CN1814860A - Compound composition and process for surface treating of metal material - Google Patents
Compound composition and process for surface treating of metal material Download PDFInfo
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- CN1814860A CN1814860A CN 200610006268 CN200610006268A CN1814860A CN 1814860 A CN1814860 A CN 1814860A CN 200610006268 CN200610006268 CN 200610006268 CN 200610006268 A CN200610006268 A CN 200610006268A CN 1814860 A CN1814860 A CN 1814860A
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- silane coupling
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
To provide a composition for surface treatment of a non-chromium metallic material capable of depositing a film having excellent corrosion resistance, black discoloration resistance and coating adhesivity on the surface of the metallic material, and to provide a surface treatment method using the composition. In the composition for surface treatment of the metallic material, (A) at least one kind of phosphoric compound to be selected from a group consisting of phosphoric acid, condensed phosphoric acid, organic phosphonic acid, and ammonium salt thereof, (B) fluoro acid having at least one element selected from a group consisting of at least four fluorine atoms, titanium, zirconium, silicon, hafnium, aluminum and boron, and (C) silane coupling agent (C1) having at least one active hydrogen containing amino radical, and silane coupling agent (C2) having at least one epoxy radical are dissolved in aqueous medium or blended in a dispersive state, and the ratio of the solid of the component (A) to the total solids of the components (A)-(C) is 0.1-80 mass%. The composition is used for the surface treatment method of the metallic material.
Description
Technical field
The present invention relates to a kind of surface treatment composition and treatment process, this surface treatment can be given high erosion resistance to metal material surface with composition, can also form filming of anti-blackening and coating adhesion excellence simultaneously.
Background technology
Metallic substance such as zinciferous Metal plating steel plate, aluminium sheet use in the relevant many fields of automobile, building materials and household electrical appliances.But zinc that uses in these metallic substance and aluminium have following shortcoming: corrode in atmosphere, produce the corrosion product that is called white rust, this can reduce the outward appearance of metallic substance, and then brings detrimentally affect to coating adhesion.
Therefore, to contain chromic acid, dichromic acid or its esters be that the treatment solution of main component carries out chromate treating to the surface of metallic substance in order to improve erosion resistance and coating adhesion, to typically use.
Yet 6 valency chromium in the chromate treating liquid that uses in the surface treatment of metallic substance have to human body and directly bring dysgenic shortcoming, in recent years because the consciousness of environment protection is improved gradually, so should avoid chromate treating.In addition, the waste water that contains 6 valency chromium must be prevented the special processing of water quality pollution method defined, and this becomes the reason that whole cost significantly raises.In addition, the metallic substance that carries out chromate treating has unrenewable significant drawbacks when becoming the trade waste that contains chromium, and this also becomes social concern.
On the other hand, be known that the method for handling with composition with the surface treatment that contains tannic acid as the surface treatment method beyond the chromate treating, tannic acid is a kind of polybasic phenol carboxylic acid.The aqueous solution by tannic acid is handled metallic substance, and tannic acid forms protective membrane with the metallic substance reaction, because protective membrane becomes the blocking layer that prevents the corrosive deposit intrusion, so think and can improve erosion resistance.
Yet in recent years, because the quality of product improves, itself requires high corrosion resistance protective membrane, therefore, uses tannic acid separately or tannic acid and inorganic components are used the erosion resistance deficiency of the protective membrane that obtains together, in practice can't practicability.
Therefore, as the treatment process that improves erosion resistance, in patent documentation 1, disclose and a kind ofly will be applied to the method (with reference to the claim of patent documentation 1) of metallic surface by the aqueous solution of the silica complex of water-dispersible silica, water-soluble or aqueous-dispersing alkyd resin and trialkoxy silane compound formation.
In addition; in patent documentation 2, also disclose and to have dissolved the aqueous solution of hydroxy pyrone or derivatives thereof or in this aqueous solution, to have added the aqueous solution that water-soluble high-molecular compound forms; coating, drying on metallic substance, the metal surface treating method (with reference to the claim of patent documentation 2) of formation antirust protective film.
In addition, a kind of metal finishing aqueous solution is disclosed in patent documentation 3, this aqueous solution contain following must composition: or metal finishing that self dispersed polymer form water-soluble by the hydroxy styrenes class be water-soluble or self dispersed polymer and the metal ion (with reference to the claim of patent documentation 3) that is selected from Ti, Zr, Hf, Zn, Ni, Co, Cr, Mn, Al, Ca and Mg with additive and this.This metal finishing is used in chromate treating and non-chromate processing with the aqueous solution with additive and metal finishing, can improve erosion resistance and coating adhesion (with reference to the industrial suitable application area and the embodiment of patent documentation 3) in either case.
But above-mentioned any method all cannot form the protective membrane that high corrosion resistance is provided, and replaces chromate protective film.
As this way to solve the problem, the applicant has proposed to contain the specific water soluble resin of aqueous medium, (A) specific silane coupling agent, (B) in patent documentation 4 metallic substance is with surface treating composition (with reference to the claim of patent documentation 4); In patent documentation 5, proposed to contain the specific acidic component that is selected from fluoric acid, phosphoric acid and acetic acid, (C) of metal ion, (B) more than the specific divalent of aqueous medium, (A) have the silane coupling agent of specific functional group and (D) metallic substance of specific water-soluble polymers with surface treating composition (with reference to the claim of patent documentation 5); In patent documentation 6, proposed to contain specific resin compound of (A) specific water soluble resin or aqueous emulsion, (B) and (C) specific metallic compound, can contain (D) specific acid and/or (E) silane coupling agent as the metal conditioner (with reference to the claim of patent documentation 6) of optional member.
When using these metal surface treating compositions, erosion resistance improves usually significantly, but anti-blackening is also not enough.
Therefore, need develop non-chromium class surface treatment agent and the treatment process that the also excellent metallic substance of erosion resistance and anti-blackening excellence and coating adhesion is used now strongly.
Patent documentation 1: the spy opens clear 53-121034 communique
Patent documentation 2: the spy opens clear 54-56037 communique
Patent documentation 3: the spy opens flat 1-177380 communique
Patent documentation 4: the spy opens flat 9-241576 communique
Patent documentation 5: the spy opens flat 11-106945 communique
Patent documentation 6: the spy opens the 2003-13252 communique
Summary of the invention
The objective of the invention is to solve the foregoing problems that prior art has; the surface treatment method of the metallic substance of a kind of non-chromium metal material surface composition for treating and use said composition is provided; this surface treating composition can form excellent corrosion resistance at metal material surface, and anti-blackening and the also excellent protective membrane of coating adhesion.
