CN102308026B - Method for producing tin-plated steel sheet - Google Patents

Method for producing tin-plated steel sheet Download PDF

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Publication number
CN102308026B
CN102308026B CN201080006593.2A CN201080006593A CN102308026B CN 102308026 B CN102308026 B CN 102308026B CN 201080006593 A CN201080006593 A CN 201080006593A CN 102308026 B CN102308026 B CN 102308026B
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tin
carry out
current density
sodium dichromate
plated
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CN102308026A (en
Inventor
西田浩
平野茂
长谷川和成
太田正之
横矢博一
高宫利明
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Nippon Steel Corp
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Nippon Steel Corp
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Priority claimed from JP2009056962A external-priority patent/JP5187239B2/en
Priority claimed from JP2009058804A external-priority patent/JP4660598B2/en
Priority claimed from JP2010011939A external-priority patent/JP4660626B2/en
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority claimed from PCT/JP2010/051629 external-priority patent/WO2010090267A1/en
Publication of CN102308026A publication Critical patent/CN102308026A/en
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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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C25D11/38—Chromatising
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

A tin-plated steel sheet consists of a steel sheet (1); a tin plating film (3) formed on one surface of the steel sheet (1) at 1.2 g/m2 or greater; a tin-iron alloy film (2) formed between the steel sheet (1) and the tin plating film (3) by alloying the steel sheet (1) and the tin plating film (3); and a chromate film (4) formed on the tin plating film (3) at between 3 mg/m2 and 8 mg/m2 in terms of metallic chromium. At the surface of the tin plating film (3), the ratio of bivalent tin atoms to the total amount of tin atoms is 35% or greater but less than 75%; the ratio of tetravalent tin atoms to the total amount of tin atoms is less than 50%; and the ratio of nonvalent tin atoms to the total amount of tin atoms is 30% or less.

Description

The manufacture method of tin plate
Technical field
The present invention relates to the tin plate and manufacture method thereof that are suitable for food cans etc.
Background technology
Tin plate is widely used as metal tin starting material.The content of tank is various.When content is fruit, tank internal surface is used in the mode without application sometimes, but, when content is other materials, generally form the films such as resin coating at tank internal surface.In addition, after the Contents Fill except the acidic foods such as soda pop, nectar and fruit is in tank, in most cases, at the temperature more than 100 DEG C, heat-sterilization process is carried out.Therefore, for tin plate, require the adaptation of the film under high temperature moist environment.This heat-sterilization process processes sometimes referred to as boiling (retort) in Japan.Below, sometimes film is called boiling film adaptation relative to the adaptation of the steel plate after heat-sterilization process.
On the other hand, according to the difference of content, the mechanism that boiling film adaptation is reduced is different.Also consider the composition etc. changing tin plate corresponding to various content, but management etc. become numerous and diverse at that rate.Therefore, preferably good boiling film adaptation is guaranteed for most content.
Propose various technology in patent documentation 1 ~ 6, but any one technology all cannot obtain sufficient boiling film adaptation.
In addition, tin plate uses boats and ships to be transferred in high-temperature area sometimes, or is preserved for a long time in warehouse etc.Therefore, sometimes there is rheological parameters' change with time in tin plate, and along with rheological parameters' change with time, boiling film adaptation reduces sometimes.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 7-11483 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 54-142135 publication
Patent documentation 3: Japanese Laid-Open Patent Publication 56-127776 publication
Patent documentation 4: Japanese Unexamined Patent Publication 5-302196 publication
Patent documentation 5: Japanese Laid-Open Patent Publication 57-123998 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2002-356785 publication
Patent documentation 7: Japanese Laid-Open Patent Publication 61-104099 publication
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide not by the species influence of content, the tin plate that can obtain good boiling film adaptation and manufacture method thereof.
For solving the means of problem
The present application person conducts in-depth research repeatedly in order to solve above-mentioned problem, and result contemplates the various modes of invention shown below.
The feature of the tin plate that the 1st viewpoint of the present invention relates to is, it has steel plate, on a surface of above-mentioned steel plate with 1.2g/m 2the tin-plated coating film more than formed, by above-mentioned steel plate and the alloying of above-mentioned tin-plated coating film and the alloy film of the tin formed between above-mentioned steel plate and above-mentioned tin-plated coating film and iron and converting with chromium metal of being formed on above-mentioned tin-plated coating film count 3mg/m 2above and 8mg/m 2following chromic salt epithelium, on the surface of above-mentioned tin-plated coating film, divalent tin atom is more than 35% relative to the ratio of the total amount of tin atom and lower than 75%, and 4 valency tin atoms are relative to the ratio of the total amount of tin atom lower than 50%, and 0 valency tin atom is less than 30% relative to the ratio of the total amount of tin atom.
The feature of the manufacture method of the tin plate that the 2nd viewpoint of the present invention relates to is, it has following operation: on a surface of steel plate, form 1.2g/m 2the operation of above tin-plated coating film, to be made above-mentioned tin-plated coating film and above-mentioned steel plate alloying by mild melt treatment and form the operation of alloy film and on above-mentioned tin-plated coating film, form the operation of chromic salt epithelium, the time of tin-plated coating film melting above-mentioned in above-mentioned mild melt treatment is set to more than 0.1 second and less than 0.7 second, and the operation of above-mentioned formation chromic salt epithelium has following operation: above-mentioned steel plate is flooded more than 0.5 second in the mode of non-electrolytic in sodium dichromate aqueous solutio and the operation of less than 4.0 seconds and then to above-mentioned steel plate in sodium dichromate aqueous solutio with 0.8C/dm 2above and 6.5C/dm 2following turn on angle implements the operation utilizing the chemical conversion treatment of catholyte (also referred to as " chemical tunicle generating process ").
The feature of the manufacture method of the tin plate that the 3rd viewpoint of the present invention relates to is, it has following operation: on a surface of steel plate, form 1.2g/m 2the operation of above tin-plated coating film, to be made above-mentioned tin-plated coating film and above-mentioned steel plate alloying by mild melt treatment and form the operation of alloy film and formed to convert with chromium metal on above-mentioned tin-plated coating film and count 3mg/m 2above and 8mg/m 2the operation of following chromic salt epithelium.
Invention effect
According to the present invention, owing to suitably defining the ratio etc. of the tin atom of the various valence states on tin-plated coating film surface, good boiling film adaptation can be obtained.
Accompanying drawing explanation
Fig. 1 is the sectional view representing the tin plate that embodiments of the present invention relate to.
Embodiment
Below, for embodiments of the present invention, be specifically described with reference to the accompanying drawing added.Fig. 1 is the sectional view representing the tin plate that embodiments of the present invention relate to.
