CN102308026A - Tin-plated steel sheet and method for producing the same - Google Patents

Tin-plated steel sheet and method for producing the same Download PDF

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Publication number
CN102308026A
CN102308026A CN2010800065932A CN201080006593A CN102308026A CN 102308026 A CN102308026 A CN 102308026A CN 2010800065932 A CN2010800065932 A CN 2010800065932A CN 201080006593 A CN201080006593 A CN 201080006593A CN 102308026 A CN102308026 A CN 102308026A
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Prior art keywords
tin
current density
catholyte
handle
sodium dichromate
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CN102308026B (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

Tin plate and method of manufacture thereof
Technical field
The present invention relates to be suitable for the tin plate and the method for manufacture thereof of food cans etc.
Background technology
Tin plate is widely used as metal tin and uses starting material.The content of jar is various.At content is under the situation of fruit, and jar internal surface is used with the mode of no application sometimes, still, is under the situation of other materials at content, generally films at jar internal surface formation resin coating etc.In addition, after the contents the acidic food such as soda pop, nectar and fruit are filled in the jar, in most cases, handling above carrying out heat-sterilization under 100 ℃ the temperature.Therefore, for tin plate, require the adaptation of filming under the high temperature moist environment.This heat-sterilization is handled in Japan and is called as boiling (retort) processing sometimes.Below, the adaptation of the steel plate after handling with respect to heat-sterilization of will filming sometimes is called the boiling adaptation of filming.
On the other hand, according to the difference of content, boiling is filmed, and mechanism that adaptation reduces is different.Also consider to change corresponding to various contents the composition of tin plate etc., still, management waits and becoming numerous and diverse at that rate.Therefore, preferably guarantee the good boiling adaptation of filming for most contents.
Proposed various technology in the patent documentation 1～6, but any technology all can't obtain the sufficient boiling adaptation of filming.
In addition, tin plate uses boats and ships in high-temperature area, to be transferred sometimes, perhaps in the warehouse, waits by prolonged preservation.Therefore, tin plate take place sometimes through the time change, be accompanied by through the time change, the adaptation of filming of boiling sometimes reduces.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 7-11483 communique
Patent documentation 2: japanese kokai publication sho 54-142135 communique
Patent documentation 3: japanese kokai publication sho 56-127776 communique
Patent documentation 4: japanese kokai publication hei 5-302196 communique
Patent documentation 5: japanese kokai publication sho 57-123998 communique
Patent documentation 6: TOHKEMY 2002-356785 communique
Patent documentation 7: japanese kokai publication sho 61-104099 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide the kind that does not receive content to influence, can obtain good boiling the film tin plate and the method for manufacture thereof of adaptation.
Be used to solve the means of problem
The application inventor furthers investigate in order to solve above-mentioned problem repeatedly, the variety of way of the invention shown in below the result has expected.
The tin plate that the 1st viewpoint of the present invention relates to is characterised in that, it has steel plate, on a surface of above-mentioned steel plate with 1.2g/m 2The alloy film of tin-plated coating film, the tin that between above-mentioned steel plate and above-mentioned tin-plated coating film, forms through the alloying of above-mentioned steel plate and above-mentioned tin-plated coating film and the iron that more than forms and on above-mentioned tin-plated coating film, form count 3mg/m with the chromium metal conversion 2More than and 8mg/m 2Following chromic salt epithelium; Surface at above-mentioned tin-plated coating film; The divalent tin atom is more than 35% with respect to the ratio of the total amount of tin atom and is lower than 75%, 4 valency tin atom to be lower than 50%, 0 valency tin atom with respect to the ratio of the total amount of tin atom be below 30% with respect to the ratio of the total amount of tin atom.
The method of manufacture of the tin plate that the 2nd viewpoint of the present invention relates to is characterised in that it has following operation: on a surface of steel plate, form 1.2g/m 2The operation of above tin-plated coating film, handle through soft heat and to make above-mentioned tin-plated coating film and above-mentioned steel plate alloying form the operation of alloy film and the operation of formation chromic salt epithelium on above-mentioned tin-plated coating film; Will be in above-mentioned soft heat be handled the above-mentioned tin-plated coating film fused time be made as more than 0.1 second and below 0.7 second, the operation of above-mentioned formation chromic salt epithelium has following operation: with above-mentioned steel plate in sodium dichromate aqueous solutio, flood more than 0.5 second with non-electrolytic mode and the operation below 4.0 seconds and then to above-mentioned steel plate in sodium dichromate aqueous solutio with 0.8C/dm 2More than and 6.5C/dm 2Following energising amount implements to utilize the operation of the chemical conversion processing (being also referred to as " chemical tunicle generates and handles ") of catholyte.
