CN1950544B - Agent for reducing conversion film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate conversion film reduced in overall friction coefficient and method for production thereof - Google Patents
Agent for reducing conversion film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate conversion film reduced in overall friction coefficient and method for production thereof Download PDFInfo
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- CN1950544B CN1950544B CN200580014275XA CN200580014275A CN1950544B CN 1950544 B CN1950544 B CN 1950544B CN 200580014275X A CN200580014275X A CN 200580014275XA CN 200580014275 A CN200580014275 A CN 200580014275A CN 1950544 B CN1950544 B CN 1950544B
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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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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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
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
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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
- C23C22/46—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 oxalates
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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
- C23C22/46—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 oxalates
- C23C22/47—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 oxalates containing also phosphates
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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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
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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Abstract
An agent for reducing a coating film overall friction coefficient for a trivalent chromate treating solution, characterized in that it comprises a quinoline based compound or a derivative thereof. A coating film formed by the contact of a zinc or zinc alloy plating with the trivalent chromate treating solution containing no hexavalent chromium and containing the above agent on the surface of the plating exhibits a corrosion resistance equivalent to that of a coating film formed by a chromate treatment with a treating solution having a conventional hexavalent chromium as a main component, and also exhibits an overall friction coefficient equivalent to or less than that of a coating film formed by a conventional hexavalent chromate.
Description
Technical field
The present invention relates to a kind of be used to the be reduced in zinc that wherein needs fastening ability or the technology of the total frictional coefficient that does not contain sexavalent chrome and corrosion resistant trivalent chromate conversion film on the Zinc alloy electroplating layer.More specifically, the present invention relates to a kind of reagent that is used to reduce the total frictional coefficient of conversion film of trivalent chromate treating solution, be used to reduce the trivalent chromate treating solution and its preparation method of total frictional coefficient of trivalent chromate conversion film, and total frictional coefficient the trivalent chromate conversion film and its preparation method that reduce.
Background technology
As the method that prevents that the metallic surface from getting rusty, in this industrial circle, adopted on zinc or Zinc alloy electroplating layer and contained chromic chromate treating.In recent years, strengthening may be harmful in the control of environment and the mankind's material.The sexavalent chrome of having pointed out its carinogenicity etc. has also become controlled object, and therefore develops wherein not chromyl trivalent chromate substitute technology in treatment soln and conversion film.
Proposed a kind of by contacting the conversion film that obtains with zinc or Zinc alloy electroplating layer based on chromic treatment soln, this film does not contain sexavalent chrome, and this film has and the identical erosion resistance of passing through to obtain based on chromic conventional chromate treating of conversion film.Its heat/corrosion resistance is than much higher based on chromic conventional conversion film further, and a kind of treatment soln of this conversion film and formation method of this treatment soln patent disclosure (hereinafter being called " the TOHKEMY ") No.2003-268562 of Japanese Patent No.3332373, Japanese Patent No.3332374 and Japanese unexamined (for example referring to) of being used for.
Yet, handle the conversion film that obtains by the trivalent chromate of a step and caused usually than the conventional higher total frictional coefficient of hexavalent chromate conversion film.Therefore, for the bolt that wherein needs fastening ability in the automotive industry for example, nut etc., carry out trivalent chromate thereon and external coating (EC) etc. is applied thereon to handle the total frictional coefficient that raises safely after handling.
Summary of the invention
The problem that the present invention solves
Therefore, the purpose of this invention is to provide a kind of by contacting the conversion film that obtains with zinc or Zinc alloy electroplating layer based on chromic treatment soln, this film does not contain sexavalent chrome, this film has and the identical erosion resistance of passing through to obtain based on chromic conventional chromate treating of conversion film, and it makes total frictional coefficient identical or lower with conventional hexavalent chromate conversion film further.
The mode of dealing with problems
Finished the present invention based on such discovery: comprise the treatment soln of quinoline compound or derivatives thereof and trivalent chromate handled by use and be applied on zinc or the Zinc alloy electroplating layer, can solve the problems referred to above relevant effectively with routine techniques.
That is to say that the invention provides a kind of reagent that is used to reduce the total frictional coefficient of conversion film of trivalent chromate treating solution, this reagent comprises the quinoline compound or derivatives thereof.
In addition, the invention provides the purposes that the quinoline compound or derivatives thereof is used to reduce total frictional coefficient of trivalent chromate conversion film.
In addition, the invention provides the method that a kind of preparation is used to form the trivalent chromate treating solution of the conversion film that total frictional coefficient reduces, it may further comprise the steps: the quinoline compound or derivatives thereof is added described trivalent chromate treating solution.
In addition, the invention provides a kind of trivalent chromate treating solution, it comprises 0.1 to 25g/L quinoline compound or derivatives thereof.
In addition, the invention provides a kind of method that forms the trivalent chromate conversion film, it comprises: the step that zinc or Zinc alloy electroplating layer are contacted with treatment in accordance with the present invention solution.
In addition, the invention provides a kind of trivalent chromate conversion film, it comprises the quinoline compound or derivatives thereof.