In tin plate of the present embodiment, be formed with the alloy film 2 of tin and iron on the surface at least one of steel plate 1.In addition, alloy film 2 is formed with tin-plated coating film 3, tin-plated coating film 3 is formed chromic salt epithelium 4.The area occupation ratio of chromic salt epithelium 4 is such as 60% ~ 80%, but is not limited to this.
The tin plate of formation like this such as forms film on chromic salt epithelium 4, is used as the tank body being internal surface with this face.In addition, sometimes after filling content, carry out heat-sterilization process, boiling film adaptation comes into one's own.Although content relates to multiple, as the material of representational saprophagy contained in these contents, acetic acid, lactic acid, citric acid, halfcystine etc. can be enumerated.Therefore, guarantee that the boiling film adaptation under the existence of these saprophagy materials is important.
Then, to for guaranteeing that the various conditions of such boiling film adaptation are described.
In the present embodiment, the total amount of contained in alloy film 2 and tin-plated coating film 3 tin is 1.2g/m 2above.In addition, the adhesion amount of chromic salt epithelium 4 converts with chromium metal and counts 3mg/m 2~ 8mg/m 2.And then on the surface of tin-plated coating film 3, divalent Sn atom is more than 35% relative to the ratio of the total amount of Sn atom and lower than 75%, 4 valency Sn atoms are relative to the ratio of the total amount of Sn atom lower than 50%, and 0 valency Sn atom (metal Sn) is less than 30% relative to the ratio of the total amount of Sn atom.
If the total amount of tin contained in alloy film 2 and tin-plated coating film 3 is lower than 1.2g/m 2, then steel plate 1 exposes from alloy film 2 and tin-plated coating film 3 sometimes.Iron as the main material of steel plate 1 is easily dissolved in acetic acid, and therefore, when content comprises acetic acid or citric acid, boiling film adaptation easily reduces.Therefore, the total amount of tin contained in alloy film 2 and tin-plated coating film 3 is set to 1.2g/m 2above.In addition, the total amount of tin is preferably 1.5g/m 2above.If this is because the total amount of tin is 1.5g/m 2above, then the erosion resistance after application is stablized.On the other hand, the total amount of tin is preferably 6.0g/m 2below.If this is because the total amount of tin is more than 6.0g/m 2although then available good erosion resistance, this effect is saturated a little, and cost efficiency reduces.
If the adhesion amount of chromic salt epithelium 4 converts lower than 3mg/m in chromium metal 2, then the boiling film adaptation when content comprises halfcystine becomes insufficient.Infer this is because the tin-plated coating film 3 exposed from chromic salt epithelium 4 reacts with halfcystine.On the other hand, if the adhesion amount of chromic salt epithelium 4 converts more than 8mg/m in chromium metal 2, then the boiling film adaptation when content comprises acetic acid becomes insufficient.Think this is because a part for chromic salt epithelium 4 is dissolved in acetic acid.Therefore, the adhesion amount of chromic salt epithelium 4 converts in chromium metal and is set to 3mg/m 2above and 8mg/m 2below.
In addition, in the surface of tin-plated coating film 3, divalent Sn atom is more than 35% relative to the ratio of the total amount of Sn atom and is less than 30% lower than 50%, 0 valency Sn atom (metal Sn) relative to the ratio of the total amount of Sn atom relative to the ratio of the total amount of Sn atom lower than 75%, 4 valency Sn atoms is important.
Details describes later, but in the manufacturing processed of tin plate, in the mild melt treatment after zinc-plated, Sn is melted, and mainly when this process, Sn is oxidized.The more stable oxide compound of tin is SnO and SnO 2, correspond respectively to 4 valencys of the divalent of Sn, Sn.The present inventors have carried out various research, find, by the balance of 0 valency of Sn, divalent and 4 valencys is set to suitable value, can obtain good boiling film adaptation.
The present inventors find, if the ratio of SnO is more than 75%, then the boiling film adaptation when content comprises acetic acid significantly reduces.Think that this reason is because SnO is soluble in acetic acid.Therefore, divalent Sn atom is set to lower than 75% relative to the ratio of the total amount of Sn atom.In addition, the ratio of preferred divalent Sn atom is lower than 65%.
In addition, the present inventors find, if SnO 2ratio be more than 50%, then easily produce stain.If generation stain, then, in coating process, printing process and/or can welding process etc., roller and fixture easily generate pollution.Therefore, 4 valency Sn atoms are set to lower than 50% relative to the ratio of the total amount of Sn atom.
Like this, if SnO excessively exists, then have problems in boiling film adaptation, if SnO 2excessively exist, then produce the problem relevant to stain.
0 valency Sn atom itself is not the material making boiling film adaptation reduce or easily make stain produce.But a part for 0 valency Sn atom is sometimes oxidized by chemical conversion treatment during formation chromic salt epithelium 4, long-term preservation or thermal treatment.That is, in the situation of being preserved for a long time by tin plate etc., 0 valency Sn atom becomes 4 valency Sn atoms sometimes, and 4 valency Sn atoms increase.In addition, sintering when film is formed generally carries out at the temperature more than 100 DEG C, and therefore, now, 0 valency Sn atomic change is divalent Sn atom sometimes, and divalent Sn atom increases.Further, the present inventors find, if the ratio of 0 valency Sn atom is more than 30%, then easily produce the impact brought by such oxidation.Therefore, 0 valency Sn atom is set to lower than 30% relative to the ratio of the total amount of Sn atom.In addition, preferably the ratio of 0 valency Sn atom lower than 10%.
And then owing to considering 0 valency Sn atom, and be set to lower than 50% by 4 valency Sn atoms relative to the ratio of the total amount of Sn atom, therefore, the ratio of divalent Sn atom is set to more than 35%.In addition, the ratio of 4 valency Sn atoms is preferably more than 40%.
Here, the example of method for the ratio obtaining 0 valency on tin-plated coating film 3 surface, divalent and 4 valency Sn atoms is described.
First, the spectrum of the 3d5/2 of Sn is measured by x-ray photoelectron spectroscopy analysis (XPS).More specifically, as the x-ray source in XPS, use AlK α (1486.6eV), output rating is set to 15kV, 25W, the diameter measuring region is set to 100 μm, the vacuum tightness of analyzer room is set to 1.5 × 10 -7pa, takes out angle and is set to 90 ° by electronics, measure the spectrum of the 3d5/2 of Sn.
Then, for the spectrum measured, waveform separation (peak separation) is carried out by following 3 conditions.
(1) the bond energy value of 0 valency Sn atom is set to 484.7eV ~ 484.8eV.
(2) the bond energy difference between the bond energy value of divalent Sn atom and the bond energy value of 4 valency Sn atoms is set to about 0.7eV.
(3) as half-width (FWHM), the measured value of standard test specimen is used.