The method of manufacture of the tin plate that the 3rd viewpoint of the present invention relates to is characterised in that it has following operation: on a surface of steel plate, form 1.2g/m 2The operation of above tin-plated coating film, handle to make above-mentioned tin-plated coating film and above-mentioned steel plate alloying form the operation of alloy film and on above-mentioned tin-plated coating film, form through soft heat and count 3mg/m with the chromium metal conversion 2More than and 8mg/m 2The operation of following chromic salt epithelium.
The invention effect
According to the present invention, owing to suitably stipulated the ratio etc. of tin atom of the various valence states on tin-plated coating film surface, can obtain the good boiling adaptation of filming.
Description of drawings
Fig. 1 is the sectional view of the tin plate that relates to of expression embodiment of the present invention.
Embodiment
Below, for embodiment of the present invention, specify with reference to the accompanying drawing that adds.Fig. 1 is the sectional view of the tin plate that relates to of expression embodiment of the present invention.
In the tin plate that this embodiment relates to, at least one surface of steel plate 1, be formed with the alloy film 2 of tin and iron.In addition, on alloy film 2, be formed with tin-plated coating film 3, on tin-plated coating film 3, be formed with chromic salt epithelium 4.The area occupation ratio of chromic salt epithelium 4 for example is 60%～80%, but is not limited to this.
The tin plate that so constitutes for example forms on chromic salt epithelium 4 films, and is used as the tank body that with this face is internal surface.In addition, after filling content, carry out heat-sterilization sometimes and handle, the boiling adaptation of filming comes into one's own.Though content relates to multiple,, as the material of representational saprophagy contained in these contents, can enumerate acetate, lactic acid, Hydrocerol A, halfcystine etc.Therefore, guarantee that boiling in the presence of these saprophagy materials adaptation of filming is important.
Then, to being used to guarantee that the film various conditions of adaptation of such boiling describe.
In this embodiment, the total amount of contained tin is 1.2g/m in alloy film 2 and the tin-plated coating film 3 2More than.In addition, the adhesion amount of chromic salt epithelium 4 converts with chromium metal and counts 3mg/m 2～8mg/m 2And then on the surface of tin-plated coating film 3; Divalent Sn atom is more than 35% and is lower than 75% with respect to the ratio of the total amount of Sn atom; It is below 30% with respect to the ratio of the total amount of Sn atom that 4 valency Sn atoms are lower than 50%, 0 valency Sn atom (metal Sn) with respect to the ratio of the total amount of Sn atom.
If the total amount of contained tin is lower than 1.2g/m in alloy film 2 and the tin-plated coating film 3 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 dissolved in acetate easily, therefore, comprises at content under the situation of acetate or Hydrocerol A, and the boiling adaptation of filming reduces easily.Therefore, the total amount with tin contained in alloy film 2 and the tin-plated coating film 3 is made as 1.2g/m 2More than.In addition, the total amount of tin is preferably 1.5g/m 2More than.The total amount of tin is 1.5g/m if this is 2More than, then the erosion resistance after the application is stable.On the other hand, the total amount of tin is preferably 6.0g/m 2Below.The total amount of tin surpasses 6.0g/m if this is 2Though, then available good anti-corrosion, this effect is saturated a little, and cost efficiency reduces.
If converting in chromium metal, the adhesion amount of chromic salt epithelium 4 is lower than 3mg/m 2, then comprise boiling under the situation of the halfcystine adaptation of filming and become insufficient at content.Infer that this is because the tin-plated coating film 3 that exposes from chromic salt epithelium 4 reacts with halfcystine.On the other hand, if the adhesion amount of chromic salt epithelium 4 converts above 8mg/m in chromium metal 2, then comprise boiling under the situation of the acetate adaptation of filming and become insufficient at content.Think that this is because the part of chromic salt epithelium 4 is dissolved in acetate.Therefore, the adhesion amount of chromic salt epithelium 4 converts in chromium metal and is made as 3mg/m 2More than and 8mg/m 2Below.
