CN1316061C - Composition and treatment liquid for surface treatment, surface treatment method and product with metal material - Google Patents

Composition and treatment liquid for surface treatment, surface treatment method and product with metal material Download PDF

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Publication number
CN1316061C
CN1316061C CNB031587208A CN03158720A CN1316061C CN 1316061 C CN1316061 C CN 1316061C CN B031587208 A CNB031587208 A CN B031587208A CN 03158720 A CN03158720 A CN 03158720A CN 1316061 C CN1316061 C CN 1316061C
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Prior art keywords
surface treatment
concentration
protective membrane
zinc
mol
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CN1493712A (en
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中山隆臣
相岛敏行
鹫巢正人
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The composition for surface treatment comprises zinc, phosphoric acid and an aromatic nitro compound. The concentration of the zinc [Zn] (the unit is mol/L), the concentration of the phosphoric acid [PO<SB>4</SB>] (the unit is mol/L), and the concentration of the aromatic nitrocompound [NO<SB>2</SB>] (the unit is mol/L) satisfy the relation of 100<={[Zn]/[PO<SB>4</SB>]}/[NO<SB>2</SB>]<=700.

Description

Surface treatment with composition, surface treatment with treatment solution, surface treatment method and goods with metallic substance
Technical field that the present invention belongs to
The invention relates to provides a kind of and all has the technology of good corrosion proof atomic thin zinc phosphate chemical treatment protective membrane at not painting state or painting state, and it is formed on for example iron, zinc and is coated with on the surface of metallic substance of zinc, aluminium and aluminium alloy, magnesium and magnesium alloy etc.
Background technology
Patent documentation 1 (spy opens flat 2-197581 communique)
Patent documentation 2 (special public clear 46-17047 communique)
Patent documentation 3 (spy opens clear 54-118349 communique)
Patent documentation 4 (special public clear 61-36588 communique)
Patent documentation 5 (special public clear 58-11513 communique)
Patent documentation 6 (spy opens clear 56-142872 communique)
Patent documentation 7 (the flat 9-502224 communique of special table)
In the past, compacting (press) adds the metal die in man-hour and anti-the coagulating property between the metal of being formed in order to improve, and raising is filmed and metallic substance between stopping property, so carry out phosphatizing at metal material surface.
Also have,, form the big and big phosphatizing protective membrane of protective membrane weight of crystal size so preferably adopt in order to improve press processability.Also have,, form the phosphatizing protective membrane that crystal size is little and protective membrane weight is little so preferably adopt in order to improve the solidity to corrosion and the stopping property of filming after the application.Therefore, different use classification is arranged in order to adapt to various various objectives.
Therefore, when carrying out phosphatizing, can use promotor, for example, well known nitrite, hydrogen peroxide, azanol (hydroxylamine) class or nitrobenzene-sulfonic acid salt (nitrobenzenesulfonic acid salt).
Yet nearly all occasion only adopts nitrite.
Its reason is that nitrite has very large facilitation effect to the phosphate chemical processing reaction.And the method for measurement of concentration that phosphate chemical is handled in bathing is established, so carry out the concentration management easily.
Also have, use the example of nitrite promotor in addition, for example be disclosed in the spy and open flat 2-197581 communique.
In this communique, be cold the plastic working swabbing method that discloses iron and steel, it adopts the zinc phosphate treatment solution that contains 0.02～0.25% water-soluble aromatic compounds of group, and this water-soluble aromatic compounds of group has zine ion, the 1st iron ion, phosphate ion, nitrate ion, nitro and the sulfo group of specific concentrations.
The technology of this communique declares that sedimentary generating capacity is few.And can to obtain being used as be the high-quality phosphatizing protective membrane of cold working substrate.
Yet this technology is to be purpose and being invented with the cold forging swabbing.
Therefore, if the zinc ion concentration of phosphate chemical in handle bathing is 0.3～2.5% words then can say so unusual height, and the protective membrane weight of the protective membrane of gained is 7～12g/m 2Though, be fine and close degree as the plastic working purposes, can not be used as the application substrate.
To be applicable to the employed fine phosphate coating of application substrate in order accessing, to be suggested so there is phosphate chemical to handle the modification method of bathing.
For example, in the public clear 46-17047 communique of spy, be disclosed in acid phosphatase zinc and coat in the treatment solution, be added with one or more the method for decomposing the polyose that connects that generated via starch or derivatives thereof or their acid of 0.01～1 weight %.
Also have; in the spy opens according to the 54-118349 communique; disclose a kind of zinc phosphate protective membrane method of chemical treatment, this method is to use to add has starch or the zinc phosphate protective membrane chemical treatment of the Phosphation thing of the sour decomposition product of this starch bath of 0.5～2.5% weight in conjunction with phosphoric acid.
Yet, aforesaid which technology no matter, its purpose all is to be to improve the application stopping property that the zinc phosphate that is used in pre-coated steel plate is handled protective membrane.Therefore, the metallic substance of being used as practical object only limits to steel plate galvanized.And, for obtaining the purpose effect, be necessary that handling line in precoating with zinc phosphate uses the zinc phosphate of jet printing type to handle.
Therefore, aforementioned techniques is for the vehicle body that for example is automobile, and being only applicable to it, to constitute metallic substance be to comprise the cold ferrous material that prolongs steel plate etc., and be not suitable for the processed object with bag columnar structure that can not directly spray.
At this, in order to improve the rustless property of the body of a motor car with bag columnar structure, a kind of phosphate chemical that is called the dip treating of full dipping method is handled by motion.
For example; in the public clear 61-36588 communique of spy; have and disclose the phosphatizing of a kind of cationic electro dipping with the metallic surface; this processing is zine ion, phosphate ion, mn ion and the fluorion of selecting for use from specific concentrations, and more the person selects a kind of protective membrane chemical treatment promotor to be used as principal constituent among nitrite ion, m-nitrobenzene-sulfonic acid ion and the hydrogen peroxide of specific concentrations at least.
According to aforementioned techniques, after dip treating, carry out spray treatment, and zinc phosphate chemical treatment protective membrane is separated out in bag cage structure inside.
Yet zinc ion concentration and phosphate ion concentration that the corresponding phosphate chemical of aforementioned techniques is handled in bathing are not controlled m-nitrobenzene-sulfonic acid ionic concn.Therefore, be not easy to obtain the crystallization of the even compact of low protective membrane weight.
For example, employed protective membrane chemical treatment promotor is to be defined in nitrite ion among the embodiment in this communique.And, do not disclose m-nitrobenzene-sulfonic acid ionic proper range yet.Person more, also not mentioned m-nitrobenzene-sulfonic acid ionic simple determination method.Therefore, in the behaviour in service of reality, be to be not easy m-nitrobenzene-sulfonic acid ionic concentration is maintained certain limit.
Also have, it is that parkerized promotor use is well known that the organic nitro-compound of nitrobenzene-sulfonic acid etc. is used as, and in other documents of aforementioned communique motion miscellaneous is arranged.
For example, open in the clear 58-11513 communique the spy, a kind of electro dipping of announcement metallic surface treatment process is arranged, the feature of this method be select for use the zine ion of specific concentrations, phosphate ion, nitrite ion with and/or m-nitrobenzene-sulfonic acid ion be used as principal constituent, more the person comprise nitrate ion with and/or the chlorate ions.
Also have, open in the clear 56-142872 communique, have and disclose phosphoric acid salt coating (coating) solution that a kind of mn ion by zine ion, phosphate ion, specific concentrations, oxymuriate and nitrobenzene-sulfonic acid salt are constituted the spy.
