CN108779570A - The manufacturing method of chemical conversion treatment steel plate and chemical conversion treatment steel plate - Google Patents

The manufacturing method of chemical conversion treatment steel plate and chemical conversion treatment steel plate Download PDF

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Publication number
CN108779570A
CN108779570A CN201680083802.0A CN201680083802A CN108779570A CN 108779570 A CN108779570 A CN 108779570A CN 201680083802 A CN201680083802 A CN 201680083802A CN 108779570 A CN108779570 A CN 108779570A
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China
Prior art keywords
chemical conversion
conversion treatment
steel plate
coating
metal
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Chinese (zh)
Inventor
谷贤明
平野茂
立木光
柳原伟男
河端诚
横矢博
横矢博一
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Nippon Steel Corp
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Nippon Steel Corp
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Publication of CN108779570A publication Critical patent/CN108779570A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C22/361—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 titanium, zirconium or hafnium compounds
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
    • 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
    • C23C22/20—Orthophosphates containing aluminium cations

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

This chemical conversion treatment steel plate has steel plate, is formed at least one surface of above-mentioned steel plate and the coating containing Ni and the chemical conversion treatment skin membrane that is formed on above-mentioned coating, and the chemical conversion treatment skin membrane contains is calculated as 1.0~150mg/m with metal Zr amounts2Zr compounds, 1.0~100mg/m is calculated as with P amounts2Phosphate cpd and 0.10~30.0mg/m is calculated as with metal Al amounts2Al compounds.Above-mentioned coating is comprising being calculated as 5.0~3000mg/m with W metal amount2Ni Ni coating or comprising being calculated as 2.0~200mg/m with W metal amount2Ni and 0.10~10.0g/m is calculated as with metal Sn amounts2Sn and the composite deposite of island Sn coating is formed on Fe-Ni-Sn alloy-layers.

Description

The manufacturing method of chemical conversion treatment steel plate and chemical conversion treatment steel plate
Technical field
The present invention relates to the manufacturing methods of chemical conversion treatment steel plate and chemical conversion treatment steel plate.
Background technology
By continuously with metal, will produce corrosion sometimes.The corrosion generated in metal in order to prevent, carries all the time Various technologies are gone out.As the technology proposed, it can enumerate and the technology of plating is implemented, to metallic plate or coating to metallic plate Surface carries out the technology of various surface treatments.
Such as the following patent document 1 discloses a kind of technologies, wherein the Al- used in building materials or household appliances The surface of Zn systems alloy plating steel plate formed with comprising at least one of vfanadium compound, phosphoric acid and phosphoric acid based compound, have In the silane compound and water-soluble organic resin and water dispersible organic resin of at least one of epoxy group and amino extremely The organic resin of few one makees organic resin epithelium as main component.
On the other hand, in the manufacture of canister for the purpose of to preserve beverage or food, used Ni coated steel sheets, Sn coated steel sheets or Sn systems alloy plating steel plate etc..Following Al-Zn systems alloy plating steel plates disclosed in Patent Document 1 are so-called Alternative corrosion-proof type coated steel sheet, in contrast, Ni coated steel sheets, Sn coated steel sheets or Sn systems alloy plating steel plate be it is so-called Barrier type coated steel sheet.
For the purpose of using Ni coated steel sheets, Sn coated steel sheets or Sn systems alloy plating steel plate as to preserve beverage or food Canister steel plate (hereinafter referred to as steel plate for container) use in the case of, in order to ensure steel plate and application or film Implement chemical conversion treatment using 6 valence chromium in the surface of adaptation and corrosion resistance, big multipair coated steel sheet.It includes 6 valences that will use The chemical conversion treatment of the solution of chromium is known as chromic acid salt treatment.
However, since the 6 valence chromium used in chromic acid salt treatment are harmful in the environment, as in the past to container use The replacement for the chromic acid salt treatment that steel plate is implemented, develops the chemical conversion treatments epitheliums such as Zr- phosphorus epitheliums.Such as in following patents text It offers and discloses the steel plate for container with the chemical conversion treatment epithelium comprising Zr, phosphoric acid and phenolic resin etc. in 2.
Here, as the food preserved in the canister for having used steel plate for container, including meat, vegetables etc..Meat, vegetable Dish contains various protein, but these protein contain the amino acid comprising S (with L-cysteine, L-Methionine, L- sometimes (-)-cystine is the sulfur-containing amino acid of representative).
If being heated in sterilization processing for the food containing sulfur-containing amino acid, will produce S in sulfur-containing amino acid with The phenomenon that Sn, Fe included in steel plate for container etc. are bonded and change colour compared with unregistered land.The phenomenon is known as sulphur blackening.If due to Generating the design of sulphur blackening then canister inner surface can decline, therefore seek countermeasure always to prevent sulphur black Become.
In addition, Patent Document 3 discloses a kind of manufacturing method of steel plate for container, comprising selected from by Al ions, The reaction of at least one of group that borate ion, Cu ions, Ca ions, metal Al and Ni metal are constituted promote ingredient, Zr from In son and the solution of F ion, dipping or the electrolysis processing of steel plate are carried out, epithelium containing Zr is formed in surface of steel plate.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-290535 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2007-284789 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2012-62521 bulletins
Invention content
Problems to be solved by the invention
The epithelium (hereinafter referred to as chromate epithelium) formed by chromic acid salt treatment is even if the adhesion amount due to epithelium is few Also fine and close, therefore the steel plate for container for being formed with chromate epithelium on surface has excellent corrosion resistance and the blackening of resistance to vulcanization. However, as noted previously, as 6 valence chromium are harmful in the environment, therefore steel plate for container does not preferably contain 6 valence chromium as far as possible.
On the other hand, the organic resin epithelium described in patent document 1 and the chemical conversion treatment described in patent document 2 Epithelium is suitable in the environment due to not containing 6 valence chromium.However, with regard to described in patent document 1 organic resin epithelium and specially For chemical conversion treatment epithelium described in sharp document 2, in order to obtain the suitable blackening of resistance to vulcanization, form fine and close skin Film needs the adhesion amount for increasing epithelium.In the case where increasing the adhesion amount of epithelium, the coating of the lower layer of epithelium and epithelium Adaptation can decline, while weldability declines, therefore not preferably.In addition, the adhesion amount for increasing epithelium is not economically also preferred.
For the manufacturing method of the steel plate for container described in patent document 3, due in chemical conversion treatment epithelium Al content is few, therefore is difficult to obtain the suitable blackening of resistance to vulcanization sometimes.
The present invention is to carry out in view of the above circumstances, it is therefore an objective to even providing the attached of chemical conversion treatment skin membrane Also have in the case that the amount of wearing is few at chemical conversion treatment steel plate and the chemical conversion of excellent corrosion resistance and resistance to vulcanization blackening Manage the manufacturing method of steel plate.
Means for solving the problems
The present invention in order to solve the above problems, reach the purpose and use means below.
(1) the chemical conversion treatment steel plate of a scheme of the invention has steel plate, is formed at least the one of above-mentioned steel plate A surface and coating containing Ni and the chemical conversion treatment skin membrane being formed on above-mentioned coating, the chemical conversion treatment Skin membrane contains is calculated as 1.0~150mg/m with metal Zr amounts2Zr compounds, 1.0~100mg/m is calculated as with P amounts2Phosphorylation It closes object and 0.10~30.0mg/m is calculated as with metal Al amounts2Al compounds.Above-mentioned coating is comprising being calculated as 5.0 with W metal amount ~3000mg/m2Ni Ni coating or comprising being calculated as 2.0~200mg/m with W metal amount2Ni and be calculated as with metal Sn amounts 0.10~10.0g/m2Sn and the composite deposite of island Sn coating is formed on Fe-Ni-Sn alloy-layers.