The invention effect
According to the present invention, can on zinc or Zinc alloy electroplating layer, make that total frictional coefficient reduces, do not contain sexavalent chrome and corrosion resistant trivalent chromate conversion film.The trivalent chromate conversion film that obtains by this method give to since the erosion resistance of zinc or Zinc alloy electroplating layer itself with inherent, extra superior corrosion resistance.In addition, because total frictional coefficient of this conversion film and conventional hexavalent chromate conversion film is identical or lower, so can design bolt, nut etc. so that fastening strength safety.In addition, because identical device that uses and technology can be used and not need to improve like this, therefore can keep productivity in the hexavalent chromate of routine is handled.
In addition, in hexavalent chromate is handled, depend on plating bath kind (for example sulfuric acid bath of acid bath, ammonium chloride are bathed and Repone K is bathed, and alkali bath for example alkaline non--cyanide bath and alkaline cyanide bathe) and the difference of total frictional coefficient has appearred.According to the present invention, although can regulate total friction co-efficient value so that used dissimilar plating baths but they also all are identical, and can expect that in future the present invention will help to design the tightening member with fastening ability with regard to improved security and economy.
Embodiment
The reagent that is used to reduce the total frictional coefficient of conversion film of trivalent chromate treating solution according to the present invention comprises the quinoline compound or derivatives thereof.This quinoline compound or their derivative comprise for example having derived from the unit price of quinoline (it has seven isomer structures) or acid or its salt (for example sodium, potassium, ammonium salt etc.) of divalent substituent.Water-soluble quinoline compound or their derivative are preferred.Have substituting group for example-SO
3H ,-COOH ,-OH ,-CHO ,-CH
2COOH ,-NH
2,-C
8H
4O
3(C
2O
3C
6H
4) and-C
8H
5O
2(CH=CO
2C
6H
4) acid or their sodium, potassium, ammonium salt etc. be preferred.Particularly, preferred quinoline sulfonic acid, quinardinic acid, quinophthalone (quinophthalone), quinolyl acetate, preferred especially quinoline sulfonic acid.In the present invention, above-mentioned quinoline compound or their derivative can be used at least separately or with two kinds in them arbitrary combination.
Depressant according to the present invention can be used for any trivalent chromate treating solution.The amount that adds the described depressant in the trivalent chromate treating solution is preferably and makes that in trivalent chromate treating solution the concentration of quinoline compound or derivatives thereof is 0.1 to 25g/L, and more preferably 0.2 to 15g/L.The concentration of quinoline compound or derivatives thereof is in the suitable trivalent chromate treating solution that makes acquisition be used to form the conversion film of total frictional coefficient reduction in the above-mentioned scope.
Be used to form the conversion film of the total frictional coefficient with reduction, the trivalent chromate treating solution that comprises the quinoline compound or derivatives thereof comprises for example following treatment soln.The concentration of quinoline compound or derivatives thereof is preferably 0.1 to 25g/L in each treatment soln, and more preferably 0.2 to 15g/L.
[trivalent chromate treating solution (1)]
This treatment soln comprises:
Trivalent chromic ion and the oxalate ion of mol ratio (trivalent chromic ion/oxalate ion) in from 0.5/1 to 1.5/1 scope, wherein this trivalent chromium exists with the water-soluble complexes form with oxalic acid; And
Cobalt ion stably is present in this treatment soln, and can not form the metal-salt of indissoluble and therefore cause any precipitation owing to them and oxalic acid;
This treatment soln is when contacting with zinc or Zinc alloy electroplating layer and zinc reaction and form the trivalent chromate conversion film that contains zinc, chromium, cobalt, oxalic acid and quinoline compound or derivatives thereof on electrolytic coating.
[trivalent chromate treating solution (2)]
This treatment soln comprises:
Trivalent chromic ion;
Be selected from by the ion in Al ion, Si ion, Ti ion, Mn ion, Fe ion, Co ion, Ni ion, Zn ion and its group of forming; With
Be selected from middle inorganic acid ion by chlorion, nitrate ion, sulfate ion, phosphate ion and its group of forming.
This treatment soln comprises:
Trivalent chromic ion;
Be selected from by the ion in Al ion, Si ion, Ti ion, Mn ion, Fe ion, Co ion, Ni ion, Zn ion and its group of forming;
Be selected from by the inorganic acid ion in chlorion, nitrate ion, sulfate ion, phosphate ion and its group of forming; With
Organic acid with trivalent chromic ion formation water-soluble complexes.
The base material of handling with trivalent chromate treating solution according to the present invention can be for example iron, nickel and copper of various metals, its alloy and carried out for example aluminium of metal or alloy that zincate handles, and this base material can have that different shape is for example tabular, right-angled prismatic, column, cylindrical and spherical.
According to common method above-mentioned base material is electroplated upward zinc or zinc alloy.Can for example use for example sulfuric acid bath of acid bath, ammonium chloride to bathe and the Repone K bath, perhaps for example alkaline non-cyanide bath of alkali bath and alkaline cyanide are bathed and are deposited upon on the base material galvanized.Can at random select to be deposited over the zinc on the base material or the thickness of Zinc alloy electroplating layer, but wish that it is not less than 1 μ m, and be preferably 5 to 25 μ m.
