described metal finishing composition, make to film in the electrolysis treatment operation of metal to be treated material as negative electrode and separate out at metal material surface.The metal surface treating method that the present invention relates to comprises that following operation is then better: separate out at metallic substance in order to make epithelium, the metallic substance that the surface has been changed with cleaning is implemented electrolysis treatment operation, the washing of implementing and the sintering circuit of electrolysis treatment after the electrolysis treatment operation.Below, distinctive electrolysis treatment operation in present method is described in detail.
This electrolysis treatment operation (catholyte) has: make described metallic substance impregnated in metal finishing with the state in the composition under, the following electrolysis of voltage 15V first operation in 10～120 seconds, make described metallic substance impregnated in metal finishing with the state in the composition under, second operation of after described first operation, implementing in 30～300 seconds of electrolysis under voltage 50～400V, herein, described second operation and then described first operation in same bath, implement.
Herein, first operation is to be mainly used in Bi is adhered to and the operation of carrying out, and second operation is to be mainly used in making resin preferentially to separate out and the operation of carrying out.In order to obtain sufficient erosion resistance, be necessary to exist the Bi that directly contacts with metallic substance, the interface Bi that exists at the interface of metallic substance and epithelium just, therefore, the order of first operation and second operation and condition become very important.
The voltage of first operation is 15V following (for example being 0.01V though lower value is not particularly limited), 10～120 seconds of preferred electrolysis.When voltage was lower than 0V, when being about to metallic substance and carrying out electrolysis as anode, metallic substance can stripping in composition, and the stability of composition is reduced, and the required interface Bi of raising of erosion resistance is become fully do not adhere to.Surpass and upward also to be in limited time, because of Bi preferentially before separate out the metallic surface resin will begin to separate out, be still and can not obtain sufficient erosion resistance.
Treatment time is lower than can not separate out sufficient interface Bi down in limited time yet, surpasses the last adhesion amount of interface Bi in limited time and becomes too much, and the impaired situation of adaptation of epithelium is arranged.
The voltage of second operation is 50～400V, 30～300 seconds of preferred electrolysis.Voltage is lower than down in limited time, and the quantitative change of separating out of resin involucra gets insufficiently, surpasses that last separating out of resin involucra too much and not only causes the unfavorable of economic aspect in limited time, and the situation of the appearance damage after the epithelium processing is arranged.
When after first operation, moving to second operation, need not to make voltage instantaneous to increase, even slowly make its increase also can not damage effect of the present invention.In addition, all to need not voltage constant for a long time for first operation and second operation.
Then, the metal finishing that the present invention relates to is described in detail with composition.
" metal surface treating composition "
The metal finishing that the present invention relates to is characterised in that with composition, contains aqueous resin and Bi ion, and aqueous resin herein must contain the cationic resin, for example, is equivalent to be used as the F2 agent of electrocoating paint.
The metal finishing that the present invention relates to except above-mentioned aqueous resin, Bi ion, also can cooperate for example pigment composition arbitrarily with composition, and this pigment composition is equivalent to be used as for example F1 agent of electrocoating paint.
In the aqueous resin that the present invention relates to, also can cooperate arbitrarily with the end-blocking polyisocyanates is the solidifying agent of representative.And the aqueous resin among the present invention refers to the emulsion of water-dispersion and the general name of water soluble resin.In addition, also can use resin dispersion beyond cationic resin and the decationize resin in water and resin emulsion.
The metal finishing composition that the present invention relates to is that at least a kind of dispersion of cationic resin is formed.
The present invention is by the Z-electromotive force of control cationic resin emulsion, and the stability of the resin emulsion when making the low voltage catholyte keeps, and consequently, can make the raising of the Bi property separated out.
By carrying out catholyte, the electrolysis of water causes that hydroxide ion produces, and the pH of raw material near interface rises.
At this moment, the Z-electromotive force of cationic resin reduces, and finally arrives iso-electric point, emulsion loss of stability and separating out.
Therefore, by controlling the Z-electromotive force of the resin emulsion under each pH condition, can arrange separating out of Bi in low voltage catholyte and the high-voltage catholyte and resin emulsion thus.
The Z-electromotive force of the resin emulsion of measuring in the water medium of pH5～pH9 that the present invention relates to preferably is shown as+40mV～+ 100mV, if consider treatment solution stability, more preferably demonstration+50mV～+ 100mV.Discovery is shown as by measure the Z-electromotive force obtain in the water medium of pH5～pH9+40mV～+ 100mV, even the pH of the raw material near interface during for the low voltage catholyte rises, the stability of resin emulsion is also kept.