(2) the chemical conversion treatment steel plate according to above-mentioned (1), wherein above-mentioned chemical conversion treatment skin membrane also may be used 0.10~30.0mg/m is calculated as with metal Al amounts to contain2Al2O3。
(3) the chemical conversion treatment steel plate according to above-mentioned (1) or (2), wherein above-mentioned chemical conversion treatment skin membrane It can also contain and 1.0~120mg/m is calculated as with metal Zr amounts2Zr compounds, 2.0~70.0mg/m is calculated as with P amounts2Phosphoric acid Compound and 0.20~20.0mg/m is calculated as with metal Al amounts2Al compounds.
(4) the chemical conversion treatment steel plate according to either a program in above-mentioned (1)~(3), wherein above-mentioned Ni coating It can contain with W metal amount for 10.0~2000mg/m2Ni.
(5) the chemical conversion treatment steel plate according to either a program in above-mentioned (1)~(3), wherein above-mentioned composite deposite It can also contain and 5.0~100mg/m is calculated as with W metal amount2Ni and 0.30~7.0g/m is calculated as with metal Sn amounts2Sn.
(6) the chemical conversion treatment steel plate according to either a program in above-mentioned (1)~(5), wherein above-mentioned chemical conversion The surface for handling skin membrane can also be not coating with film or coating.
(7) manufacturing method of the chemical conversion treatment steel plate of a scheme of the invention is with the following process：In steel plate It includes to be calculated as 5.0~3000mg/m with W metal amount that surface, which is formed,2Ni Ni coating or comprising being calculated as 2.0 with W metal amount ~200mg/m2Ni and 0.10~10.0g/m is calculated as with metal Sn amounts2Sn and be formed with island on Fe-Ni-Sn alloy-layers The plating process of the composite deposite of Sn coating；Be 5 DEG C less than 90 DEG C of chemical conversion treatment solution by using temperature, In 1.0~100A/dm2Current density and 0.20~150 second electrolytic processing time under conditions of carry out electrolysis processing, to The electrolysis treatment process of chemical conversion treatment skin membrane, the chemical conversion are formed on above-mentioned Ni coating or above-mentioned composite deposite Treatment fluid includes the Zr ions of 10~20000ppm, the F ion of 10~20000ppm, the phosphate anion of 10~3000ppm, conjunction It is calculated as the nitrate ion of 100~30000ppm and the Al ions of sulfate ion and 500~5000ppm, above-mentioned Al ions Supply source is (NH4)3AlF6。
(8) manufacturing method of the chemical conversion treatment steel plate according to above-mentioned (7), wherein above-mentioned chemical conversion treatment The F ion of Zr ions, 200~17000ppm that liquid can also be containing 200~17000ppm, the phosphate radical of 100~2000ppm from Son adds up to the nitrate ion of 1000~23000ppm and the Al ions of sulfate ion and 500~3000ppm.
Invention effect
According to above-mentioned each scheme, even also having in the case that the adhesion amount for being capable of providing chemical conversion treatment skin membrane is few There are the chemical conversion treatment steel plate of excellent corrosion resistance and resistance to vulcanization blackening and the manufacturing method of chemical conversion treatment steel plate.
Description of the drawings
Figure 1A is the layer structure for the chemical conversion treatment steel plate for being formed with Ni coating on one side for being shown schematically in steel plate Definition graph.
Figure 1B be shown schematically in steel plate two sides be formed with Ni coating chemical conversion treatment steel plate layer structure Definition graph.
Fig. 2A is one of the chemical conversion treatment steel plate for being formed with composite deposite on one side for being shown schematically in steel plate The definition graph of example.
Fig. 2 B are to be shown schematically in the two sides of steel plate to be formed with one of chemical conversion treatment steel plate of composite deposite The definition graph of example.
Fig. 3 is one of the flow for the manufacturing method for indicating the chemical conversion treatment steel plate described in embodiments of the present invention The flow chart of example.
Fig. 4 is the chart for the result for indicating embodiment 1.
Specific implementation mode
Referring to appended attached drawing, the suitable embodiment of the present invention is described in detail.It should be noted that this In embodiment, for the inscape similarly constituted, repeated explanation is omitted by the identical symbol of mark.
<Composition about chemical conversion treatment steel plate>
First, A~Fig. 2 B referring to Fig.1 carry out the composition of the chemical conversion treatment steel plate described in present embodiment detailed Explanation.Figure 1A and Figure 1B is the definition graph for the layer structure for schematically showing the chemical conversion treatment steel plate described in present embodiment.
Chemical conversion treatment steel plate 10 described in present embodiment has steel plate as shown in Figure 1A~Fig. 2 B 103, any one of Ni coating 105 and composite deposite 106 and chemical conversion treatment skin membrane 107.It should be noted that Ni Any one of coating 105 and composite deposite 106 and chemical conversion treatment skin membrane 107 can be as shown in Figure 1A and Fig. 2A It is only formed in a surface of steel plate 103 like that, that of steel plate 103 can also be formed in as shown in Figure 1B and Fig. 2 B This two opposite surface.
[about steel plate 103]
Steel plate 103 is used as the base material of the chemical conversion treatment steel plate 10 described in present embodiment.For this embodiment party The steel plate 103 used in formula is not particularly limited, the well known steel plate that can be used used as steel plate for container.For steel plate 103 manufacturing method and material is also not particularly limited, can use from common steel billet manufacturing process via hot rolling, pickling, Process well known to cold rolling, annealing, modulation rolling etc. and the steel plate 103 that manufactures.
The plate thickness of steel plate 103 in view of the practicability and economy when being used as steel plate for container, preferably 0.05~ 1mm。
[about coating]
On the surface of steel plate 103, any one of Ni coating 105 and composite deposite 106 are formed.Ni coating 105 and compound Coating 106 is the coating of the barrier type containing Ni.Wherein, the coating of so-called barrier type is to use and constitute the steel as base material Metals of the Fe of plate 103 compared to metal, that is, Ni or Sn expensive in terms of electrochemistry, by forming Ni or Sn on the surface of steel plate 103 Film and prevent corrosion factor act on base material, corrosion to inhibit steel plate 103 coating.
On the other hand, the coating of alternative corrosion-proof type has the function opposite with the coating of barrier type.With regard to alternative corrosion-proof type For coating, using (such as such as above-mentioned special with constituting metal low-priced in terms of electrochemistry as the Fe of the steel plate 103 of base material compared with Sharp document 1 is Zn like that) metal film is formed on the surface of steel plate 103, by metals such as the Zn of composition coating prior to constituting steel plate 103 Fe corrodes, to inhibit the corrosion of steel plate 103.
It should be noted that for the coating of the coating of barrier type and alternative corrosion-proof type, with chemical conversion treatment epithelium The interaction of layer 107 is different.
Hereinafter, A~Fig. 2 B referring to Fig.1, to the example of Ni coating 105 and composite deposite 106 described in present embodiment into Row illustrates.
[the case where the surface of steel plate 103 forms coating 105 Ni]
A referring to Fig.1, to being described in detail the case where the surface of steel plate 103 is formed with Ni coating 105.
Ni coating 105 includes Ni, can as shown in Figure 1A as be formed in the one side of steel plate 103, can also be such as figure The two sides of steel plate 103 is formed in shown in 1B like that.In Ni coating 105, Ni is preferably being on one side so that W metal gauge is every 5.0~3000mg/m2In the range of contain.
Ni has excellent coating adhesion, film adaptation, corrosion resistance and weldability.In order to play above-mentioned excellent effect Fruit needs every in terms of W metal to contain 5.0mg/m on one side2Above Ni.
