CN100510177C - Composition and method for surface treatment of metal materials - Google Patents
Composition and method for surface treatment of metal materials Download PDFInfo
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- CN100510177C CN100510177C CNB2004100118955A CN200410011895A CN100510177C CN 100510177 C CN100510177 C CN 100510177C CN B2004100118955 A CNB2004100118955 A CN B2004100118955A CN 200410011895 A CN200410011895 A CN 200410011895A CN 100510177 C CN100510177 C CN 100510177C
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Abstract
Provided is a composition for treating a surface capable of forming a film having excellent corrosion resistance, fingerprint resistance, blackening resistance, adhesion of a coating material or the like on the surface of a metallic material, and to provide a surface treatment method. The composition for treating the surface of a metallic material comprises: a water base medium; and the following components: (A) metallic ions selected from Mn ions, Co ions, Zn ions, Mg ions, Ni ions, Ti ions, V ions and Zr ions; (B) fluoro acid having at least four fluorine atoms, and at least one element selected from Ti, Zr, Si, Hf, Al and B; (C) a silane coupling agent having a reactive functional group selected from an active hydrogen-containing amino group, an epoxy group, a vinyl group, a mercapto group and a methacryloxy group; and (D) cationic or nonionic water base emulsion resin including resin selected from urethane resin, acrylic resin, epoxy resin, polyester resin and polyamide resin as a resin component(s). The surface treatment method for a metallic material uses the same.
Description
Technical field
The present invention relates to can pay high solidity to corrosion at metal material surface, can form simultaneously have good anti-finger printing, the surface treatment of the tunicle of anti-blackening, coating adhesion etc. is with composition and surface treatment method.
Background technology
Metallic substance such as zinciferous metal plating steel plate, aluminium sheet are widely used in fields such as automobile, material of construction and household electrical appliances.The zinc and the aluminium that are used for these metallic substance corrode in atmosphere, generate the corrosion product of so-called white rust, exist the visual appearance that makes metallic substance to reduce the shortcoming that coating adhesion is worsened.
In order to improve solidity to corrosion and coating adhesion, it is that the treatment solution of main component carries out chromate treating at metal material surface that general using contains chromic acid, dichromic acid or its salt.
Exist the 6 valency chromium handled in the chromate treating liquid that metal material surface uses that human body is directly had the shortcoming of bad influence, the consciousness to environment protection improves in recent years, so often avoid chromate treating as far as possible.In addition, need carry out preventing the special processing of stipulating in the method that this just becomes the reason that raises the cost on the whole to the waste water that contains 6 valency chromium in water pollution.In addition, the metallic substance that carries out chromate treating exists it becoming when containing the chromium trade waste the big shortcoming of can not recirculation using, and this has become social concern.
On the other hand, as everyone knows as the metallic material surface treating method beyond the chromate treating, the surface treatment that utilizes the Weibull that the contains polynary phenolic acid processing of composition is arranged.Handle metallic substance with the Weibull aqueous solution, think that the protection tunicle that utilizes Weibull and metallic substance reaction to form becomes the submerged barrier to corrosive deposit, so solidity to corrosion improves.
, require the high anti-corrosion of tunicle itself, so Weibull uses separately or use the tunicle solidity to corrosion that obtains not enough with inorganic components in recent years along with the raising that quality product is required, can not practicability under existing situation.
And as improving corrosion proof treatment process, patent documentation 1 discloses the method (with reference to the claim of patent documentation 1) that is coated to the metallic surface by the Synolac of the silicon-dioxide of water dispersible, water-soluble or water dispersible and/or the silica composite aqueous solution that tri-alkoxy (or alkoxyl group alkoxyl group) silane compound is formed.
In addition, patent documentation 2 discloses the aqueous solution of dissolving hydroxy pyrone or its derivative or the aqueous solution that adds water-soluble high-molecular compound in this aqueous solution has been coated to the metal surface treating method (with reference to the claim of patent documentation 2) that forms antirust tunicle after the drying of metallic surface.
And then, patent documentation 3 disclose by the water-soluble of hydroxy styrenes system or from the molecular metal finishing of water dispersible high score with additive and contain that this is water-soluble or be the metal finishing usefulness aqueous solution (with reference to the claim of patent documentation 3) of neccessary composition from water dispersible polymer and the metal ion selected from Ti, Zr, Hf, Zn, Ni, Co, Cr, Mn, Al, Ca and Mg.This metal finishing is used for chromate treating and non-chromate and handles with the additive and the metal finishing aqueous solution, can both improve solidity to corrosion and coating adhesion (field that utilizes on the industry with reference to patent documentation 3 and embodiment) under the various situations.
Above-mentioned these methods are not to generate the tunicle with high anti-corrosion, substitute chromate film.