Therefore, separating out of the resin emulsion during the low voltage catholyte is suppressed, and can promote that Bi separates out.
Further, be lower than+10mV by making the Z-electromotive force that mensuration obtains in the water medium more than pH11, when the high-voltage catholyte, film and normally separate out.Measure in the water medium more than pH11 the Z-electromotive force obtain+when 10mV was above, even the pH of the raw material near interface during the high-voltage catholyte rises, the stability of emulsion was also kept, separating out of filming can be suppressed.Therefore, by the bismuth ion that exists in water medium and the reaction of hydroxide ion, bismuth hydroxide can preferentially be separated out or separate out simultaneously with resin involucra, and the adaptation of filming can be impaired.
Therefore, be shown as by in the water medium of pH5～pH9, measuring the Z-electromotive force that obtains+40mV～+ 100mV, and the Z-electromotive force that mensuration obtains in the water medium more than pH11 is shown as and is lower than+10mV, becoming when the low voltage catholyte to promote that Bi separates out, and further can normally separate out to film and form the multilayer epithelium when the high-voltage catholyte.
＜composition constituent: cationic resin 〉
The cationic resin that the present invention relates to all is not particularly limited, as an example, and the material that can use the matrix resin cationization with Resins, epoxy, urethane resin, acrylic resin etc. to form.Be good with Resins, epoxy among these, modified epoxy is then better, bisphenol type, phenolic varnish type modified epoxy the best.
Below, as the cationic resin and especially suitable bisphenol type modified epoxy is described in detail.
(bisphenol A-type modified epoxy)
Herein, suitable especially bisphenol A-type modified epoxy (A) is illustrated.The bisphenol A-type modified epoxy is to use the Resins, epoxy (C) of modified resin (B), epoxy equivalent (weight) 180～2500 or further re-uses dihydroxyphenyl propane (D) as raw material, make their the reaction and modified epoxy.Below, each composition is illustrated.
* the raw material of bisphenol A-type modified epoxy (A)
At first, modified resin (B) uses for the purpose of the flexible grade that improves Resins, epoxy.Can specifically list the polyol resin of polyester polyol, polyether glycol, polyurethane polyol, acrylic polyol etc.; Addition phenol and have aromatic condensation compound of hydroxyl etc. endways.Can further list polycaprolactone glycol, polyoxyethylene glycol, polypropylene glycol, have the xylene formaldehyde resin of phenol hydroxyl etc.Utilizing these compounds to carry out modification is the technology of in the past continuing to use.
As the Resins, epoxy (C) of epoxy equivalent (weight) 180～2500, from the viewpoint of the non-corrosibility of filming etc., particularly suitable is by polyphenol compound and epihalohydrins, the Resins, epoxy that for example obtains with the reaction of Epicholorohydrin.Wherein, making the dihydroxyphenyl propane that obtains with the reaction by dihydroxyphenyl propane and Epicholorohydrin is that the Resins, epoxy that the basic structure polymerization gets also demonstrates same effect, optimum is to be 180～2500 as epoxy equivalent (weight), is preferably 180～2000, more preferably 180～1500 Resins, epoxy.
* the compound (E) that contains the NH base
Then, the cationization method of matrix resin is narrated.Cationization adopts usually and introduce amino method in matrix resin.And the compound (E) that contains the NH base comprises primary amine and secondary amine compound.
The compound (E) that contains the NH base is that the cationic of cationization is given composition for introducing amino at the matrix resin that the present invention relates to.
Find that in the present invention the compound (E) that contains the NH base is relevant with the Z-electromotive force that the resin emulsion of having introduced it has, and is very important key element concerning the Bi property separated out and the property separated out of filming.
Form desirable Bi and the required Z-electromotive force behavior of multilayer epithelium of resin in order to reach, the pH scope that is incorporated into the compound that contains the NH base (E) the demonstration regulation of matrix resin in the present invention is advisable.
With regard to the compound that contains the NH base (E) that specifically is incorporated into matrix resin, be preferably more than the pH11 as the 1mol/L aqueous solution, more preferably pH11～13 are preferably pH11.5～13 especially.
Reason is still indeterminate, but finds: by introducing amine compound more than the pH11, the 1mol/L aqueous solution, the Z-electromotive force of the resin emulsion under each pH can be adjusted in the described scope.