Yet, the narration among the embodiment in aforementioned all motions, the effect that does not all have research to have protective membrane weight to lower via the interpolation of chloric acid.That is to say, all do not disclose the effect that is had about nitrobenzene-sulfonic acid salt.Person more, via in containing chlorate ions's phosphatizing liquid, handling the phosphatizing protective membrane, be problem with anti-pitting difference.
Also have, show in the flat 9-502224 communique the spy, a kind of phosphatizing method of using the phosphatizing aqueous solution of announcement is arranged, this phosphatizing aqueous solution contains zinc, manganese, phosphate ion and azanol and/or the m-nitrobenzene-sulfonic acid ester of specific concentrations, and the oxo-anions of not nickeliferous, cobalt, copper, nitrite and halogen.
Particularly from the point of the environment regulations in Europe, this technology is to limit not nickeliferous and treatment solution nitrite, and can separate out the good corrosion proof phosphatizing protective membrane that has after application.
Yet the technology of this motion is applicable to the replacement nitrite and uses m-nitrobenzene-sulfonic acid ester.But the method for this motion also can't be separated out as the suitableeest fine and close and atomic thin zinc phosphate of application substrate and handle crystallization.
Treatment temp when therefore, being necessary phosphatizing maintains under the high temperature.
And, in order to reach corrosion proof target, after zinc phosphate is handled, be necessary to bestow again chromium and wash (chrome rinse) processing.
Summary of the invention
According to above-mentioned; prior art does not propose to be applicable to the metal to be treated material of the complex structure with bag columnar structure as can be known; and need not the auxiliary processing procedure of aftertreatment, and can separate out the control of bathing via phosphatizing and can obtain the good and atomic thin fine and close phosphate coating crystallization of solidity to corrosion.
Therefore, the objective of the invention is for solving above-mentioned prior art problems point.
Particularly; the invention provides and a kind ofly all have good corrosion proof atomic thin zinc phosphate chemical treatment protective membrane at not painting state and painting state, it is formed on for example iron, zinc and is coated with on the surface of metallic substance of zinc, aluminium and aluminium alloy, magnesium and magnesium alloy etc.
Person more, the present invention in the known phosphatizing processing procedure that adopts, even and do not improve existing treatment unit, also can provide solidity to corrosion good atomic thin phosphate coating.
Particularly, owing to be the phosphate coating of the good atomic again thin low protective membrane weight of solidity to corrosion, a kind ofly can reduce reagent consumption amount and cheap again zinc phosphate chemical treatment protective membrane so the invention provides.
The present inventor studies intensively out the method for solution in view of above-mentioned problem, and it is to bathe by the control phosphatizing, can separate out the purpose that all has good corrosion proof atomic thin zinc phosphate chemical treatment protective membrane at not painting state and painting state and reach.
The present invention is based on following knowledge and reach.
So the method feature that solves aforementioned problems is: contain the surface treatment composition of zinc, phosphoric acid, aromatic nitro compound, wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700.
Particularly, the method feature of solution aforementioned problems is: contain the surface treatment composition of zinc, phosphoric acid, aromatic nitro compound, wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] (mol/L of unit), satisfy 0.05≤[Zn]/[PO 4The relational expression of]≤0.2; Also have wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700.
Also have, the method feature that solves aforementioned problems is: contain the surface treatment treatment solution of zinc, phosphoric acid, aromatic nitro compound, wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700.
Particularly, the method feature of solution aforementioned problems is: contain the surface treatment treatment solution of zinc, phosphoric acid, aromatic nitro compound, wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] (mol/L of unit), satisfy 0.05≤[Zn]/[PO 4The relational expression of]≤0.2; Also have wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700.
Person more, the method feature that solves aforementioned problems is: contain the surface treatment treatment solution of zinc, phosphoric acid, aromatic nitro compound, wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] (mol/L of unit), satisfy 0.05≤[Zn]/[PO 4The relational expression of]≤0.2; Also have wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700; Wherein concentration of phosphoric acid is that 50～250m mol/L (annotates: m:milli).
Also have, above-mentioned surface treatment is with in the composition (treatment solution), more includes one or more the compound in the cohort that is selected from aromatic amino compound and aromatic series diazo (diazo) compound.
The volumetric molar concentration of the total of aforesaid compound is 0.1 times～10 times a value of the volumetric molar concentration of aromatic nitro compound.
Also have, above-mentioned surface treatment is used in the composition (treatment solution), more includes in the cohort that is selected from nickel, manganese, magnesium, calcium, iron (II) and cobalt one or more, particularly two or more cation constituents.
Also have, above-mentioned surface treatment is with in the composition (treatment solution), more includes to be selected from azanol and to supply with one or more compound in the cohort of material, nitrous acid and nitrite.
Also have, the surface treatment method that solves aforementioned problems is characterised in that: this surface treatment method possesses has the surface to adjust processing procedure and surface treatment process, should surface adjustment processing procedure be to adjust in the liquid on the surface that is principal constituent to handle metallic substance with titanium colloid (titan colloid) wherein; And this surface treatment process is after processing procedure is adjusted on this surface, uses this surface to adjust liquid and handles this metallic substance.
Or, the surface treatment method that solves aforementioned problems is characterised in that: this surface treatment method possesses has the surface to adjust processing procedure and surface treatment process, wherein should the surface adjusting processing procedure be to include one or more phosphoric acid salt, and this phosphoric acid salt has one or more the divalent or the metallic surface of 3 valencys and adjusts and handle metallic substance in the liquid; And this surface treatment process is after processing procedure is adjusted on this surface, uses this surface treatment to handle this metallic substance with composition (treatment solution).
Also have, the goods with metallic substance that solve aforementioned problems are characterised in that: possessing has a metallic substance, and the weight that designs on this metal material surface is 0.5～5g/m 2Protective membrane, and this protective membrane is to form via above-mentioned surface treatment method.
Also have, when this metallic substance is the occasion of Ferrious material material, be formed at the protective membrane weight 0.5～3g/m preferably on this Ferrious material material surface 2And be zinc when being the occasion of metallic substance at this metallic substance, be formed at this zinc and be the protective membrane weight 1～4.5g/m preferably on the metal material surface 2
Embodiment
Surface treatment of the present invention is the surface treatment composition that contains zinc, phosphoric acid, aromatic nitro compound with composition (treatment solution), wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700 (particularly meets 150≤{ [Zn]/[PO 4]/[NO 2]≤650 preferably meet 200≤{ [Zn]/[PO 4]/[NO 2]≤600).
Also have, satisfy 0.05≤[Zn]/[PO 4The relational expression of]≤0.2 (particularly meets 0.06≤[Zn]/[PO 4]≤0.19 preferably meets 0.7≤[Zn]/[PO 4]≤0.18).
Particularly, contain the surface treatment treatment solution of zinc, phosphoric acid, aromatic nitro compound, wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700 (particularly meets 1 50≤{ [Zn]/[PO 4]/[NO 2]≤650 preferably meet 200≤{ [Zn]/[PO 4]/[NO 2And satisfy 0.05≤[Zn]/[PO]≤600), 4The relational expression of]≤0.2 (particularly meets 0.06≤[Zn]/[PO 4]≤0.19 preferably meets 0.7≤[Zn]/[PO 4]≤0.18), wherein concentration of phosphoric acid is 50～250m mol/L (particularly 80～200m mol/L).