In order to address these problems, the applicant has proposed to contain aqueous medium and (A) metal ion more than the specific divalent in patent documentation 4, (B) from specific fluoro-acid, the sour composition of selecting in phosphoric acid and the acetic acid, (C) have the silane coupling agent of specific reactive functional groups and (D) metallic substance of specific water-soluble polymers with surface treating composition (with reference to the claim of patent documentation 4), (A) specific water soluble resin or water system emulsifying resins in patent documentation 5, have been proposed to contain, (B) specific resin compound, (C) specific metallic compound also can contain (D) specific acid and/or (E) metal conditioner of silane coupling agent (with reference to the claim of patent documentation 5) as composition arbitrarily.
Under the situation of using these metal surface treating compositions, solidity to corrosion can increase substantially substantially, but can't say enough about anti-blackening.
Therefore, present situation still be the Chrome-free used of the good metallic substance of strong request exploitation solidity to corrosion be surface treatment agent and treatment process.
[patent documentation 1] spy opens clear 53-121034 communique
[patent documentation 2] spy opens clear 54-56037 communique
[patent documentation 3] spy opens flat 1-177380 communique
[patent documentation 4] spy opens flat 11-106945 communique
[patent documentation 5] spy opens the 2003-13252 communique
Summary of the invention
The objective of the invention is to solve the above-mentioned problems in the prior art, provide and can form the good tunicle of solidity to corrosion at metal material surface, have simultaneously good anti-finger printing, anti-blackening, coating adhesion non-chromium the metal material surface composition for treating and use the surface treatment method of its metallic substance.
The inventor has carried out wholwe-hearted research repeatedly to the problems of the prior art that will solve, found that and use the aqueous surface composition for treating contain the above metal ion of specific divalent, specific fluoro-acid, specific silane coupling agent, specific water system emulsifying resins, metal material surface is handled, can form the good tunicle of solidity to corrosion, can form simultaneously have good anti-finger printing, the tunicle of anti-blackening, coating adhesion, so far finished the present invention.
That is, the present invention relates to the metal material surface composition for treating that contains aqueous medium and dissolving or be dispersed in the following compositions in this aqueous medium.
(A) metal ion more than the divalent of from mn ion, cobalt ion, zine ion, magnesium ion, nickel ion, titanium ion, vanadium ion and zirconium ion, selecting;
(B) have at least 4 fluorine atoms and a fluoro-acid of at least 1 element from titanium, zirconium, silicon, hafnium, aluminium and boron, selecting;
(C) has the silane coupling agent of at least 1 reactive functional groups from the amino, epoxy group(ing), vinyl, sulfydryl and the methacryloxy that contain active hydrogen, selecting; With
(D) the water system emulsifying resins of the resin of the urethane resin that is selected from cationic or non-ionic type, acrylic resin, Resins, epoxy, vibrin and polyamide resin as resinous principle.
The present invention also relates to the surface treatment method of metallic substance, it is characterized in that being adjusted into pH2.0～6.5, as required can the use medium, be coated to metal material surface as operation with the above-mentioned metal material surface composition for treating of composition, the formation of dry back has 0.01～5.0g/m
2The tunicle of dry mass.
Use the metal material surface composition for treating of chromium and the surface treatment method of metallic substance of not containing of the present invention, can form based on good solidity to corrosion, have the tunicle of good anti-finger printing, anti-blackening, coating adhesion etc. at metal material surface.The present invention is very effective as the solution of social concerns such as environment protection and recycling, and practical value is very high.
Embodiment
Metal material surface composition for treating of the present invention is that the specific resin of specific divalent above metal ion (A), specific fluoro-acid (B), the silane coupling agent (C) with specific reactivity functional group and cationic or non-ionic type dissolves as the water system emulsifying resins (D) of resinous principle or is dispersed in solution or dispersion liquid in the aqueous medium.