In addition, the example of Zinc alloy electroplating layer is the zinc-iron alloys electrolytic coating, has zinc nickel alloy electroplating layer, zinc-cobalt alloy electrolytic coating and a tin-zinc alloy electroplating layer that nickel codeposition rate is 5 to 20 quality %.Can at random select to be deposited over the zinc on the base material or the thickness of Zinc alloy electroplating layer, but wish that it is not less than 1 μ m, and be preferably 5 to 25 μ m.
In the present invention, after being deposited upon zinc or Zinc alloy electroplating on the base material according to aforesaid method, if desired, then with galvanized base material water flushing, and then it is contacted with the treatment soln that is used to form the trivalent chromate film according to the present invention, for example use this treatment soln to carry out dip treating.
In trivalent chromate treating solution of the present invention (1), the trivalent chromium source can be to contain chromic any chromium cpd, but its spendable in this article preferred example is for example chromium chloride, chromium sulphate, chromium nitrate, Plessy's green and a chromium acetate of chromic salt, and for example chromic acid or dichromic acid are reduced into trivalent chromium with sexavalent chrome perhaps can also to use reductive agent.Above-mentioned trivalent chromium source can be used separately or with two kinds in them arbitrary combination at least.From making wastewater treatment be easy to viewpoint as far as possible, chromic concentration is preferably low as much as possible in the treatment soln, but when considering erosion resistance, it is preferably 0.2 to 10g/L, most preferably is 1 to 5g/L.In the present invention, from the viewpoint of wastewater treatment and processing cost, it also is very favourable using trivalent chromium with the lower concentration like this that falls into above-mentioned scope.
In addition, spendable herein oxalic acid source is oxalic acid and its salt (for example sodium, potassium and ammonium salt), and it can use separately or with two kinds in them arbitrary combination at least.The concentration of oxalic acid used herein is preferably 0.2 to 13g/L, and more preferably 2 to 11g/L.
Spendable herein cobalt ion source can be to contain cobaltous any cobalt compound, and preferred here its object lesson that uses is Xiao Suangu, rose vitriol and cobalt chloride.Concentration of cobalt ions in the treatment soln is preferably 0.2 to 10g/L, and more preferably 0.5 to 8g/L.Especially, in order after conversion film heating, to improve erosion resistance, wish that concentration of cobalt ions is not less than 2.0g/L with gained.Because the concentration of cobalt ions that is present in the treatment soln increases, the amount that is present in the cobalt in the gained film increases, and the raising proportional with it of the erosion resistance of gained conversion film.
Be present in the trivalent chromium in the treatment soln and the mol ratio of oxalic acid and be preferably 0.5/1 to 1.5/1, more preferably 0.8/1 to 1.3/1.
In addition, above-mentioned treatment soln (1) can comprise the inorganic salt that are selected from the group of being made up of the inorganic salt of nitric acid, sulfuric acid and hydrochloric acid in addition.Mineral acid (hydrochloric acid, sulfuric acid, nitric acid) the ionic concentration that is present in the treatment soln is preferably 1 to 50g/L, and more preferably 5 to 20g/L.
Except said components, treatment soln also can comprise and is selected from by phosphorus oxyacid at least a in the group formed of phosphoric acid and phosphorous acid and an alkali metal salt thereof for example.These component concentrations are preferably 0.1 to 50g/L, and more preferably 0.5 to 20g/L.
Can also be with dicarboxylic acid for example citric acid, tartrate or oxysuccinic acid of propanedioic acid or Succinic Acid, oxycarboxylic acid (oxycarboxylicacid) for example, and/or the polyvalent carboxylic acid for example tricarballylic acid (tricarballylic acid) add in the treatment soln.Will add its concentration in the treatment soln preferably drops in 1 to 30g/L the scope.
Preferably the pH value with treatment soln of the present invention is adjusted to 0.5 to 4, and more preferably 2 to 2.5.In this respect, can use above-mentioned inorganic acid ion or alkaline reagents for example alkaline hydrated oxide or ammoniacal liquor so that its pH value is adjusted to above-mentioned scope.
Trivalent chromium and oxalic acid should be present in the treatment soln with the stable water-soluble complexes form that forms between it, this title complex is pushed measuring tool the structure of being represented by following general formula, and cobalt ion will stably be present in this solution, and can be owing to they and oxalic acid have formed the metal-salt of indissoluble and therefore caused any precipitation.
[(Cr)
1·(C
2O
4)
m·(H
2O)
n]+(n-3)
Wherein the mol ratio of Cr and oxalic acid satisfies following relation: 0.5＜m/l＜1.5 and n=6-2m/l, and to counter ion without any restriction.
For example, if do not form above-mentioned stable complex or have excessive oxalate ion in solution in treatment soln, then cobalt ion forms cobalt oxalate precipitation with its free state thus with being present in the oxalic acid reaction in the treatment soln.As a result, treatment soln can not form any chemical conversion film (coating) with excellent corrosion resistance.