Then, the various area ratio obtained by such waveform separation (peak separation) are set to the ratio of 0 valency on the surface of tin-plated coating film 3, divalent and 4 valency Sn atoms.
In addition, in the present embodiment, the amount of having carried out the tin of alloying by mild melt treatment and the iron contained by steel plate 1 in the tin of amount, the i.e. plating of contained in alloy film 2 tin is preferably 0.1g/m 2~ 0.56g/m 2.
The amount of the tin of alloying has been carried out lower than 0.1g/m with iron 2time, in the formation of alloy film 2, produce deviation, the outward appearance sometimes after soft heat becomes uneven.On the other hand, if carried out the amount of the tin of alloying more than 0.56g/m with iron 2, then the boiling film adaptation sometimes when content comprises acetic acid etc. becomes insufficient a little.Therefore, the amount of contained in preferred alloy film 2 tin is 0.1g/m 2~ 0.56g/m 2.
In addition, the amount of contained in alloy film 2 tin such as can be measured by the electrolytic stripping method recorded in JIS G3303 2002.In the method, 1 equivalent hydrochloric acid of normal temperature is used as electrolytic solution, using test film as anode (area: 2500mm 2), using carbon-point as negative electrode, the constant current of circulation 250mA carries out electrolysis.Then, while electrolysis starts, start the current potential of the test film that mensuration is benchmark with silvery reference electrode, then, this current potential of METHOD FOR CONTINUOUS DETERMINATION.After mensuration current potential, make the time changing curve of current potential, with point of inflexion on a curve be benchmark go out the tin of non-alloying, alloying tin separately required for electricity, be converted into the tin amount of having carried out alloying with iron.
And then in the present embodiment, the area occupation ratio of preferred chromium hydrochlorate epithelium 4 is 60% ~ 80%.Here, " area occupation ratio " of chromic salt epithelium 4 refers to, the surface-area of chromic salt epithelium 4 is relative to the ratio of the surface-area entirety of tin-plated coating film 3.That is, preferred chromium hydrochlorate epithelium 4 by the surface of tin-plated coating film 3 with 60% ~ 80% area occupation ratio cover.If this area occupation ratio is lower than 60%, then the boiling film adaptation sometimes when content comprises halfcystine etc. significantly reduces.On the other hand, if this area occupation ratio is more than 80%, then sometimes when content comprises acetic acid etc. through time before boiling film adaptation become insufficient.Therefore, the area occupation ratio of preferred chromium hydrochlorate epithelium 4 is 60% ~ 80%.
The area occupation ratio of chromic salt epithelium 4 such as can pass through EPMA (electron microprobe analysis method) and measure.Such as by beam diameter is set to 10 μm, surface analysis is carried out to the intensity of chromium in 100 positions on arbitrary 1st direction on the surface of tin plate and 50 positions on the 2nd direction vertical with the 1st direction, measures the area occupation ratio of chromic salt epithelium 4 thus.From such a viewpoint, the area occupation ratio of preferred chromium hydrochlorate epithelium 4 is at 0.5mm 2face in measure.As the device of EPMA, use commercially available analytical equipment.
Then, the example of the method manufacturing tin plate as described above is described.
First, making, plater mother board (steel plate).Composition and the making method of plater mother board are not particularly limited.As long as such as manufacture steel billet by usual method, hot rolling, pickling, cold rolling, annealing, skin-pass etc. are implemented to this steel billet.
Then, plater mother board is implemented as the degreasing of zinc-plated pre-treatment and pickling.Degreasing is used for the rolling wet goods oil component removing on the surface by remaining in plater mother board and implements, and pickling is used for the removing of the oxide film on the surface of plater mother board and implements.If degreasing or pickling insufficient, then at remained on surface oil component or the oxide film of plater mother board.The electroconductibility of oil component and oxide film is low, if therefore they remain, then suitably cannot implement plating, or produces dendrite, or the adaptation of plated film reduces.Therefore, preferably sufficient degreasing and pickling is carried out.
As degreasing, preferably be implemented in the alkaline electrolysis degreasing in common caustic soda, water glass or sodium phosphate etc. and the alkaline electrolysis degreasing in their mixed solution.
As pickling, the catholyte process preferably in common dilute sulphuric acid or dilute hydrochloric acid or dip treating.
Then, eleetrotinplate is implemented to plater mother board.As plating bath, such as, can use zinc-plated bath, Phenylsulfonic acid bath, sulfuric acid bath, methylsulfonic acid bath, halogen bath and alkaline bath etc.In addition, in zinc-plated, due to tin ion reduction electrolysis, the valence state of the Sn therefore existed on plater mother board is 0 valency.
Now, zinc-plated adhesion amount is set to 1.2g/m at least one face of plater mother board 2above.If this is because zinc-plated adhesion amount is lower than 1.2g/m 2, then plater mother board exposes from the coating by zinc-plated formation.Iron as the main material of plater mother board is soluble in acetic acid, and therefore when content comprises acetic acid system solution, boiling film adaptation easily reduces.In addition, preferably zinc-plated adhesion amount is 1.5g/m 2above.If this is because zinc-plated adhesion amount is 1.5g/m 2above, then the erosion resistance after application is stablized.On the other hand, preferably zinc-plated adhesion amount is 6.0g/m 2below.If this is because zinc-plated adhesion amount is more than 6.0g/m 2although then can obtain good erosion resistance, this effect is saturated a little, cost efficiency reduces.
Zinc-plated rear enforcement mild melt treatment, by a part of alloying of a part for coating and plater mother board, forms the alloy film 2 of tin and iron.Then, the remainder of coating is equivalent to the tin-plated coating film 3 in Fig. 1, and the remainder of plater mother board (steel plate) is equivalent to the steel plate 1 in Fig. 1.
In mild melt treatment, such as, after the coating melting making tin, use warm water quenching.If by temporary transient for tin melting, then the easy alloying of the iron of tin and substrate, forms very uniform alloy film 2.Therefore, there is the alloy film 2 of excellent corrosion resistance in steel plate 1 side of tin-plated coating film 3, even if therefore existing defects in tin-plated coating film 3, also can obtain higher erosion resistance.In addition, at the Surface Creation stannic oxide of coating.This stannic oxide is SnO and SnO 2these 2 kinds.When the temperature of mild melt treatment is below 100 DEG C, SnO 2become principal product, from 100 DEG C, to the fusing point of Sn that is 232 DEG C, SnO becomes principal product, the SnO when exceeding fusing point 2become principal product.Therefore, by suitably controlling the transition of the temperature in mild melt treatment, can easily control SnO and SnO 2ratio.In addition, by suitably controlling the time of mild melt treatment, the growing amount of energy controlled oxidization tin.In addition, the heating means in mild melt treatment are not particularly limited, from temperature controlled aspect, preferably by electrified regulation, induction heating or electrified regulation and induction heating and be used for carrying out.