Being used for the above metal ion (A) of divalent of the present invention is the above metal ion of divalent that is selected from mn ion, cobalt ion, zine ion, magnesium ion, nickel ion, titanium ion, vanadium ion and zirconium ion.This metal ion can be to constitute by a kind, also can be by constituting more than 2 kinds.Can not obtain high solidity to corrosion with the metal ion beyond above-mentioned.These ionic sources of supply are not had special qualification, and what can exemplify has carbonate, phosphoric acid salt, nitrate, vitriol, acetate, fluorochemical, oxide compound, a metal etc.What can exemplify specifically has, the manganous carbonate in the carbonate (II), cobaltous carbonate (II), cobalt carbonate hydroxide (II), zinc carbonate, magnesiumcarbonate, hydroxyl magnesiumcarbonate, nickelous carbonate (II), alkaline carbonic acid nickel (II), acid nickelous carbonate (II), alkaline carbonic acid zirconium, zirconium carbonate hydroxide etc.; Manganous phosphate in the phosphoric acid salt (II), manganous phosphate (III), cobaltous phosphate (II), zinc phosphate, trimagnesium phosphate, nickelous phosphate (II), nickel pyrophosphate, hydroxyl zirconium phosphate, zirconium pyrophosphate, biphosphate zirconium etc.; Manganous nitrate in the nitrate (II), Xiao Suangu (II), alkaline Xiao Suangu (II), Xiao Suangu (III), zinc nitrate, magnesium nitrate, nickelous nitrate (II), alkaline nickelous nitrate, Titanium Nitrate, zirconium nitrate etc.; Manganous sulfate in the vitriol (II), manganous sulfate (III), manganous sulfate (IV), rose vitriol (II), rose vitriol (III), zinc sulfate, sal epsom, single nickel salt (II), titanium sulfate (III), titanium sulfate (IV), Vanadosulfuric acid (II), Vanadosulfuric acid (III), zirconium sulfate (IV) etc.; Manganese acetate in the acetate (II), manganese acetate (III), Cobaltous diacetate (II), Cobaltous diacetate (III), zinc acetate, alkaline zinc acetate, magnesium acetate, nickel acetate (II), nickel acetate (III) etc.; Manganous fluoride in the fluorochemical, manganic fluoride, cobaltous fluoride (II), cobaltous fluoride (III), zinc fluoride, magnesium fluoride, nickelous fluoride (II), titanium fluoride (III), titanium fluoride (IV), vanadium fluoride (III), vanadium fluoride (IV), vanadium fluoride (V), Zirconium tetrafluoride etc.; Manganese oxide in the oxide compound (II), trimanganese tetroxide, manganese oxide (III), manganese oxide (IV), manganic anhydride, cobalt oxide (II), cobalt oxide (III), tricobalt tetroxide, zinc oxide, magnesium oxide, nickel oxide (II), nickelous-nickelic oxide, nickel oxide (III), titanium oxide (IV), vanadium oxide (II), vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), zirconium white etc.; Manganese metal in the metal, cobalt metal, metallic zinc, MAGNESIUM METAL, metallic nickel, metal titanium, vanadium metal and metal zirconium.They can be anhydrides, also can be the hydrates under the situation about existing.
Surface treatment of the present invention is wished to be preferably 0.1～5 quality % for 0.01～10 quality % of surface treatment with the total solids composition of the composition (A)～(D) of composition with the content (solid component content) of the above metal ion (A) of the divalent in the composition.This content is under the situation less than 0.01 quality %, and the film-forming properties of the tunicle that obtains is not enough, and solidity to corrosion is low sometimes.In addition, cation constituent surpasses 10 quality %, and surface treatment has the tendency of reduction with the stability of composition.
Surface treatment of the present invention is the fluoro-acid that has at least 4 fluorine atoms and be selected from least 1 element of titanium, zirconium, silicon, hafnium, aluminium and boron with the fluoro-acid in the composition (B).This fluoro-acid can constitute by a kind, also can be by constituting more than 2 kinds.
As the concrete example of this fluoro-acid, what can exemplify has a hexafluoro metatitanic acid (H
2TiF
6), hexafluoro zirconate (H
2ZrF
6), hexafluorosilicic acid (H
2SiF
6), hexafluoro hafnium acid (H
2HfF
6), hexafluoro aluminic acid (H
3AlF
6), Tetrafluoroboric acid (HBF
4) etc.
This surface treatment is wished to be preferably 0.5～10 quality % for 0.1～15 quality % of the total solids composition of composition (A)～(D) with fluoro-acid (B) content (solid component content) in the composition.Wish surface treatment to be adjusted to 2.0～6.5 with the pH value of composition with this fluoro-acid.Under the situation of fluoro-acid less than 0.1 quality % of the total solids composition of composition (A)～(D), can not adjust to the pH value in the above-mentioned scope, its film-forming properties deterioration as a result has the tendency that solidity to corrosion reduces.In addition, fluoro-acid surpasses 15 quality % of the total solids composition of composition (A)～(D), and surface treatment sometimes reduces with the stability of composition.
Surface treatment of the present invention is the silane coupling agent with at least 1 reactive functional groups that is selected from the amino, epoxy group(ing), vinyl, sulfydryl and the methacryloxy that contain active hydrogen with the silane coupling agent in the composition (C), and there is no particular limitation for its structure.This silane coupling agent can constitute by a kind, also can be by constituting more than 2 kinds.As silane coupling agent, (i)～(material that v) exemplifies below for example can using.
(i) has the material of the amino that contains active hydrogen: N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-(aminoethyl) 3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane;
The material that (ii) has epoxy group(ing): 3-glycidoxy Trimethoxy silane, 3-glycidoxy methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane;
The material that (iii) has vinyl: vinyltriethoxysilane;
The material that (iv) has sulfydryl: 3-sulfydryl propyl trimethoxy silicane;
(the material that v) has methacryloxy: 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane.
Be used for silane coupling agent of the present invention (C), hope is by the silane coupling agent with the amino that has 1 active hydrogen at least (a) and have at least the silane coupling agent (b) of 1 epoxy group(ing) to constitute.This silane coupling agent (a) and silane coupling agent (b) can constitute by a kind respectively, also can be by constituting more than 2 kinds.