As what infer among the Japanese Patent No.3332373, if zinc or Zinc alloy electroplating layer are contacted with above-mentioned treatment in accordance with the present invention solution (1), the then component of solution and zinc reaction forms on zinc or Zinc alloy electroplating layer thus and does not contain sexavalent chrome, corrosion resistant, the trivalent chromate film that comprises zinc, chromium, cobalt, oxalic acid and quinoline compound or derivatives thereof.
In trivalent chromate treating solution of the present invention (2), identical in trivalent chromium source and the above-mentioned treatment soln (1).From making wastewater treatment be easy to viewpoint as far as possible, chromic concentration is preferably low as much as possible in the treatment soln, but when considering erosion resistance, it is preferably 0.2 to 10g/L, most preferably is 1 to 5g/L.In the present invention, from the viewpoint of wastewater treatment and processing cost, it also is very favourable using trivalent chromium with the lower concentration like this that falls into above-mentioned scope.
Ion source in the group that the spendable in this article Al of being selected from ion, Si ion, Ti ion, Mn ion, Fe ion, Co ion, Ni ion, Zn ion and its combination are formed can be to contain any compound of these ionic, and its preferred in this article specific ion of using is easy ionized inorganic acid salt, for example nitrate, vitriol and a hydrochloride in the aqueous solution.These ionic concentration preferably add up to 0.2 to 10g/L in the treatment soln, and more preferably 0.5 to 8g/L.Especially, in order to improve erosion resistance, wish that this concentration is not less than 2.0g/L.These ionic amounts in the gained film of being present in are owing to their concentration that is present in the treatment soln increases, and the raising proportional with it of the erosion resistance of gained conversion film.
The concentration that is selected from the treatment soln by the inorganic acid ion in hydrochloride ion, nitrate ion, sulfate ion, phosphate ion and its group of forming is preferably 1 to 50g/L, and more preferably 5 to 20g/L.
Preferably the pH value with described treatment soln of the present invention (2) is adjusted to 0.5 to 4, and more preferably 1 to 3.In this respect, can use above-mentioned inorganic acid ion or alkaline reagents for example alkaline hydrated oxide or ammoniacal liquor so that its pH value is adjusted to above-mentioned scope.
In trivalent chromate treating solution of the present invention (3), will add in the above-mentioned treatment soln (2) with the organic acid that trivalent chromic ion forms water-soluble complexes.Spendable herein organic acid can be for example oxalic acid and its salt (for example sodium, potassium and ammonium salt) of carboxylic acid, and it can use separately or with two kinds in them arbitrary combination at least.Organic acid concentration is preferably 0.2 to 13g/L, and more preferably 2 to 11g/L.The trivalent chromium and the organic acid mol ratio that are present in the treatment soln are preferably 0.5/1 to 1.5/1, and more preferably 0.8/1 to 1.3/1.
Except above-mentioned basal component, the remainder (surplus) that is used for above-mentioned treatment soln of the present invention (1) to (3) is a water.
Can on zinc or Zinc alloy electroplating layer, form the trivalent chromate conversion film that comprises the quinoline compound or derivatives thereof by zinc or Zinc alloy electroplating layer are contacted with above-mentioned treatment soln according to the present invention.The concentration of quinoline compound or derivatives thereof is preferably 0.1 to 15mg/dm in this trivalent chromate conversion film
2, more preferably 0.2 to 10mg/dm
2
As the method that zinc or Zinc alloy electroplating layer are contacted with above-mentioned treatment soln according to the present invention, the goods that will be coated with zinc or zinc alloy usually impregnated in the above-mentioned treatment soln.For example, these goods be impregnated in remain on 10 to 50 ℃, more preferably in the solution under 20 to 40 ℃ the temperature preferred 5 to 600 seconds, more preferably 20 to 60 seconds.
In this, with regard to zinc-plated, object that will be processed impregnated in before it carries out the trivalent chromate processing in rare salpeter solution to improve the gloss of gained trivalent chromate film usually.Yet, can adopt in the present invention or can not adopt such pre-treatment.
In addition, the method that forms above-mentioned conversion film may further include: by take partially disposed solution, depressant of the present invention is added in the partially disposed solution of being taken and with the partial replacement of being taken to handling the step for preparing trivalent chromate treating solution in the solution.This step makes it possible to easily that the concentration maintenance of quinoline compound or derivatives thereof in the treatment soln is constant.Especially, if the quinoline compound or derivatives thereof is powdery or butyrous, then from its solvability and inhomogeneity viewpoint, this step ratio is more favourable as the method that the quinoline compound or derivatives thereof is directly added in the treatment soln in the treatment tank.In this respect, form that can the aqueous solution provides the quinoline compound or derivatives thereof, but the total amount of treatment soln can increase according to the amount that is provided.The method of taking the part trivalent chromate treating solution comprises, for example wherein with its method of taking out from treatment tank as overflowing liquid, wherein use pump with its method of taking out from treatment tank or the like.When being put back into it in treatment soln, preferably described partially disposed solution is filtered.
Except above-mentioned condition and process operations those can be determined or select according to the chromate treating of routine.