The inventor is in order to solve the problem that these prior aries have; carried out conscientious repeatedly research; found that by use and mixed phosphate compound, had the fluoric acid of specific metal and the surface treatment composition of 2 kinds of specific silane coupling agents; metal material surface is handled; can form all excellent protective membrane of excellent corrosion resistance and anti-blackening and coating adhesion, thereby finish the present invention.
Just, the present invention relates to a kind of metal material surface composition for treating, said composition is to mix with dissolving or dispersion state in aqueous medium
(A) be selected from phosphoric acid, contract and at least a kind of phosphate compound of phosphoric acid and organic phospho acid and their ammonia salt,
(B) have the fluorine atom more than at least 4 and be selected from the fluoric acid of at least 1 element of titanium, zirconium, silicon, hafnium, aluminium and boron, and
(C) have at least 1 silane coupling agent (C2) that contains the silane coupling agent (C1) of the amino of active hydrogen and have at least 1 epoxy group(ing),
Formed metal material surface composition for treating, and with respect to all solid state components of composition (A)～(C), the ratio of the solid state component of composition (A) is 0.1～80 weight %.
The invention still further relates to a kind of surface treatment method of metallic substance, it is characterized in that: the above-mentioned metal material surface composition for treating as the operation composition that will be adjusted to pH2.0～6.5 is applied to metallic surface, drying, and the formation dry weight is 0.01～5.0g/m
2Protective membrane.
The metal material surface composition for treating that does not contain chromium of the application of the invention and the surface treatment method of metallic substance can form the protective membrane of erosion resistance and anti-blackening and coating adhesion excellence at metal material surface.The present invention is as the countermeasure aspect to social concerns such as environment protection and recovery property, and is very effective, the practical value height.
Embodiment
Metal material surface composition for treating of the present invention is that phosphate compound (A), the fluoric acid (B) with specific metal and 2 kinds specific silane coupling agent (C) are mixed solution or the dispersion liquid that forms with dissolving or dispersion state in aqueous medium.
The phosphate compound that uses among the present invention (A) is to be selected from phosphoric acid (=ortho-phosphoric acid), to contract and phosphoric acid and organic phospho acid and their ammonia salt at least a kind.Contract and phosphoric acid comprise metaphosphoric acid and Tripyrophosphoric acid.Metaphosphoric acid is a cyclic phosphoric acid condensation compound, comprises three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid etc.; Tripyrophosphoric acid is a catenate phosphoric acid condensation compound, comprises tetra-sodium, tripolyphosphate, four polyphosphoric acids etc.In addition, can use Amino Trimethylene Phosphonic Acid, 1-hydroxyl-1,1-ethylidene-1,1-di 2 ethylhexyl phosphonic acid, ethylene diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP) etc. as the organic phospho acid compound.Ammonia salt can be the material that phosphate/phosphonate group partly forms ammonia salt, also can be the material that all forms ammonia salt.These phosphate compounds can use separately, two or more can be used together.
With respect to the whole solid state component of surface treatment with the composition (A)～(C) of composition, the combined amount of phosphate compound (A) in surface treatment usefulness composition of the present invention, in solid state component, be preferably 0.1～80 weight %, more preferably 10～60 weight %.During less than 0.1 weight %, erosion resistance may reduce in this combined amount.In addition, when phosphate compound surpasses 80 weight %, there be the tendency of surface treatment with the stability reduction of composition.
Surface treatment of the present invention is the fluoric 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 fluoric acid in the composition (B).As the object lesson of this fluoric acid, can list 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.They can use separately, perhaps two or more are used together.
With respect to whole solid state component of composition (A)～(C), fluoric acid (B) with the combined amount in the composition, in solid state component, is preferably 0.1～15 weight %, more preferably 0.5～10 weight % in surface treatment of the present invention.Be 2.0～6.5 with surface treatment with the pH regulator of composition preferably by this fluoric acid.With respect to whole solid state component of composition (A)～(C), the combined amount of fluoric acid can't be with pH regulator to above-mentioned scope less than 0.1 weight % the time, and the result is the film-forming properties variation, and erosion resistance has the trend of variation.In addition, with respect to whole solid state component of composition (A)～(C), when the combined amount of fluoric acid surpasses 15 weight %, may reduce the stability of surface treatment with composition.
Surface treatment of the present invention is with the solid state component weight ratio (B) of fluoric acid in the composition (B) and phosphate compound (A): (A) be preferably 1: 100～50: 1, more preferably 1: 50～30: 1.If this solid state component weight ratio was less than 1: 100, then the solid state component containing ratio of fluoric acid is low, and the erosion resistance of the protective membrane of gained has the trend of reduction.In addition, if greater than 50: 1, the solid state component containing ratio height of fluoric acid then, the erosion resistance of the protective membrane of gained has the trend of reduction.
Surface treatment of the present invention constitutes by having 1 silane coupling agent (C2) that contains the silane coupling agent (C1) of the amino of active hydrogen and have 1 epoxy group(ing) with the silane coupling agent in the composition (C) at least at least.Concrete example is: have amino silane coupling agent as (C1) and can use N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330,3-aminopropyltriethoxywerene werene etc.; The silane coupling agent that has epoxy group(ing) as (C2) can use 3-glycidyl ether propyl trimethoxy silicane, 3-glycidyl ether propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.
In addition, surface treatment of the present invention with 2 kinds of silane coupling agents in the composition in, the equivalence ratio that contains the amino of active hydrogen and epoxy group(ing) is preferably 3: 1～1: 5 scope.This contains the amino of active hydrogen and the equivalence ratio of epoxy group(ing) surpasses 3: 1, and then amino more, the film-forming properties of the protective membrane of formation is low, and erosion resistance, anti-blackening and coating adhesion have insufficient trend.In addition, this equivalence ratio then contained the amino less of active hydrogen less than 1: 5, and the performance of the erosion resistance of the protective membrane of formation, anti-blackening and coating adhesion is saturated, and silane coupling agent is wasted at economic aspect.