In addition, under the situation that surface treatment of the present invention is made of amino that contains active hydrogen and epoxy group(ing) with the reactive functional groups of the silane coupling agent in the composition, wish to contain the amino of active hydrogen and the equivalence ratio of epoxy group(ing) is the scope of 3:1～1:3.The equivalence ratio that contains the amino of active hydrogen and epoxy group(ing) surpasses 3:1 and contains the amino many of active hydrogen, and the film-forming properties of the tunicle of formation reduces, and has solidity to corrosion, anti-finger printing, anti-blackening, the coating adhesion inadequate tendency that becomes.In addition, this equivalence ratio contains less than 1:3 under the few situation of the amino of active hydrogen, and performances such as the solidity to corrosion of the tunicle of formation, anti-finger printing, anti-blackening, coating adhesion reach capacity, and have wasted silane coupling agent from saying economically.
In addition, surface treatment of the present invention is the water system emulsifying resins of the resin of selecting from urethane resin, acrylic resin, Resins, epoxy, vibrin and the polyamide resin of cationic or non-ionic type as resinous principle with the water system emulsifying resins (D) in the composition.This water system emulsifying resins can constitute by a kind, also can be by constituting more than 2 kinds.These water system emulsifying resins have the cationic functional group of a kind of primary amino, secondary amino group, uncle's amino, season amino etc. at least in molecular structure, or have the functional group of the non-ionic type of at least a kind of poly-oxyethylene chain, hydroxyl, uncle's amido, secondary amido, uncle's amido etc., or has the functional group of at least a kind of this cationic functional group and at least a kind of this non-ionic type.
It is water-soluble or water dispersible requiring this resin.Just this water system emulsifying resins (D) is as hydrophilic group with above-mentioned cationic functional group and/or non-ionic type functional group, can in water, dissolve or self-dispersed emulsifying resins, or utilize the tensio-active agent of cationic and/or non-ionic type, can in water, dissolve or force dispersive water system emulsifying resins.
This water system emulsifying resins (D) but preferably do not use soap-free as the tensio-active agent of solvation, emulsifying dispersant, or do one's utmost to suppress its usage quantity.
Water system emulsifying resins (D) for the tunicle that makes formation has good alkali resistance, need be cationic and/or non-ionic type.In addition, be cationic and/or non-ionic type, general because the intermiscibility of metal ion (A), fluoro-acid (B) and silane coupling agent (C) that divalent is above is an ideal.
As water system emulsifying resins (D), preferably using weight-average molecular weight is 1,000～1,000,000, the most handy 2,000～500,000.Under the situation of above-mentioned molecular weight less than 1,000, worry that tunicle formation property is insufficient, surpass 1,000,000, worry that surface treatment reduces with the stability of composition.
Urethane resin as above-mentioned cationic or non-ionic type, its example has at polyester polyols (particularly binary) alcohol, polyethers polynary (particularly binary) alcohol, polynary (particularly binary) isocyanic ester of polynary (particularly binary) alcohols and fatty of polycarbonate polynary (particularly binary) alcohol etc. and/or with the urethane resin of the polycondensate of aromatic series polynary (particularly binary) isocyanate compound in, use is as the part of polyvalent alcohol, has N, the polyvalent alcohol of the displacement amino of N-dimethylamino dihydroxy methylpropane etc., urethane that polyvalent alcohol with the such polyoxyethylene chain of polyoxyethylene glycol etc. obtains etc.
Acrylic resin as above-mentioned cationic or non-ionic type, its example has the N of containing, N-dimethyl aminopropyl acrylate, the cationic monomer of the displacement amino that (two) alkylamino (methyl) acrylate of N-methyl aminoethyl methacrylic ester etc. is such, and/or have and polyethylene glycol methacrylate-styrene polymer, the nonionic monomers of hydrophilic groups such as the polyoxyethylene chain of 2-hydroxyethyl meth acrylate etc. and hydroxyl, the Acrylic Acid Monomer of (methyl) propenyl ester etc., vinylbenzene, vinyl cyanide, the co-polypropylene acid resin of addition polymerization unsaturated monomers such as vinyl acetate between to for plastic etc.
Resins, epoxy as above-mentioned cationic or non-ionic type, its example has in bisphenol type epoxy compound or other diglycidyl ether compound, make diamines effects such as quadrol, cationization and the Resins, epoxy that obtains, the non-ionic type Resins, epoxy etc. of additional polyoxyethylene glycol on the side chain of bisphenol type epoxy compound or other diglycidyl ether compound.
Vibrin as above-mentioned cationic or non-ionic type, what can exemplify has in the vibrin of the condenses of polyprotonic acids such as polyhydroxy reactants such as ethylene glycol, neopentyl alcohol and terephthalic acid, make the diol component surplus, not vibrin of the esterification of residual carboxyl etc.
Polyamide resin as above-mentioned cationic or non-ionic type, useful poly carboxylic acid that can exemplify and polyamine polycondensation, for example nylon of obtaining of the polycondensation of the ring-opening polymerization of the polycondensation of diamines such as dicarboxylic acid such as hexanodioic acid, sebacic acid and quadrol, hexanediamine, lactan or aminocarboxylic acid etc.