In addition; In the surface of tin-plated coating film 3, divalent Sn atom is more than 35% with respect to the ratio of the total amount of Sn atom and is lower than 75%, 4 valency Sn atoms to be lower than 50%, 0 valency Sn atom (metal Sn) with respect to the ratio of the total amount of Sn atom be to be important below 30% with respect to the ratio of the total amount of Sn atom.
Details is narrated in the back, and still, in the manufacturing processed of tin plate, Sn was melted during the soft heat after zinc-plated was handled, and mainly when this was handled, Sn was oxidized.Tin be SnO and SnO than stable oxide 2, correspond respectively to the divalent of Sn, 4 valencys of Sn.Present inventors have carried out various researchs, find to be made as suitable value through the balance with 0 valency, divalent and 4 valencys of Sn, can obtain the good boiling adaptation of filming.
Present inventors find, if the ratio of SnO is more than 75%, then comprises boiling under the situation of the acetate adaptation of filming at content and significantly reduce.Think that this reason is because SnO is soluble in the acetate.Therefore, divalent Sn atom is made as with respect to the ratio of the total amount of Sn atom and is lower than 75%.In addition, the ratio of preferred divalent Sn atom is lower than 65%.
In addition, present inventors find, if SnO 2Ratio be more than 50%, then be easy to generate stain.If the generation stain then in coating process, printing process and/or can welding process etc., generates easily on roller and the anchor clamps and pollutes.Therefore, 4 valency Sn atoms are made as with respect to the ratio of the total amount of Sn atom and are lower than 50%.
Like this, if SnO excessively exists, then, boiling has problems on filming adaptation, if SnO 2Excessively exist, then produce the problem relevant with stain.
0 valency Sn atom itself is not the material that makes boiling film the adaptation reduction or stain is produced.But, the part of 0 valency Sn atom chemical conversion processing, prolonged preservation or the thermal treatment when forming chromic salt epithelium 4 sometimes and oxidized.That is, with the situation of tin plate prolonged preservation etc. down, 0 valency Sn becomes 4 valency Sn atoms sometimes, and 4 valency Sn atoms increase.In addition, the sintering of filming when forming is generally carrying out above under 100 ℃ the temperature, and therefore, at this moment, 0 valency Sn atomic change is a divalent Sn atom sometimes, and divalent Sn atom increases.And present inventors find, if the ratio of 0 valency Sn atom is more than 30%, then are easy to generate the influence that is brought by such oxidation.Therefore, 0 valency Sn atom is made as with respect to the ratio of the total amount of Sn atom and is lower than 30%.In addition, the ratio of preferred 0 valency Sn atom is lower than 10%.
And then, owing to considered 0 valency Sn atom, and 4 valency Sn atoms are made as with respect to the ratio of the total amount of Sn atom are lower than 50%, therefore, the ratio of divalent Sn atom is made as more than 35%.In addition, the ratio of 4 valency Sn atoms is preferably more than 40%.
Here, an example for the method for the ratio of 0 valency, divalent and the 4 valency Sn atoms of obtaining tin-plated coating film 3 surface describes.
At first, measure the spectrum of the 3d5/2 of Sn through x-ray photoelectron spectroscopy analysis (XPS).More detailed, as the x-ray source among the XPS, use AlK α (1486.6eV), output rating is made as 15kV, 25W, the diameter of measuring the zone is made as 100 μ m, the vacuum tightness of analyzer room is made as 1.5 * 10 -7Pa takes out angle with electronics and is made as 90 °, measures the spectrum of the 3d5/2 of Sn.
Then, for the spectrum of measuring, carry out waveform by following 3 conditions and separate (peak separation).
(1) the bond energy value with 0 valency Sn is made as 484.7eV～484.8eV.
(2) the bond energy difference between the bond energy value of the bond energy value of divalent Sn and 4 valency Sn is made as about 0.7eV.
(3), use the measured value of standard test specimen as half-width (FWHM).
The various areas that will be obtained by such waveform separation (peak separation) then, are than the ratio of 0 valency, divalent and the 4 valency Sn atoms on the surface that is made as tin-plated coating film 3.