Along with the increase of the content of Ni, excellent effect possessed by Ni improves, but super per one side with W metal gauge Cross 3000mg/m2When, since its effect is saturated, economically not preferably.Therefore, the content of Ni is set as with W metal amount Meter is 3000mg/m per one side2Below.
The content of Ni in Ni coating is more preferably with W metal gauge per on one side for 10.0mg/m2Above and 2000mg/m2With Under.By containing with W metal gauge per one side for 10.0mg/m2Above Ni, above-mentioned effect become more significantly.In addition, By being set as the content of Ni with W metal gauge per one side for 2000mg/m2Hereinafter, Ni coating 105 can further be cut down Manufacturing cost.
Ratio in Ni coating 105 shared by Ni is calculated as 50 matter at the layer central part of Ni coating 105 with W metal amount Measure % or more.It is preferred that the ratio in Ni coating 105 shared by Ni is calculated as 70 at the layer central part of Ni coating 105 with W metal amount Quality % or more.
Ni coating 105 other than containing above-mentioned Ni, can also contain with metal Fe gauge per one side for 1.0~ 2000mg/m2Fe.In addition, Ni coating 105 is further included in mixed inevitable impurity in manufacturing process etc..
[the case where the surface of steel plate 103 forms composite deposite 106]
With reference to Fig. 2A and Fig. 2 B, to forming composite deposite 106 containing Ni and Sn on the surface of steel plate 103 the case where carries out It is described in detail.
Composite deposite 106 described in present embodiment can as shown in Figure 2 A as be formed in the one side of steel plate 103, Can also as shown in Figure 2 B as be formed in the two sides of steel plate 103.Composite deposite 106 has Fe-Ni-Sn alloy-layers 105d With the island Sn coating 105e being formed on Fe-Ni-Sn alloy-layers 105d.
In order to form composite deposite 106, Ni coating (not shown) is initially formed on steel plate 103.Ni coating (not shown) It is formed by Ni or Fe-Ni alloy/C, is formed in order to ensure the corrosion resistance of chemical conversion treatment steel plate 10.
The effect that the corrosion resistance of the chemical conversion treatment steel plate 10 brought by Ni improves depends on Ni amounts.If the Ni amounts in composite deposite 106 are with W metal gauge per one side for 2mg/m2More than, then it shows to be brought by Ni The effect that corrosion resistance improves.
On the other hand, the effect that the more at most corrosion resistance of the Ni amounts in composite deposite 106 improves more increases, if but composite deposite Ni amounts in 106 are with W metal gauge per on one side more than 200mg/m2, then by the effect saturation of the Ni corrosion resistance raisings brought.Separately Outside, due to the metal that Ni is high price, if the Ni amounts in composite deposite 106 are every on one side more than 200mg/ with W metal gauge m2, then economically not preferred.
Therefore, the Ni amounts in composite deposite 106 are set as with W metal gauge per one side for 2.0mg/m2~200mg/m2。 Ni amounts in composite deposite 106 are more preferably with W metal gauge per on one side for 5.0mg/m2~100mg/m2.Pass through composite deposite 106 containing every on one side for 5.0mg/m with W metal gauge2Above Ni can be played more effectively and be carried by the corrosion resistance that Ni is brought High effect.In addition, by being set as the Ni amounts in composite deposite 106 with W metal gauge per one side for 100mg/m2With Under, it can further cut down manufacturing cost.
After foring above-mentioned Ni coating (not shown), Sn coating (not shown) is formed.It should be noted that this reality The Sn coating (not shown) applied in mode can be only made of Sn, and impurity or trace element can also be also contained other than Sn.
Sn coating (not shown) is formed in order to ensure corrosion resistance and the weldability of chemical conversion treatment steel plate 10.Sn Not only Sn itself has high corrosion resistance, but also the Sn alloys of formation also have excellent corrosion resistance by tin processing is melted in melting And weldability.
Molten tin processing is melted by carrying out after foring Sn coating (not shown), Fe-Ni-Sn is formed on steel plate 103 Alloy-layer 105d forms island Sn coating 105e on Fe-Ni-Sn alloy-layers 105d.
In island Sn coating 105e, Sn exists with island, and the Fe-Ni-Sn alloy-layers 105d of lower layer is exposed to extra large portion.Profit With island Sn coating 105e, it can be ensured that the film adaptation and coating adhesion of chemical conversion treatment steel plate 10.
In heat treatment after film layer pressure or coating coating, chemical conversion treatment steel plate 10 is heated to the fusing point of Sn sometimes More than (232 DEG C).It is different from present embodiment, in the case where Sn is coating by the whole surface of Fe-Ni-Sn alloy-layers 105d, Due to Sn meltings or oxidation possibly through above-mentioned heat treatment, it is unable to ensure the film adaptation of chemical conversion treatment steel plate 10 And coating adhesion, therefore not preferably.
Composite deposite 106 described in present embodiment contains with metal Sn gauge per one side for 0.10~10.0g/m2's Sn。
Sn has excellent processability, weldability and corrosion resistance, melts molten tin processing by being carried out after plating Sn, can make The corrosion resistance of chemical conversion treatment steel plate 10 further increases, while making the appearance (minute surface of chemical conversion treatment steel plate 10 Appearance) become more preferable.In order to play above-mentioned effect, in composite deposite 106, it is necessary to containing with the every one side of metal Sn gauge For 0.10g/m2Sn.
In addition, the content of the Sn in composite deposite 106 more increases the processability, weldability of then chemical conversion treatment steel plate 10 And corrosion resistance more improves, if but Sn content with metal Sn gauge per one side more than 10.0g/m2, then brought by Sn above-mentioned Effect is saturated.In addition, if the content of Sn is every on one side more than 10.0g/m with metal Sn gauge2, then economically not preferred.From upper The reasons why stating is set out, and the content of the Sn in composite deposite 106 is set as with metal Sn gauge per one side for 10.0g/m2Below.
The content of Sn in composite deposite 106 is more preferably with metal Sn gauge per on one side for 0.30g/m2~7.0g/m2.It is logical Composite deposite 106 is crossed to contain with metal Sn gauge per one side for 0.30g/m2Above Sn can be played more reliably by Sn bands The above-mentioned effect come.In addition, being contained with metal Sn gauge per one side for 7.0g/m by composite deposite 1062Sn below, energy It is enough further to cut down manufacturing cost.
Add up to composite deposite 106 50 of the W metal amount for the Ni for including in composite deposite 106 and the metal Sn amounts of Sn Quality % or more.It is preferred that the metal Sn amounts of the W metal amount and Sn for the Ni for including in composite deposite 106 add up to composite deposite 106 70 mass % or more.
Composite deposite 106 can also contain with metal Fe gauge per one side for 1.0 other than containing above-mentioned Ni and Sn ~3500mg/m2Fe.In addition, composite deposite 106 can also contain the mixed inevitable impurity in manufacturing process etc..
In the feelings for using the steel plate 103 for being formed with Ni coating 105 or composite deposite 106 on surface as steel plate for container Under condition, even if in the superficial layer press mold of Ni coating 105 or composite deposite 106 or even if coating coating, it is also difficult to prevent sulphur black Become.As its reason, it is believed that be as the S for including in the beverage of content or food etc. in coating 105 Ni or Sn be bonded And form NiS, SnS, SnS of black2Deng.
It should be noted that compositions of the S as sulfur-containing amino acid such as L-cysteine, L- (-)-cystine, L-Methionines Ingredient and be contained in beverage or food.
In addition, in the case where Ni coating 105 or composite deposite 106 do not densely be formed, the steel plate 103 as base material A part expose.In this case, the S for including in the Fe in steel plate 103 and beverage or food etc. sometimes is bonded, and is formed FeS, Fe of black2S3、Fe2S。
It is above-mentioned due to NiS, SnS, SnS in order to reduce2、FeS、Fe2S3、Fe2The blacking of S etc. is mainly so far Chromate epithelium is formed on the surface of Ni coating 105 or composite deposite 106.