With in the composition, the solids component mass ratio of silane coupling agent (C) and water system emulsifying resins (D) wishes to be 1:100～10:1 in surface treatment of the present invention, more wishes to be 1:10～5:1.This mass ratio is lower than 1:100 and under the low situation of the ratio of silane coupling agent because the sticking power of the tunicle that forms and matrix surface reduces, have tunicle solidity to corrosion and with the tendency of the adaptation reduction of matrix.In addition, this mass ratio surpasses 10:1 and under the high situation of the ratio of silane coupling agent, because the surface treatment that obtains reduces with the film-forming properties of composition, has the inadequate tendency of film solidity to corrosion that obtains.
In addition, with in the composition, can cooperate the additive of weighting agent, lubricant etc. in surface treatment of the present invention as composition arbitrarily.Zirconia sol, aluminium colloidal sol, silicon dioxide gel etc. can be used as weighting agent, polyethylene wax, Poly Propylene Wax etc. can be used as lubricant.Above-mentioned additive also can also can cooperate (just modulating surperficial composition for treating from aqueous medium, necessary composition (A)～(D) with additive) cooperating behind aqueous medium and the surperficial composition for treating of necessary composition (A)～(D) modulation before modulation.
Surface treatment of the present invention is general water with the aqueous medium in the composition, for example for promote in the water system emulsifying resins (D) resin purpose such as dissolve, also can contain the organic solvent of the lower alcohols such as methyl alcohol, ethanol, propyl alcohol etc. of a small amount of (for example 5 quality % are following).
Surface treatment composition of the present invention comprises building and bathes with composition (concentrated solution) and operation composition (diluent) two kinds.Building bath, be preferably 15～30 quality % with preferred 10～40 quality % of total solids constituent concentration in the composition.Operation is preferably 5～30 quality % with preferred 1～40 quality % of composition total solids constituent concentration.In addition, wish build bathe with composition and in operating with composition the total solids components in proportions of composition (A)～(D) account for more than the 50 quality % of total solids composition, be preferably in more than the 80 quality %.
When composition is used in manufacturing surface treatment of the present invention, need not note especially and can be undertaken by general method, for example can be simply composition (A)～(D) with dissolve or be dispersed in the aqueous medium as the random additive of composition as required, composition (A)～(D) dissolved or be dispersed in make in the aqueous medium surface treatment with composition after, cooperate as required as the random additive of composition and make.
Surface of the present invention composition as the pH value of operating under the situation about using with composition, is wished to adjust to 2.0～6.5 scopes, preferably adjust to 2.5～5.0 scopes.At this moment, adjust agent as the pH value, improving under the situation of surface treatment with the pH value of composition, the alkaline carbonate of the alkali metal hydroxide of use ammoniacal liquor, sodium hydroxide etc., yellow soda ash etc. etc., reducing under the situation of surface treatment with the pH value of composition, hope uses in the present invention the fluoro-acid of usefulness (B) to adjust.The pH value less than 2.0 situation under since with the hyperergy of matrix surface, the film-forming properties of the tunicle that obtains is bad, the inadequate tendency that becomes of solidity to corrosion, anti-finger printing, anti-blackening, the coating adhesion with tunicle.In addition, this pH value surpasses 6.5, because water system emulsifying resins (D) separates out with precipitating the composition from surface treatment easily, with life-span of composition the tendency that shortens is arranged so have surface treatment.
The invention still further relates to the surface treatment method of metallic substance, it is characterized in that adjusting pH to 2.0～6.5 scopes, use medium as required be coated to metal material surface as operation with the above-mentioned metal material surface composition for treating of composition, the formation of dry back has 0.01～5.0g/m
2, wish it is 0.1～3.0g/m
2The tunicle of dry mass.Dried film by quality less than 0.01g/m
2Situation under, be difficult to cover metallic substance, solidity to corrosion, anti-finger printing, anti-blackening, coating adhesion are insufficient.In addition, driedly surpassed 5.0g/m by film quality
2, coating adhesion reduces.
There is no particular limitation with method for compositions to apply this surface treatment, for example can use dipping method, spray method and method of roll coating etc.In addition, also there is no particular limitation about treatment temp, treatment time.
The surface treatment that forms on metal material surface is wished to carry out under the situation of heating with the drying of composition layer, wishes that Heating temperature is 50～250 ℃.Also can carry out water-cooled as required then.
There is no particular limitation with the metallic substance of composition to apply surface treatment of the present invention, and adducible have steel plate, zinciferous Coated Steel, tin plate, stainless steel plate, aluminium sheet and an aluminium alloy plate etc.Be not only the kind of this metallic substance, size, shape (above-mentioned be example with sheet material) etc. also there is no particular limitation.