In addition, in this embodiment, the amount of contained tin in the alloy film 2, be to handle with the amount of having carried out the tin of alloying at steel plate 1 contained iron through soft heat in the tin of plating to be preferably 0.1g/m 2～0.56g/m 2
The amount of having carried out the tin of alloying with iron is lower than 0.1g/m 2The time, in the formation of alloy film 2, producing deviation, the outward appearance after the soft heat becomes inhomogeneous sometimes.On the other hand, if the amount of having carried out the tin of alloying with iron surpasses 0.56g/m 2, then comprise boiling under the situation of acetate etc. the adaptation of filming at content sometimes and become insufficient a little.Therefore, the amount of contained tin is 0.1g/m in the preferred alloy film 2 2～0.56g/m 2
In addition, the amount of contained tin for example can be measured through the electrolytic stripping method of record among the JIS G3303 2002 in the alloy film 2.In the method, use 1 equivalent hydrochloric acid of normal temperature as electrolytic solution, with test film as anode (area: 2500mm 2), as negative electrode, the constant current of circulation 250mA carries out electrolysis with carbon-point.Then, when electrolysis begins, beginning to measure with the silvery reference electrode is the current potential of the test film of benchmark, then, and this current potential of METHOD FOR CONTINUOUS DETERMINATION.After measuring current potential, make the time changing curve of current potential, with the point of inflexion on a curve be the benchmark tin that calculates alloying not, alloying the needed separately electric weight of tin, be converted into the tin amount of having carried out alloying with iron.
And then in this embodiment, the area occupation ratio of preferred chromium hydrochlorate epithelium 4 is 60%～80%.Here, " area occupation ratio " of chromic salt epithelium 4 is meant, the ratio that the surface-area of chromic salt epithelium 4 is whole with respect to the surface-area of tin-plated coating film 3.That is to say that preferred chromium hydrochlorate epithelium 4 covers the surface of tin-plated coating film 3 with 60%～80% area occupation ratio.If this area occupation ratio is lower than 60%, then comprises boiling under the situation of halfcystine etc. the adaptation of filming at content sometimes and significantly reduce.On the other hand, if this area occupation ratio surpasses 80%, then sometimes content comprise under the situation of acetate etc. through the time before the boiling adaptation of filming 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 for example can pass through EPMA (electron microprobe analysis method) and measure.For example through beam diameter being made as 10 μ m; At 100 positions on the 1st direction arbitrarily on the surface of tin plate and with 50 positions on vertical the 2nd direction of the 1st direction the intensity of chromium is carried out surface analysis, measure the area occupation ratio of chromic salt epithelium 4 thus.From such 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 to get final product.
Then, the example to the method for the tin plate of making above-mentioned that kind describes.
At first, making, plating raw sheet (steel plate).The composition of plating raw sheet and making method are not special to be limited.For example as long as make steel billet, this steel billet is implemented hot rolling, pickling, cold rolling, annealing, skin-pass etc. get final product through usual method.
Then, the plating raw sheet is implemented degreasing and pickling as tinned pre-treatment.Degreasing is used for the rolling wet goods oil component on the surface that remains in the plating raw sheet is removed and implemented, and pickling is used for the sull on the surface of plating raw sheet is removed and implemented.If degreasing or pickling are insufficient, then at the remained on surface oil component or the sull of plating raw sheet.The electroconductibility of oil component and sull is low, if therefore they are residual, then can't suitably implement plating and handle, and perhaps produces dendrite, and perhaps the adaptation of plated film reduces.Therefore, preferably carry out sufficient degreasing and pickling.
As degreasing, the alkaline electrolysis degreasing that preferably is implemented in common caustic soda, water glass or the sodium phosphate etc. reaches the alkaline electrolysis degreasing in their mixed solution.
As pickling, preferably handle or dip treating at common dilute sulphuric acid or the catholyte in the Hydrogen chloride.
Then, the plating raw sheet is implemented eleetrotinplate.As plating bath, for example can use zinc-plated bath, Phenylsulfonic acid bath, sulfuric acid bath, methylsulfonic acid bath, halogen to bathe, reach alkaline bath etc.In addition, in zinc-plated, because tin ion reduction electricity is analysed, the valence state of the Sn that therefore on the plating raw sheet, exists is 0 valency.