For the chemical conversion treatment steel plate 10 described in present embodiment, in order to improve the blackening of resistance to vulcanization, in Ni coating 105 or the upper layer of composite deposite 106 formed containing Zr compounds, phosphate cpd as the replacement of previous chromate epithelium And the chemical conversion treatment skin membrane 107 of Al compounds.
[about chemical conversion treatment skin membrane 107]
As shown in Figure 1A~Fig. 2 B, in the chemical conversion treatment steel plate 10 of present embodiment, in Ni coating 105 or composite deposite 106 on form chemical conversion treatment skin membrane 107.Chemical conversion treatment skin membrane 107 is with Zr compounds As the Composite Skin film layer of main body, containing every on one side for 1.0~150mg/m with metal Zr gauge2Zr compounds, with P gauge It is 1.0~100mg/m per one side2Phosphate cpd and with metal Al gauge per one side be 0.10~30.0mg/m2Al chemical combination Object.
It should be noted that in present embodiment, so-called Composite Skin film layer indicates Zr compounds, phosphate cpd and Alization Object is closed without fully mixing and with skin membrane existing for the state of part mixing.
By the Zr epitheliums containing Zr compounds, the phosphoric acid epithelium containing phosphate cpd and the Al skins containing Al compounds In the case that this 3 epitheliums of film are overlappingly formed on Ni coating 105 or composite deposite 106, although about corrosion resistance and closely sealed A degree of effect can be obtained in property, but in practical and insufficient.However, as in the present embodiment, passing through Zr compounds Exist with the state that part mixes in chemical conversion treatment skin membrane 107 with phosphate cpd and Al compounds, with institute as above It states the case where 3 epitheliums overlap to form to compare, excellent corrosion resistance and adaptation can be obtained.
The Zr compounds for including in chemical conversion treatment skin membrane 107 described in present embodiment have improve corrosion resistance, Adaptation and the function of processing adaptation.As the Zr compounds described in present embodiment, such as oxidation Zr, phosphoric acid can be enumerated Zr, hydroxide Zr and fluorination Zr etc., chemical conversion treatment skin membrane 107 is containing there are many above-mentioned Zr compounds.Preferred Zrization That closes object is combined as oxidation Zr, phosphoric acid Zr and fluorination Zr.
The content for the Zr compounds for including in chemical conversion treatment skin membrane 107 is with metal Zr gauge per being on one side 1.0mg/m2In the case of above, it can be ensured that suitable corrosion resistance, adaptation and processing adaptation in practical.
On the other hand, along with the increase of the content of Zr compounds, corrosion resistance, adaptation and processing adaptation improve.So And if the content of Zr compounds is every on one side more than 150mg/m with metal Zr gauge2, then chemical conversion treatment skin membrane 107 become Blocked up, mainly since cohesion destroys, chemical conversion treatment skin membrane 107 is close relative to Ni coating 105 or composite deposite 106 Conjunction property declines, while resistance rises and weldability decline.In addition, if the content of Zr compounds is more than 150mg/ with metal Zr gauge m2, then the attachment due to chemical conversion treatment skin membrane 107 is uneven, and appearance becomes uneven sometimes.
Therefore, the content of the Zr compounds of the chemical conversion treatment skin membrane 107 described in present embodiment is (that is, Zr's contains Amount) it is set as with metal Zr gauge per one side for 1.0mg/m2~150mg/m2.The content of Zr compounds is more preferably with metal Zr amounts Meter is 1.0~120mg/m per one side2.By the way that metal Zr amounts are set as 120g/m2Hereinafter, chemical conversion can further be cut down Handle the manufacturing cost of skin membrane 107.
Chemical conversion treatment skin membrane 107 further comprises a kind or 2 kinds other than comprising above-mentioned Zr compounds Above phosphate cpd.
Phosphate cpd described in present embodiment has the function of improving corrosion resistance, adaptation and processing adaptation.Make For the example of the phosphate cpd described in present embodiment, phosphate anion and steel plate 103, Ni coating 105 or multiple can be enumerated Phosphoric acid Fe, phosphoric acid Ni, the phosphoric acid for closing the compound reaction for including in coating 106 and chemical conversion treatment skin membrane 107 and being formed Sn, phosphoric acid Zr, phosphoric acid Al etc..Chemical conversion treatment skin membrane 107 can include a kind of above-mentioned phosphate cpd, can also wrap Containing two or more.
The content for the phosphate cpd for including in chemical conversion treatment skin membrane 107 is more, then chemical conversion treatment steel plate 10 corrosion resistance, adaptation and processing adaptation more improves.Specifically, the phosphorus in chemical conversion treatment skin membrane 107 It is 1.0mg/m that the content of acid compound, which is converted into P amounts,2In the case of above, it can be ensured that suitable corrosion resistance, closely sealed in practical Property and processing adaptation.
On the other hand, increasing along with the content of phosphate cpd, corrosion resistance, adaptation and processing adaptation also improve, If but the content of phosphate cpd is every on one side more than 100mg/m with P gauge2, then chemical conversion treatment skin membrane 107 became Thickness, mainly since cohesion destroys, chemical conversion treatment skin membrane 107 is closely sealed relative to Ni coating 105 or composite deposite 106 Property decline, while resistance rise and weldability decline.In addition, if the content of phosphate cpd is more than on one side so that P gauge is every 100mg/m2, then the attachment due to chemical conversion treatment skin membrane 107 is uneven, and appearance becomes uneven sometimes.
Therefore, the content of the phosphate cpd of the chemical conversion treatment skin membrane 107 described in present embodiment is set as with P Gauge is 1.0mg/m per one side2~100mg/m2。
The content of the phosphate cpd of chemical conversion treatment skin membrane 107 more preferably with P gauge per one side for 2.0~ 70.0mg/m2.By being set as the content of the phosphate cpd of chemical conversion treatment skin membrane 107 with P gauge per being on one side 2.0mg/m2More than, the preferred blackening of resistance to vulcanization can be obtained.In addition, by by chemical conversion treatment skin membrane 107 The content of phosphate cpd is set as with P gauge per one side for 70.0mg/m2Hereinafter, chemical conversion treatment can further be cut down The manufacturing cost of skin membrane 107.
Chemical conversion treatment skin membrane 107 is also further other than comprising above-mentioned Zr compounds and phosphate cpd Including Al compounds.The Al compounds of chemical conversion treatment skin membrane 107 in chemical conversion treatment skin membrane 107 mainly as Al oxides exist.The epithelium for making chemical conversion treatment skin membrane 107 as main component with Zr by the reinforcement of Al oxides lacks It falls into, chemical conversion treatment steel plate 10 can obtain the excellent blackening of resistance to vulcanization.
Make chemical conversion treatment skin membrane 107 as main component due to being originally used for extremely uniform epithelium with Zr, is Reinforcement epithelium defect and as long as the amount for being added to Al compounds in chemical conversion treatment skin membrane 107 is every with metal Al gauge It is 0.10mg/m on one side2It is above.By the content of Al compounds with metal Al gauge per on one side for 0.10mg/m2More than, energy Enough blackenings of resistance to vulcanization for suitably improving chemical conversion treatment steel plate 10.
On the other hand, increase along with the content of the Al compounds of chemical conversion treatment skin membrane 107, the blackening of resistance to vulcanization Also improve, if but Al compounds content with metal Al gauge per one side more than 30.0mg/m2, then resistance to vulcanization blackening saturation, It is economically not preferred simultaneously.Therefore, by the content for the Al compounds for including in chemical conversion treatment skin membrane 107 be set as with Metal Al gauge is 30.0mg/m per one side2Below.