Whole solid state component with respect to composition (A)～(C), the combined amount of silane coupling agent (C) (total amount of silane coupling agent (C1) and silane coupling agent (C2) just) in surface treatment usefulness composition of the present invention, with solid component meter, be preferably 10～90 weight %, more preferably 20～80 weight %.With respect to whole solid state component of composition (A)～(C), the combined amount of silane coupling agent (C) can't give full play of the effect as the blocking layer less than 10 weight % the time, and erosion resistance may reduce.In addition, with respect to whole solid state component of composition (A)～(C), when the combined amount of silane coupling agent (C) surpassed 90 weight %, composition (A) and combined amount (B) tailed off, and erosion resistance, anti-blackening and coating adhesion may reduce.
Use in the composition weight ratio (C) of the solid state component of silane coupling agent (C) and phosphate compound (A): (A) be preferably 1: 10～100: 1, more preferably 1: 5～60: 1 in surface treatment of the present invention.This solid state component weight ratio was less than 1: 10, and the ratio of silane coupling agent is lower, the surface treatment bad stability of composition, and erosion resistance and coating adhesion have the trend of reduction.In addition, this solid state component weight ratio was greater than 100: 1, and then the containing ratio of the solid state component of phosphoric acid class solid chemical compound is lower, and the erosion resistance of the protective membrane of formation has the trend of reduction.
With composition (A), (B) and (C) serving as when adding the amino modified resol of real mass in must the composition of the present invention of composition, be judged to be the black possibility height that becomes of the metallic substance that is capped of gained.Therefore, surface treatment of the present invention does not preferably contain the amino modified resol of real mass with composition.Described " not containing real mass " is meant and do not contain, also only contain than making black amount (real mass) amount still less that becomes of the metallic substance that is capped even perhaps contain." real mass " has certain variation according to composition (A), (B) and kind (C), usually with respect to composition (A), (B) and total solid state component (C), for surpassing about 5 weight %.Therefore, surface treatment of the present invention preferably only contains amino modified resol below the 5 weight % with composition, more preferably only contain the following amino modified resol of 3 weight %, more preferably only contain the following amino modified resol of 1 weight %, most preferably do not contain amino modified resol.
In the present invention, described water miscible amino modified resol is the polycondensate of phenolic (phenol, naphthols, dihydroxyphenyl propane etc.) and formaldehyde, is meant the ring bonded material of (replacement) amino methyl and phenols.Typically can the following general formula of illustration (I) or (II) shown in resin.
[in the formula, X
1Expression hydrogen atom, hydroxyl, carbonatoms are that 1～5 alkyl, carbonatoms are that 1～10 hydroxyalkyl, carbonatoms are the group shown in 6～12 aryl, benzyl or the general formula (III)
(in the formula, R
1And R
2Represent that identical or differently hydrogen atom or carbonatoms are 1～5 alkyl, Y
2Following explanation),
X
2Expression hydrogen atom, hydroxyl, carbonatoms are that 1～5 alkyl, carbonatoms are that 1～10 hydroxyalkyl, carbonatoms are 6～12 aryl or benzyl,
At X
1And X
2Definition in, aryl comprises phenyl, naphthyl etc., aryl and benzyl with carbocyclic ring bonded hydrogen atom can be that 1～5 alkyl or carbonatoms are that 1～10 hydroxyalkyl replaces with hydroxyl, carbonatoms,
Y
1And Y
2Represent hydrogen atom or group Z independently of one another,
With naphthalene nucleus bonded X
2And Y
1Be positioned at the optional position of naphthalene nucleus,
Z represent general formula (IV) or (V) shown in group,
(in the formula, R
3, R
4And R
5Represent that independently of one another hydrogen atom, carbonatoms are that 1～5 alkyl or carbonatoms are 1～10 hydroxyalkyl, A-represents hydroxyl ion or acid ion), n represents 2～50 integer].
Use in the composition in surface treatment of the present invention; mix to be selected from the above metal ion (D) of mn ion, cobalt ion, zine ion, magnesium ion, nickel ion, titanium ion, vanadium ion, zirconium ion, tin ion, calcium ion, tungsten ion, molybdenum ion, hafnium ion and aluminum ions divalent when appending composition, can further improve the erosion resistance of the protective membrane of formation.This metal ion can use separately, also two or more can be used together.In addition, above-mentioned metal ion in addition can't improve erosion resistance usually.There is no particular limitation for the valence mumber upper limit of metal ion (D), and normally suitable is till 6 valencys.
There is no particular limitation for the source of supply of this metal ion, for example can list carbonate, phosphoric acid salt, nitrate, vitriol, acetate, fluorochemical, oxide compound, metal etc.Particularly, can list manganous carbonate (II), cobaltous carbonate (II), zinc carbonate, magnesiumcarbonate, nickelous carbonate (II), lime carbonate, alkaline carbonic acid zirconium (ZrCO as carbonate
4ZrCO
28H
2O) etc.; Can list manganous phosphate (II), manganous phosphate (III), cobaltous phosphate (II), zinc phosphate, trimagnesium phosphate, nickelous phosphate (II), phosphoric acid tin (II), calcium phosphate, phosphoric acid hafnium (IV) etc. as phosphoric acid salt; Can list manganous nitrate (II), Xiao Suangu (II), Xiao Suangu (III), zinc nitrate, magnesium nitrate, nickelous nitrate (II), Titanium Nitrate (IV), zirconium nitrate (IV), nitric acid tin (II), nitric acid tin (IV), nitrocalcite, aluminum nitrate etc. as nitrate; Can list manganous sulfate (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), tin sulphate (II), tin sulphate (IV), calcium sulfate, hafnium sulfate (IV), Tai-Ace S 150 etc. as vitriol; Can list manganese acetate (II), manganese acetate (III), Cobaltous diacetate (II), Cobaltous diacetate (III), zinc acetate, magnesium acetate, nickel acetate (II), nickel acetate (III) etc. as acetate; Can list manganous fluoride, 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 (IV), tungsten fluoride (IV), tungsten fluoride (VI), molybdenum fluoride (III), molybdenum fluoride (VI), aluminum fluoride etc. as fluorochemical; Can list manganese oxide (II), manganese oxide (III), manganese oxide (IV), manganic anhydride, cobalt oxide (II), cobalt oxide (III), zinc oxide, magnesium oxide, nickel oxide (II), nickel oxide (III), titanium oxide (IV), vanadium oxide (II), vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), zirconium white (IV), Tungsten oxide 99.999 (VI), molybdenum oxide (VI) etc. as oxide compound; Can list zinc, nickel, titanium, tin, aluminium etc. as metal.They can be anhydrides, when having water, can be hydrates.