At this moment, tinned adhesion amount is made as 1.2g/m at least one face of plating raw sheet 2More than.Tinned adhesion amount is lower than 1.2g/m if this is 2, then the plating raw sheet exposes from the coating through zinc-plated formation.Iron as the main material of plating raw sheet is soluble in acetate, therefore comprises under the situation that acetate is solution at content, and the boiling adaptation of filming reduces easily.In addition, preferred tinned adhesion amount is 1.5g/m 2More than.Tinned adhesion amount is 1.5g/m if this is 2More than, then the erosion resistance after the application is stable.On the other hand, preferred tinned adhesion amount is 6.0g/m 2Below.Tinned adhesion amount surpasses 6.0g/m if this is 2Though, then can obtain good anti-corrosion, this effect is saturated a little, and cost efficiency reduces.
Zinc-plated back is implemented soft heat and is handled, and with the part of coating and a part of alloying of plating raw sheet, forms the alloy film 2 of tin and iron.Then, the remainder of coating is equivalent to the tin-plated coating film 3 among Fig. 1, and the remainder of plating raw sheet (steel plate) is equivalent to the steel plate 1 among Fig. 1.
In soft heat is handled, for example after the coating fusion that makes tin, use the warm water quenching.If with the temporary transient fusion of tin, then the easy alloying of the iron of tin and substrate forms alloy film 2 very uniformly.Therefore, there is the alloy film 2 of excellent corrosion resistance,, also can obtains higher erosion resistance even therefore have defective in the tin-plated coating film 3 in steel plate 1 side of tin-plated coating film 3.In addition, generate White tin oxide on the surface of coating.This White tin oxide is SnO and SnO 2These 2 kinds.In the soft heat treatment temperature is under the situation below 100 ℃, SnO 2Become principal product, SnO became principal product till the fusing point from 100 ℃ to Sn was 232 ℃, was surpassing SnO under the situation of fusing point 2Become principal product.Therefore, through the transition of the temperature in the suitable control soft heat processing, can easily control SnO and SnO 2Ratio.In addition, through suitably controlling the time that soft heat is handled, the growing amount of ability controlled oxidation tin.In addition, the heating means during soft heat is handled are not special to be limited, from temperature controlled aspect, preferably through energising heating, induction heating or energising heating and induction heating and be used for carrying out.
In addition, the coating of the tin before soft heat is handled is microgranular at microscopically, sticking power a little less than, tarnish demonstrates gloss but handle through soft heat.
Here, the condition of handling for soft heat describes.In this embodiment, was made as 0.1 second～0.7 second the coating fused time.If make the coating fused time be lower than 0.1 second, then become inhomogeneous on the width that is formed on the plating raw sheet of alloy film 2 and/or the length direction sometimes, and can't obtain glossiness outward appearance equably sometimes.On the other hand, if make the coating fused time surpass 0.7 second, then White tin oxide, particularly SnO increase, and comprise boiling under the situation that acetate the is solution adaptation of filming at content and significantly reduce.Therefore, was made as 0.1 second～0.7 second the coating fused time.
In addition, the soft heat processing is 0g/m at water vapor concentration preferably 3～40g/m 3Atmosphere in carry out.Water vapor concentration surpasses 40g/m if this is 3, then SnO shared ratio in the White tin oxide that the surface of coating generates becomes too high.
After soft heat is handled, carry out chromate treating, form chromic salt epithelium 4.In the present embodiment, handle as chromate, enforcement has used the chemical conversion in 2 stages of sodium dichromate solution to handle.That is, carry out non-electrolysis dip treating, then, carry out catholyte and handle.
Time of immersion in the non-electrolysis dip treating (chemical conversion handle the 1st stage) is made as more than 0.5 second and below 4.0 seconds.If non-electrolytic time of immersion is lower than 0.5 second in sodium dichromate aqueous solutio, be that acetate is that boiling under the situation of the solution adaptation of filming significantly reduces then at content.This reason is indeterminate, and still, deduction is that the dissolving of SnO in sodium dichromate aqueous solutio becomes insufficient because time of immersion is too short.On the other hand, if non-electrolytic time of immersion surpasses 4.0 seconds in sodium dichromate aqueous solutio, then productivity reduces.That is, production rate significantly reduces, and perhaps needs to be used for the equipment enlarging of this processing.In the latter case, need high facility investment.Therefore, the time of immersion in the non-electrolysis dip treating is set at more than 0.5 second and below 4.0 seconds.In addition, this time of immersion was preferably more than 0.7 second, was preferably below 2.0 seconds.