In addition, the coating of the tin before mild melt treatment is microgranular under the microscope, and sticking power is more weak, matt, but presents gloss by mild melt treatment.
Here, the condition for mild melt treatment is described.In the present embodiment, will in mild melt treatment, the time of coating melting be made to be set to 0.1 second ~ 0.7 second.If make the time of coating melting lower than 0.1 second, then sometimes the width being formed in plater mother board of alloy film 2 and/or length direction become uneven, and sometimes cannot obtain glossiness outward appearance equably.On the other hand, if make the time of coating melting more than 0.7 second, then stannic oxide, particularly SnO increase, and the boiling film adaptation when content comprises acetic acid system solution significantly reduces.Therefore, will in mild melt treatment, the time of coating melting be made to be set to 0.1 second ~ 0.7 second.
In addition, mild melt treatment is preferably 0g/m at water vapor concentration 3~ 40g/m 3atmosphere in carry out.If this is because water vapor concentration is more than 40g/m 3, then the ratio that SnO is shared in the stannic oxide of the Surface Creation of coating becomes too high.
After mild melt treatment, carry out chromic salt process, form chromic salt epithelium 4.In the present embodiment, as chromic salt process, implement the chemical conversion treatment employing 2 stages of sodium dichromate solution.That is, carry out non-electrolytic dip treating, then, carry out catholyte process.
Dipping time in non-electrolytic dip treating (the 1st stage of chemical conversion treatment) is set to more than 0.5 second and less than 4.0 seconds.If the dipping time of non-electrolytic was lower than 0.5 second in sodium dichromate aqueous solutio, then the boiling film adaptation when content is acetic acid system solution significantly reduces.This reason is indefinite, but deduction is because dipping time is too short, and SnO becomes insufficient to the dissolving in sodium dichromate aqueous solutio.On the other hand, if the dipping time of non-electrolytic was more than 4.0 seconds in sodium dichromate aqueous solutio, then productivity reduces.That is, production rate significantly reduces, or needs to be used for the equipment enlarging of this process.In the latter case, high facility investment is needed.Therefore, the dipping time in non-electrolytic dip treating is set as more than 0.5 second and less than 4.0 seconds.In addition, this dipping time is preferably more than 0.7 second, is preferably less than 2.0 seconds.
The turn on angle of the catholyte in sodium dichromate aqueous solutio in catholyte process (the 2nd stage of chemical conversion treatment) is set to 0.8C/dm 2above and 6.5C/dm 2below.In addition, turn on angle (C/dm 2) with " current density (A/dm 2) × conduction time (second) " relational expression illustrate.If the turn on angle of catholyte is lower than 0.8C/dm 2, sometimes because of through time and be called as the variable color of xanthochromia.On the other hand, if the turn on angle of catholyte is more than 6.5C/dm 2, then the effect of chromic salt epithelium 4 is saturated, and along with the excessive formation of chromic salt epithelium 4, saprophage focuses on a bit, likely causes the perforation saprophage of tank body.Therefore, the turn on angle of the catholyte in sodium dichromate aqueous solutio in catholyte process is set to 0.8C/dm 2above and 6.5C/dm 2below.In addition, this turn on angle is preferably 4.0C/dm 2below.
In addition, the cathode current density in catholyte process (the 2nd stage of chemical conversion treatment) is preferably 0.1A/dm 2~ 10.0A/dm 2.What the impact of current density significantly occurred is through time after.Tin plate uses boats and ships region conveying under the line sometimes, or waits long-term preservation in warehouse.Therefore, also consider because of through time and boiling film adaptation is changed.If cathode current density is lower than 0.1A/dm 2, be then coated be contained in through time after carry out when, there is the tendency that boiling film adaptation when content is acetic acid system solution reduces a little.Infer this is because chromic salt epithelium 4 becomes uneven, because of through time and the SnO on tin plate surface is grown up.In addition, if cathode current density is more than 10A/dm 2although then chromic salt epithelium 4 is formed uniformly, be coated be contained in through time after carry out time, have the tendency that the boiling film adaptation when content is acetic acid system solution reduces a little.In addition, this cathode current density is preferably 0.2A/dm 2above, 5.0A/dm is preferably 2below.
In addition, in order to the area occupation ratio of chromic salt epithelium 4 is set to 60% ~ 80%, the adjustment of current density is effective.If carry out electrolysis treatment with high current density, then focus on core happening part and separate out, coating area occupation ratio reduces.On the other hand, if carry out electrolysis treatment with low current density, then separate out more equably.
Therefore, in order to ensure high productivity, and by chromic salt epithelium 4 with 60% ~ 80% area occupation ratio dispersion and formed, preferably carry out combined electrolysis.Such as, preferably with 2.0A/dm 2~ 10.0A/dm 2current density carry out the electrolysis of 0.001 second ~ 0.2 second, then with 0.1A/dm 2~ 5.0A/dm 2current density implement the electrolysis of 0.01 second ~ 2.0 seconds.
And then, from workability and equipment aspect, preferably the bath temperature of chemical conversion treatment is set to 40 DEG C ~ 55 DEG C.Sodium dichromate aqueous solutio as chemical conversion treatment solution carries out impedance heating when electrolysis, and the temperature of sodium dichromate aqueous solutio rises.Therefore, particularly in summer in order to bath temperature control is made lower than 40 DEG C, sometimes need refrigerating unit.On the other hand, if bath temperature is more than 55 DEG C, then moisture increases from the steam output bath, and the concentration of sodium dichromate aqueous solutio easily changes.In addition, along with the evaporation of moisture, the saprophagy of bath increases, and therefore as electrolyzer and tank, sometimes must use the material of high corrosion resistance.Therefore, the bath temperature of chemical conversion treatment is preferably 40 DEG C ~ 55 DEG C.
In addition, from workability and equipment aspect, the concentration of sodium dichromate aqueous solutio is preferably set to 20g/L ~ 30g/L.
According to such method, in mild melt treatment, make the time of tin melting and the condition of chemical conversion treatment due to suitably defining, therefore no matter through time presence or absence, the tin plate that boiling film adaptation is good can be obtained.
In addition, after mild melt treatment, as the pre-treatment of chemical conversion treatment, also the stannic oxide generated in mild melt treatment can be immersed in acidic liquid and dissolve removing.If to SnO and SnO 2compare, then from the aspect of stability, SnO is soluble, by controlling the concentration of acidic liquid, temperature and dipping time, and can the residual quantity of controlled oxidization tin.In addition, by not containing to the catholyte process in the electrolytic solution of the material of electrolysis on tin at sodium bicarbonate aqueous solution etc., can by stannic oxide reduction removing.