With respect to the whole solid state components of surface treatment with the composition (A)～(C) of composition, the combined amount of above-mentioned metal ion (D) is preferably 0.01～10 weight %, more preferably 0.05～5 weight %.This content finds that erosion resistance does not improve less than 0.01 weight % the time.In addition, if metal ion surpasses 10 weight %, then surface treatment has the trend of reduction with the stability of composition.
Surface treatment of the present invention with composition in mixed-cation or nonionic with urethane resin, acrylic resin, Resins, epoxy, vibrin or polyamide resin be the water soluble resin of resinous principle or aqueous emulsion resin (E) (below; also abbreviate above-mentioned water soluble resin or aqueous emulsion resin as water-base resin) when appending composition; can further improve the coating adhesion of the protective membrane of formation, but also give excellent alkali resistance can for the protective membrane that forms.These water-base resins have primary amino, secondary amino group, uncle's amino and season at least a kind of cationic functional group such as amino in molecular structure, perhaps have at least a kind of nonionic functional groups such as polyoxygenated ethylidene chain, hydroxyl, primary amide base, secondary amide base, teritary amide base, perhaps have at least a kind of this cationic functional group and at least a kind of this nonionic functional group.Above-mentioned water-base resin can use separately, two or more can be used together.
It is water-soluble or water dispersible that above-mentioned water-base resin also needs.Just, this water-base resin is a water soluble resin, or be that hydrophilic group can dissolve in water or self dispersive emulsion resin with aforementioned cationic functional group and/or nonionic functional group, or use cationic and/or nonionic surface active agent solvable or force dispersive aqueous emulsion resin in water.
Yet, but this water-base resin does not preferably use tensio-active agent as solvation, emulsifying dispersant, but do not have soap, maybe can do one's utmost to suppress the material of its consumption.
Above-mentioned resin is given excellent alkali resistance in order to give the protective membrane that forms, and is necessary for cationic or nonionic.In addition, if be cationic or nonionic, then usually with the intermiscibility excellence of phosphate compound (A), fluoric acid (B) and silane coupling agent (C), so preferably.
Preferably using weight-average molecular weight as water-base resin (E) is 1,000～1,000,000 water-base resin, and more preferably using weight-average molecular weight is 2,000～500,000 water-base resin.If aforementioned molecular weight is less than 1000, then the formation of protective membrane may be not enough, if surpass 1,000,000, then may reduce the stability of surface treatment with composition.
Ionic or the nonionic acrylic resin as aforementioned male, can routine illustrate and be selected from following acrylic resin: with N, N-dimethylaminopropyl acrylate, the cationic monomer that N-(two) alkylamino alkyl (methyl) acrylate such as N-methylamino ethyl propylene acid esters are such with amino, and/or polyethylene glycol methacrylate-styrene polymer, the 2-hydroxyethyl meth acrylate is such has polyoxygenated ethylidene chain, the non-ionic monomer of hydrophilic groups such as hydroxyl is with Acrylic Acid Monomers such as (methyl) acrylate, vinylbenzene, vinyl cyanide, the acrylic resin that addition polymerization unsaturated monomer copolymerization such as vinyl acetate obtain.
The urethane resin of or nonionic ionic as aforementioned male, can the following urethane that obtains of illustration etc.: in urethane resin, this urethane resin is polyester polyols (particularly binary) alcohol, polyethers polynary (particularly binary) alcohol, polynary (particularly binary) alcohol such as polycarbonate polynary (particularly binary) alcohol, polycondensate with aliphatics many (particularly two) isocyanic ester and/or aromatic series many (particularly two) isocyanate compound, part as employed polyvalent alcohol is used N, and N-dimethylamino dihydroxy methylpropane etc. has amino polyvalent alcohol, polyoxyethylene glycol has the polyvalent alcohol of polyoxygenated ethylidene chain like this.
The Resins, epoxy of or nonionic ionic as aforementioned male can illustration: make diamines and bisphenol type epoxy compound or other diglycidylether compound effects such as ethylene diamine, the Resins, epoxy that cationization obtains; The nonionic Resins, epoxy that the polyoxyethylene glycol addition forms on the side chain of bisphenol-A epoxy compound or other 2-glycidyl ether compound etc.
Ionic or nonionic polyesters resin can list as aforementioned male: in the such polyester material of the condenses of polyprotonic acids such as polyhydroxy reactants such as ethylene glycol, neopentyl glycol and terephthalic acid, make the superfluous effect of pure composition, not residual carboxyl and carry out vibrin that esterification obtains etc.
Ionic or nonionic polyamide resin can the illustration polycarboxylic acid and the polycondensation of polyvalent alcohol as aforementioned male, for example di-carboxylic acid such as hexanodioic acid, sebacic acid and ethylene diamine, 1, the nylon that the polycondensation of the polycondensation of diamines such as 6-hexanediamine, random ring-opening polymerization or aminocarboxylic acid obtains etc.
Use in composition water-base resin (E) when appending composition in surface treatment of the present invention, with respect to all solid state component of surface treatment with the composition (A)～(C) of composition, the solid state component combined amount of water-base resin is preferably 5～50 weight %, more preferably 20～40 weight %.During less than 5 weight %, can worry further to improve the adaptation of coating in this combined amount.In addition, if this combined amount surpasses 50 weight %, the adaptation that then further improves coating becomes difficult, and water-base resin is wasted economically.
In addition, surface treatment of the present invention with can mixed filler in the composition and additive such as lubricant as optional member.Can use zirconia sol, alumina sol, silicon dioxide gel etc. as weighting agent; Can use polyethylene wax, Poly Propylene Wax etc. as lubricant.Above-mentioned weighting agent can with the composition (D) of must composition (A)～(C) and appending as required and/or (E) prepare from aqueous medium surface treatment with composition after, mix, also can before preparation, mix (just, from aqueous medium with must composition (A)～(C) and use as required append composition (D) and/or (E) with additive preparation surface treatment composition).