The compound (E) that contains the NH base is by formula 1 expression, in cationic resin 1 molecule, preferably contain among 5 weight %～30 weight % more than at least a kind, more preferably contain 5 weight %～25 weight %.
The R1 of formula 1, R2 independently of one another and respectively by-(R) m-represents, R is alkylidene group, arylidene or carbonyl, m is (for example be 10 though higher limit is not particularly limited) more than 0 or 1, and X, Y are independent of one another, are preferably hydrogen, hydroxyl, alkyl, aryl, carboxyl, amino or imino-.Herein, " imino-" refers to, removes a residue that alkyl forms with imine bound.In addition, for reaching " alkyl " at " alkylidene group " described in this patent claims and this specification sheets, being not particularly limited though constitute its carbonatoms, is good with C1～C6, and C2～C3 is then better.In addition, for reaching " aryl " at " arylidene " described in this patent claims and this specification sheets, being not particularly limited though constitute its carbonatoms, is good with C6～C14.And, comprise that also the part of carbon skeleton is replaced the heteroaryl (being good with C5～C13 at this moment) that forms by heteroatoms (N, S etc.).In addition, R, X and Y are independent of one another, can by other substituting groups more than for example, alkyl (for example, C1～C6), aryl (for example, C6～C14), hydroxyl, carboxyl, amino, halogen radical } replace.
The compound (E) that contains the NH base can be enumerated as monoethanolamine, list (2-hydroxypropyl) amine, single methylethylolamine, single ethylaminoethyl alcohol, single phenyl ethylaminoethyl alcohol, monoacylphosphine monoethanolamine etc. monoalkanolamine.
The compound that contains the NH base (E) about shown in the formula 1 preferably uses more than a kind at least, and more preferably using any one of X, Y more than a kind is the monoalkanolamines that are selected from hydroxyl.Herein, " monoalkanolamine " refers to, uncle or secondary amine that the end of NH and hydroxyalkyl { R-OH (herein, R is alkylidene group, and it has described preferable range, can further be replaced by described group) } bonding forms.And, as with the group of the other end bonding of NH, be good (herein, alkyl can be further by described group, and for example aryl replaces) with hydrogen atom, alkyl.Wherein, the monoalkanolamine with second month in a season of the other end be combined into of alkyl and NH is good.
As the compound that contains the NH base (E), by using monoalkanolamine, the not only Bi property separated out raising is because existing hydroxyl, so also emulsifying property is produced desirable influence in compound.
Preferably in 1 molecular cation resin, contain 5 weight %～30 weight % formula 1 X, Y only one in the compound that contains the NH base (E) of hydroxyl more than at least a kind.
In addition, more preferably contain any one of X, Y in the formula 1 only be both that be selected from the compound that contains the NH base (E1) of hydroxyl and X, Y all be selected from the amino compound that contains the NH base (E2) the two.
By and be that both that be selected from the compound that contains the NH base (E1) of hydroxyl and X, Y all are the compounds that contains the NH base (E2) that is selected from amino with any one of only X, Y, can be easily the Z-electromotive force of having introduced under their pH11 of resin emulsion be remained on deficiency+10mV.
Particularly, contain the compound (E1) of NH base with monoalkanolamine the best, contain the compound (E2) of NH base with diethylenetriamine the best.
Contain monoalkanolamine (E1) contained in the compound (E) of NH base and preferably contain 10～100 weight %, more preferably contain 30～90 weight %.
And all be that the situation that is selected from the amino compound that contains the NH base (E2) more preferably contains 10～70 weight % in the compound that contains the NH base (E) with both of X, Y.
* the amic preparation method of bisphenol A-type modified epoxy
At first, modified resin (B), Resins, epoxy (C), bis-phenol (D) that hybrid regulatory is quantitative carry out heated and stirred.Heating temperature is preferably 70～100 ℃.Behind each material dissolution, add catalyzer, the rising Heating temperature is synthesized.Catalyzer uses the tertiary amine as the dimethyl benzylamine usually.Usually synthesis temperature is controlled at 120 ℃～150 ℃.
By adjusting synthesis temperature and time, can synthesize the Resins, epoxy of the epoxy equivalent (weight) with regulation.Epoxy equivalent (weight) is measured to calculate according to the epoxy equivalent (weight) of JIS K7236 defined.The epoxy equivalent (weight) of this moment is good with 800～10000, and 800～5000 better, 800～3000 the bests.Epoxy equivalent (weight) is more big, the tendency that emulsifying stability reduces when then having emulsion to make.