The energising amount that catholyte is handled the catholyte in sodium dichromate aqueous solutio in (the 2nd stage that chemical conversion is handled) is made as 0.8C/dm 2More than and 6.5C/dm 2Below.In addition, energising amount (C/dm 2) with " current density (A/dm 2) * conduction time (second) " relational expression illustrate.If the energising amount of catholyte is lower than 0.8C/dm 2, sometimes because of through the time be called as xanthochromic variable color.On the other hand, if the energising amount of catholyte surpasses 6.5C/dm 2, then the effect of chromic salt epithelium 4 is saturated, and is accompanied by the excessive formation of chromic salt epithelium 4, and saprophage focuses on a bit, might cause the perforation saprophage of tank body.The energising amount of the catholyte in sodium dichromate aqueous solutio during therefore, catholyte is handled is made as 0.8C/dm 2More than and 6.5C/dm 2Below.In addition, this energising amount is preferably 4.0C/dm 2Below.
In addition, the cathode current density in the catholyte processing (the 2nd stage that chemical conversion is handled) is preferably 0.1A/dm 2～10.0A/dm 2The influence of current density significantly occurs be through the time after.Tin plate uses boats and ships to carry in the zone under the line sometimes, perhaps in the warehouse, waits long-term the preservation.Therefore, also consider because of through the time boiling adaptation of filming is changed.If cathode current density is lower than 0.1A/dm 2, then be coated be contained in through the time after under the situation of carrying out, having content is the boiling of acetate when the being solution tendency that adaptation reduces a little of filming.Infer that this is because chromic salt epithelium 4 becomes inhomogeneous, because of through the time make the SnO on tin plate surface grow up.In addition, if cathode current density surpasses 10A/dm 2Though then chromic salt epithelium 4 is formed uniformly, be coated be contained in through the time after when carrying out, having at content is the boiling of acetate when the being solution tendency that adaptation reduces a little of filming.In addition, this cathode current density is preferably 0.2A/dm 2More than, be preferably 5.0A/dm 2Below.
In addition, for the area occupation ratio with chromic salt epithelium 4 is made as 60%～80%, the adjustment of current density is effective.If carry out electrolysis treatment, then focus on nuclear and the position takes place and separate out the reduction of lining area occupation ratio with HCD.On the other hand, if carry out electrolysis treatment, then separate out more equably with low current density.
Therefore,, and chromic salt epithelium 4 disperseed with 60%～80% area occupation ratio and form, preferably carry out combined electrolysis in order to ensure high productivity.For example, preferably with 2.0A/dm 2～10.0A/dm 2Current density carry out 0.001 second～0.2 second electrolysis, then with 0.1A/dm 2～5.0A/dm 2Current density implement 0.01 second～2.0 seconds electrolysis.
And then from operation property and equipment aspect, the bath temperature of preferably chemical conversion being handled is made as 40 ℃～55 ℃.The sodium dichromate aqueous solutio of handling solution as chemical conversion carries out the impedance heating when electrolysis, the temperature of sodium dichromate aqueous solutio rises.Therefore, particularly process and be lower than 40 ℃ in order to bathe temperature control, need refrigerating unit sometimes in summer.On the other hand, surpass 55 ℃ if bathe temperature, then the steam output of moisture from bathe increases, and the concentration of sodium dichromate aqueous solutio changes easily.In addition, be accompanied by the evaporation of moisture, the saprophagy of bath increases, and therefore as electrolyzer and jar, must use the material of high corrosion resistance sometimes.Therefore, the bath temperature of chemical conversion processing is preferably 40 ℃～55 ℃.
In addition, from operation property and equipment aspect, the concentration of sodium dichromate aqueous solutio preferably is made as 20g/L～30g/L.
According to such method owing to suitably stipulated condition that tin fused time and chemical conversion are handled, therefore no matter through the time have or not, can both obtain the boiling good tin plate of adaptation of filming.