Aqueous medium in the surface treatment usefulness composition of the present invention is water normally, for example, based on regulating rate of drying or making purposes such as the coating of aqueous medium is better, the organic solvents such as lower alcohol such as methyl alcohol, ethanol, propyl alcohol that can contain a small amount of (for example, 5 capacity % of aqueous medium integral body are following).
Surface treatment of the present invention comprises original composition (concentrated solution) and operation composition (diluent) two kinds with composition.Whole solid component concentration in the original composition is preferably 10～40 weight %, more preferably 15～30 weight %.Operation is preferably 1～40 weight % with the whole solid component concentrations in the composition, more preferably 5～30 weight %.In addition, with in any of composition, composition (A)～(C) is preferably more than the 50 weight % in the ratio that whole solid state components occupy in all solid state components, more preferably more than the 80 weight % in original composition and operation.
In addition, when surface treatment of the present invention was used with composition as operation with composition, pH preferably was adjusted to 2.0～6.5 scope, more preferably is adjusted to 2.5～5.5 scope.At this moment, when the pH of composition is used in the raising surface treatment, can use alkaline carbonates such as alkali metal hydroxides such as ammoniacal liquor, sodium hydroxide, yellow soda ash etc. as the pH regulator agent; When the pH of composition is used in the reduction surface treatment, preferably use the fluoric acid (B) that uses among the present invention to regulate., became too much less than 2.0 o'clock at pH with the reactivity of substrate surface, so the film-forming properties of the protective membrane of gained is not good, the adaptation of the erosion resistance of protective membrane, anti-blackening and the coating insufficient trend that becomes.In addition, if this pH surpasses 6.5, then fluoric acid (B) is separated out with composition from surface treatment easily, and surface treatment has the trend that shortens with the life-span of composition.
The invention still further relates to the surface treatment method of metallic substance, it is characterized in that: with pH regulator is 2.5～6.5, use medium as required, to be applied to metal material surface as the above-mentioned metal material surface composition for treating of operation composition, drying, the formation dry weight is 0.01～5.0g/m
2, be preferably 0.1～3.0g/m
2Protective membrane.Dried protective membrane weight is less than 0.01g/m
2The time, being difficult to cover metallic substance, it is not enough that the adaptation of erosion resistance, anti-blackening and coating becomes.In addition, if the weight of dried protective membrane surpasses 5.0g/m
2, then the adaptation of coating is low.
There is no particular limitation with method for compositions to be coated with this surface treatment, for example can use pickling process, spray method, rolling method etc.In addition, also there is no particular limitation treatment temp, treatment time.
The surface treatment that forms on metal material surface is preferably heated with composition layer and is carried out drying, and Heating temperature is preferably 50～250 ℃.Afterwards, carry out water-cooled as required.
Be coated with surface treatment of the present invention and have no particular limits, for example can list iron plate, zinciferous Metal plating steel plate, tin electroplating steel plate, stainless steel plate, aluminium sheet, aluminium alloy plate etc. with the metallic substance of composition.The not only kind of this metallic substance, and size, (illustrative at preamble is tabular body) shape etc. also have no particular limits.
Though to being illustrated with the mechanism of action of surface treatment of the present invention with the erosion resistance of the metallic substance of compositions-treated, anti-blackening and coating adhesion phenomenal growth, but this mechanism of action is a kind of inference, and the present invention should not be bound by this inference.At first, metal material surface is contacted with surface treatment with composition, cause etching in the metallic surface by the fluoric acid in the surface treating composition.Because etching, the specific ion reaction between titanium, zirconium, silicon, hafnium, aluminium or the boron just by from the metal ion of metal material surface stripping and phosphate compound (A), fluoric acid (B) forms insoluble chemical compound in the metallic surface.In addition, if the metallic surface of heat drying coating, could be because the dehydrating condensation between the silanol group that the hydrolysis of silane coupling agent (C) produces would form the successive protective membrane.Think the blocking layer effect of the coupling agent protective membrane that contains insoluble chemical compound by having given play to above-mentioned generation, can improve the erosion resistance and the anti-blackening of metallic substance.On the other hand, can infer: the silanol group that the hydrolysis of silane coupling agent (C) produces also reacts with metal material surface, form the oxyethane key, and then the functional group in the reactive functional groups (amino and the glycidyl that contain active hydrogen) that contained of silane coupling agent (C) and the organic coating (for example, carboxyl and ester group) reaction, so improve the adaptation of metallic substance and organic coating, just improve the adaptation of coating.In addition, with the composition comprises water resin when (E), can also infer the reactions such as ester group in functional group such as the carboxyl that contains in the water-base resin and hydroxyl and the organic coating, further improve adaptation in surface treatment.In addition, can also infer: as append the divalent that is selected from manganese, cobalt, zinc, magnesium, nickel, titanium, vanadium, zirconium, tin, calcium, tungsten, molybdenum, hafnium and aluminium that composition uses or more the polyvalent metal ion be as giving rust-preventing characteristic known ion, by adding in the surface treatment liquid of the present invention, can further improve erosion resistance.
[embodiment]
Then, enumerate embodiment and comparative example specifically describes the present invention, but scope of the present invention is not to limit by these embodiment.The cleaning method on the metallic substance that uses in following embodiment and the comparative example, its surface and the surface treatment of the present invention following explanation of composition.
1. specimen material
Cold-rolled steel sheet (SPC)
Commercially available product, thickness of slab 0.6mm JIS G314
Zinciferous Metal plating steel plate
(A) commercially available product, thickness of slab 0.6mm, two sides electrogalvanizing steel plate (EG), adhesion amount 20g/m
2
(B) commercially available product, thickness of slab 0.6mm, hot-dip galvanized steel sheet (GI), adhesion amount 40g/m
2
Aluminium sheet (AL): commercially available product, thickness of slab 0.8mm, JIS A5052
2. the cleaning method of sample panel
Use neutral and alkali grease-removing agent (registered trademark: Off ア イ Application Network リ one Na 1, the manufacturing of the rapids smart company of Japan's handkerchief card) the aqueous solution (reagent concentration: 20g/l), in treatment temp: 60 ℃, treatment time: under 20 seconds the condition, to the processing of spraying of the surface of above-mentioned sample panel, remove the dirt and the oil of surface adhesion.Then, clean the alkali composition that remains in the surface with tap water, with the surface cleaningization of sample panel.