Embodiment
(embodiment 1 to 18)
The zinc of 8 μ m thickness (zincic acid salt bath (NZ-87 separately will be coated with, can be from DipsolChemicals Co., Ltd. acquisition), cyanide bath (L-800, can be from DipsolChemicals Co., Ltd. M6 bolt (S45C material acquisition), muriate bath (EZ-988 can be from DipsolChemicals Co., and Ltd. obtains)), intensity calibration (strength division 8.8) impregnated in the trivalent chromate treating solution with the composition shown in following table 1 and 2, and water cleans then.
Table 1
| Embodiment number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Cr 3+ (g/L) | 1 | 2 | 2 | 4 | 4 | 5 | 5 | 2 | 2 | 2 |
| 2-quinolyl acetate (g/L) | 0 | 2 | 0 | 0 | 0 | 0 | 0 | 0 | 2 | 0 |
| Quinardinic acid (g/L) | 6 | 0 | 8 | 0 | 5 | 2 | 1 | 0 | 0 | 8 |
| Quinoline-8-sulfonic acid (g/L) sodium | 0 | 0 | 0 | 10 | 0 | 0 | 5 | 0 | 0 | 0 |
| Quinophthalone (g/L) | 0 | 0 | 0 | 0 | 0 | 0.2 | 0.1 | 10 | 0 | 0 |
| Quinolinone (g/L) (Qunolinole) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| NO 3 - (g/L) | 15 | 5 | 10 | 10 | 20 | 20 | 15 | 0 | 5 | 10 |
| Cl - (g/L) | 0 | 0 | 0 | 0 | 0 | 0 | 3.0 | 0.5 | 0 | 0 |
| PO 4 - (g/L) | 0 | 0 | 1.5 | 0 | 1 | 0 | 1 | 12 | 0 | 1.5 |
| Oxalic acid (g/L) | 3 | 3 | 4 | 8 | 10 | 12 | 12 | 0 | 3 | 4 |
| Succinic Acid (g/L) | 0 | 0 | 1 | 0 | 0 | 0 | 1 | 0 | 0 | 0 |
| Oxysuccinic acid (g/L) | 0 | 1 | 0 | 0 | 0 | 0 | 0 | 12 | 0 | 0 |
| Co (g/L) | 2 | 1 | 2 | 1 | 2 | 1 | 2 | 1 | 1 | 2 |
| Si (g/L) | 0 | 0 | 0 | 1.5 | 0 | 2 | 2 | 0 | 0 | 0 |
| V (g/L) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Ni (g/L) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.3 | 0 | 0 |
| Treatment soln pH | 2.0 | 1.8 | 2.0 | 2.4 | 2.2 | 1.8 | 2.0 | 2.5 | 1.8 | 2.0 |
| Treatment temp (℃) | 30 | 25 | 35 | 30 | 35 | 30 | 40 | 30 | 25 | 35 |
| Treatment time (second) (second) | 60 | 60 | 40 | 40 | 30 | 40 | 20 | 60 | 60 | 40 |
Table 2
| Embodiment number | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 |
| Cr 3+ (g/L) | 4 | 5 | 5 | 5 | 1 | 1 | 1.5 | 2 |
| 2-quinolyl acetate (g/L) | 0 | 0 | 0 | 0 | 1 | 0 | 0 | 0 |
| Quinardinic acid (g/L) | 0 | 0 | 2 | 0 | 0 | 1 | 0 | 0 |
| Quinoline-8-sodium sulfonate (g/L) | 10 | 0 | 0 | 12 | 0 | 0 | 8 | 0 |
| Quinophthalone (g/L) | 0 | 0.2 | 0.1 | 0 | 0 | 0.1 | 0 | 0 |
| Quinolinone (g/L) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 5 |
| NO 3 - (g/L) | 10 | 20 | 15 | 10 | 10 | 0 | 10 | 7 |
| Cl - (g/L) | 0 | 0 | 0 | 0 | 0 | 7 | 0 | 5 |
| PO 4 - (g/L) | 0 | 0 | 1 | 0 | 0 | 0 | 0 | 0.5 |
| Oxalic acid (g/L) | 8 | 12 | 12 | 15 | 0 | 0 | 0 | 0 |
| Succinic Acid (g/L) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Oxysuccinic acid (g/L) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Co (g/L) | 1 | 1 | 2 | 2 | 1 | 0 | 1.5 | 1 |
| Si (g/L) | 0 | 0 | 0 | 0 | 4 | 0 | 4 | 2 |
| V (g/L) | 0 | 0 | 0 | 0 | 0 | 1 | 1.5 | 0 |
| Ni (g/L) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Treatment soln pH | 2.4 | 1.8 | 2.0 | 2.0 | 2.0 | 2.4 | 2.1 | 2.0 |
| Treatment temp (℃) | 30 | 30 | 40 | 40 | 30 | 40 | 30 | 30 |
| Treatment time (sec.) | 40 | 40 | 20 | 30 | 40 | 20 | 40 | 25 |
In table 1 and 2, the Cr of use
3+The source is CrCl
3(in embodiment 1,3,5,8,10,15 and 18) and Cr (NO
3)
3(in embodiment 2,4,6,7,9,11 to 14,16 and 17); The oxalic acid that uses is dihydrate; The Co source of using is Co (NO
3)
2In addition, the Si source of use is a silica gel; The V source of using is VOSO
4The Ni source of using is NiSO
4Further, the NO of use
3 -The source is HNO
3(in embodiment 2,3,4,9 to 11,14,15 and 18) and NaNO
3(in embodiment 1,5 to 7,12,13,16 and 17).Further, the Cl of use
-The source is NaCl; The PO that uses
4 -The source is NaH
2PO
4The surplus of each treatment soln is a water.In addition, the pH value of using NaOH to regulate each solution.