Person more, above-mentioned surface treatment more includes one or more the compound in the cohort that is selected from aromatic amino compound and aromatic series diazo compound with composition (treatment solution), and aforementioned one or more the total volumetric molar concentration of compound is the value of 0.1 times～10 times (particularly 0.2～5 times) of the volumetric molar concentration of aromatic nitro compound.
Also have, above-mentioned surface treatment is used in the composition (treatment solution), more includes in the cohort that is selected from nickel, manganese, magnesium, calcium, iron (II) and cobalt one or more, particularly two or more cation constituents.And above-mentioned surface treatment is with in the composition (treatment solution), more includes to be selected from azanol and to supply with one or more compound in the cohort of material, nitrous acid and nitrite.
The surface that surface treatment method of the present invention is to use above-mentioned surface treatment to handle metallic substance with composition (treatment solution).
Particularly, this surface treatment method possesses has the surface to adjust processing procedure and surface treatment process, should surface adjustment processing procedure be to adjust in the liquid on the surface that is principal constituent to handle metallic substance with the titanium colloid wherein; And this surface treatment process is after processing procedure is adjusted on this surface, uses this surface to adjust liquid and handles this metallic substance.Or, the surface treatment method that solves aforementioned problems is characterised in that: this surface treatment method possesses has the surface to adjust processing procedure and surface treatment process, wherein should the surface adjusting processing procedure be to include one or more phosphoric acid salt, and this phosphoric acid salt has one or more the divalent or the metallic surface of 3 valencys and adjusts and handle metallic substance in the liquid; And this surface treatment process is after processing procedure is adjusted on this surface, uses this surface treatment to handle this metallic substance with composition (treatment solution).
The goods of metallic substance of the present invention are to possess a metallic substance is arranged, and the weight that designs on this metal material surface is 0.5～5g/m 2Protective membrane, and this protective membrane is to form via above-mentioned surface treatment method.Also have, when this metallic substance is the occasion of Ferrious material material, be formed at the protective membrane weight 0.5～3g/m preferably on this Ferrious material material surface 2And be zinc when being the occasion of metallic substance at this metallic substance, be formed at this zinc and be the protective membrane weight 1～4.5g/m preferably on the metal material surface 2
The present invention is to be object with the metallic substance.Particularly be applicable to iron, zinc and the metallic substance that is coated with zinc, aluminium and aluminium alloy, magnesium and magnesium alloy etc.At this metal to be treated material that is taken as object, be that each independent aforementioned metal material is also passable, even also have the combination of from aforementioned metallic substance, choosing wantonly more than two kinds also fine.Also having, in this so-called plating that contains zinc, is electro-galvanizing or zinc and other metals, at least a alloy of nickel, iron, aluminium, manganese, chromium, magnesium, cobalt, lead or antimony etc. for example, and more the person is the plating that contains inevitable impurity.Electric plating method for example is to dissolve plating, metallide, steaming that electroplate or the like can.Also have, the present invention also can adopt the phosphatizing processing procedure, and does not limit grease-removing agent kind and the degreasing condition that is used in skimming treatment.
Below, bright in more detail.
Surface treatment of the present invention is to contain zinc and phosphoric acid with composition (treatment solution).
About the supply source of zinc and phosphoric acid, can use known zinc phosphate to handle used compound.
The supply source of zinc is for example to adopt the zinc source material of selecting more than one among metallic zinc, zinc oxide, zinc hydroxide, zincate, zinc nitrate, zinc nitrite, zinc carbonate, zinc phosphate, zinc fluoride, zinc sulfate and the hydrochloric acid zinc etc.
The supply source of phosphoric acid for example can adopt and select more than one among phosphoric acid alkali metal salt, phosphoric acid ammonia and the phosphate metal salt etc. of ortho-phosphoric acid, sodium phosphate etc.The supply source of phosphoric acid when using the occasion of phosphate metal salt, preferably adopts to be contained in the phosphate metal salt of surface treatment of the present invention with the metal ingredient in the treatment solution.
Surface treatment of the present invention also contains aromatic nitro compound with composition (treatment solution).
It for example is nitro methyl oxyaniline (nitroanisidin) that aromatic nitro compound preferably adopts, N-methyl-p-nitroaniline (nitroaniline), nitroaniline sulfoacid (nitroaniline sulfonic acid) and salt thereof, nitro amino benzene (nitroaminobenzene), ethyl nitrobenzoate (ethylnitrobenzoate) and salt thereof, nitrocresol (nitrocresol), nitrosalicylic acid (nitrosalicylic) and salt thereof, nitro thiophenol (nitrothiophenol), nitro terephthalic acid (nitroterephthalic acid) and salt thereof, nitrotoluidine (nitrotoluidine), nitrotoluene sulfonic acid (nitrotoluene sulfonic acid) and salt thereof, nitro-naphthalene-monosulfonic acid (nitronaphthalenesulfonic acid) and salt thereof, nitronaphthylamine (nitronaphthyamine), nitro quinhydrones (nitrohydroquinone), nitro pyrogallol (nitropyrogallol), nitrophenyl hydrazine (nitrophenylhydrazine), nitro phenylurea (nitrophenylurea), nitrophenols (nitrophenol), nitrophthalic acid (nitrophthalic acid) and salt thereof, nitro Phloroglucinol (nitrophloroglucinol), nitro-benzylamine (nitrobenzylamine), nitrobenzyl alcohol (nitrobenzylalcohol), oil of mirbane acid amides (nitrobenzamide), nitrobenzene-sulfonic acid (nitrobenzenesulfonic acid) and derivative and salt, and nitrobenzonitrile (nitrobenzonitrile) etc.Preferred nitrobenzene-sulfonic acid (nitrobenzene sulfonic acid), nitroaniline sulfoacid (nitroaniline sulfonicacid), nitrotoluene sulfonic acid (nitrotoluene sulfonic acid), nitro-xylene sulfonic acid (nitroxylenesulfonic acid) and their salt thereof of adopting.
Metallic surface of the present invention is handled and is with aforementioned surfaces composition for treating dilute with water or is dissolved in the water with treatment solution.
When dilute with water or dissolving, for the full acidity (pt: draw surface treatment treatment solution 10mL that will adjust treatment solution with dropper, being used as with the caustic soda aqueous solution of 0.1mol/L then is that phenolphthalein (phenolphthalein) indicator drips periodic titer) and free acidity (pt: draw surface treatment treatment solution 10mL with dropper, being used as with the caustic soda aqueous solution of 0.1mol/L then is that tetrabromophenol sulfonphthalein (bromophenol blue) indicator drips periodic titer) to fixed value, and add the acid of nitric acid etc., caustic soda, Ke Xingjia, the alkali composition of aqua ammonia or amine etc.
Full acidity fixed value be the limit value of certainty to be arranged with the whole ionic concn in the treatment solution via being contained in surface treatment, but special qualification is not arranged in the present invention.The value of free acidity was that treatment temp and the treatment time when handling object being treated with surface treatment with treatment solution is fixed originally, but special qualification was not arranged in the present invention.Yet, adopt the parkerized treatment temp and the treatment time that now generally are used in Japan, be used in when of the present invention, free acidity preferably is adjusted at the scope of 0.3～2pt, is more preferably the scope of 0.5～1.5pt.
When using surface treatment of the present invention to use treatment solution, dilute with water or dissolving surface treatment composition, and make surface treatment become 50～250m mol/L with the phosphoric acid concentration in the treatment solution.