Then add the compound (E) that contains the NH base in the modified epoxy after this is synthetic.The limit remains on 70～110 ℃ of limits with modified epoxy and adds the compound (E) that contains the NH base, by carrying out 1～3 hour synthetic, can obtain the amide of modified epoxy.Use when containing the compound of NH base more than 2 kinds, they can add respectively or add simultaneously.
(cationization of modified epoxy)
Add neutralizing acid in the amide of the modified epoxy after synthetic, after mixing, dilute with water is made the resin emulsion of normality.Neutralizing acid can use formic acid, acetic acid, lactic acid, thionamic acid etc.
At this moment, before adding neutralizing acid, preferably add solidifying agent, curing catalysts, organic solvent etc. in advance.By adding like this in advance, can obtain uniform emulsion.Then, such added ingredients is described in detail.
* solidifying agent
Solidifying agent uses blocked polyisocyanates usually.Blocked polyisocyanates is that polyisocyanate compound and isocyanate-terminated dose are shown the addition reaction product that stoichiometry forms greatly.As the polyisocyanate compound that uses herein, can enumerate as tolylene diisocyanate, Xylene Diisocyanate, phenylene diisocyanate, ditan-2,4 '-vulcabond, ditan-4,4 '-aromatic series such as vulcabond (being commonly referred to " MDI "), thick MDI, two (isocyanatomethyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate; Aliphatics or alicyclic polyisocyanates compound; The cyclized polymer of these polyisocyanate compounds; Isocyanic ester biuret body; The end that makes these excessive isocyanate compounds and ethylene glycol, propylene glycol, TriMethylolPropane(TMP), hexanetriol, the low molecule of castor-oil plant wet goods contain the compound bearing active hydrogen reaction and get contains the compound of isocyanic ester etc.They can distinguish use more than 2 kinds alone or in combination.
On the other hand, described isocyanate-terminated dose is and the isocyanate group addition of polyisocyanate compound and the material of end-blocking, though and the blocked polyisocyanates compound that generates by addition is stable at normal temperatures, but be preferably following material: when being heated to the sintering temperature (about 100～about 200 ℃ usually) of filming, end-capping reagent dissociates and can generate free isocyanate group again.
As the end-capping reagent that satisfies such prerequisite, can enumerate as lactan based compounds such as ε-Ji Neixianan, butyrolactams; Oxime compound such as methyl ethyl ketoxime, cyclohexanone-oxime; Phenol system compounds such as phenol, p-tert-butylphenol, cresols; Aliphatics such as propyl carbinol, 2-Ethylhexyl Alcohol alcohols; Aromatic series alkyl alcohols such as phenyl Trivalin SF, aminomethyl phenyl Trivalin SF; Ether alcohol such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether based compound etc.These end-capping reagents can be distinguished use more than 2 kinds alone or in combination.In addition, in order effectively to promote the dissociating of end-capping reagent, curing reaction etc., and the curing reaction thing wanted is generated, also can adopt the isocyanate group of an addition part on the skeleton of modified epoxy in advance, and the isocyanate-terminated method that will be left with end-capping reagent.
＜composition constituent: the bismuth ion of 3 valencys 〉
Bi ion of the present invention refers to not solidification in composition, becomes the Bi composition of complete dissolved state.
As the supply source of Bi ion, so long as the bismuth compound of 3 valencys just is not particularly limited, but can enumerate as inorganic bismuth compounds such as Bismuth trinitrate, bismuth phosphate, bismuth sulfate, bismuth oxide, bismuth hydroxides; Fluoridize halogenation bismuth compounds such as bismuth, bismuth chloride, bismuth bromide, bismuth iodide; Organic acid bismuth compounds such as bismuth acetate, formic acid bismuth, bismuth lactate, bismuth citrate.
In the present invention, can contain aminopolycarboxylic.Aminopolycarboxylic is the general name that has the sequestrant of amino and a plurality of carboxyls in molecule.Aminopolycarboxylic is used for making 3 valency Bi ions of composition be in the state of more stable water-solubleization, so can contain aminopolycarboxylic.Particularly, EDTA (ethylenediamine tetraacetic acid (EDTA)), HEDTA (hydroxyethylethylene diamine tri-acetic acid), NTA (triacetamide), DTPA (diethylene triaminepentaacetic acid(DTPA)), TTHA (triethylenetetraaminehexaacetic acid) etc. are fit to, but from the viewpoint of the chelating stability of Bi ion more preferably EDTA, HEDTA, NTA.