(embodiment 19 to 22)
The alkaline Zn-Ni alloy of 8 μ m thickness ((IZ-262 (Ni:7%) separately will be coated with, can be from Dipsol Chemicals Co., Ltd. obtain), IZ-252 (Ni:14%), can be from Dipsol Chemicals Co., Ltd. M6 bolt (S45C material, intensity calibration 8.8) acquisition)) impregnated in the trivalent chromate treating solution with composition as shown in table 3 below, and water cleans then.
Table 3
| Embodiment number | 19 | 20 | 21 | 22 |
| Cr 3+ (g/L) | 4 | 4 | 5 | 5 |
| 2-quinolyl acetate (g/L) | 0 | 0 | 0.5 | 0 |
| Quinardinic acid (g/L) | 0.5 | 1 | 0 | 0 |
| Quinoline-8-sulfonic acid (g/L) sodium | 5 | 3 | 0 | 8 |
| Quinophthalone (g/L) | 0 | 0.1 | 0.1 | 0 |
| Quinolinone (g/L) | 0 | 0 | 0 | 0 |
| NO 3 - (g/L) | 10 | 0 | 15 | 0 |
| Cl - (g/L) | 0 | 10 | 0 | 11 |
| PO 4 - (g/L) | 0 | 12 | 0 | 15 |
| Oxalic acid (g/L) | 8 | 6 | 10 | 7 |
| Succinic Acid (g/L) | 1 | 0 | 1 | 0 |
| Oxysuccinic acid (g/L) | 0 | 6 | 0 | 7 |
| Co (g/L) | 2 | 1 | 2 | 1 |
| Si (g/L) | 1 | 0 | 1 | 0 |
| V (g/L) | 0 | 0 | 0 | 0 |
| Ni (g/L) | 0 | 0.3 | 0 | 0.3 |
| Treatment soln pH | 2.4 | 2.6 | 2.0 | 2.4 |
| Treatment temp (℃) | 30 | 35 | 40 | 50 |
| Treatment time (sec.) | 45 | 60 | 25 | 45 |
| Cr 3+ (g/L) | 7.0 | 7.0 | 14 | 14 |
In table 3, the Cr of use
3+The source is Cr (NO
3)
3(in embodiment 15 and 17) and CrCl
3(in embodiment 16 and 18); The oxalic acid that uses is dihydrate; The Co source of using is Co (NO
3)
2In addition, the Si source of use is a silica gel; The Ni source of using is NiSO
4Further, NO
3 -The source is NaNO
3The Cl that uses
-The source is NaCl; The PO that uses
4 -The source is NaH
2PO
4The surplus of each treatment soln is a water.In addition, the pH value of using NaOH to regulate each solution.
(comparative example 1)
The zinc of 8 μ m thickness (zincic acid salt bath (NZ-87 separately will be coated with, can be from DipsolChemicals Co., Ltd. acquisition), cyanide bath (L-800, can be from DipsolChemicals Co., Ltd. acquisition), muriate is bathed (EZ-988, can be from DipsolChemicals Co., Ltd. obtains)) M6 bolt (S45C material, intensity calibration 8.8) carry out hexavalent chromate and handle.It is can be from DipsolChemicals Co. that hexavalent chromate used herein is bathed, the Z-493 (10mL/L) that Ltd. obtains, and under 30 ℃, carry out this hexavalent chromate and handled 40 seconds.
(comparative example 2)
Use has as the following composition among the embodiment that is disclosed in Japanese Patent No.3332373: 14g/L is (with Cr
3+Be expressed as 3g/L) Cr (NO
3)
3The NaNO of 7g/L
3The oxalic acid dihydrate of 8g/L; And the Co (NO of 3g/L (being expressed as 1g/L) with Co
3)
2Treatment soln (pH:2.0, use NaOH to regulate) will be coated with the zinc of 8 μ m thickness (zincic acid salt bath (NZ-87 separately, can be from Dipsol Chemicals Co., Ltd. acquisition), cyanide bath (L-800, can be from Dipsol Chemicals Co., Ltd. obtains), muriate bathes that (EZ-988 can be from Dipsol Chemicals Co., Ltd. M6 bolt (S45C material, intensity calibration 8.8) acquisition)) carries out trivalent chromate to be handled.In this, carrying out this trivalent chromate under 30 ℃ handled 40 seconds.