The mechanism of action of handling the solidity to corrosion that can significantly improve metallic substance, anti-finger printing, anti-blackening, coating adhesion with composition with surface treatment of the present invention is described, this mechanism of action is a kind of supposition, and the present invention is not that restriction is in this infers.At first, after making metal material surface and surface treatment contacting with composition, utilize surface treatment, make the metallic surface that etch take place with the fluoro-acid in the composition.Utilize owing to metal ion and the surface treatment of etch from the metal material surface stripping raises with the reaction of metal ion more than the divalent the composition and water system emulsifying resins and because of etch causes the pH value at interface, form the resin coating of insoluble at the interface.Solidity to corrosion, anti-finger printing, the anti-blackening that has improved metallic substance owing to this reason thought in this insoluble resin coating performance shielding effect.But the adaptation owing to tunicle and metallic substance reduces under the situation of Shi Yonging like this, so use silane coupling agent in the lump.Supposition just is functional group's (methoxyl group, oxyethyl group etc.) hydrolysis in the silane coupling agent, form and combine with the oxane of metal material surface, and then the reactive functional groups that has of silane coupling agent and the resin in the water system emulsifying resins and the organic coating that generally forms on above-mentioned resin coating are improved the adaptation of metallic substance and above-mentioned resin coating and organic coating film by film reaction.
Embodiment
[embodiment]
With embodiment and comparative example the present invention is specifically described below, but scope of the present invention is not limited to these embodiment.Be described as follows with composition about metallic substance, its surperficial purifying method and the surface treatment of in following embodiment and comparative example, using of the present invention.
1. test panels
Cold-rolled steel sheet (SPC)
Market sale product, thickness of slab 0.6mm JIS G314
The zinc-containing metal Coated Steel
(A) market sale product, thickness of slab 0.6mm two sides electrogalvanizing steel plate (EG) plating amount 20g/m
2
(B) market sale product, thickness of slab 0.6mm hot-dip galvanizing sheet steel (GI) plating amount 40g/m
2
Aluminium sheet (AL): market sale product, thickness of slab 0.8mm JIS A 5052
2. the purifying method of test panels
The aqueous solution (drug concentration: 20g/L) with alkaline defatting agent (registered trademark: Off ア イ Application Network リ-Na 4336, the rapids essence of Japanese handkerchief card (strain) system), in treatment temp: 60 ℃, treatment time: to the processing of spraying of above-mentioned test panels surface, remove under 20 seconds the condition attached to lip-deep dust and oil.Clean with tap water then and remain in lip-deep alkaline components, test panels is cleaned up.
3. surface treatment composition
Table 1 is illustrated in the surface treatment composition that uses in present embodiment and the comparative example.
The note of table 1
Annotate 1) c1: γ-Qiu Jibingjisanjiayangjiguiwan
C2: gamma-amino propyl trimethoxy silicane
C3: γ-glycidoxypropyltrime,hoxysilane
C4: γ-methacryloxypropyl trimethoxy silane
Annotate 2) d1: cationic modified epoxy resin (bisphenol A-type, molecular weight 30,000, latex particle diameter 0.15 μ m)
D2: non-ionic water-soluble vibrin (terephthaldehyde's acid type, molecular weight 10,000, latex particle diameter 0.1 μ m)
D3: cation type polyurethane resin (polyether glycol aliphatic polymeric isocyanate type, molecular weight 20,000, latex particle diameter 0.01 μ m)
D4: cationic acrylic resin (N-methyl aminoethyl methacrylic ester, molecular weight 50,000, latex particle diameter 0.3 μ m)
D5: nonionic polyurethane resin (polyester polyol aliphatic polymeric isocyanate type, molecular weight 15,000, latex particle diameter 0.08 μ m)
D6: the water-soluble polymers that constitutes by following unit repeatedly
[changing 1]
Y＝-CH
2N(CH
3)
2
N＝2-50
Annotate 3) the relative total solids components in proportions (%) of each solids component (A)～(D).
Notes 4) surface treatment is adjusted to 20 quality % with total solids composition in the composition (the total solids composition of (A)～(D) of=composition) concentration.Aqueous medium is a water.
Annotate 5) chromic salt: TOP-5241 (the rapids essence of Japanese handkerchief card (strain) system)
4. the treatment process of test panels
The treatment process of table 2 expression test panels.Surface treatment is carried out with the method that is coated with the application roller coat of composition.
The treatment process of table 2 test panels
| Test panels | Tunicle amount (g/m 2) | The plate temperature that reaches (℃) 1) | |
| Embodiment 1 | EG | 0.9 | 110 |
| Embodiment 2 | EG | 0.8 | 110 |
| Embodiment 3 | GI | 0.6 | 80 |
| Embodiment 4 | GI | 0.6 | 80 |
| Embodiment 5 | EG | 0.8 | 180 |
| Embodiment 6 | EG | 1.2 | 180 |
| Embodiment 7 | GI | 0.8 | 110 |
| Embodiment 8 | GI | 0.6 | 80 |
| Embodiment 9 | AL | 1.0 | 80 |
| Embodiment 10 | SPC | 1.0 | 180 |
| Embodiment 11 | EG | 0.8 | 150 |
| Comparative example 1 | EG | 0.9 | 100 |
| Comparative example 2 | EG | 1.2 | 100 |
| Comparative example 3 | GI | 0.6 | 180 |
| Comparative example 4 | GI | 0.6 | 150 |
| Comparative example 5 | EG | 0.8 | 80 |
| Comparative example 6 | EG | 0.8 | 80 |
| Comparative example 7 | EG | 0.8 | 80 |
| Comparative example 8 | GI | 0.7 | 80 |
Annotate 1) the plate temperature that reaches when dry.