The present invention is that the ratio with the volumetric molar concentration of zinc, phosphoric acid, aromatic nitro compound is controlled in the specific scope.Preferably be controlled in the specific scope, and can separate out the crystallization of atomic thin and fine and close phosphate coating by ratio with the volumetric molar concentration of zinc, phosphoric acid, aromatic nitro compound.
Therefore, in the present invention,, inevitably, also zinc and aromatic nitro compound can be fixed in suitable concentration range if fixed surface is handled with the phosphoric acid concentration in the treatment solution.Therefore, than 50m mol/L hour, then the zinc of protective membrane principal constituent and phosphoric acid concentration will be little as if the phosphoric acid concentration in the surface treatment usefulness treatment solution.Therefore, just be not easy the phosphate coating crystallization is separated out in fixed time.On the contrary, when bigger than 250m mol/L as if the phosphoric acid concentration in the surface treatment usefulness treatment solution, though separate out the phosphate coating crystallization, surface treatment is big with the concentration of treatment solution.Therefore, will become many via the drag-out of the treatment solution composition of metal to be treated material, this is to unfavorable economically.
Separate out mechanism about the protective membrane crystalline that zinc phosphate is handled, the metal to be treated material is if contact with the zinc phosphate treatment solution, and the dissolving of metal to be treated material (etching) reaction will take place.Then, via etching reaction, the pH value of metal to be treated material surface will rise.Therefore, the protective membrane that zinc phosphate is handled in bathing becomes branch's destabilization, and has precipitation to separate out.
At this, be that the iron of metal to be treated material is used as example to be used as, from the viewpoint of chemical equilibrium and represent the aforementioned mechanism of separating out with reaction formula.
Fe+2H 3PO 4→ Fe (H 2PO 4) 2+ H 2Formula (1)
3Zn (H 2PO 4) 2 Zn 3(PO 4) 2+ 4H 3PO 4Formula (2)
Above-mentioned formula (1) is the etching reaction of the iron of metal to be treated material.
Above-mentioned formula (2) is to be presented at the 1st zinc phosphate in the zinc phosphate treatment solution and the balanced reaction of the 3rd zinc phosphate.
According to aforementioned chemical formula, the zinc phosphate processing reaction is for the H that is consumed in the etching reaction of wanting compensation type (1) 3PO 4Concentration, and the balanced reaction of formula (2) is carried out towards right-hand.And, insoluble the 3rd zinc phosphate Zn 3(PO 4) 2Separate out.
Therefore, for the reactivity that zinc phosphate is handled, ratio [Zn]/[PO of zinc and concentration of phosphoric acid ratio 4] be very important key element.
At aforementioned [Zn]/[PO 4] when being very large occasion, the phosphoric acid concentration in the zinc phosphate treatment solution is very low, or zinc concentration height very.
When phosphoric acid concentration is unusual low occasion, be that the etching reaction of metal to be treated material of the 1st step of reaction is to be not easy to take place, therefore, just be not easy to separate out the crystallization of zinc phosphate protective membrane.When the unusual high occasion of zinc concentration, the balance of formula (2) is just carried out towards right-hand easily, therefore, just separates out the crystallization of zinc phosphate protective membrane easily.Yet, but can form the big and big crystallization of protective membrane weight of crystal size.
Also have, when zinc concentration was extremely high occasion, the balance of the formula in the zinc phosphate treatment solution (2) was carried out towards right-hand, therefore, forms the throw out of the 3rd zinc phosphate of separating out.
At aforementioned [Zn]/[PO 4] when being very little occasion, the phosphoric acid concentration in the zinc phosphate treatment solution is a height very, or zinc concentration low situation very.
No matter be which kind of situation, all be not easy to make the balance of formula (2) to carry out, therefore, just be not easy to separate out the crystallization of zinc phosphate protective membrane towards right-hand.
According to above explanation, can know via concentration of phosphoric acid being fixed on a certain concentration range and control [Zn]/[PO 4] ratio, can control the zinc phosphate processing reaction.
Yet, if the aforementioned phosphoric acid concentration of control and [Zn]/[PO are only arranged 4], be the finer and fine and close crystallization of zinc phosphate protective membrane that can't obtain than being used now.
That is to say; via the meticulous research of present inventor; in order to obtain fine and fine and close zinc phosphate crystallization; be in the zinc phosphate treatment solution, to add aromatic nitro compound; and; have zinc, phosphoric acid and the aromatic nitro compound of specific concentrations ratio via use, then can access in that painting state and painting state all do not have good corrosion proof atomic thin zinc phosphate protective membrane crystallization.
Reaction mechanism for the aromatic nitro compound of zinc phosphate protective membrane crystalline miniaturization is not easy to understand with present viewpoint.
Yet the present invention is the action effect that studies intensively out when aforesaid compound is added into the zinc phosphate treatment solution.This found that when handling steel plate with the zinc phosphate treatment solution that is added with aforesaid compound, the etch quantity of the steel plate of metal to be treated material can increase, and also has, and the discovery zinc phosphate chemical reaction initial stage is separated out the crystalline number also to be increased.Person more, the more known oxidizing power that uses nitrite and aromatic nitro compound is then found the oxidizing power from iron (II) to iron (III), the oxidizing power that is this side of aromatic nitro compound is very little.
Therefore, aromatic nitro compound is the etching reaction that promotes the metal to be treated material, and promotes the very evolution reaction at initial stage of zinc phosphate protective membrane crystalline.And, remain on metal to be treated material and surface treatment iron (II) ion, and the zinc phosphate protective membrane crystalline that suppresses to have separated out is grown up with interface between the treatment solution.So, lasting because zinc phosphate protective membrane crystalline is separated out when the growth of zinc phosphate protective membrane crystalline is suppressed, and make the zinc phosphate protective membrane crystallization of final gained become atomic thin and fine and close.
At this, grow up the surface treatment reactivity of treatment solution, that is [Zn]/[PO of corresponding surface treatment in the treatment solution in order to suppress aforementioned zinc phosphate protective membrane crystalline 4] the concentration of aromatic nitro compound be necessary to stipulate.
That is to say [Zn]/[PO in surface treatment usefulness treatment solution 4] when being big occasion, separate out easily in order to make the crystallization of zinc phosphate protective membrane, then must improve the concentration of aromatic nitro compound.But on the contrary, at [Zn]/[PO 4] when being little occasion, then must reduce the concentration of aromatic nitro compound.
Present inventors etc. are [Zn]/[PO of investigation surface treatment in the treatment solution 4] and the zinc phosphate protective membrane crystallization of the volumetric molar concentration of aromatic nitro compound and gained between relation.The present invention finds can access atomic thin and fine and close zinc phosphate protective membrane crystallization in the concentration range of regulation.
At this, at { [Zn]/[PO 4]/[NO 2] during less than 100 occasion, corresponding to [Zn]/[PO 4] the concentration of aromatic nitro compound be big.Therefore, zinc phosphate protective membrane crystalline grow up to suppress effect will be excessive, and what the protective membrane that just is easy to generate gained had what is called " transparent " in appearance does not separate out the crystalline position.
On the contrary, at { [Zn]/[PO 4]/[NO 2] during greater than 700 occasion, corresponding to [Zn]/[PO 4] the concentration of aromatic nitro compound be little.Therefore, though the crystallization of zinc phosphate protective membrane is separated out, can't reach the atomic thin and fine and close zinc phosphate protective membrane crystallization of the object of the invention.
With in the treatment solution,, then can access the better protection film in surface treatment of the present invention if be added with the aromatic amino compound and more than a kind of aromatic series diazo compound from 0.1 times to 10 times volumetric molar concentration of aromatic nitro compound.