(comparative example 3)
Use has as the following composition among the embodiment 7 that is disclosed in TOHKEMY No.2003-313675: 7g/L is (with Cr
3+Be expressed as 1.5g/L) Cr (NO
3)
2The urea of 1g/L; The sulfuric acid of 2g/L; The ammonium vanadate of 5g/L (being expressed as 2.2g/L) with V; Co (the NO of 3g/L (being expressed as 1g/L) with Co
3)
2And the treatment soln (pH:2.0 of the silica gel of 20g/L (being expressed as 4g/L) with Si, use NaOH to regulate), the zinc of 8 μ m thickness (zincic acid salt bath (NZ-87 separately will be coated with, can be from Dipsol Chemicals Co., Ltd. obtains), (L-800 can be from Dipsol Chemicals Co. for cyanide bath, Ltd. acquisition), muriate is bathed (EZ-988, can be from Dipsol Chemicals Co., Ltd. obtains)) M6 bolt (S45C material, intensity calibration 8.8) carry out trivalent chromate and handle.In this, carrying out this trivalent chromate under 30 ℃ handled 30 seconds.
(comparative example 4)
Use has as the following composition among the embodiment 2 that is disclosed in TOHKEMY No.2000-509434: 50g/L is (with Cr
3+Be expressed as 9.8g/L) CrCl
36H
2O; Co (the NO of 3g/L (being expressed as 1.0g/L) with Co
3)
2The NaNO of 100g/L
3Treatment soln (pH:2.0 with the oxysuccinic acid of 31.2g/L, use NaOH to regulate), the zinc of 8 μ m thickness (zincic acid salt bath (NZ-87 separately will be coated with, can be from Dipsol Chemicals Co., Ltd. obtains), (L-800 can be from Dipsol Chemicals Co. for cyanide bath, Ltd. acquisition), muriate is bathed (EZ-988, can be from Dipsol Chemicals Co., Ltd. obtains)) M6 bolt (S45C material, intensity calibration 8.8) carry out trivalent chromate and handle.In this, carrying out this trivalent chromate under 30 ℃ handled 30 seconds.
(comparative example 5)
The M6 bolt (S45C material, intensity calibration 8.8) that is coated with the alkaline Zn-Ni alloy (IZ-262 (Ni:7%) can be from Dipsol Chemicals Co., and Ltd. obtains) of 8 μ m thickness is carried out hexavalent chromate to be handled.It is can be from Dipsol Chemicals Co. that hexavalent chromate used herein is bathed, the IZ-268 (30mL/L) that Ltd. obtains, and under 30 ℃, carry out this hexavalent chromate and handled 30 seconds.
(comparative example 6)
The M6 bolt (S45C material, intensity calibration 8.8) that is coated with the alkaline Zn-Ni alloy (IZ-252 (Ni:14%) can be from Dipsol Chemicals Co., and Ltd. obtains) of 8 μ m thickness is carried out hexavalent chromate to be handled.It is can be from Dipsol Chemicals Co. that hexavalent chromate used herein is bathed, the IZ-258 (S:200mL/L that Ltd. obtains; And under 30 ℃, carry out this hexavalent chromate and handled 40 seconds E:10g/L).
Treatment step:
In these embodiment and comparative example, the details of treatment step is as follows:
Plating → washing → with rare nitric acid activation → washing → chromate treating → washing → drying
1
Note 1: under 60 to 80 ℃ temperature, carried out this drying step 10 minutes.
Be used to measure the salt-fog test of total erosion resistance:
The chromate conversion coating that will obtain in embodiment 1 to 22 and comparative example 1 to 6 carries out salt-fog test (JIS-Z-2371).The gained result is summarized in following table 4 and 5.
The fastening ability test:
The bolt that has the chromate conversion coating that obtains on it in embodiment 1 to 22 and comparative example 1 to 6 is carried out the fastening ability test.The total frictional coefficient that obtains thus from these results is summarized in following table 4 and 5.According to being described in " frictional coefficient of threaded fasteners ", Tomotsugu Sakai, Transactions of the Japan Society ofMechanical Engineers, the 3rd section, 43-370,1977-6, the method among the pp.2372-2381 is carried out the measurement of total frictional coefficient.Calculate total frictional coefficient by nut (having) with without any the observed value of the axial force of the packing ring of handling under the estimation moment of torsion of 4 fastening rotations of circle and 11.8Nm as surface treatment identical in respective embodiments or the comparative example.
In the data that will from table 4 and 5, list, obviously finding out, find the conversion film that in embodiment 1 to 22, obtains in addition show with for the hexavalent chromate conversion film (comparative example 1,5 and 6) of routine and in comparative example 2 to 4 the trivalent chromate conversion film of acquisition viewed those much at one or be better than those erosion resistance.In addition, the conversion film of embodiment 1 to 22 shows and viewed those identical or littler a little total frictional coefficient of hexavalent chromate conversion film (comparative example 1,5 and 6) for routine, and with obtain for the conversion film that in comparative example 2 to 4, obtains those compare and show total friction co-efficient value that fastening ability improves.
Table 4
Table 5
*: comparative example
Embodiment 23
When the trivalent chromate treating solution that uses embodiment 1 forms conversion film on bolt, the overflowing liquid of gained is transferred in the slack tank.Rate of pumping is 800L/ hour.Next, quinardinic acid is joined in the treatment soln in the slack tank so that its concentration in treatment soln is 8g/L, by strainer (K-05 can obtain from KizaiCompany) the gained treatment soln is turned back to the treatment tank then.Therefore, the concentration that is present in the quinardinic acid in the treatment soln in this treatment tank can keep constant.