5. evaluation test method
Utilize the performance of the surface treatment test panels that the foregoing description and comparative example obtain to estimate with following method.
5.1. solidity to corrosion
A) solidity to corrosion (1) (SST)
Test panels is the situation that contains zinc coating steel plate (SG, GI) and aluminium sheet (Al): the surface treatment test panels is carried out salt spray testing (JIS Z 2371), reach time of 5% and estimate with producing the white rust area in visual observations.
B) solidity to corrosion (2) (HCT)
Test panels is the situation of cold-rolled steel sheet: the surface treatment test panels is remained under the atmospheric condition of 50 ℃-humidity of temperature 95%, reach time of 5% and estimate with producing the white rust area in visual observations.
5.2. coating adhesion
The surface treatment test panels is carried out application under the following conditions and is obtained coated plate, carries out the coating adhesion test.＜application condition〉pure acid is coating (big Japanese coating (strain) trade name デ リ コ Application #700) application: bar shaped coating method, sintering condition: 140 ℃ * 20 minutes, form filming of 25 μ m.
5.2.1. adaptation
(1) grid test: switch to steel matrix with the NT cutting unit on the filming of coated plate, be cut into the square grid of 100 1mm, peel off with glass ribbon afterwards, the remaining number that usefulness is filmed is estimated.
(2) grid drawing test: on the coating of coated plate, switch to steel matrix, be cut into the square grid of 100 1mm, behind cupping testing machine extrusion 5mm, the part of this protrusion is peeled off, estimate with the remaining number of coating with glass ribbon with the NT cutting unit.
5.2.2. secondary adaptation
Coated plate flooded 2 hours in the ebullient pure water after, carry out and an identical evaluation of adaptation.
5.3. anti-finger printing
The pressure that press...withes one's finger on the processing sheet material that obtains with table 2 is estimated with the state of range estimation fingerprint trace.Result by following expression evaluation.
◎: do not stay fingerprint trace fully.
Zero: residual extremely slight fingerprint trace.
△: residual slight fingerprint trace.
*: residual distinct fingerprint trace.
5.4. anti-blackening
Cut out polylith test plate from the processing sheet material that obtains at table 2, make 2 tests make 1 pair sample relatively with the application face of plate, overlapping 5～10 pairs, behind vinyl film paper bale packing, 4 angle bolting,, take out after in 70 ℃, the humidity cabinet of 98% relative humidity, placing 240 hours then to the 6.96Nm scale with the torque spanner applying load, the situation of superposed part blackening is judged with estimating.Criterion is as follows.
5: not blackening
4: become very light grey
3: blackening is less than 25%
2: blackening is 25～＜50%
1: blackening is more than 50%.
Above-mentioned test-results is shown in table 3.
Table 3 evaluation test result
From the result of table 3 as can be seen, the comparative example 1 of containing metal composition (A) and fluoro-acid (B) and not contain comparative example 2 solidity to corrosions of fluoro-acid (B) poor not, comparative example 3 solidity to corrosions that do not contain silane coupler (C) are poor.In addition, the comparative example 4 that does not contain water system emulsifying resins (D) is except the solidity to corrosion difference, and anti-finger printing is obviously poor.Comparative example 5 solidity to corrosions and the anti-blackening that do not contain fluoro-acid (B) and silane coupling agent (C) are poor.The surface treatment that is equivalent to patent documentation 4 that the applicant proposes and patent documentation 5 records is good with the comparative example 6 of composition and comparative example 7 solidity to corrosions, anti-finger printing, but anti-blackening is poor.With these contrasts, use surface treatment of the present invention to demonstrate good solidity to corrosion, coating adhesion, anti-finger printing and anti-blackening with the embodiment 1～11 of composition, can obtain with comparative example 8 in the identical～identical performance of resin chromic salt cardinal principle.
Claims (19)
1. metal material surface composition for treating, contain aqueous medium and be dissolved or dispersed in following compositions in this aqueous medium:
(A) be selected from the above metal ion of divalent in mn ion, cobalt ion, zine ion, magnesium ion, nickel ion, titanium ion, vanadium ion and the zirconium ion,
(B) have at least 4 fluorine atoms and be selected from least 1 element of titanium, zirconium, silicon, hafnium, aluminium and boron fluoro-acid,
(C) have be selected from the silane coupling agent of selecting 1 reactive functional groups in amino, epoxy group(ing), vinyl, sulfydryl and the methacryloxy that contains active hydrogen at least and
(D) the urethane resin of non-ionic type or acrylic resin water system emulsifying resins as resinous principle.