But as these processes, owing to using the solution of the composition different from chemical conversion treatment solution to carry out pre-treatment, therefore, the washing of pretreatment solution becomes required.That is, the equipment of the equipment of pre-treatment and the washing of pretreatment solution becomes required, needs a large amount of facility investments.To this, according to above-mentioned embodiment, such equipment becomes and does not need.
Then, the actual various experiments carried out of the present application person are described.
(the 1st experiment)
In the 1st experiment, be that the aqueous sodium hydroxide solution of the cold-rolled steel sheet 10 quality % of 0.20mm carries out electrolytic degreasing by thickness, then wash.Then, in the aqueous hydrochloric acid of 10 quality %, carry out dip pickling, and wash.Then, as described below, carry out zinc-plated and chemical conversion treatment etc. under various conditions.
[embodiment No.1-1]
In embodiment No.1-1, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, flood 0.6 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is set to 3.7A/dm 2, the current density in the 2nd stage is set to 1.1A/dm 2.In addition, total turn on angle is set to 0.88C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 3mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 19%, divalent be 40%, 4 valencys is 41%.In addition, the area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-2]
In embodiment No.1-2, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, in the sodium bicarbonate aqueous solution of 20g/L, current density is set to 1A/dm 2, carried out the catholyte process of 0.15 second, and washed.Then, 50 DEG C, flood 3.0 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 6.2C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 7mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 22%, divalent be 40%, 4 valencys is 38%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-3]
In embodiment No.1-3, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 2.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, current density is set to 3A/dm 2and carry out catholyte process.Turn on angle is set to 1.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 7mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 4%, divalent be 65%, 4 valencys is 31%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-4]
In embodiment No.1-4, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 10g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The tin having been carried out alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 0.8 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 1.9C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 35%, 4 valencys is 45%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-5]
In embodiment No.1-5, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 30g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 0.6 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 15%, divalent be 70%, 4 valencys is 15%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-6]
In embodiment No.1-6, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, in the sodium bicarbonate aqueous solution of 20g/L, current density is set to 1A/dm 2, carry out the catholyte process of 0.8 second, and wash.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 3.2A/dm 2, the current density in the 2nd stage is set to 1.5A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 27%, divalent be 37%, 4 valencys is 36%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-7]
In embodiment No.1-7, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.3 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.3g/m 2.Then, 50 DEG C, in the sodium bicarbonate aqueous solution of 20g/L, current density is set to 1A/dm 2, carry out the catholyte process of 1 second, wash.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 3.2A/dm 2, the current density in the 2nd stage is set to 1.5A/dm 2.In addition, total turn on angle is set to 1.7C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 29%, divalent be 40%, 4 valencys is 31%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-8]
In embodiment No.1-8, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.3 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.3g/m 2.Then, 50 DEG C, in the sodium bicarbonate aqueous solution of 20g/L, current density is set to 1A/dm 2, carry out the catholyte process of 1 second, and wash.Then, 53 DEG C, flood 0.1 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 2.2A/dm 2, the current density in the 2nd stage is set to 1.5A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 27%, divalent be 48%, 4 valencys is 25%.The coating area occupation ratio of chromic salt epithelium is 65%.
[embodiment No.1-9]
In embodiment No.1-9, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.1 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.08g/m 2.Then, 53 DEG C, flood 0.5 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-10]
In embodiment No.1-10, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, first, the water vapor concentration by means of only inside is 25g/m 3electric heating device be warming up to 100 DEG C with 2.4 seconds, then, and with induction heating carry out 3.2 seconds heating, by tin melting 0.7 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.7g/m 2.Then, 53 DEG C, flood 2.2 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-11]
In embodiment No.1-11, in Phenylsulfonic acid bath, implement 1.4g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-12]
In embodiment No.1-12, in Phenylsulfonic acid bath, implement 1.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-13]
In embodiment No.1-13, in Phenylsulfonic acid bath, implement 5.6g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the tin of effects on surface composition has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-14]
In embodiment No.1-14, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 9A/dm 2and carry out catholyte process.Turn on angle is set to 1.7C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 50%.
[embodiment No.1-15]
In embodiment No.1-15, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 2.0A/dm 2and carry out catholyte process.Turn on angle is set to 1.8C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 6mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 90%.
[embodiment No.1-16]
In embodiment No.1-16, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.2 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.2g/m 2.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 1.5C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-17]
In embodiment No.1-17, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.5 second, quenching in the warm water of 80 DEG C.The tin having been carried out alloying by this process with iron is 0.5g/m 2.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 1.5C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-18]
In embodiment No.1-18, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is set to 3.0A/dm 2, the current density in the 2nd stage is set to 2.0A/dm 2.In addition, total turn on angle is set to 1.9C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 62%.
[embodiment No.1-19]
In embodiment No.1-19, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, flood 3.0 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 2.3A/dm 2.In addition, total turn on angle is set to 1.5C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 78%.
[embodiment No.1-20]
In embodiment No.1-20, in methylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, in the sodium bicarbonate aqueous solution of 20g/L, current density is set to 1A/dm 2, carry out the catholyte process of 0.9 second, and wash.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is set to 4.8A/dm 2, the current density in the 2nd stage is set to 1.9A/dm 2.In addition, total turn on angle is set to 1.5C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 30%, divalent be 38%, 4 valencys is 32%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-21]
In comparative example No.1-21, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 2.1A/dm 2, the current density in the 2nd stage is set to 0.5A/dm 2.In addition, total turn on angle is set to 0.5C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 2mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 19%, divalent be 39%, 4 valencys is 42%.The area occupation ratio of chromic salt epithelium is 62%.
[comparative example No.1-22]
In comparative example No.1-22, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 4.9A/dm 2, the current density in the 2nd stage is set to 2.5A/dm 2.In addition, total turn on angle is set to 9.5C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 10mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 19%, divalent be 42%, 4 valencys is 39%.The area occupation ratio of chromic salt epithelium is 78%.