＜composition constituent: other compositions 〉
In composition of the present invention, also can further use normally used additive in paint field such as pigment, curing catalysts, organic solvent, pigment dispersing agent, tensio-active agent as required.As pigment, can list painted pigment such as titanium white, carbon black; Pigment extenders such as clay, talcum, barium oxide; Rust-stabilising pigment such as aluminium triphosphate, zinc phosphate; Organo-tin compound such as Dibutyltin oxide, dioctyl tin oxide; Tin compounds such as the lipid acid of dialkyl tins such as dibutyl tin laurate, dibutyl tin dibenzoate or aromatic carboxylic acid salt.
＜composition constituent: liquid medium 〉
As the liquid medium of the metal finishing that the present invention relates to composition, be good with aqueous medium, water is then better.And, when liquid medium is water, can contain other water solvents (for example, water soluble alcohols) except water as liquid medium.
" composition of metal surface treating composition "
Then, the metal finishing that the present invention relates to composition with composition is illustrated.
(cationic resin)
At first, with regard to composition, water is with the material dilution of high density and be adjusted to desirable concentration aptly with regard to the metal finishing that the present invention relates to.Gross weight with composition is benchmark, contains the cationic resin of 5～30 weight %, is good to contain 10～25 weight %, and it is then better to contain 10～20 weight %.
(bismuth ions of 3 valencys)
Then, the metal finishing that the present invention relates to contains the 3 valency Bi ions of 100～5000ppm with composition.Further preferably contain 500～4000ppm, most preferably contain 1000～3000ppm.The Bi ionic concn is crossed when hanging down, can not obtain to improve the required sufficient Bi adhesion amount of erosion resistance, if the specific conductivity of too high then composition becomes too high, when the covering power deterioration to the epithelium of metallic substance with complicated shape was arranged, the Bi adhesion amount became too much and the worry of infringement epithelium adaptation.With regard to the Bi ionic concn in the composition, can utilize ultracentrifuge that composition is carried out solid-liquid separation, utilize jigger coupling high frequency plasma emission spectroanalysis (ICP) or atomic absorption spectrochemical analysis (AA) that liquid phase is carried out quantitatively.
" rerum natura of metal surface treating composition "
Then, the metal finishing that the present invention relates to rerum natura with composition is illustrated.
(temperature)
Be not particularly limited about the metal finishing that the present invention relates to temperature with composition, but when by electrolysis treatment epithelium being separated out, can be usually at 15～40 ℃, be preferably in 20～35 ℃ the scope and use.
(pH)
The metal finishing that the present invention relates to is not particularly limited with the pH of composition, but can tune to 2.0～7.0 usually, and 3.0～6.5 the scope of preferably being adjusted to is used.
" metal finishing epithelium "
The metal finishing epithelium that the present invention relates to can use metal finishing of the present invention to obtain by treatment process of the present invention with composition.Herein, the Bi that is present in the epithelium exists with the form of metal and oxide compound.The Bi that separates out by catholyte is the metal Bi that reduction is separated out substantially, but its part becomes the oxide compound that especially oxidation forms in the sintering circuit of epithelium.In addition, when applying high-voltage in second operation, along with the pH on epithelium surface rises, the stabilization of the Bi that is caused by aminopolycarboxylic becomes insufficient, thereby especially separates out with oxidation Bi form in the epithelium face side.
The Bi adhesion amount is preferably 20～500mg/m 2, 30～400mg/m more preferably 2, most preferably be 50～300mg/m 2If the Bi adhesion amount is crossed and low then can not be obtained sufficient erosion resistance, if too highly then not only can not expect the raising of erosion resistance but also the situation of infringement epithelium adaptation is arranged.And the Bi adhesion amount can come quantitatively by x-ray fluorescence analysis.And it is the value that quantitatively obtains by this x-ray fluorescence analysis that " the metal Bi adhesion amount " in this patent claims and this specification sheets reaches " oxidation Bi adhesion amount ".And, though can not negate the existence of other forms of oxyhydroxide, in this measuring method, carry out its numerical value being designated as " metal Bi adhesion amount " or " oxidation Bi adhesion amount " when quantitative with " metal Bi " or " oxidation Bi ".
Total leather film thickness of the epithelium that obtains is preferably 5～40 μ m, and more preferably 5～30 μ m most preferably are 7～25 μ m.If cross and thinly then can not obtain sufficient erosion resistance, if the blocked up then but also situation that have covering power reduce unfavorable in economic aspect not only.Then can be by induction film thickness gauge, if base metal is that non-magnetic metal then can be measured leather film thickness by the eddy current type film thickness gauge if base metal is magneticmetal.