2. metal material surface composition for treating as claimed in claim 1, described metal ion (A) contains 0.01～10 quality % with respect to the total solids composition of the composition (A)～(D) of metal material surface composition for treating.
3. metal material surface composition for treating as claimed in claim 1, described fluoro-acid (B) contains 0.1～15 quality % with respect to the total solids composition of the composition (A)～(D) of metal material surface composition for treating.
4. metal material surface composition for treating as claimed in claim 1, the solids component mass ratio (C) of described silane coupling agent (C) and described water system emulsifying resins (D): (D) be 1:100～10:1.
5. metal material surface composition for treating as claimed in claim 1, total solids composition with respect to the composition (A)～(D) of metal material surface composition for treating, containing described metal ion (A) is that 0.01～10 quality % and described fluoro-acid (B) are 0.1～15 quality %, and the solids component mass ratio (C) of silane coupling agent (C) and water system emulsifying resins (D): (D) be 1:100～10:1.
6. metal material surface composition for treating as claimed in claim 1, described silane coupling agent (C) be by (a) contain the amino that contains 1 active hydrogen at least, at least a kind of the 1st silane coupling agent and (b) contain at least 1 epoxy group(ing), at least a kind of the 2nd silane coupling agent constitute.
7. metal material surface composition for treating as claimed in claim 5, described silane coupling agent (C) be by (a) contain the amino that contains 1 active hydrogen at least, at least a kind of the 1st silane coupling agent and (b) contain at least 1 epoxy group(ing), at least a kind of the 2nd silane coupling agent constitute.
8. metal material surface composition for treating as claimed in claim 6, the amino that contains active hydrogen that is contained in described the 1st silane coupling agent (a) is 3:1～1:3 with the equivalence ratio that is contained in the epoxy group(ing) in described the 2nd silane coupling agent (b).
9. metal material surface composition for treating as claimed in claim 7, the amino that contains active hydrogen that is contained in described the 1st silane coupling agent (a) is 3: 1～1: 3 with the equivalence ratio that is contained in the epoxy group(ing) in described the 2nd silane coupling agent (b).
10. metal material surface composition for treating as claimed in claim 6, the total amount of described the 1st silane coupling agent (a) and described the 2nd silane coupling agent (b) and the solids component mass ratio [(a)+(b)] of described water system emulsifying resins (D): (D) be 1:100～10:1.
11. metal material surface composition for treating as claimed in claim 7, the total amount of described the 1st silane coupling agent (a) and described the 2nd silane coupling agent (b) and the solids component mass ratio [(a)+(b)] of described water system emulsifying resins (D): (D) be 1:100～10:1.
12. as wantonly 1 described metal material surface composition for treating in the claim 1～11, metallic substance is steel plate, zinciferous Coated Steel, tin plate, stainless steel plate, aluminium sheet or aluminium alloy plate.
13. metal material surface composition for treating as claimed in claim 1, described metal ion (A) are from least a kind of supply of carbonate, phosphoric acid salt, nitrate, vitriol, acetate, fluoride salt, saline oxide and the metal that is selected from this metal itself.
14. metal material surface composition for treating as claimed in claim 1, described fluoro-acid (B) are to be selected from hexafluoro metatitanic acid, hexafluoro zirconate, hexafluorosilicic acid, the acid of hexafluoro hafnium, hexafluoro aluminic acid and Tetrafluoroboric acid at least a kind.
15. metal material surface composition for treating as claimed in claim 1, described silane coupling agent (C) is to be selected from N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-(aminoethyl) 3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, vinyltriethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane and 3-methacryloxypropyl methyl dimethoxysilane at least a kind.
16. metal material surface composition for treating as claimed in claim 6, described the 1st silane coupling agent is to be selected from N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-(aminoethyl) 3-aminopropyl trimethoxysilane and 3-aminopropyl triethoxysilane at least a kind, described the 2nd silane coupling agent is to be selected from least a kind of 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane and 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane.
17. metal material surface composition for treating as claimed in claim 7, described the 1st silane coupling agent is to be selected from N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-(aminoethyl) 3-aminopropyl trimethoxysilane and 3-aminopropyl triethoxysilane at least a kind, described the 2nd silane coupling agent is to be selected from least a kind of 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane and 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane.
18. the surface treatment method of metallic substance, it is characterized in that, pH is adjusted into 2.0～6.5, as required the use medium, as operation with wantonly 1 described metal material surface composition for treating in the claim 1～11 and 13～17 of composition, be coated to metal material surface, dry back forms has 0.01～5.0g/m
2The tunicle of dry mass.
19. surface treatment method as claimed in claim 18, metallic substance are steel plate, zinciferous Coated Steel, tin plate, stainless steel plate, aluminium sheet or aluminium alloy plate.
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