Claims (7)
1. the quinoline compound or derivatives thereof is used to reduce the purposes of total frictional coefficient of trivalent chromate conversion film.
2. method that reduces the total frictional coefficient of conversion film, it is characterized in that, this conversion film forms by zinc or Zinc alloy electroplating layer are contacted with trivalent chromate treating solution, wherein, the quinoline compound or derivatives thereof is added described trivalent chromate treating solution.
3. method according to claim 2, described trivalent chromate treating solution comprise 0.1 to 25g/L quinoline compound or derivatives thereof.
4. according to claim 2 or 3 described methods, described trivalent chromate treating solution comprises:
Trivalent chromic ion and oxalate ion, wherein the mol ratio of trivalent chromic ion/oxalate ion is in 0.5/1 to 1.5/1 scope, and wherein this trivalent chromium exists with the water-soluble complexes form with oxalic acid; And
Cobalt ion stably is present in the described trivalent chromate treating solution, and can not cause any precipitation owing to the metal-salt that they and oxalic acid have formed indissoluble;
This treatment soln is when it contacts with zinc or Zinc alloy electroplating layer and zinc reaction and form the trivalent chromate conversion film that contains zinc, chromium, cobalt, oxalic acid and quinoline compound or derivatives thereof on zinc or Zinc alloy electroplating layer.
5. according to claim 2 or 3 methods, described trivalent chromate treating solution comprises:
Trivalent chromic ion;
Be selected from by the ion in Al ion, Si ion, Ti ion, Mn ion, Fe ion, Co ion, Ni ion, Zn ion and its group of forming; With
Be selected from by the inorganic acid ion in chlorion, nitrate ion, sulfate ion, phosphate ion and its group of forming.
6. according to claim 2 or 3 described methods, described trivalent chromate treating solution comprises:
Trivalent chromic ion;
Be selected from by the ion in Al ion, Si ion, Ti ion, Mn ion, Fe ion, Co ion, Ni ion, Zn ion and its group of forming;
Be selected from by the inorganic acid ion in the group of forming of chlorion, nitrate ion, sulfate ion, phosphate ion and its combination; With
Organic acid with trivalent chromic ion formation water-soluble complexes.
7. a method that forms the trivalent chromate conversion film is characterized in that, zinc or Zinc alloy electroplating layer are contacted with the trivalent chromate treating solution that comprises 0.1 to 25g/L quinoline compound or derivatives thereof, wherein,
Further comprise: by taking partially disposed solution, the reagent that will be used for reducing the total frictional coefficient of conversion film of trivalent chromate treating solution adds the partially disposed solution of being taken, and in described treatment soln and the step of preparation trivalent chromate treating solution, described reagent comprises the quinoline compound or derivatives thereof with the partial replacement of being taken.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP2004058857A JP4446233B2 (en) | 2004-03-03 | 2004-03-03 | Covalent friction coefficient reducing agent for trivalent chromate treatment solution, trivalent chromate treatment solution and production method thereof, trivalent chromate coating with reduced overall friction coefficient and production method thereof |
| JP058857/2004 | 2004-03-03 | ||
| PCT/JP2005/003597 WO2005085497A1 (en) | 2004-03-03 | 2005-03-03 | Agent for reducing coating film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate coating film reduced in overall friction coefficient and method for production thereof |
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| CN1950544B true CN1950544B (en) | 2011-12-21 |
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| US (1) | US20070023104A1 (en) |
| EP (1) | EP1734152A4 (en) |
| JP (1) | JP4446233B2 (en) |
| KR (1) | KR100799845B1 (en) |
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-
2004
- 2004-03-03 JP JP2004058857A patent/JP4446233B2/en not_active Expired - Fee Related
-
2005
- 2005-03-03 CN CN200580014275XA patent/CN1950544B/en not_active Expired - Fee Related
- 2005-03-03 KR KR1020067018882A patent/KR100799845B1/en not_active IP Right Cessation
- 2005-03-03 WO PCT/JP2005/003597 patent/WO2005085497A1/en active Application Filing
- 2005-03-03 EP EP05719901A patent/EP1734152A4/en not_active Withdrawn
-
2006
- 2006-09-01 US US11/514,505 patent/US20070023104A1/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10305449A1 (en) * | 2003-02-11 | 2004-08-26 | Walter Hillebrand Gmbh & Co. | Reaction solution for producing colored passivation film on zinc and its alloys, e.g. on iron or steel, is based on aqueous acid solution containing trivalent chromium ions and contains quinoline dye, preferably quinoline yellow |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060123628A (en) | 2006-12-01 |
| JP4446233B2 (en) | 2010-04-07 |
| EP1734152A4 (en) | 2011-03-02 |
| JP2005248233A (en) | 2005-09-15 |
| EP1734152A1 (en) | 2006-12-20 |
| US20070023104A1 (en) | 2007-02-01 |
| KR100799845B1 (en) | 2008-01-31 |
| WO2005085497A1 (en) | 2005-09-15 |
| CN1950544A (en) | 2007-04-18 |
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