3. surface treatment composition
The surface treatment of using in present embodiment and the comparative example is as shown in table 1 with composition.
Table 1 surface treatment composition
6)
| The surface treatment liquid sequence number | Phosphate compound (A) | Fluoric acid (B) | Silane coupling agent (C) | Composition (D) and (E) | |||||||
| Kind | Combined amount 3) | Kind | Combined amount 3) | The kind of silane coupling agent 1) | Ratio of mixture (equivalence ratio) | Combined amount 3) | The metal ion (D) that divalent is above 5) | Combined amount 4) | Water-base resin (E) 2) | Combined amount 4) | |
| 1 | Phosphoric acid | 15 | H 2ZrF 6 | 1 | C1a∶C2a | 2∶1 | 84 | - | - | - | - |
| 2 | Phosphoric acid | 25 | H 2ZrF 6 | 2 | C1a∶C2a | 2∶1 | 73 | - | - | - | - |
| 3 | Phosphoric acid | 50 | H 2ZrF 6 | 4 | C1a∶C2a | 2∶1 | 46 | - | - | - | - |
| 4 | Phosphoric acid | 14 | H 3AlF 6 | 1 | C1a∶C2a | 2∶1 | 85 | - | - | - | - |
| 5 | Tetra-sodium | 20 | H 2HfF 6 | 2 | C1a∶C2a | 2∶1 | 78 | - | - | - | - |
| 6 | Metaphosphoric acid | 35 | HBF 4 | 4 | C1a∶C2a | 2∶1 | 61 | - | - | - | - |
| 7 | The ethylene diamine tetramethylene phosphonic acid | 18 | H 2TiF 6 | 2 | C1a∶C2a | 1∶1 | 80 | V(IV) | 1 | E1 | 30 |
| 8 | The ethylene diamine tetramethylene phosphonic acid | 18 | H 2TiF 6 | 2 | C1a∶C2a | 1∶1 | 80 | - | - | - | - |
| 9 | Phosphoric acid | 12 | H 2SiF 6 | 1.5 | C1b∶C2a | 1∶1 | 86.5 | Zn(II) | 3 | - | - |
| 10 | Phosphoric acid | 12 | H 2SiF 6 | 1.5 | C1b∶C2a | 1∶1 | 86.5 | - | - | - | - |
| 11 | Phosphoric acid | 12 | H 2SiF 6 | 1.5 | C1b∶C2a | 1∶1 | 86.5 | Co(II) | 5 | - | - |
| 12 | Phosphoric acid | 12 | H 2SiF 6 | 1.5 | C1b∶C2a | 1∶1 | 86.5 | Mn(II) | 3 | - | - |
| 13 | Phosphoric acid | 12 | H 2SiF 6 | 1.5 | C1b∶C2a | 1∶1 | 86.5 | W(VI) | 5 | - | - |
| 14 | Phosphoric acid | 12 | H 2SiF 6 | 1.5 | C1b∶C2a | 1∶1 | 86.5 | Zr(IV) | 3 | - | - |
| 15 | Phosphoric acid ammonia | 50 | H 2ZrF 6 | 3 | C1b∶C2a | 1∶1 | 47 | Ni(II) | 5 | - | - |
| 16 | Phosphoric acid ammonia | 50 | H 2ZrF 6 | 3 | C1b∶C2a | 1∶1 | 47 | - | - | - | - |
| 17 | Phosphoric acid ammonia | 20 | H 2TiF 6 | 4 | C1b∶C2a | 2∶1 | 76 | Mg(II) | 3 | - | - |
| 18 | Phosphoric acid ammonia | 20 | H 2TiF 6 | 4 | C1b∶C2a | 2∶1 | 76 | - | - | - | - |
| 19 | Phosphoric acid | 15 | H 2ZrF 6 | 1 | C1a∶C2a | 2∶1 | 84 | - | - | E1 | 15 |
| 20 | Phosphoric acid | 15 | H 2ZrF 6 | 1 | C1a∶C2a | 2∶1 | 84 | - | - | E2 | 10 |
| 21 | Phosphoric acid | 25 | - | - | C1b∶C2a | 2∶1 | 75 | - | - | - | - |
| 22 | - | - | H 2ZrF 6 | 2 | C1b∶C2a | 2∶1 | 98 | - | - | - | - |
| 23 | Phosphoric acid | 15 | H 2ZrF 6 | 1 | C1a∶C2a | 2∶1 | 84 | - | - | E3 | 15 |
| 24 | Phosphoric acid | 15 | H 2ZrF 6 | 1 | C1a | - | 84 | - | - | E1 | 15 |
| 25 | The resin chromic salt 7) | ||||||||||
The notes of table 1
Annotate 1) C1a: the gamma-amino propyl trimethoxy silicane
C1b: γ-An Jibingjisanyiyangjiguiwan
C2a: γ-glycidyl ether propyl trimethoxy silicane
C2b: β-glycidyl ether propyl group methyl dimethoxysilane
Annotate 2) E1: the cationic urethane resin: polyether glycol aliphatic category polymeric polyisocyanate type, median size are 0.01 μ m, 30 ℃ of MFT (the minimum film temperature of making), intensity 51N/mm
2, extensibility 6%
E2: nonionic acrylic resin: pH7～9,41 ℃ of Tg (second-order transition temperature), MFT＜50 ℃
E3: the water-soluble polymers that forms by following repeating unit
Notes 3) solid state component of each composition is with respect to the ratio (%) of whole solid state components of composition (A)～(C).
Notes 4) be 100% o'clock at whole solid state components with composition (A)～(C), the ratio of the solid state component of each composition (%).
Annotate 5) concerning the source of supply of the above metal ion of divalent, zinc, cobalt, manganese, magnesium use nitrate, and zirconium uses basic carbonate, and nickel uses carbonate, and tungsten, vanadium use oxide compound.
Notes 6) surface treatment is 20 weight % with the concentration adjustment of the whole solid state components in the composition (=composition (A)～(E)).Aqueous medium is a water.
Annotate 7) resin chromic salt: TOP-5241 (the rapids smart company of Japanese handkerchief card makes)
4. the treatment process of sample panel
The treatment process of table 2 expression sample panel.In addition, surface treatment is undertaken by rolling method with the coating of composition.