" preparation example "
The making of aqueous resin emulsion
Preparation example 1
In the 1000ml detachable flask that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (Mitsubishi chemical Co., Ltd's system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of Mono Methyl Ethanol Amine 12.5g, diethylenetriamine: 8.6g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, obtains the aqueous resin emulsion (A1) of the Z-electromotive force 8.2mV in the water medium of Z-electromotive force 69.3mV, pH11 in the water medium of solid component concentration 33%, pH7.
Preparation example 2
In the 1000ml detachable flask that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (Mitsubishi chemical Co., Ltd's system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add Mono Methyl Ethanol Amine 11.3g, diethylamine: 7.8g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, obtains the aqueous resin emulsion (A2) of the Z-electromotive force 8.1mV in the water medium of Z-electromotive force 55.1mV, pH11 in the water medium of solid component concentration 33%, pH7.
Preparation example 3
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin (Japan Epoxy Resins) Co., Ltd.'s system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add Mono Methyl Ethanol Amine 21.1g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 54.3mV, pH11 is the aqueous resin emulsion (A3) of 7.9mV.
Preparation example 4
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of Mono Methyl Ethanol Amine: 5.6g, diethylenetriamine: 15.5g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 65.2mV, pH11 is the aqueous resin emulsion (A4) of 8.3mV.
Preparation example 5
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of Mono Methyl Ethanol Amine: 2.4g, diethylenetriamine: 15.5g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 63.1mV, pH11 is the aqueous resin emulsion (A5) of 9.6mV.
Preparation example 6
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of ehtylethanolamine: 14.8g, diethylenetriamine: 10.3g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 63.4mV, pH11 is the aqueous resin emulsion (A6) of 6.1mV.
Preparation example 7
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of benzyl ethyl alcohol amine: 28.1g, diethylenetriamine: 19.4g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 52.0mV, pH11 is the aqueous resin emulsion (A7) of 7.4mV.
Preparation example 8
In the 1000ml detachable flask that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (Mitsubishi chemical Co., Ltd's system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of thanomin 6.1g, diethylenetriamine: 13.4g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, obtains the aqueous resin emulsion (A8) of the Z-electromotive force 9.8mV in the water medium of Z-electromotive force 72.3mV, pH11 in the water medium of solid component concentration 33%, pH7.
Preparation example 9
In the 1000ml detachable flask that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (Mitsubishi chemical Co., Ltd's system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of diethylamine 7.3g, diethylenetriamine: 13.3g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, obtains the aqueous resin emulsion (A9) of the Z-electromotive force 6.2mV in the water medium of Z-electromotive force 51.3mV, pH11 in the water medium of solid component concentration 33%, pH7.
Preparation example 10
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of diethanolamine: 12.7g, diethylenetriamine: 8.8g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 49.7mV, pH11 is the aqueous resin emulsion (A10) of 0mV.
Preparation example 11
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of diisopropanolamine (DIPA): 13.5g, diethylenetriamine: 9.3g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 47.1mV, pH11 is the aqueous resin emulsion (A11) of 0mV.
Preparation example 12
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 114.0g, as the polycaprolactone glycol Placcel 208 (Daicel KCC system) of modified resin: 41.5g, dihydroxyphenyl propane: 45.6g, dimethyl benzylamine 0.1g, under 130 ℃, react to epoxy equivalent (weight) and become till 1000.Finish the back in reaction and add the 55.5g ethylene glycol butyl ether, further add the ketoimine thing of diethylenetriamine: 40.3g, reaction is 2 hours under 90 ℃.Add end-blocking isocyanic ester: 105.5g, dibutyltin diacetate: 3.2g, acetic acid 5.4g therein, after stirring, the limit is firmly stirred the limit and was splashed into deionized water 578.1g with about 1 hour, and the Z-electromotive force that obtains Z-electromotive force in the water medium of solid component concentration 33%, pH7 and be in the water medium of 38.4mV, pH11 is the aqueous resin emulsion (A12) of 0mV.
The making of end-blocking isocyanic ester
In Cosmonate M200 (Mitsui Chemicals, Inc's system): add methyl iso-butyl ketone (MIBK): 115.6g among the 678.4g, be warming up to 70 ℃ after, slowly splash into 2-Ethylhexyl Alcohol: 706.0g, after dropwising, be warming up to 90 ℃.Under 90 ℃ condition, make its reaction 12 hours, obtain the end-blocking isocyanic ester.Carry out infrared absorption spectrometry, the result does not find to be derived from the absorption of unreacted isocyanate group, can confirm that isocyanic ester is by complete end-blockingization.