The content of the Al compounds of chemical conversion treatment skin membrane 107 more preferably with metal Al gauge per one side for 0.20~ 20.0mg/m2.By being set as the content of Al compounds with metal Al gauge per one side for 0.20mg/m2More than, it can be suitable Improve the blackening of resistance to vulcanization in ground.In addition, by being set as the content of Al compounds with metal Al gauge per one side for 20.0mg/ m2Hereinafter, the manufacturing cost of chemical conversion treatment skin membrane 107 can further be cut down.
Al oxides (Al in chemical conversion treatment skin membrane 1072O3) content preferably with metal Al amounts be calculated as 0.10 ~30.0mg/m2.Content by the Al oxides in chemical conversion treatment skin membrane 107 is above-mentioned range, can be suitable The epithelium defect of ground reinforcement chemical conversion treatment skin membrane 107, can obtain the excellent blackening of resistance to vulcanization.
In addition, by make in chemical conversion treatment skin membrane 107 contain Al compounds, can reduce make in the same manner as Al it is resistance to The content for the phosphate cpd that sulphur black denaturation improves.
Phosphate anion in the phosphate cpd contained in chemical conversion treatment skin membrane 107 is given birth to Zr ionic reactions At the chemical conversion treatment solutions that are used when forming chemical conversion treatment skin membrane 107 of phosphoric acid Zr in exist in large quantities the case where Gonorrhoea occurs for lower precipitation, chemical conversion treatment solution.
Wherein, Al compounds contribute to the raising of resistance to vulcanization blackening compared with phosphate cpd.Therefore, turned by chemistry Change processing skin membrane 107 and contain Al compounds, can suitably improve the blackening of resistance to vulcanization, and reduce as at chemical conversion The content of the phosphate cpd for the reason of managing the gonorrhoea of liquid.
In addition, the content by reducing phosphate cpd, can cut down hinder Zr and phosphoric acid be bonded and Al and phosphoric acid The amount of the F ion of bonding.As a result, more easily Zr can be made to be precipitated, therefore it can improve and be used to form at chemical conversion Manage the electrolytic efficiency of skin membrane 107.
It should be noted that chemical conversion treatment skin membrane 107 in addition to comprising above-mentioned Zr compounds, phosphate cpd and Other than Al compounds, it is further included in mixed inevitable impurity in manufacturing process etc..In addition, in chemical conversion treatment In the case that skin membrane 107 contains Cr, the upper limit of the content of Cr is 2.0mg/m2。
Even if the chemical conversion treatment steel plate 10 described in present embodiment is reduction of chemical conversion treatment skin membrane 107 In the case of adhesion amount, the excellent blackening of resistance to vulcanization is also showed that.
Such as the surface of chemical conversion treatment steel plate 10 is made to adhere to coating, it is sintered and forms film.It is 1 small keeping having boiled When 0.6 mass %L- cysteine liquid heat-resisting bottle mouth on, the chemical conversion treatment steel plate of film will be formed on surface 10 load and fix as lid, implement at 110 DEG C heat treatment in 30 minutes using soaking pit etc..After above-mentioned heat treatment Chemical conversion treatment steel plate 10 in, if the appearance of observation and the contact portion of heat-resisting bottle, is using present embodiment institute In the case of the chemical conversion treatment steel plate 10 stated, 50% or more no generation blacking of the area of contact portion.
As described above, the chemical conversion treatment steel plate 10 described in present embodiment has excellent corrosion resistance and resistance to sulphur black Denaturation.Therefore, even not by the surface of chemical conversion treatment skin membrane 107 with film or coating it is coating in the case of, also can It is enough to use chemical conversion treatment steel plate 10 as steel plate for container.
<Layer structure about chemical conversion treatment steel plate 10>
Chemical conversion treatment steel plate 10 has Ni coating 105 or composite deposite 106 on steel plate 103 as described above, in Ni There is chemical conversion treatment skin membrane 107 on coating 105 or composite deposite 106.That is, in chemical conversion treatment steel plate 10, steel Plate 103 is in contact with Ni coating 105 or composite deposite 106, does not have between steel plate 103 and Ni coating 105 or composite deposite 106 There is other layer.Similarly, in chemical conversion treatment steel plate 10, Ni coating 105 or composite deposite 106 and chemical conversion treatment skin Film layer 107 is in contact, and does not have between Ni coating 105 or composite deposite 106 and chemical conversion treatment skin membrane 107 other Layer.
<Assay method about component content>
W metal amount or metal Sn amounts in Ni coating 105 and composite deposite 106 for example can by fluorescent X-ray method come It is measured.In this case, using sample known to W metal amount, standard curve of the pre-production about W metal amount makes W metal amount is relatively determined with made standard curve.About metal Sn amounts, similarly use known to metal Sn amounts Sample, standard curve of the pre-production about metal Sn amounts relatively determine metal Sn amounts using made standard curve.
Metal Zr amounts, P amounts and metal Al amounts in chemical conversion treatment skin membrane 107 can for example pass through fluorescent X-ray The quantitative analysis methods such as analysis are measured.In addition, about in chemical conversion treatment skin membrane 107 there are what kind of compound, It can be by using x-ray photoelectron spectroscopy measuring method (X-ray Photoelectron Spectroscopy：XPS) divided It analyses to determine.
In addition, about the Al in chemical conversion treatment skin membrane 1072O3Content, first with X-ray photoelectricity optical spectroscopy (X-ray Photoelectron Spectroscopy, XPS), finds out Al2O3, metal Al and other Al compounds peak intensity Than.Moreover, being asked by the whole metal Al amounts found out as described above by quantitative analysis methods such as x-ray fluorescence analysis and by XPS The peak intensity ratio gone out calculates the Al in chemical conversion treatment skin membrane 1072O3Content.
It should be noted that the assay method of each ingredient is not limited to above-mentioned method, well known measurement side can be applicable in Method.
<Manufacturing method about chemical conversion treatment steel plate 10>
Then, with reference to Fig. 3, the manufacturing method of the chemical conversion treatment steel plate 10 described in present embodiment is carried out specifically It is bright.Fig. 3 be the flow for the manufacturing method to the chemical conversion treatment steel plate 10 described in present embodiment an example into The flow chart of row explanation.
[pretreatment procedure]
In the manufacturing method of chemical conversion treatment steel plate 10 described in present embodiment, first, as needed to steel plate 103 implement well known pre-treatment (step S101).
[plating process]
Later, the surface relative to steel plate 103 forms any one of Ni coating 105 and composite deposite 106 (step S103)。
In the case where the surface of steel plate 103 forms coating 105 Ni, can use known in galvanoplastic or vacuum vapour deposition etc. Technology.It should be noted that in addition, (not scheming to form Fe-Ni diffusion layers at the interface of steel plate 103 and Ni coating 105 Show), it can also be heated after the formation of Ni coating 105.
The composite deposite with Fe-Ni-Sn alloy-layers 105d and island Sn coating 105e is formed on the surface of steel plate 103 In the case of 106, by forming the Ni coating (not shown) formed by Ni or Fe-Ni alloy/C on the surface of steel plate 103, in Ni After being further formed Sn coating (not shown) on coating (not shown), carry out melting molten tin processing (mild melt treatment, reflow Treatment), thus formed.
That is, tin processing is melted by melting, Ni and the Sn coating (not shown) of Fe and the Ni coating (not shown) of steel plate 103 The Sn of a part occurs alloying and forms Fe-Ni-Sn alloy-layer 105d, while the Sn coating of remainder becomes island, shape At island Sn coating 105e.
As the forming method of the Ni coating (not shown) formed by Ni or Fe-Ni alloy/C, general plating can be utilized Method (such as katholysis).