Aromatic amino compound that is adopted and aromatic series diazo compound preferably adopt for example nitro methyl oxyaniline, N-methyl-p-nitroaniline, nitroaniline sulfoacid and salt thereof, nitro amino benzene, ethyl nitrobenzoate and salt thereof, nitrocresol, nitrosalicylic acid and salt thereof, nitro thiophenol, nitro terephthalic acid and salt thereof, nitrotoluidine, nitrotoluene sulfonic acid and salt thereof, nitro-naphthalene-monosulfonic acid and salt thereof, nitronaphthylamine, the nitro quinhydrones, the nitro pyrogallol, nitrophenyl hydrazine, the nitro phenylurea, nitrophenols, nitrophthalic acid and salt thereof, the nitro Phloroglucinol, nitro-benzylamine, nitrobenzyl alcohol, the oil of mirbane acid amides, nitrobenzene-sulfonic acid and derivative thereof and salt, and nitrobenzonitrile etc. with the nitro of aromatic nitro compound through amidized compound or with the nitro of aromatic nitro compound compound through diazoization.The preferred nitro with aromatic nitro compound of nitrobenzene-sulfonic acid, nitroaniline sulfoacid, nitrotoluene sulfonic acid, nitro-xylene sulfonic acid and their salt thereof that adopts passes through amidized compound or the nitro of aromatic nitro compound is passed through the compound of diazoization.
Also have, more than one of aromatic amino compound used in the present invention and aromatic series diazo compound, even be added into surface treatment of the present invention aforehand with also passable in the treatment solution, also have, adopt the compound that redox reaction was generated of the aromatic nitro compound when handling the metal to be treated material also passable with surface treatment method of the present invention.
Aromatic amino compound used in the present invention and aromatic series diazo compound have the corrosion proof effect of not application that improves surface treated metallic substance.
The atomic thin and fine and close phosphoric acid that surface treatment of the present invention can can't obtain known technology with treatment solution is handled protective membrane and is separated out.Therefore, can provide and have than solidity to corrosion after the good application of known technology and the corrosion proof metallic substance of application not.At this, when more than one of aromatic amino compound and aromatic series diazo compound are added into surface treatment and use treatment solution, handle side by side with zinc phosphate, aforementioned aromatic amino compound and aromatic series diazo compound meeting sorption particularly more can improve not application solidity to corrosion on the metallic surface.
The aromatic amino compound that contained and aromatic series diazo compound concentration preferably aromatic nitro compound from 0.1 times to 10 times volumetric molar concentration.The aromatic amino compound that contained and the concentration of aromatic series diazo compound, if during occasion than 0.1 times little of aromatic nitro compound, surface treatment is little with the absolute magnitude in the treatment solution, therefore, improves the corrosion proof effect of not application and will reduce.On the contrary, if during occasion, just do not have obstacle on the performance of surface treated metallic substance than 10 times big of aromatic nitro compound.But, keep the concentration of aromatic amino compound and aromatic series diazo compound via the supply of outside, be disadvantageous economically.
Surface treatment liquid of the present invention is to select one or more from the cohort of nickel, manganese, magnesium, calcium, iron (II) and cobalt, particularly contains two or more cation constituents.For example, selected cationic total amount is 0.01～0.06mol/L from the cohort of nickel, manganese, magnesium, calcium, iron (II) and cobalt, therefore the cationic amount of the maximum involved kinds in involved positively charged ion preferably more than the 50wt%, below the 100wt%.That is, particularly comprising two or more cationic occasions, zinc phosphate protective membrane crystalline performance is improved, the performance when particularly improving after the application with application not.So when adopting above-mentioned surface treatment to use the occasion of treatment solution, the atomic thin and fine and close phosphoric acid that known technology can't be able to be obtained is handled protective membrane and is separated out.Therefore, can provide and have than solidity to corrosion after the good application of known technology and the corrosion proof metallic substance of application not.
Surface treatment of the present invention further includes with treatment solution and is selected from azanol and supplies with one or more compound in the cohort of material, nitrous acid and nitrite.
It for example is to adopt oxammonium sulfate, phosphatic hydroxylamine, hydroxylamine nitriate, free hydroxylamine etc. that azanol is supplied with material.Nitrite for example is to adopt Sodium Nitrite or zinc nitrite.Therefore, it is for example when using azanol to supply with the occasion of material that their phosphate chemical is handled the film formed promotor of protection, preferably contains the azanol of 3～100m mol/L.And when adopting the occasion of nitrite, preferably contain the nitrite of 1～5mmol/L.
Surface treatment method of the present invention, according to required, be preferably in adopt the zinc phosphate treatment project that zinc phosphate handles before, carry out surface in advance and adjust processing.
Treatment solution is adjusted on employed surface, it for example is the surface adjustment treatment solution of the so-called ジ ャ one Application ス テ ッ De salt of principal constituent with the titanium colloid, or being disclosed in the spy opens flat 10-245685 communique and the special phosphoric acid salt of opening in the 2000-96256 communique that includes more than one, and this phosphoric acid salt has the metallic surface adjustment treatment solution of at least a divalent or 3 valencys.Particularly; the aforesaid phosphoric acid salt that includes more than one and this phosphoric acid salt have the metallic surface of at least a divalent or 3 valencys and adjust treatment solution; than adopting with the titanium colloid is the occasion of the surface adjustment treatment solution of principal constituent, can easily obtain careful protective membrane.
Via the protective membrane of surface treatment gained of the present invention, be the atomic thin and fine and close zinc phosphate crystallization that can't obtain since in the past.Therefore, be very high via the clad ratio of the metal to be treated material surface of zinc phosphate, and can access solidity to corrosion and not application solidity to corrosion after the good application.At this, when the Ferrious material material surface was carried out surface-treated occasion via surface treatment method of the present invention, the surface treatment protective film preferably protective membrane weight of one deck was 0.5～3g/m 2(0.5～2.5g/m particularly 2).To zinc is metal material surface when carrying out surface-treated occasion via surface treatment method of the present invention, and the surface treatment protective film preferably protective membrane weight of one deck is 1.0～4.5g/m 2(1.0～4.0g/m particularly 2).Therefore, the zinc phosphate protective membrane crystallization of gained of the present invention is atomic thin.Therefore, with than known light protective membrane weight, bring into play solidity to corrosion and not application solidity to corrosion after the good application.Yet, if protective membrane weight be less than aforementioned down in limited time, what the protective membrane that just is easy to generate gained had what is called " transparent " in appearance does not separate out zinc phosphate protective membrane crystalline position.On the contrary, if protective membrane weight is to go up in limited time greater than aforementioned, the tendency that just has the stopping property of filming after the application to descend.
Below, lift some specific embodiments the present invention is described.
Embodiment
[for test plate (panel)]
CRS (the cold steel plate that prolongs: JIS-G-3041)
(the hot dip alloyed zinc electroplating steel plate in two sides: electroplate unit is 45g/m to GA 2)
Al (aluminium alloy plate: 6000 line aluminium alloys)
[zinc phosphate processing]
Embodiment and comparative example are handled according to the processing processing procedure that alkali degreasing → washing → surface adjustment → protective membrane chemical treatment → washing → pure water is washed.