The making of 30% quaternary saltization (Si Grade saltization) Resins, epoxy
In the detachable flask of 1000ml that has been equipped with thermometer, condenser, stirrer, add Resins, epoxy #828 (japan epoxy resin Co., Ltd. system, epoxy equivalent (weight): 180): 134.9g, dihydroxyphenyl propane: 80.94g, dimethyl benzylamine 0.1g react under 130 ℃ to epoxy equivalent (weight) and become till 1200.React and finish back adding ethylene glycol butyl ether 71.7g, further add dimethylaminoethanol 13.16g, 90% lactic acid 14.79g and reacted 1 hour down at 90 ℃.After the reaction, the limit is firmly stirred the limit and is splashed into deionized water 613.36g with about 1 time, has made the quaternary salt Resins, epoxy of solid state component 30%.
The making of pigment paste
16.6 parts of quaternary salt Resins, epoxy with respect to 30% add 7.0 parts of refining clays, 0.3 part of carbon black, 3.0 parts of zinc phosphates and deionized water, disperse 20 hours in ball mill, obtain the colo(u)rant dispersion paste of solid state component 50 weight %.
The making of Bi ionic liquid
Make HEDTA:13.3g be dissolved in distilled water: among the 500g, be heated to 60 ℃ after, add till Bismuth trinitrate pentahydrate: 23.2g is stirred to solid state component and dissolves fully.Further add distilled water so that final total amount becomes 1.0L, made Bi deionized water solution (B1).
" embodiment "
Embodiment 1
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 1 prepared resin emulsion (A1).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 2
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 2 prepared resin emulsions (A2).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 3
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 3 prepared resin emulsions (A3).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 4
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 4 prepared resin emulsions (A4).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 5
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 5 prepared resin emulsions (A5).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 6
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 6 prepared resin emulsions (A6).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 7
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 7 prepared resin emulsions (A7).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 8
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 8 prepared resin emulsions (A8).And, use deionized water that concentration is separately diluted adjustment, make composition.
Embodiment 9
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 9 prepared resin emulsions (A9).And, use deionized water that concentration is separately diluted adjustment, make composition.
Comparative example 1
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 10 prepared resin emulsions (A10).And, use deionized water that concentration is separately diluted adjustment, make composition.
Comparative example 2
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 11 prepared resin emulsions (A11).And, use deionized water that concentration is separately diluted adjustment, make composition.
Comparative example 3
Be that the solid state component of 16.0 weight %, pigment paste is that the mode that 4.0 weight % and Bi deionized water solution (B1) are counted the amount of 1200ppm with the Bi ion is mixed them with the solid state component of preparation example 12 prepared resin emulsions (A12).And, use deionized water that concentration is separately diluted adjustment, make composition.
Electrolytic condition
After 60 seconds of electrolysis under the 8V, under 180V, carry out the electrolysis treatment in 180 seconds as electrowinning process (1) immediately as electrowinning process (2).
The making of test board
As test board, use cold-rolled steel sheet: SPCC (JIS3141) 70 * 150 * 0.8mm (below, slightly be designated as SPC), in advance Nihon Parkerizing Co., Ltd.'s alkaline defatting agent processed " FC-E2001 " is used on its surface, carry out skimming treatment by carrying out spraying processing in 120 seconds.Spraying washed for 30 seconds after the skimming treatment, and it be impregnated in the composition shown in embodiment and the comparative example, implements catholyte and handle under the electrolytic condition shown in embodiment and the comparative example.Test board after electrolysis finishes washed for 30 seconds with the deionized water spray water immediately, carried out 20 minutes sintering in electric oven under 180 ℃.
The investigation of epithelium characteristic
Investigate the epithelium characteristic of the epithelium of separating out at test board by the following method.
Leather film thickness is measured: use induction film thickness gauge to measure.
Bi adhesion amount: quantitative by fluorescent X-ray spectrometry.
Corrosion resistance test method and evaluation method
Implement crosscut at the resin-coating plate of handling making by catholyte, implement salt spray testing (JIS-Z2371), measure the one-sided maximum swelling width of the crosscut portion after 1000 hours.Be that the basis is estimated with the measurement result: below the above 3mm of 2mm: ◎, 2mm: zero, below the above 4mm of 3mm: △, more than the 4mm: *.