The method for forming Sn coating (not shown) is also not particularly limited, and well known galvanoplastic can be used for example or molten The method etc. for impregnating steel plate 103 in the Sn melted and carrying out plating.
In the case of forming Ni coating (not shown), the surface of steel plate 103 is implemented to plate Ni by spreading plating method Afterwards, the DIFFUSION TREATMENT for being used to form diffusion layer is carried out in the lehr.It can also be before and after DIFFUSION TREATMENT or and DIFFUSION TREATMENT It is carried out at the same time Nitrizing Treatment.Even in the case of having carried out Nitrizing Treatment, in the Ni coating (not shown) in present embodiment Ni possessed by effect and the effect brought by Nitrizing Treatment also do not interfere, these effects can be played jointly.
After forming Sn coating (not shown), carry out melting molten tin processing (mild melt treatment).By carrying out melting molten tin Processing, the Sn for making melting and the Ni alloyings in Fe the and Ni coating (not shown) in steel plate 103, form Fe-Ni-Sn alloy-layers The 105d and island Sn coating 105e formed by Sn formed with island.Island Sn coating 105e can be by suitably controlling Melting melts tin processing to be formed.
[electrolysis treatment process]
It after forming any one of Ni coating 105 and composite deposite 106, is handled by electrolysis, forms chemical conversion Handle skin membrane 107 (step S105).
Chemical conversion treatment skin membrane 107 handles (such as catholyte processing) by electrolysis by is formed.In order to pass through electricity The chemical conversion treatment solution that solution processing forms chemical conversion treatment skin membrane 107 and uses includes 10ppm or more and 20000ppm Zr ions, 10ppm or more and 20000ppm F ions below below, 10ppm or more and 3000ppm phosphate radicals below from Son, add up to 100ppm or more and 30000ppm nitrate ions below and sulfate ion and 500ppm or more and 5000ppm Al ions below.In addition, in chemical conversion treatment solution, (NH is used4)3AlF6Supply source as Al ions.
As long as it should be noted that nitrate ion and sulfate ion in chemical conversion treatment solution with two kinds of ions Total meter includes 10ppm or more and 3000ppm or less, can be nitrate ion and sulfate ion both ion packets Contained in chemical conversion treatment solution, can also be that only any one of nitrate ion and sulfate ion is contained in chemical conversion In treatment fluid.
Chemical conversion treatment solution preferably comprise 200ppm or more and 17000ppm Zr ions below, 200ppm or more and 17000ppm F ions below, 100ppm or more and 2000ppm phosphate anions below, add up to 1000ppm or more and 23000ppm nitrate ions below and sulfate ion and 500ppm or more and 3000 Al ions below.
By the way that the concentration of Zr ions is set as 200ppm or more, the adhesion amount that can be more reliably prevented from Zr declines.Separately Outside, by the way that the concentration of F ion is set as 200ppm or more, it can be more reliably prevented from and generate with phosphatic precipitation The gonorrhoea of chemical conversion treatment skin membrane 107.
Similarly, it by the way that the concentration of phosphate anion is set as 100ppm or more, can be more reliably prevented from phosphorus The precipitation of hydrochlorate and the gonorrhoea of chemical conversion treatment skin membrane 107 generated.In addition, by by nitrate ion and sulfate radical from The concentration of at least one of son is set as 1000ppm or more, can be more reliably prevented from chemical conversion treatment skin membrane 107 The decline of deposit efficiency.In addition, by the way that the concentration of Al ions is set as 500ppm or more, resistance to vulcanization can be more reliably realized The improvement effect of blackening.
It should be noted that by the way that the upper limit value of each ingredient of chemical conversion treatment solution is set as value as described above, The manufacturing cost of chemical conversion treatment skin membrane 107 can more reliably be cut down.
The temperature of chemical conversion treatment solution is preferably 5 DEG C less than 90 DEG C.It is low in the temperature of chemical conversion treatment solution In the case of 5 DEG C, since the formation efficiency of chemical conversion treatment skin membrane 107 is poor, uneconomical, not preferably.In addition, In the case that the temperature of chemical conversion treatment solution is 90 DEG C or more, due to being formed by the group of chemical conversion treatment skin membrane 107 Knit it is uneven, generate cracking, micro-crack the defects of and these defects can become corrosion etc. starting point, therefore not preferably.
It should be noted that in order to improve the reactivity of the chemical conversion treatment solution in interface while make at chemical conversion The deposit efficiency for managing skin membrane 107 improves, and the temperature of chemical conversion treatment solution is preferably higher than formed with Ni coating 105 and Composite Coatings The surface temperature of the steel plate 103 of any one of layer 106.
Current density when carrying out electrolysis processing is preferably 1.0A/dm2Above and 100A/dm2Below.It is low in current density In 1.0A/dm2In the case of, since the adhesion amount of chemical conversion treatment skin membrane 107 sometimes declines while electrolytic processing time It is elongated, therefore not preferably.In addition, being more than 100A/dm in current density2In the case of, due to chemical conversion treatment skin membrane 107 Adhesion amount become excessive, the insufficient chemical conversion treatment skin of the attachment being formed by chemical conversion treatment skin membrane 107 Film layer 107 is possible to be rinsed (stripping) in the electrolysis washing procedure that treated using washing etc., therefore not preferably.
The time (electrolytic processing time) for carrying out electrolysis processing is preferably 0.20 second or more and 150 seconds or less.At electrolysis In the case of the time is managed less than 0.20 second, since the adhesion amount of chemical conversion treatment skin membrane 107 declines, it cannot get desired Performance, therefore not preferably.On the other hand, in the case where electrolytic processing time is more than 150 seconds, due to chemical conversion treatment epithelium The adhesion amount of layer 107 becomes excessive, at the insufficient chemical conversion of the attachment being formed by chemical conversion treatment skin membrane 107 Reason skin membrane 107 is possible to be rinsed (stripping) in the electrolysis washing procedure that treated using washing etc., therefore unexcellent Choosing.
The pH of chemical conversion treatment solution is preferably 3.1~3.7 range, more preferably 3.5 or so.At chemical conversion The adjustment for managing the pH of liquid, can also be added nitric acid or ammonia etc. as needed.
It, can be in any one of Ni coating 105 and composite deposite 106 by carrying out electrolysis processing under the conditions described above Surface formed present embodiment described in chemical conversion treatment skin membrane 107.
It should be noted that formed present embodiment described in chemical conversion treatment skin membrane when, can also for It is electrolysed in the chemical conversion treatment solution of processing and further adds tannic acid.By adding tannic acid in chemical conversion treatment solution, To which tannic acid reacts with the Fe in steel plate 103, the epithelium of tannic acid Fe is formed on the surface of steel plate 103.Tannic acid Fe Epithelium since resistance to rust and adaptation can be made to improve, preferably.
As the solvent of chemical conversion treatment solution, deionized water, distilled water etc. can be used for example.Chemical conversion treatment solution Solvent preferred conductivity be 10 μ S/cm or less, further preferably 5 μ S/cm or less, more preferably 3 μ S/cm or less. But it's not limited to that for the solvent of above-mentioned chemical conversion treatment solution, it can be according to the material or forming method that are dissolved and change It learns formation condition of conversion processing skin membrane 107 etc. and suitably selects.But stablize from the adhesion amount based on stable each ingredient Property industrial productivity, cost, set out, it is preferable to use deionized water or distilled water in terms of environment.
As the supply source of Zr, H can be used for example2ZrF6Such Zr complex compounds.In Zr complex compounds as described above Zr is by the hydrolysis of the rising of the adjoint pH in cathode electrode interface, as Zr4+And it is present in chemical conversion treatment solution. Such Zr ions are anti-by carrying out dehydrating condensation with the hydroxyl (- OH) for being present in metal surface in chemical conversion treatment solution It answers, to form ZrO2、Zr3(PO4)4Etc. compounds.