[comparative example No.1-23]
In comparative example No.1-23, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 45g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, carry out the catholyte process in 2 stages.In this catholyte process, the current density in the 1st stage is set to 2.1A/dm 2, the current density in the 2nd stage is set to 0.5A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of chromic salt epithelium converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 10%, divalent be 78%, 4 valencys is 12%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-24]
In comparative example No.1-24, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, 50 DEG C, in the sodium bicarbonate aqueous solution of 20g/L, current density is set to 7A/dm 2, carry out the catholyte process of 1 second, and wash.Then, the catholyte process in 2 stages is being carried out.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 2.1A/dm 2, the current density in the 2nd stage is set to 0.5A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 35%, divalent be 40%, 4 valencys is 25%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-25]
In comparative example No.1-25, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, at 50 DEG C, dipping 1.8 seconds after washing in 5 quality % aqueous hydrochloric acids, dry at 220 DEG C.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 2.1A/dm 2, the current density in the 2nd stage is set to 0.5A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 8%, divalent be 40%, 4 valencys is 52%.The generation of the stain of this tin plate is very serious.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-26]
In comparative example No.1-26, in Phenylsulfonic acid bath, implement 0.9g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 25g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, at 50 DEG C, dipping 2 seconds after washing in 5 quality % aqueous hydrochloric acids, dry at 220 DEG C.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 2.1A/dm 2, the current density in the 2nd stage is set to 0.5A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the tin of effects on surface composition has carried out investigating, 0 valency is 20%, divalent be 40%, 4 valencys is 40%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-27]
In comparative example No.1-27, in Phenylsulfonic acid bath, implement 2.8g/m 2zinc-plated.Then, mild melt treatment is carried out.In mild melt treatment, the water vapor concentration in inside is 15g/m 3electric heating device cathetus intensification heating 5.6 seconds, by tin melting 0.4 second, quenching in the warm water of 80 DEG C.The amount of having been carried out the tin of alloying by this process with iron is 0.4g/m 2.Then, at 50 DEG C, dipping 2 seconds washing in 5 quality % aqueous hydrochloric acids.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.In this catholyte process, 53 DEG C, in the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is set to 2.1A/dm 2, the current density in the 2nd stage is set to 0.5A/dm 2.In addition, total turn on angle is set to 2.1C/dm 2.The amount of the chromic salt epithelium formed converts with Metal Cr and counts 5mg/m 2.In addition, after the composition of the tin of effects on surface has carried out investigating, 0 valency is 28%, divalent be 32%, 4 valencys is 40%.The coating area occupation ratio of chromic salt epithelium is 70%.
Like this, the sample of 27 kinds of tin plates has been made.
Then, to each sample coating 8g/m 2epoxy-phenol resin paint, heat after 10 minutes at 204 DEG C, cool to room temperature, thus form film.And then at room temperature preserve after more than 8 hours, the cover that the mode becoming tank internal surface with application face makes diameter be 50mm is shaping.
Then, following 3 kinds of characteristics of shaping cover are evaluated.
[without time process boiling film adaptation]
Cover is immersed in 4 kinds of aqueous solution the heat treated of carrying out at 120 DEG C 90 minutes.This process is relative to the makers' heat-sterilization process of can.After heat treated, carry out at once washing and drying, then, cover engraves with the interval of 3mm the 100 pieces of tessellated indentations reaching cold-rolled steel sheet (substrate), carry out tape stripping, evaluated the adaptation of 10 grades by the revolution mark of film.In this evaluation, by the revolution mark of film be that the cover (do not occur peel off cover) of 100% is designated as 10 points, the revolution mark of film is more than 90% and lower than 100% be designated as 9 points.And then the scope of the revolution mark of film often departs from 10%, respectively mark is reduced by 1 point, the revolution mark of film is more than 0% and is designated as 0 point lower than the cover of 10%.Then, the cover of more than 9 points is designated as qualified.In addition, in the test in 4 kinds of aqueous solution, it is qualified to be designated as by the cover being all more than 7 points.
In addition, as the solute of 4 kinds of aqueous solution, use following (a) ~ (d) 4 kinds.
(a) 3 quality % acetic acid+2 quality %NaCl
(b) 1.1 quality % lactic acid
(c) 2 quality % citric acid+0.4 quality % xitix
(d) 0.056 quality % halfcystine HCl+0.4 quality %KH 2pO 4+ 0.81 quality %Na 2hPO 4
[through time process after boiling film adaptation]
During each making cover, before coating epoxy-phenol resin paint, be that under the condition of 90%RH, bale packing, in anti-tarnish paper, is so stored 7 days in humidity at 50 DEG C by the sample of tin plate.Then, make cover as described above, carry out with [without time the boiling film adaptation that processes] same evaluation, in the test in 4 kinds of aqueous solution, it is qualified to be designated as by the cover all reaching more than 7 points.
[evaluation of the composition of tin]
Use PHI Inc. Quantum2000 type XPS analysis device, undertaken analyzing and resolving by above-mentioned method.
These results are shown in table 1.
Table 1
As shown in table 1, in embodiment No.1-1 ~ No.1-20, the no matter kind of steeping fluid, through time boiling film adaptation before treatment and through time process after boiling film adaptation good.The amount of the tin of alloying has been carried out lower than 0.1g/m with iron 2embodiment No.1-9 in, it is uneven that the outward appearance after soft heat becomes part, but be enough to use as the tin plate of tank body.
On the other hand, in the comparative example No.1-21 that the amount of chromic salt epithelium is fewer than scope of the present invention, the boiling film adaptation in the steeping fluid (d) comprising halfcystine when dipping is low.This result teaching is when the amount of chromic salt epithelium is fewer than scope of the present invention, and the boiling film adaptation for the content comprising halfcystine is low.
In addition, in the comparative example No.1-25 that the ratio of the ratio of the amount of the chromic salt epithelium comparative example No.1-22 more than scope of the present invention, the divalent Sn atom comparative example No.1-23 higher than scope of the present invention and 4 valency Sn atoms is higher than scope of the present invention, the boiling film adaptation in the steeping fluid (a) comprising acetic acid when dipping is low.This result teaching is when the amount of chromic salt epithelium is more than scope of the present invention, when the ratio of divalent Sn atom is higher than scope of the present invention and when the ratio of 4 valency Sn atoms is higher than scope of the present invention, and the boiling film adaptation for the content comprising acetic acid is low.Particularly in comparative example No.1-25, the ratio of 4 valency Sn atoms is high, therefore, produces stain, becomes the steel plate that cannot be used as the tin plate of tank body.
In addition, in the comparative example No.1-24 that the ratio of 0 valency Sn atom is higher than scope of the present invention, through time boiling film adaptation before treatment good, but when in the steeping fluid (a) comprising acetic acid when dipping through time process after boiling film adaptation low.
In addition, in the comparative example No.1-26 that zinc-plated amount is fewer than scope of the present invention, the boiling film adaptation in the steeping fluid (a) comprising acetic acid when dipping, the boiling film adaptation in the steeping fluid (c) comprising citric acid when dipping and the boiling film adaptation in the steeping fluid (d) comprising halfcystine when dipping are low.This result teaching is when zinc-plated amount is fewer than scope of the present invention, and the boiling film adaptation for the content comprising acetic acid, citric acid or halfcystine is low.
In addition, in the comparative example No.1-27 that the ratio of divalent Sn atom is fewer than scope of the present invention, by rheological parameters' change with time, regardless of the kind of steeping fluid, boiling film adaptation is low.This result teaching when the ratio of divalent Sn atom is fewer than scope of the present invention, through time after boiling film adaptation low.