[alkali degreasing]
No matter be to adopt any grease-removing agent, for example Finecleaner-L4460A (registered trademark: Japanese parkerizing company product, contracted notation FC-L4460A) 2% or Finecleaner-L4460B (registered trademark: Japanese parkerizing company product, contracted notation FC-L4460B), make the concentration of Finecleaner-L4460A become 2% or make the concentration of Finecleaner-L4460B become 1.4% all earlier with the tap water dilution, be heated to 42 ℃ then.Afterwards, it is sprayed on the metal to be treated material.
[washing]
Behind the alkali degreasing and the washing after the protective membrane chemical treatment and pure water wash, no matter be any, it at room temperature is sprayed to handle on the metallic substance cleaned 30 seconds.
[surface is adjusted]
In embodiment 1, comparative example 1 and comparative example 2, make commercially available surface adjust the SprayZN of treatment agent (registered trademark: concentration Japanese parkerizing company product) becomes 0.1%, it at room temperature is sprayed to carries out surface on the metal to be treated material and adjust processing 30 seconds with tap water dilution.
In embodiment 2,3,4,5, the adjusted surface of sprinkling/spraying is in the following manner adjusted treatment solution and is carried out surface adjustment and handle.
At first make commercially available 1-hydroxy ethylene-1, the concentration of 1-tetra-na diphosphate salt (1-hydroyyethylidene-1,1-diphosphonate acid natrium salt) become 20wt%, get its 1kg then and be added into Zn with the tap water dilution 3(PO 4) 24H 2Among the O reagent 1kg.Afterwards, pulverize in the said mixture with the ball milling of the zirconium white piece that uses diameter 0.5mm.After the pulverizing, with tap water with the Zn in the suspension liquid 3(PO 4) 24H 2The concentration of O is adjusted to 0.5g/L, adjusts treatment solution and make the surface.
Also have, use laser refraction/formula particle size distribution device at random (LA-920: the hole field makes institute's product) to measure through the adjusted surperficial atomic median size of adjusting in the treatment solution.Its result's median size is 0.6 μ m.
[protective membrane chemical treatment]
The 1st embodiment
In order to make [Zn]/[PO 4]=0.05, { [Zn]/[PO 4]/[NO 2]=100 (zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit), below all with), so cooperate commercially available zinc oxide reagent, phosphoric acid reagent and the reagent of m-nitrobenzene-sulfonic acid, and adjust surperficial composition for treating.
Adding quantitative nickelous nitrate reagent, manganous carbonate reagent and hexafluorosilicic acid (hexafluorosilicicacid) reagent uses in the composition in this surface treatment.Afterwards, make the phosphoric acid concentration after the dilution become 210m mol/L with tap water dilution, nickel concentration becomes 17m mol/L, and manganese concentration becomes 9m mol/L, and the plain concentration of perfluor becomes 53m mol/L.
Add the sodium hydroxide reagent in this diluent, and make the phosphoric acid concentration of diluent become 0.5pt.Afterwards, add again 180ppm Sodium Nitrite reagent, 20ppm 4,4 '-diazoamino-DAADBSA 2 sodium (4,4 '-diazoamino-dibenzene sulfonic acid 2 natrium) reagent and make the surface treatment treatment solution.
Then, handle with in the treatment solution 90 seconds and carry out surface treatment carrying out the metal to be treated material that degreasing, washing and surface adjustment are handled, impregnated in heating to 40 ℃ aforementioned surfaces.
The 2nd embodiment
In order to make [Zn]/[PO 4]=0.1, { [Zn]/[PO 4]/[NO 2Surperficial composition for treating cooperating commercially available zinc oxide 4 water and thing reagent, phosphoric acid reagent and the reagent of m-nitrobenzene-sulfonic acid, and is adjusted in]=400.
Adding quantitative manganous carbonate reagent, magnesium nitrate reagent and hexafluorosilicic acid reagent uses in the composition in this surface treatment.Afterwards, make the phosphoric acid concentration after the dilution become 53m mol/L with tap water dilution, manganese concentration becomes 9m mol/L, and magnesium density becomes 80m mol/L, and the plain concentration of perfluor becomes 53m mol/L.
Add the sodium hydroxide reagent in this diluent, and make the phosphoric acid concentration of diluent become 0.5pt.Afterwards, add the Sodium Nitrite reagent of 300ppm again and make the surface treatment treatment solution.
Then, handle with in the treatment solution 60 seconds and carry out surface treatment carrying out the metal to be treated material that degreasing, washing and surface adjustment are handled, impregnated in heating to 50 ℃ aforementioned surfaces.
The 3rd embodiment
In order to make [Zn]/[PO 4]=0.1, { [Zn]/[PO 4]/[NO 2Surperficial composition for treating cooperating commercially available zinc oxide 4 water and thing reagent, phosphoric acid reagent and the reagent of m-nitrobenzene-sulfonic acid, and is adjusted in]=700.
Adding quantitative Xiao Suangu reagent, lime carbonate reagent and hexafluorosilicic acid reagent uses in the composition in this surface treatment.Afterwards, make the phosphoric acid concentration after the dilution become 158mmol/L with tap water dilution, cobalt concentration becomes 17m mol/L, and calcium concn becomes 12m mol/L, and the plain concentration of perfluor becomes 53m mol/L.
Add the reagent of heavy carbonic ammonia in this diluent, and make the free acidity of diluent become 1.0pt.Afterwards, add again 120ppm Sodium Nitrite reagent, 100ppm the reagent of m-nitrobenzene-sulfonic acid and make the surface treatment treatment solution.
Then, handle with in the treatment solution 60 seconds and carry out surface treatment carrying out the metal to be treated material that degreasing, washing and surface adjustment are handled, impregnated in heating to 35 ℃ aforementioned surfaces.
The 4th embodiment
In order to make [Zn]/[PO 4]=0.2, { [Zn]/[PO 4]/[NO 2Surperficial composition for treating cooperating commercially available zinc oxide reagent, phosphoric acid reagent and 4-N-methyl-p-nitroaniline-2-sulfonic acid (4-niroaniline-2-sulfonic acid) reagent, and is adjusted in]=200.
Adding quantitative magnesium nitrate reagent, iron carbonate (II) reagent, azanol reagent and hexafluorosilicic acid reagent uses in the composition in this surface treatment.Afterwards, make the phosphoric acid concentration after the dilution become 105m mol/L with tap water dilution, magnesium density becomes 82m mol/L, and concentration of iron becomes 4m mol/L, and azanol concentration becomes 0.06m mol/L, and the plain concentration of perfluor becomes 53m mol/L.
Add the reagent of heavy hydrogen sodium oxide in this diluent, and make the free acidity of diluent become 1.5pt.Afterwards, add the m-nitrobenzene-sulfonic acid reagent of 200ppm again and make the surface treatment treatment solution.
Then, handle with in the treatment solution 90 seconds and carry out surface treatment carrying out the metal to be treated material that degreasing, washing and surface adjustment are handled, impregnated in heating to 40 ℃ aforementioned surfaces.
The 5th embodiment
In order to make [Zn]/[PO 4]=0.15, { [Zn]/[PO 4]/[NO 2Surperficial composition for treating cooperating commercially available zinc oxide reagent, phosphoric acid reagent and the reagent of m-nitrobenzene-sulfonic acid, and is adjusted in]=300.
Adding quantitative nickelous nitrate reagent, manganous carbonate reagent and hexafluorosilicic acid reagent uses in the composition in this surface treatment.Afterwards, make the phosphoric acid concentration after the dilution become 126mmol/L with tap water dilution, nickel concentration becomes 17m mol/L, and manganese concentration becomes 18m mol/L, and the plain concentration of perfluor becomes 53m mol/L.