The treatment process of table 2 sample panel
| The surface treatment sequence number (table 1) of composition | Material | Protective membrane amount (g/m 2) | Arrival plate temperature (℃) 1) | |
| Embodiment 1 | 1 | GI | 0.5 | 100 |
| Embodiment 2 | 1 | EG | 0.5 | 100 |
| Embodiment 3 | 2 | GI | 0.3 | 80 |
| Embodiment 4 | 2 | EG | 0.3 | 80 |
| Embodiment 5 | 3 | EG | 0.6 | 120 |
| Embodiment 6 | 4 | GI | 0.4 | 130 |
| Embodiment 7 | 4 | EG | 0.4 | 130 |
| Embodiment 8 | 5 | EG | 1.0 | 180 |
| Embodiment 9 | 6 | AL | 1.2 | 150 |
| Embodiment 10 | 7 | EG | 0.7 | 130 |
| Embodiment 11 | 8 | EG | 0.7 | 130 |
| Embodiment 12 | 9 | EG | 0.7 | 130 |
| Embodiment 13 | 10 | EG | 0.7 | 130 |
| Embodiment 14 | 11 | EG | 0.7 | 130 |
| Embodiment 15 | 12 | EG | 0.7 | 130 |
| Embodiment 16 | 13 | EG | 0.7 | 130 |
| Embodiment 17 | 14 | EG | 0.7 | 130 |
| Embodiment 18 | 15 | GI | 0.4 | 90 |
| Embodiment 19 | 16 | GI | 0.4 | 90 |
| Embodiment 20 | 17 | GI | 0.5 | 110 |
| Embodiment 21 | 18 | GI | 0.5 | 110 |
| Embodiment 22 | 19 | EG | 0.5 | 100 |
| Embodiment 23 | 19 | SPC | 1.0 | 180 |
| Embodiment 24 | 20 | GI | 0.5 | 100 |
| Comparative example 1 | 21 | EG | 0.5 | 100 |
| Comparative example 2 | 22 | GI | 0.5 | 80 |
| Comparative example 3 | 23 | EG | 1.0 | 100 |
| Comparative example 4 | 24 | EG | 1.0 | 100 |
| Comparative example 5 | 25 | EG | 30mg/m 2 | 80 |
5. evaluation experimental method
Performance by previous embodiment and the surface treatment sample panel that relatively obtains is estimated by following method.
5.1. erosion resistance
A) erosion resistance (1) (SST)
Sample panel is under the situation of zinciferous Metal plating steel plate (EG, GI) and aluminium sheet (Al): carry out brine spray experiment (SST, JIS Z 2371), visual observation produces area by white rust and reaches for 5% time, estimates.
B) erosion resistance (2) (HCT)
Sample panel is under the situation of cold-rolled steel sheet: the surface treatment sample panel is remained under the atmosphere of 50 ℃-humidity of temperature 90%, visual observation reaches for 5% time by rust area, estimates.
5.2. coating adhesion
Under the following conditions, on the surface treatment sample panel, be coated with, obtain coated panel, be coated with the adaptation experiment.
＜coating condition〉alcohol acids coating (big Nippon Paint Co., Ltd., trade name デ リ コ Application #700) coating: the bar shaped coating method, sintering condition: 140 ℃ * 20 minutes formation 25 μ m film
5.2.1 adaptation
(1) grid test: by the NT cutting machine till arriving the steel plate materials part on the filming of coated panel, form the square grid of 100 1mm after, peel off by cellophane tape, estimate by the residual number of filming.
(2) grid Erichsen test: by the NT cutting machine till arriving the steel plate materials part on the filming of coated panel, after forming the quadrilateral mesh of 100 1mm, behind cupping testing machine extrusion 5mm, peel off this protuberance by cellophane tape, residual number is estimated by filming.
5.2.2 secondary adaptation
Coated panel flooded 2 hours in the ebullient pure water after, carry out and an identical evaluation of adaptation.
5.3. anti-blackening
Cut out the polylith sample panel from the disposable plates of table 2 gained, the coated face of 2 sample panel is relatively coincided together as 1 pair of disposable plates, overlapping 5～10 pairs, after tying up with the vinyl polymer White Board, with 4 position bolting at angle, applying heavy burden with dial torque wrench is 6.96Nm up to scale, then, after in 70 ℃, the moistening case of 80% relative humidity, keeping 240 hours, take out the black change situation of visual judgement coincidence part.In addition, judgment standard is as follows.
5: not black the change
4: extremely slight greyization
3: black diminishing in 25%
2: black change is below 25～50%
1: black change is more than 50%
Evaluation result is as shown in table 3.