(the 2nd experiment)
In the 2nd experiment, be also that the aqueous sodium hydroxide solution of the cold-rolled steel sheet 10 quality % of 0.20mm carries out electrolytic degreasing by thickness, then wash.Then, in the aqueous hydrochloric acid of 10 quality %, carry out dip pickling, and wash.Then, as described below, carry out zinc-plated and chemical conversion treatment etc. under various conditions.
[embodiment No.2-1]
In embodiment No.2-1, in Phenylsulfonic acid bath, implement 1.7g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere under mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[embodiment No.2-2]
In embodiment No.2-2, in methylsulfonic acid bath, implement 12.4g/m 2zinc-plated.Then, the mild melt treatment same with embodiment No.2-1, the dip treating of non-electrolytic and catholyte process is carried out.
[embodiment No.2-3]
In embodiment No.2-3, in Phenylsulfonic acid bath, implement 2.1g/m 2zinc-plated.Then, the mild melt treatment same with embodiment No.2-1, the dip treating of non-electrolytic and catholyte process is carried out.
[embodiment No.2-4]
In embodiment No.2-4, in Phenylsulfonic acid bath, implement 3.8g/m 2zinc-plated.Then, the mild melt treatment same with embodiment No.2-1, the dip treating of non-electrolytic and catholyte process is carried out.
[embodiment No.2-5]
In embodiment No.2-5, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.12 second.Then, 50 DEG C, flood 1.0 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.04 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 2.2A/dm 2carry out the catholyte process in the 2nd stage of 0.40 second.In addition, total turn on angle is set to 1.03C/dm 2.
[embodiment No.2-6]
In embodiment No.2-6, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 35g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.68 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in 0.10 second the 1st stage, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 1.00 seconds.In addition, total turn on angle is set to 2.17C/dm 2.
[embodiment No.2-7]
In embodiment No.2-7, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 35g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 0.6 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[embodiment No.2-8]
In embodiment No.2-8, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.65 second.Then, 50 DEG C, flood 3.7 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 1st stage of 0.15 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.1A/dm 2carry out the catholyte process in the 2nd stage of 0.15 second.In addition, total turn on angle is set to 1.92C/dm 2.
[embodiment No.2-9]
In embodiment No.2-9, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 0.8 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[embodiment No.2-10]
In embodiment No.2-10, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 10g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.65 second.Then, 50 DEG C, flood 1.8 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.10 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 1.00 seconds.In addition, total turn on angle is set to 2.17C/dm 2.
[embodiment No.2-11]
In embodiment No.2-11, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 0.3A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.10C/dm 2.
[embodiment No.2-12]
In embodiment No.2-12, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 9.0A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.62C/dm 2.
[embodiment No.2-13]
In embodiment No.2-13, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 4.6A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.36C/dm 2.
[embodiment No.2-14]
In embodiment No.2-14, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.60 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 0.3A/dm 2carry out the catholyte process in the 2nd stage of 0.06 second.In addition, total turn on angle is set to 2.24C/dm 2.
[embodiment No.2-15]
In embodiment No.2-15, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 1st stage of 0.60 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 9.0A/dm 2carry out the catholyte process in the 2nd stage of 0.06 second.In addition, total turn on angle is set to 1.62C/dm 2.
[embodiment No.2-16]
In embodiment No.2-16, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 4.6A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 2.98C/dm 2.
[embodiment No.2-17]
In embodiment No.2-17, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.1A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 0.88C/dm 2.
[embodiment No.2-18]
In embodiment No.2-18, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.65 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 4.5A/dm 2carry out the catholyte process in the 1st stage of 0.15 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 2nd stage of 1.50 seconds.In addition, total turn on angle is set to 6.23C/dm 2.
[embodiment No.2-19]
In embodiment No.2-19, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.65 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.4A/dm 2carry out the catholyte process in the 1st stage of 0.10 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.4A/dm 2carry out the catholyte process in the 2nd stage of 1.00 seconds.In addition, total turn on angle is set to 3.74C/dm 2.
[embodiment No.2-20]
In embodiment No.2-20, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 42 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 42 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 42 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[embodiment No.2-21]
In embodiment No.2-21, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 53 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 53 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 53 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[embodiment No.2-22]
In embodiment No.2-22, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 22g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 22g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 22g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[embodiment No.2-23]
In embodiment No.2-23, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 28g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 28g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 28g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[embodiment No.2-24]
In embodiment No.2-24, in methylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.26C/dm 2.
[embodiment No.2-25]
In embodiment No.2-25, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 2.2A/dm 2and carry out the catholyte process of 0.60 second.Turn on angle is set to 1.32C/dm 2.
[embodiment No.2-26]
In embodiment No.2-26, in Phenylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 0.1A/dm 2and carry out the catholyte process of 11.00 seconds.Turn on angle is set to 1.10C/dm 2.
[embodiment No.2-27]
In embodiment No.2-27, in methylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 35g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 12.0A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.5A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.62C/dm 2.
[embodiment No.2-28]
In embodiment No.2-28, in methylsulfonic acid bath, implement 2.6g/m 2zinc-plated.Then, by being 46g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.42 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[comparative example No.2-31]
In comparative example No.2-31, in Phenylsulfonic acid bath, implement 1.1g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.36 second.Then, 50 DEG C, flood 1.0 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[comparative example No.2-32]
In comparative example No.2-32, in Phenylsulfonic acid bath, implement 2.7g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.07 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.04 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.40 second.In addition, total turn on angle is set to 0.87C/dm 2.
[comparative example No.2-33]
In comparative example No.2-33, in Phenylsulfonic acid bath, implement 2.7g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.73 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.0A/dm 2carry out the catholyte process in the 1st stage of 0.15 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.1A/dm 2carry out the catholyte process in the 2nd stage of 1.50 seconds.In addition, total turn on angle is set to 2.10C/dm 2.
[comparative example No.2-34]
In comparative example No.2-34, in Phenylsulfonic acid bath, implement 2.7g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.36 second.Then, 50 DEG C, flood 0.3 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 3.7A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 1.8A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 1.30C/dm 2.
[comparative example No.2-35]
In comparative example No.2-35, in Phenylsulfonic acid bath, implement 2.7g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.36 second.Then, 50 DEG C, flood 0.7 second with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 0.9A/dm 2carry out the catholyte process in the 1st stage of 0.06 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 0.9A/dm 2carry out the catholyte process in the 2nd stage of 0.60 second.In addition, total turn on angle is set to 0.59C/dm 2.