Add the sodium hydroxide reagent in this diluent, and make the free acidity of diluent become 0.9pt.Afterwards, add again 180ppm Sodium Nitrite reagent, 50ppm 4,4 '-diazoamino-DAADBSA 2 sodium (4,4 '-diazoamino-dibenzene sulfonic acid 2 natrium) reagent and make the surface treatment treatment solution.
Then, handle with in the treatment solution 90 seconds and carry out surface treatment carrying out the metal to be treated material that degreasing, washing and surface adjustment are handled, impregnated in heating to 40 ℃ aforementioned surfaces.
[comparative example 1]
In order to make [Zn]/[PO 4]=0.05, { [Zn]/[PO 4]/[NO 2Surperficial composition for treating cooperating commercially available zinc oxide reagent, phosphoric acid reagent and the reagent of m-nitrobenzene-sulfonic acid, and is adjusted in]=80.
Adding quantitative nickelous nitrate reagent, manganous carbonate reagent and hexafluorosilicic acid reagent uses in the composition in this surface treatment.Afterwards, make the phosphoric acid concentration after the dilution become 158mmol/L with tap water dilution, nickel concentration becomes 17m mol/L, and manganese concentration becomes 9m mol/L, and the plain concentration of perfluor becomes 53mmol/L.
Add the sodium hydroxide reagent in this diluent, and make the free acidity of diluent become 0.5pt.Afterwards, add the Sodium Nitrite reagent of 180ppm again and make the surface treatment treatment solution.
Then, handle with in the treatment solution 90 seconds and carry out surface treatment carrying out the metal to be treated material that degreasing, washing and surface adjustment are handled, impregnated in heating to 40 ℃ aforementioned surfaces.
[comparative example 2]
In order to make [Zn]/[PO 4]=0.2, { [Zn]/[PO 4]/[NO 2Surperficial composition for treating cooperating commercially available zinc oxide reagent, phosphoric acid reagent and the reagent of m-nitrobenzene-sulfonic acid, and is adjusted in]=800.
Adding quantitative nickelous nitrate reagent, manganous carbonate reagent and hexafluorosilicic acid reagent uses in the composition in this surface treatment.Afterwards, make the phosphoric acid concentration after the dilution become 158mmol/L with tap water dilution, nickel concentration becomes 17m mol/L, and manganese concentration becomes 9m mol/L, and the plain concentration of perfluor becomes 53mmol/L.
Add the sodium hydroxide reagent in this diluent, and make the free acidity of diluent become 1.0pt.Afterwards, add the Sodium Nitrite reagent of 180ppm again and make the surface treatment treatment solution.
Then, handle with in the treatment solution 90 seconds and carry out surface treatment carrying out the metal to be treated material that degreasing, washing and surface adjustment are handled, impregnated in heating to 40 ℃ aforementioned surfaces.
[evaluation of the new protective membrane of phosphoric acid]
(1) outward appearance:
Estimate the zinc phosphate protective membrane with visual observation and have or not " clear area " and " dark space (or ripple) ".Its result is as shown in table 1.The meaning of its symbology such as following.
◎ homogeneous good surface appearance
Zero has the dark space of a part
△ has " clear area " and " dark space "
* have a lot of " clear area "
* * do not have chemical treatment protective membrane
(2) protective membrane weight (C.W)
The weight of the disposable plates after the mensuration chemical treatment (W1[g]).Then, when the chemical treatment plate is cold occasion of prolonging steel plate, is impregnated in 75 ℃ 50% chromic acid aqueous solution 15 minutes, and carries out the protective membrane lift-off processing.When the chemical treatment plate is the occasion of steel plate galvanized, is impregnated in the ammonium dichromate (2%) of normal temperature and ammoniacal liquor (13.7%) aqueous solution 15 minutes, and carries out the protective membrane lift-off processing.When the chemical treatment plate is the occasion of aluminium alloy plate, is impregnated in ammonium dichromate (50%) aqueous solution of normal temperature 5 minutes, and carries out the protective membrane lift-off processing.Weight after afterwards, the mensuration protective membrane is peeled off (W2[g]).Then, calculate protective membrane weight according to following formula.This result is as shown in table 1.
Protective membrane weight [g/m 2Surface-area (the m of]=(W1-W2)/disposable plates 2)
(3) protective membrane crystal size (C.S)
Use sweep electron microscope (SEM) to observe image and investigate the crystallization particle diameter, its image is to be exaggerated 1500 times.This result is as shown in table 1.
(4) not application solidity to corrosion
The zinc phosphate disposable plates of the CRS of embodiment and comparative example made put into be set in 95%RH, 50 ℃ moistening trier, judge the rust area after 24 hours then.This result is as shown in table 1.
(5) coating performance
(a) estimate making of plate
In order to estimate coating performance, so carry out application with following processing procedure via the zinc phosphate disposable plates of embodiment and comparative example gained.
Positively charged ion electrolysis application → pure water washes → sintering → in be coated with → sintering → on be coated with → sintering
Northwest paint company product), voltage 200V, thickness 20 μ m, 175 ℃ of sintering 20 minutes positively charged ion electrolysis application: epoxy is a positively charged ion electrolysis coating (エ レ Network ロ Application 9400:.
In application: Northwest paint company product), sprayed application, thickness 35 μ m, 140 ℃ of sintering 20 minutes alkyd amino (aminoalkyd) is coating (ァ ミ ラ ッ Network TP-37 グ レ one:.
On application: Northwest paint company product), sprayed application, thickness 35 μ m, 140 ℃ of sintering 20 minutes alkyd amino is that (TM-13 is white for ァ ミ ラ ッ Network: for coating.
(b) coating performance comment
Above-mentioned surface treatment plate through application is carried out the evaluation of coating performance.This result is as shown in table 2.
Also have, comment project, comment method and contracted notation are all as described below.Also have, electrolysis application the filming of time point that be over is to film with electrolysis to be referred to as, on application the filming of time point that be over be to film with 3coats to be referred to as.
1) SST: brine spray experiment (electrolysis is filmed)
The electrolysis coated plate that the crosscut with sharp keen cutter is gone into is bestowed sprayings (according to JIS-Z-2371) in 840 hours of 5% the NaCl aqueous solution.After spraying ends, measure maximum swelling width from the crosscut part to a side.
2) SDT: salt warm water experiment (electrolysis is filmed)
The electrolysis coated plate that the crosscut with sharp keen cutter is gone into is bestowed 240 hours dippings of 5% the NaCl aqueous solution that is warming up to 55 ℃.Dipping cleans with tap water after ending.Then, the Cello-tape (cellulose film pipe) (registered trademark) that passes through the crosscut portion that the electrolysis of Air drying films peels off.Afterwards, measurement is peeled off width from the crosscut part to the maximum of both sides.
3) 1stADH:1 stopping property (3coats films)
On 3coats films, cut out 100 chessboard eyes with sharp keen cutter apart from one another by 2mm, the Cello-tape (cellulose film pipe) (registered trademark) that carries out the chessboard eye portion then peels off.Afterwards, calculate the number of peeling off of chessboard eye.