Table 3 evaluation experimental result
| Handle sequence number | Erosion resistance | Coating adhesion 1) | Anti-blackening | |||||
| An adaptation | The secondary adaptation | |||||||
| (1) SST | (2) HCT | Grid | The grid cupping | Grid | The grid cupping | |||
| Embodiment 1 | 1 | 144hr | - | 95 | 95 | 92 | 92 | 5 |
| Embodiment 2 | 1 | 96hr | - | 96 | 96 | 94 | 94 | 5 |
| Embodiment 3 | 2 | 120hr | - | 94 | 93 | 92 | 92 | 5 |
| Embodiment 4 | 2 | 72hr | - | 97 | 97 | 95 | 94 | 5 |
| Embodiment 5 | 3 | 120hr | - | 96 | 95 | 94 | 94 | 5 |
| Embodiment 6 | 4 | 120hr | - | 97 | 96 | 95 | 95 | 5 |
| Embodiment 7 | 4 | 96hr | - | 96 | 96 | 95 | 94 | 5 |
| Embodiment 8 | 5 | 120hr | - | 98 | 94 | 97 | 96 | 5 |
| Embodiment 9 | 6 | 360hr | - | 97 | 95 | 95 | 93 | - |
| Embodiment 10 | 7 | 168hr | - | 100 | 100 | 100 | 100 | 5 |
| Embodiment 11 | 8 | 144hr | - | 95 | 95 | 92 | 92 | 5 |
| Embodiment 12 | 9 | 144hr | - | 94 | 94 | 94 | 94 | 4 |
| Embodiment 13 | 10 | 96hr | - | 94 | 94 | 94 | 94 | 4 |
| Embodiment 14 | 11 | 144hr | - | 94 | 96 | 92 | 94 | 5 |
| Embodiment 15 | 12 | 144hr | - | 94 | 94 | 92 | 94 | 4 |
| Embodiment 16 | 13 | 144hr | - | 94 | 96 | 94 | 94 | 4 |
| Embodiment 17 | 14 | 144hr | - | 94 | 96 | 92 | 94 | 4 |
| Embodiment 18 | 15 | 144hr | - | 96 | 94 | 97 | 96 | 4 |
| Embodiment 19 | 16 | 120hr | - | 96 | 97 | 94 | 96 | 4 |
| Embodiment 20 | 17 | 168hr | - | 98 | 97 | 97 | 95 | 5 |
| Embodiment 21 | 18 | 144hr | - | 98 | 97 | 97 | 95 | 5 |
| Embodiment 22 | 19 | 96hr | - | 100 | 100 | 100 | 100 | 5 |
| Embodiment 23 | 19 | - | 720hr | 100 | 100 | 100 | 100 | - |
| Embodiment 24 | 20 | 144hr | - | 100 | 100 | 100 | 100 | 5 |
| Comparative example 1 | 21 | 24hr | - | 80 | 61 | 78 | 72 | 3 |
| Comparative example 2 | 22 | 24hr | - | 70 | 50 | 60 | 55 | 4 |
| Comparative example 3 | 23 | 120hr | - | 100 | 100 | 100 | 100 | 2 |
| Comparative example 4 | 24 | 24hr | - | 40 | 20 | 10 | 0 | 4 |
| Comparative example 5 | 25 | 120hr | - | 100 | 93 | 95 | 93 | 4 |
Annotate 1) the residual number of grid
Show from the result of table 3, beyond scope of the present invention, the respectively comparative example 1 and 2 of fluoric-containing acid (B) and phosphate compound (A) not, and the comparative example 4 that only contains a kind of silane coupling agent (C), erosion resistance and coating adhesion are poor.The surface treatment that the patent documentation 5 that is equivalent to propose before the applicant is put down in writing is with the comparative example 3 of composition, though erosion resistance, coating adhesion are good, anti-blackening is poor.Compare with them, use surface treatment of the present invention to demonstrate good anti-corrosion, coating adhesion and anti-blackening with the embodiment 1～24 of composition, can obtain with the resin chromic salt of comparative example 5 roughly the same～better properties.In addition, from the comparison of embodiment 11 and embodiment 10, embodiment 13 and embodiment 12, embodiment 13 and embodiment 14, embodiment 13 and embodiment 15, embodiment 13 and embodiment 16, embodiment 13 and embodiment 17, can know by mix divalent or more polyvalent metal ion (D) can further improve erosion resistance.From the comparison of embodiment 1 and embodiment 24, embodiment 2 and embodiment 22, can know by mixing aqueous emulsion resin (E), can further improve coating adhesion.
Claims (11)
1. metal material surface composition for treating, said composition are to mix with dissolving or dispersion state in aqueous medium
(A) be selected from phosphoric acid, contract and at least a kind of phosphate compound of phosphoric acid and organic phospho acid and their ammonia salt,
(B) have the fluorine atom more than at least 4 and be selected from the fluoric acid of at least 1 element of titanium, zirconium, silicon, hafnium, aluminium and boron, and
(C) have at least 1 silane coupling agent (C2) that contains the silane coupling agent (C1) of the amino of active hydrogen and have at least 1 epoxy group(ing),
Formed metal material surface composition for treating, and with respect to all solid state components of composition (A)～(C), the ratio of the solid state component of composition (A) is 0.1～80 weight %.
2. the metal material surface composition for treating of putting down in writing according to claim 1, wherein with respect to all solid state components of composition (A)～(C), the combined amount of fluoric acid (B) is 0.1～15 weight %.
3. the metal material surface composition for treating of being put down in writing according to claim 1 or 2, the wherein weight ratio (B) of the solid state component of fluoric acid (B) and phosphate compound (A): (A) be 1: 100～50: 1.
4. according to each the metal material surface composition for treating put down in writing in the claim 1～3, wherein the equivalence ratio of the epoxy group(ing) that contains in amino that contains active hydrogen that contains in the silane coupling agent (C1) and the silane coupling agent (C2) is 3: 1～1: 5.
5. according to each the metal material surface composition for treating put down in writing in the claim 1～4, silane coupling agent (C) wherein, promptly as the combined amount of the silane coupling agent of the total amount of silane coupling agent (C1) and silane coupling agent (C2), all solids components with respect to composition (A)～(C), in solid state component, be 10～90 weight %.
6. according to each the metal material surface composition for treating put down in writing in the claim 1～5, the solid state component weight ratio (C) of silane coupling agent (C) and phosphate compound (A) wherein: (A) be 1: 10～100: 1.
7. according to each the metal material surface composition for treating put down in writing in the claim 1～6, the solid state component weight ratio (C) of silane coupling agent (C) and phosphate compound (A) wherein: (A) be 1: 10～100: 1, the combined amount of fluoric acid (B) is with respect to all solids components of composition (A)～(C), in solid state component, be 0.1～15 weight %.
8. according to each the metal material surface composition for treating put down in writing in the claim 1～7, it does not contain the water soluble amino resin modified phenol resin of real mass.
9. according to each the metal material surface composition for treating put down in writing in the claim 1～8, wherein with respect to all solids components of composition (A)～(C), at least a kind that mixes 0.01～10 weight % is selected from the above metal ion (D) of mn ion, cobalt ion, zine ion, magnesium ion, nickel ion, titanium ion, vanadium ion, zirconium ion, tin ion, calcium ion, tungsten ion, molybdenum ion, hafnium ion and aluminum ions divalent.
10. according to each the metal material surface composition for treating put down in writing in the claim 1～9, wherein with respect to all solids components of composition (A)～(C), in solid state component, what mix the cationic of 5～50 weight % or nonionic is the water soluble resin or the aqueous emulsion resin (E) of resinous principle with urethane resin, acrylic resin, Resins, epoxy, vibrin or polyamide resin.
11. the surface treatment method of a metallic substance, this method is that each the metal material surface composition for treating put down in writing as in the claim 1～10 of operation composition that will be adjusted to pH2.0～6.5 is applied to metallic surface, drying, and the formation dry weight is 0.01～5.0g/m
2Protective membrane.
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