[comparative example No.2-36]
In comparative example No.2-36, in Phenylsulfonic acid bath, implement 2.7g/m 2zinc-plated.Then, by being 25g/m at water vapor concentration 3atmosphere in mild melt treatment by tin melting, quenching in the warm water of 80 DEG C.The fusion time of tin is set to 0.65 second.Then, 50 DEG C, flood 1.5 seconds with the state of non-electrolytic in the sodium dichromate aqueous solutio of 25g/L, then, carry out the catholyte process in 2 stages.That is, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 4.2A/dm 2carry out the catholyte process in the 1st stage of 0.15 second, then, 50 DEG C, in the sodium dichromate aqueous solutio of 25g/L, current density is set to 4.2A/dm 2carry out the catholyte process in the 2nd stage of 1.50 seconds.In addition, total turn on angle is set to 6.93C/dm 2.
So, the sample of 34 kinds of tin plates has been made.In addition, their manufacturing condition is shown in Table 2.
Then, the evaluation of the characteristics such as boiling film adaptation is carried out in the same manner as the 1st tests.The results are shown in table 3.
Table 3
As shown in table 3, in embodiment No.2-1 ~ No.2-28, the no matter kind of steeping fluid, through time boiling film adaptation before treatment and through time process after boiling film adaptation good.In embodiment No.2-5, although seldom there is the low part of gloss, be enough to the tin plate that can be used as tank body.
On the other hand, in the comparative example No.2-31 that tin coating weight is fewer than scope of the present invention, the boiling film adaptation in the steeping fluid (a) comprising acetic acid when dipping, the boiling film adaptation in the steeping fluid (c) comprising citric acid when dipping and the boiling film adaptation in the steeping fluid (d) comprising halfcystine when dipping are low.This result teaching is when tin coating weight is fewer than scope of the present invention, and the boiling film adaptation for the content comprising acetic acid, citric acid or halfcystine is low.
In addition, in the comparative example No.2-32 that the fusion time of tin is shorter than scope of the present invention, mild melt treatment is insufficient, and part obtains lusterless outward appearance, is therefore designated as defective.
In addition, in the comparative example No.2-33 that the fusion time of tin is longer than scope of the present invention, the boiling film adaptation in the steeping fluid (a) comprising acetic acid when dipping significantly reduces.This result teaching is when the fusion time of tin is longer than scope of the present invention, and the boiling film adaptation for the content comprising acetic acid significantly reduces.
In addition, in the comparative example No.2-34 shorter than scope of the present invention to the dipping time in sodium dichromate aqueous solutio, the boiling film adaptation in the steeping fluid (a) comprising acetic acid when dipping also significantly reduces.This result teaching is when dipping time is shorter than scope of the present invention, and the boiling film adaptation for the content comprising acetic acid significantly reduces.
In addition, in the comparative example No.2-35 that the turn on angle in chemical conversion treatment is fewer than scope of the present invention, the boiling film adaptation in the steeping fluid (d) comprising halfcystine when dipping is low.This result teaching is when turn on angle is fewer than scope of the present invention, and the boiling film adaptation for the content comprising halfcystine is low.
In addition, in the comparative example No.2-36 that the turn on angle in chemical conversion treatment is more than scope of the present invention, the boiling film adaptation in the steeping fluid (a) comprising acetic acid when dipping is low.This result teaching is when turn on angle is more than scope of the present invention, and the boiling film adaptation for the content comprising acetic acid is low.
Preferred embodiment be illustrated of the present invention above, but the present invention is not limited to these, scope of the present invention is as recorded in claims.
Utilizability in industry
The present invention such as may be used for the manufacturing industry of tin plate and utilizes in industry.

Claims (6)

1. a manufacture method for tin plate, is characterized in that, it has following operation:
A surface of steel plate forms 1.2g/m 2the operation of above tin-plated coating film,
Make described tin-plated coating film and described steel plate alloying by mild melt treatment and formed alloy film operation and
Described tin-plated coating film is formed the operation of chromic salt epithelium,
Described mild melt treatment is greater than 0g/m at water vapor concentration 3and be 40g/m 3carry out in following atmosphere,
Time in tin-plated coating film melting described in described mild melt treatment is set to more than 0.1 second and less than 0.7 second,
By described mild melt treatment, make the surface at described tin-plated coating film, divalent tin atom is more than 35% relative to the ratio of the total amount of tin atom and lower than 75%, 4 valency tin atoms relative to the ratio of the total amount of tin atom lower than 50%, 0 valency tin atom is less than 30% relative to the ratio of the total amount of tin atom
The operation of described formation chromic salt epithelium has following operation:
Described steel plate is flooded more than 0.5 second in the mode of non-electrolytic in sodium dichromate aqueous solutio and the operation of less than 4.0 seconds and
Then, for described steel plate in sodium dichromate aqueous solutio with 0.8C/dm 2above and 6.5C/dm 2following turn on angle implements the operation utilizing the chemical conversion treatment of catholyte.
2. the manufacture method of tin plate according to claim 1, is characterized in that, current density during described chemical conversion treatment is set to 0.1A/dm 2above and 10.0A/dm 2below.
3. the manufacture method of tin plate according to claim 1, is characterized in that, described in carry out chemical conversion treatment operation there is following operation:
With 2.0A/dm 2above and 10.0A/dm 2following current density carry out more than 0.001 second and the operation of the electrolysis of less than 0.2 second and
Then, with 0.1A/dm 2above and 5.0A/dm 2following current density carries out more than 0.01 second and the operation of the electrolysis of less than 2.0 seconds.
4. a manufacture method for tin plate, is characterized in that, it has following operation:
A surface of steel plate forms 1.2g/m 2the operation of above tin-plated coating film,
Make described tin-plated coating film and described steel plate alloying by mild melt treatment and formed alloy film operation and
Described tin-plated coating film is formed and counts 3mg/m with chromium metal conversion 2above and 8mg/m 2the operation of following chromic salt epithelium,
Described mild melt treatment is greater than 0g/m at water vapor concentration 3and be 40g/m 3carry out in following atmosphere,
By described mild melt treatment, make the surface at described tin-plated coating film, divalent tin atom is more than 35% relative to the ratio of the total amount of tin atom and lower than 75%, 4 valency tin atoms are relative to the ratio of the total amount of tin atom lower than 50%, and 0 valency tin atom is less than 30% relative to the ratio of the total amount of tin atom.
5. the manufacture method of tin plate according to claim 4, is characterized in that, the operation of described formation chromic salt epithelium has current density is set to 0.1A/dm 2above and 10.0A/dm 2carry out the operation of chemical conversion treatment below.
6. the manufacture method of tin plate according to claim 4, is characterized in that, the operation of described formation chromic salt epithelium has following operation:
With 2.0A/dm 2above and 10.0A/dm 2following current density carry out more than 0.001 second and the operation of the electrolysis of less than 0.2 second and
Then, with 0.1A/dm 2above and 5.0A/dm 2following current density carries out more than 0.01 second and the operation of the electrolysis of less than 2.0 seconds.
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