In addition, in chemical conversion treatment solution, by (NH4)3AlF6Supply source as Al uses.By by (NH4)3AlF6 Supply source as Al uses, to which Al is present in chemistry with the state (hereinafter referred to as AlF complex compounds) for forming complex compound with F In conversion treating solution.Al in AlF complex compounds is constituted by being precipitated together with Zr in being electrolysed treatment process at chemical conversion Skin membrane 107 is managed, to contribute to the blackening of resistance to vulcanization as described above.
In addition, Al in the same manner as Zr in chemical conversion treatment solution as cation exist.Therefore, by using (NH4)3AlF6It, can be in the increased general of concentration of the phosphate anion in not making chemical conversion treatment solution as the supply source of Al Al is supplied in chemical conversion treatment solution.
On the other hand, Al is being used as described in Patent Document 32(SO4)3In the case of Deng the supply source as Al, due to not having AlF complex compounds are formed, therefore Al is not precipitated suitably when being electrolysed treatment process, in chemical conversion treatment skin membrane 107 The content of Al become considerably less.In this case, since chemical conversion treatment skin membrane 107 does not have suitable resistance to sulphur black Denaturation, therefore not preferably.
[postprocessing working procedures]
Later, as needed, to being formed with any one of Ni coating 105 and composite deposite 106 and chemical conversion treatment The steel plate 103 of skin membrane 107 implements well known post-processing (step S107).
By being handled with above-mentioned flow, the chemical conversion treatment steel plate 10 described in present embodiment can be manufactured.
It should be noted that in the above description, to by being electrolysed processing shape on Ni coating 105 or composite deposite 106 It is illustrated at the case where chemical conversion treatment skin membrane 107, but is filled in the formation cost for allowing chemical conversion treatment epithelium In the case of the time divided, chemical conversion treatment skin membrane is formed by impregnation by can not also being handled by being electrolysed 107。
Embodiment
Hereinafter, show embodiment, to described in embodiments of the present invention chemical conversion treatment steel plate and chemical conversion at The manufacturing method of reason steel plate is specifically described.It should be noted that embodiment described below is embodiments of the present invention One example of the manufacturing method of the chemical conversion treatment steel plate and chemical conversion treatment steel plate, embodiments of the present invention The manufacturing method of the chemical conversion treatment steel plate and chemical conversion treatment steel plate is not limited to following examples.
(embodiment 1)
In embodiment 1, does not change the content of the Zr compounds and phosphate cpd in chemical conversion treatment skin membrane and change The content for becoming Al compounds, is verified to how resistance to vulcanization blackening changes.
In embodiment 1, using the steel plate used generally as steel plate for container as base material, the Ni as coating is formd Coating.The content of Ni in Ni coating is set as with W metal gauge per one side in whole samples for 1000mg/m2.Moreover, The concentration of Al compounds in chemical conversion treatment skin membrane is changed to each sample and forms chemical conversion treatment skin membrane, is made Multiple samples are made.Wherein, in each sample, the content of Zr compounds is every on one side for 8mg/m with metal Zr gauge2, phosphorylation The content of object is closed with P gauge per on one side for 3mg/m2。
The evaluation of resistance to vulcanization blackening carries out as described below.First, by 1 hour 0.6 mass %L-, half Guang that boiled Propylhomoserin liquid is put into heat-resisting bottle, is loaded on the mouth of the heat-resisting bottle and fixed above-mentioned sample (φ 40mm) is as lid.Then, right In the heat-resisting bottle covered as described above, heat treatment (boiling processing) in 15 minutes has been carried out at 110 DEG C using soaking pit.It Afterwards, it in each sample, carries out having carried out 10 grades based on the following benchmarks with the visual inspection of the contact portion of heat-resisting bottle Evaluation.It should be noted that in following evaluation criteria, if scoring is 5 points or more, actual use can tolerate.
<Resistance to vulcanization blackening evaluation criteria>
With the ratio of the area for not being changing into black in the contact area of sample and 0.6 mass %L- cysteine liquid Example, provides 1~10 point of scoring.
10 points：100%~90% or more
9 points：Less than 90%~80% or more
8 points：Less than 80%~70% or more
7 points：Less than 70%~60% or more
6 points：Less than 60%~50% or more
5 points：Less than 50%~40% or more
4 points：Less than 40%~30% or more
3 points：Less than 30%~20% or more
2 points：Less than 20%~10% or more
1 point：Less than 10%~0% or more
Obtained evaluation result is shown in Figure 4.In Fig. 4, horizontal axis indicates the chemical conversion treatment skin in each sample The content (metal Al amounts) of Al compounds in film layer, the longitudinal axis indicate the evaluation result of resistance to vulcanization blackening.
As shown in Figure 4, the content of Al compounds is less than 0.1mg/m with metal Al gauge per one side2When, resistant to sulfur The evaluation result for changing blackening is scoring 1.On the other hand, the content of Al compounds is every on one side for 0.1mg/m with metal Al gauge2 When above, the evaluation result of resistance to vulcanization blackening is 7 or more scoring, shows there is the extremely excellent blackening of resistance to vulcanization.
It is shown by the result：By making the Al compounds containing specified amount in chemical conversion treatment skin membrane, has and change The blackening of resistance to vulcanization for learning the chemical conversion treatment steel plate of conversion processing epithelium improves by leaps and bounds.
(embodiment 2)
Then, each ingredient for being included according to the type of coating, chemical conversion treatment skin membrane to resistance to vulcanization blackening How content, which changes, is verified.It should be noted that in the Examples and Comparative Examples in addition to comparative example a5, plating Layer is any one of Ni coating and composite deposite.On the other hand, in comparative example a5, composite deposite is formd on Ni coating (foring 2 layers of coating).
In addition, in example A1~A31 and comparative example a1~a6, (NH has been used4)3AlF6Supply as Al ions Source in comparative example a7 and a8, uses Al in contrast2(SO4)3It is formd at chemical conversion as the supply source of Al ions Manage skin membrane.
The metal Zr amounts that include in the W metal amount and metal Sn amounts and chemical conversion treatment skin membrane that include in coating, P amounts and metal Al amounts are measured by x-ray fluorescence analysis.
About the Al in chemical conversion treatment skin membrane2O3Content, first with X-ray photoelectricity optical spectroscopy (X-ray Photoelectron Spectroscopy, XPS), find out Al2O3, metal Al and other Al compounds peak intensity ratio.And And by the whole metal Al amounts found out as described above by quantitative analysis methods such as x-ray fluorescence analysis and the peak found out by XPS Intensity ratio, has calculated the Al in chemical conversion treatment skin membrane2O3Content.
Measurement result is shown in table 1 below.
Table 1
<Corrosion proof evaluation>
Corrosion resistant test liquid has used 3% acetic acid.The steel plate is cut out into φ 35mm, is put into equipped with the resistance to of corrosion resistant test liquid It is on the mouth of hot bottle and fixed.After carrying out heat treatment in 60 minutes at 121 DEG C, with the area of corrosion relative to corrosion resistant test liquid The ratio of the area (area of the mouth of heat-resisting bottle) contacted with Ni coated steel sheets evaluates corrosion resistance.
More specifically, the ratio of the area contacted relative to test film and experimental liquid with corroded area, provides 1~10 point Scoring.It should be noted that in following evaluation criteria, if scoring is 5 points or more, actual use can tolerate.
10 points：100%~90% or more
9 points：Less than 90%~80% or more
8 points：Less than 80%~70% or more
7 points：Less than 70%~60% or more
6 points：Less than 60%~50% or more
5 points：Less than 50%~40% or more
4 points：Less than 40%~30% or more
3 points：Less than 30%~20% or more
2 points：Less than 20%~10% or more
1 point：Less than 10%~0% or more
For the project of Evaluation of Corrosion Resistance, 10 points~9 minute marks are denoted as " Very Good ", 8 points~5 minute marks are denoted as " Good ", 4 points or less labels are Not Good ".