4) 2ndADH: water-fast 2 stopping propertys (3coats films)
The 3coats coated plate be impregnated in 40 ℃ the deionized water 240 hours.Behind the dipping, cut out 100 chessboard eyes apart from one another by 2mm with sharp keen cutter, the Cello-tape (cellulose film pipe) (registered trademark) that carries out the chessboard eye portion then peels off.Afterwards, calculate the number of peeling off of chessboard eye.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
The protective membrane outward appearance CRS ◎ ◎ ◎ ◎ ◎ × ◎
GA ◎ ◎ ◎ ◎ ◎ ◎ ◎
Al ○ ◎ ◎ ◎ ◎ × △
Protective membrane weight CRS 2.1 0.8 1.7 1.7 1.8 2.8 3.2
GA 3.8 2.5 3.2 3.3 3.1 4.2 5.8
Al 1.5 1.3 1.9 1.8 1.8 0.8 1.8
Crystal size CRS 3＞ 2＞ 2＞ 2＞ 2＞ 3 5～10
GA 5＞ 5＞ 3＞ 3＞ 3＞ 5～10 10～15
Al 5＞ 3＞ 3＞ 3＞ 3＞ 5～1 0 5～10
Solidity to corrosion rust area % CRS 5＞ 10 5＞ 5＞ 5＞ All get rusty 30
Table 2
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
SST CRS 1.3 1.9 1.2 1.2 1.1 5.3 4.6
GA 2.6 2.8 2.6 2.7 2.6 5.8 6.3
Al 0.5 0.5 0.6 0.5 0.5 1.5 1.1
SDT CRS 3.5 3.8 3.2 3.4 3.3 10≤ 7.2
GA 3.8 4.1 3.3 3.5 3.6 6.0 5.9
Al 2.3 2.7 2.2 2.1 2.1 5.1 4.5
1 stADH peels off number CRS 0 0 0 0 0 0 0
GA 0 0 0 0 0 0 2
Al 0 0 0 0 0 0 0
2 ndADH peels off number CRS 0 0 0 0 0 0 0
GA 0 0 0 0 0 0 5
Al 0 0 0 0 0 0 0
According to the above description, as can be known comparative example owing to do not satisfy 0.05≤[Zn]/[PO 4]≤0.2,100≤{ [Zn]/[PO 4]/[NO 2]≤700 (wherein zinc concentration [Zn] (mol/L of unit), concentration of phosphoric acid [PO 4] concentration [NO of (mol/L of unit) and aromatic nitro compound 2] (mol/L of unit)), so do not have the speciality of the protective membrane of embodiment.
For example, { [Zn]/[PO 4]/[NO 2The comparative example 1 of]=80, particularly the zinc phosphate protective membrane on CRS is considered to the exposed portions serve of the metallic substance of what is called " clear area " in appearance.That is to say that the solidity to corrosion of comparative example 1 is than embodiment difference.
Also has { [Zn]/[PO 4]/[NO 2The comparative example 2 of]=800, the crystallization of zinc phosphate protective membrane does not become fine crystallization.And, zinc phosphate protective membrane Heavy Weight, the solidity to corrosion of zinc phosphate protective membrane is also bad.And, to film even on the zinc phosphate protective membrane, design, this stopping property of filming is also bad, so solidity to corrosion is also bad.
With respect to this, according to embodiments of the invention, the crystallization of zinc phosphate protective membrane is fine.And the zinc phosphate protective membrane is in light weight, and the solidity to corrosion of zinc phosphate protective membrane is also fine.And it is also fine and be difficult to peel off to be designed in the stopping property of filming on the zinc phosphate protective membrane, and solidity to corrosion is also fine.
Utilize possibility on the industry
According to the present invention, can be in that painting state and painting state all have the atomic thin trbasic zinc phosphate chemoproection film of excellent corrosion resistance. Particularly, in the known phosphate treated processing procedure that adopts, even and do not improve existing treating apparatus, also can provide corrosion resistance excellent atomic thin phosphate coating. So, can form again atomic thin phosphate coating of the thin and excellent corrosion resistance of diaphragm. Therefore, the present invention can reduce the reagent consumption amount, reduces the formation cost of trbasic zinc phosphate chemoproection film.

Claims (14)

1. surface treatment composition is characterized in that:
This surface treatment contains zinc, phosphoric acid, aromatic nitro compound with composition, wherein zinc concentration [Zn] (mol/L), concentration of phosphoric acid [PO 4] (mol/L) with the concentration [NO of aromatic nitro compound 2] (mol/L), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700, wherein the concentration of phosphoric acid scope is 50～200m mol/L.
2. surface treatment composition as claimed in claim 1 wherein further satisfies 0.05≤[Zn]/[PO 4The relational expression of]≤0.2.
3. surface treatment treatment solution is characterized in that:
This surface treatment contains zinc, phosphoric acid, aromatic nitro compound with composition, wherein zinc concentration [Zn] (mol/L), concentration of phosphoric acid [PO 4] (mol/L) with the concentration [NO of aromatic nitro compound 2] (mol/L), satisfy 100≤{ [Zn]/[PO 4]/[NO 2The relational expression of]≤700, wherein the concentration of phosphoric acid scope is 50～200m mol/L.
4. surface treatment treatment solution as claimed in claim 3 wherein further satisfies 0.05≤[Zn]/[PO 4The relational expression of]≤0.2.
5. as claim 3 or 4 described surface treatment treatment solutions, further include one or more the aromatics in the cohort that is selected from aromatic amino compound and aromatic series diazo compound, and the total volumetric molar concentration of aforementioned aromatics is 0.1 times～10 times a value of the volumetric molar concentration of this aromatic nitro compound.
6. as claim 3,4 or 5 described surface treatment treatment solutions, further include one or more the cation constituent in the cohort that is selected from nickel, manganese, magnesium, calcium, iron (II) and cobalt.
7. as claim 3,4,5 or 6 or described surface treatment treatment solution, further include and be selected from azanol and supply with one or more compound in the cohort of material, nitrous acid and nitrite.
8. surface treatment method is characterized in that:
The surface of using aforementioned claim 3,4,5,6 or 7 described these surface treatments to handle metallic substance with treatment solution.
9. surface treatment method is characterized in that:
Comprising surface adjustment processing procedure and surface treatment process, should surface adjustment processing procedure be to adjust in the liquid on the surface that is principal constituent to handle metallic substance with the titanium colloid wherein; And this surface treatment process is after processing procedure is adjusted on this surface, uses aforementioned claim the 3,4,5,6 or 7 described these surface treatments to handle metallic substance with treatment solution.
10. surface treatment method is characterized in that:
Comprising surface adjustment processing procedure and surface treatment process, should surface adjustment processing procedure be to adjust in the liquid on the phosphatic surface that includes one or more to handle metallic substance wherein, and this phosphoric acid salt has one or more the divalent or the metal of 3 valencys; And this surface treatment process is after processing procedure is adjusted on this surface, uses aforementioned claim 3,4,5,6 or 7 described these surface treatments to handle metallic substance with treatment solution.
11. the goods with metallic substance is characterized in that:
Have metallic substance, and the protective membrane weight that designs on this metal material surface is 0.5～5g/m 2Protective membrane, and this protective membrane is to form via described this surface treatment method of aforementioned claim 8.
12. the goods with metallic substance is characterized in that:
Have metallic substance, and the protective membrane weight that designs on this metal material surface is 0.5～5g/m 2Protective membrane, and this protective membrane is to form via aforementioned claim 9 or 10 described these surface treatment methods.
13. as claim 11 or 12 described goods with metallic substance, wherein when this metallic substance was the Ferrious material material, the protective membrane weight that is formed at this protective membrane on this Ferrious material material surface was 0.5～3g/m 2
14. as claim 11 or 12 described goods with metallic substance, wherein when this metallic substance be zinc when being metallic substance, the protective membrane weight that is formed at this zinc and is this protective membrane on the metal material surface is 1～4.5g/m 2
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