The NH based compound and the pH that when preparation relates to the emulsion of embodiment 1 to 9 and comparative example 1 to 3, use have been displayed in Table 1, be displayed in Table 2 the ratio of mixture (A=amine compound, A1=amine compound 1, A2=amine compound 2) of the NH compound that when manufacturing relates to the emulsion of embodiment 1 to 9 and comparative example 1 to 3, uses and the Z-electromotive force of emulsion, be displayed in Table 3 the evaluation result of the epithelium that the composition by embodiment 1 to 9 and comparative example 1 to 5 obtains.Confirmed that embodiment 1 to 9 all having in order to obtain the sufficient Bi adhesion amount of erosion resistance under the level, also shows good result in salt spray testing.Particularly embodiment 1 to 8 shows excellent erosion resistance.Relative therewith, comparative example 1 to 4 can not be guaranteed sufficient Bi adhesion amount, poor as a result in salt spray testing.
Comparative example 4 switches on formed epithelium by multistep with reference to citing document 11 embodiment 1 in same bath, but can not guarantee in order to obtain the sufficient Bi adhesion amount of erosion resistance, poor as a result in salt spray testing.This is because the Z-electromotive force of the emulsion of use is not in Z-potential range shown in the present, so the Bi property separated out is poor in citing document 11 embodiment 1.
Embodiment 1 to 9 has shown and result more than the erosion resistance of the combination of the zinc phosphate coat material shown in the comparative example 5 and cation electrodeposition coating is equal.
It seems that from above effect of the present invention is apparent.
[table 1]
Figure BDA00003614182400251
[table 2]
Figure BDA00003614182400261
[table 3]
Table 3
Figure BDA00003614182400271

Claims (9)

1. metal finishing composition, it is characterized in that, it contains resin emulsion and Bi ion, described resin emulsion contains at least a kind in the cationic resin, the Z-electromotive force of described resin emulsion in the water medium of pH5～pH9 be+40mV～+ 100mV, described composition is used in the multistep current flow method in the same bath.
2. metal finishing composition according to claim 1, it is characterized in that, the Z-electromotive force of described resin emulsion in the water medium of pH5～pH9 be+40mV～+ 100mV, and the Z-electromotive force of the described resin emulsion that is measured in the water medium more than pH11 is less than+10mV.
3. metal finishing composition according to claim 1 and 2 is characterized in that, at least a kind of cationization position in the described cationic resin by more than the pH11, the amine compound modification of the 1mol/L aqueous solution forms.
4. metal finishing composition according to claim 3 is characterized in that, amine compound is the compound that contains the NH base shown in the formula 1, R1, R2 independently of one another and respectively with-(R) m-expression, R is alkylidene group, arylidene or carbonyl, m is more than 0 or 1, X, Y are independent of one another and be hydrogen, hydroxyl, alkyl, aryl, carboxyl, amino or imino-, herein, R, X and Y are independent of one another, and more than one the group that can be selected from alkyl, aryl, hydroxyl, carboxyl, amino and the halogen radical further replaces.
Figure FDA00003614182300011
5. metal finishing composition according to claim 4 is characterized in that, only contains among X, the Y of the formula 1 more than a kind one at least and is the amine compound of hydroxyl.
6. metal finishing composition according to claim 5, it is characterized in that, by described cationic resins that form for the amine compound modification of hydroxyl only among X, the Y of the formula 1 more than at least a kind, its gross weight with the raw material of described cationic resin is benchmark, uses the described amine compound of 5 weight %～30 weight % to obtain.
7. according to claim 5 or 6 described metal finishing compositions, it is characterized in that the raw material of described cationic resin is only one to account for 10～100 weight % of whole amine compound for the amine compound of hydroxyl among X, the Y contained among the amine compound of formula 1.
8. a metal surface treating method is characterized in that, dipping metal to be treated material in the described composition of each in claim 1～7 is separated out in that the metal to be treated material is made to film at metallic substance in as the electrolysis treatment operation of negative electrode.
9. metal surface treating method, it is characterized in that, second operation in 30～300 seconds of electrolysis under voltage 50～400V that it has first operation and implements after described first operation, wherein, described first operation is after making the surface metallic substance of cleaningization impregnated in each described composition of claim 1～7, perhaps while flooding with described metallic substance as negative electrode, in 10～120 seconds of the following electrolysis of voltage 15V, herein, described second operation and then described first operation in same bath, implement.
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