<The evaluation of resistance to vulcanization blackening>
The evaluation of resistance to vulcanization blackening carries out as described below.By the 1 hour 0.6 mass %L- cysteine liquid that boiled It is put into heat-resisting bottle, is loaded on the mouth of the heat-resisting bottle and fixed above-mentioned sample (φ 40mm) is as lid.For with sample lid Good heat-resisting bottle has carried out heat treatment (boiling processing) in 15 minutes using soaking pit at 110 DEG C.Later, for each examination Sample, the appearance of observation and the contact portion of heat-resisting bottle are based on benchmark similar to the above, have carried out the evaluation of 10 grades.? In table 2 as shown below, 10 points~8 minute marks are denoted as " Very Good ", 7 points~5 minute marks are denoted as " Good ", 4 points or less labels For " Not Good ".
The results obtained are shown in table 2 below.
Table 2
As shown in table 2, example A1~A31 of the present invention all has excellent corrosion resistance and the blackening of resistance to vulcanization.Separately On the one hand, certain one in the corrosion resistance of comparative example a1~a8 and resistance to vulcanization blackening is poor.It should be noted that just using Al2 (SO4)3For the comparative example a7 and a8 of supply source as Al ions, Al amounts and Al2O3Amount is significantly few, resistance to vulcanization blackening For " Not Good ".
(embodiment 3)
Then, each ingredient for being included according to the type of coating, chemical conversion treatment skin membrane to resistance to vulcanization blackening It is verified containing how to change.
For each sample with Ni coating or composite deposite shown in table 3, in table 4 shown in condition (chemistry turns Change treatment fluid condition and electrolysis processing condition) under carried out chemical conversion treatment.By being formed on coating for each sample Metal Zr amounts, P amounts, metal Al amounts and Al possessed by chemical conversion treatment skin membrane2O3Amount is shown in Table 5.
In addition, for each sample with coating and chemical conversion treatment skin membrane, have rated similarly to Example 2 resistance to Corrosion and the blackening of resistance to vulcanization.It shows the result in table 5.
It should be noted that in example B1~B31 and comparative example b1~b8, (NH has been used4)3AlF6As Al from The supply source of son in comparative example b9 and b10, uses Al in contrast2(SO4)3As Al ions supply source and formed Learn conversion processing skin membrane.
Table 3
Table 4
Table 5
As shown in table 5, manufactured by the manufacturing method of the chemical conversion treatment steel plate described in present embodiment Example B1~B31 of the present invention all have excellent corrosion resistance and the blackening of resistance to vulcanization.On the other hand, although comparative example b1~b10 Excellent corrosion resistance is all had, but resistance to vulcanization blackening is poor.It should be noted that just using Al2(SO4)3Confession as Al ions For the comparative example b9 and b10 in source, Al amounts and Al2O3Amount is significantly few, and resistance to vulcanization blackening is also " Not Good ".
More than, the suitable embodiment of the present invention is described in detail with reference to appended attached drawing, but the present invention is not It is defined in the example.As long as the people with the common knowledge in the technical field belonging to the present invention, then obviously weighing In the scope of technological thought described in sharp claim, it is contemplated that various modifications or fixed case, it is possible to understand that these are certainly Also belong to the technical scope of the present invention.
Industrial availability
According to an above-mentioned embodiment, even in the case that the adhesion amount for being capable of providing chemical conversion treatment skin membrane is few Also there is the chemical conversion treatment steel plate of excellent corrosion resistance and resistance to vulcanization blackening and the manufacturer of chemical conversion treatment steel plate Method.
Symbol description
10 chemical conversion treatment steel plates
103 steel plates
105 Ni coating
105d Fe-Ni-Sn alloy-layers
105e island Sn coating
106 composite deposites
107 chemical conversion treatment skin membranes

Claims (8)

1. a kind of chemical conversion treatment steel plate, which is characterized in that it has：
Steel plate；
It is formed at least one surface of the steel plate and the coating containing Ni；With
The chemical conversion treatment skin membrane being formed on the coating, the chemical conversion treatment skin membrane contain with metal Zr amounts It is calculated as 1.0~150mg/m2Zr compounds, 1.0~100mg/m is calculated as with P amounts2Phosphate cpd and be calculated as with metal Al amounts 0.10~30.0mg/m2Al compounds；
The coating is：
Including being calculated as 5.0~3000mg/m with W metal amount2Ni Ni coating or
Including being calculated as 2.0~200mg/m with W metal amount2Ni and 0.10~10.0g/m is calculated as with metal Sn amounts2Sn and The composite deposite of island Sn coating is formed on Fe-Ni-Sn alloy-layers.
2. chemical conversion treatment steel plate according to claim 1, which is characterized in that
The chemical conversion treatment skin membrane contains is calculated as 0.10~30.0mg/m with metal Al amounts2Al2O3。
3. chemical conversion treatment steel plate according to claim 1 or 2, which is characterized in that the chemical conversion treatment epithelium Layer contains：
It is calculated as 1.0~120mg/m with metal Zr amounts2Zr compounds；
It is calculated as 2.0~70.0mg/m with P amounts2Phosphate cpd；With
It is calculated as 0.20~20.0mg/m with metal Al amounts2Al compounds.
4. chemical conversion treatment steel plate described in any one of claim 1 to 3, which is characterized in that
The Ni coating contains is calculated as 10.0~2000mg/m with W metal amount2Ni.
5. chemical conversion treatment steel plate described in any one of claim 1 to 3, which is characterized in that the composite deposite Contain：
It is calculated as 5.0~100mg/m with W metal amount2Ni；With
It is calculated as 0.30~7.0g/m with metal Sn amounts2Sn.
6. chemical conversion treatment steel plate according to any one of claims 1 to 5, which is characterized in that
The surface of the chemical conversion treatment skin membrane is not coating with film or coating.
7. a kind of manufacturing method of chemical conversion treatment steel plate, which is characterized in that with the following process：
It includes to be calculated as 5.0~3000mg/m with W metal amount to be formed on the surface of steel plate2Ni Ni coating or comprising with metal Ni amounts are calculated as 2.0~200mg/m2Ni and 0.10~10.0g/m is calculated as with metal Sn amounts2Sn and in Fe-Ni-Sn alloy-layers On be formed with island Sn coating composite deposite plating process；With
It it is 5 DEG C less than 90 DEG C of chemical conversion treatment solution by using temperature, in 1.0~100A/dm2Current density And electrolysis processing is carried out under conditions of 0.20~150 second electrolytic processing time, in the Ni coating or the Composite Coatings The electrolysis treatment process of chemical conversion treatment skin membrane is formed on layer, the chemical conversion treatment solution includes 10~20000ppm's Zr ions, the F ion of 10~20000ppm, 10~3000ppm phosphate anion, add up to the nitric acid of 100~30000ppm The supply source of the Al ions of radical ion and sulfate ion and 500~5000ppm, the Al ions is (NH4)3AlF6。
8. the manufacturing method of chemical conversion treatment steel plate according to claim 7, which is characterized in that at the chemical conversion Reason liquid contains：
The Zr ions of 200~17000ppm；
The F ion of 200~17000ppm；
The phosphate anion of 100~2000ppm；
Add up to the nitrate ion and sulfate ion of 1000~23000ppm；With
The Al ions of 500~3000ppm.
CN201680083802.0A 2016-03-22 2016-03-22 The manufacturing method of chemical conversion treatment steel plate and chemical conversion treatment steel plate Pending CN108779570A (en)

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