In addition, after soft heat was handled, as the pre-treatment that chemical conversion is handled, the White tin oxide that also can in soft heat is handled, generate was immersed in the acidic liq and dissolves and remove.If to SnO and SnO 2Compare, then from the aspect of stability, SnO is prone to dissolving, through concentration, temperature and the time of immersion of control acidic liq, and the residual quantity of ability controlled oxidation tin.In addition, handle, can the White tin oxide reduction be removed through the catholyte that does not contain at sodium bicarbonate aqueous solution etc. in tin powers on the electrolytic solution of the material of analysing.
But, handle as these, owing to use the solution of the composition different with chemical conversion processing solution to carry out pre-treatment, therefore, it is essential that the washing of pre-treatment solution becomes.That is to say that it is essential that the equipment of the washing usefulness of equipment that pre-treatment is used and pre-treatment solution becomes, need 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 of carrying out of the application inventor are described.
(the 1st experiment)
In the 1st experiment, be that the cold-rolled steel sheet of 0.20mm carries out electrolytic degreasing with the aqueous sodium hydroxide solution of 10 quality % with thickness, wash then.Then, in the aqueous hydrochloric acid of 10 quality %, carry out dip pickling, and wash.Then, be described below, carry out zinc-plated under various conditions and chemical conversion processing etc.
[embodiment No.1-1]
In embodiment No.1-1,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.6 second.In this catholyte is handled, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is made as 3.7A/dm 2, the current density in the 2nd stage is made as 1.1A/dm 2In addition, total energising amount is made as 0.88C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 3mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 19%, divalent is that 40%, 4 valencys are 41%.In addition, the area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-2]
In embodiment No.1-2,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium bicarbonate aqueous solution of 20g/L, current density is made as 1A/dm 2, the catholyte that has carried out 0.15 second is handled, and washes.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 3.0 seconds.In this catholyte is handled, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 6.2C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 7mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 22%, divalent is that 40%, 4 valencys are 38%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-3]
In embodiment No.1-3,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, current density is made as 3A/dm with non-electrolytic state dipping 2.5 seconds 2Handle and carry out catholyte.The energising amount is made as 1.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 7mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 4%, divalent is that 65%, 4 valencys are 31%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-4]
In embodiment No.1-4,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 10g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The tin that has carried out alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.8 second.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 1.9C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 35%, 4 valencys are 45%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-5]
In embodiment No.1-5,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 30g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.6 second.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 15%, divalent is that 70%, 4 valencys are 15%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-6]
In embodiment No.1-6,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium bicarbonate aqueous solution of 20g/L, current density is made as 1A/dm 2, the catholyte that carried out 0.8 second is handled, and washes.Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 3.2A/dm 2, the current density in the 2nd stage is made as 1.5A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 27%, divalent is that 37%, 4 valencys are 36%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-7]
In embodiment No.1-7,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.3 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.3g/m 2Then, in 50 ℃, the sodium bicarbonate aqueous solution of 20g/L, current density is made as 1A/dm 2, the catholyte that carried out 1 second is handled, and washes.Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 3.2A/dm 2, the current density in the 2nd stage is made as 1.5A/dm 2In addition, total energising amount is made as 1.7C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 29%, divalent is that 40%, 4 valencys are 31%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-8]
In embodiment No.1-8,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.3 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.3g/m 2Then, in 50 ℃, the sodium bicarbonate aqueous solution of 20g/L, current density is made as 1A/dm 2, the catholyte that carried out 1 second is handled, and washes.Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.1 second.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 2.2A/dm 2, the current density in the 2nd stage is made as 1.5A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 27%, divalent is that 48%, 4 valencys are 25%.The lining area occupation ratio of chromic salt epithelium is 65%.
[embodiment No.1-9]
In embodiment No.1-9,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.1 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.08g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.5 second.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-10]
In embodiment No.1-10,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, at first, only the water vapor concentration through inside was 25g/m 3Electric heating device be warming up to 100 ℃ with 2.4 seconds, then, and with induction heating carry out 3.2 seconds the heating, with tin fusion 0.7 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.7g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 2.2 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-11]
In embodiment No.1-11,, Phenylsulfonic acid implemented 1.4g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-12]
In embodiment No.1-12,, Phenylsulfonic acid implemented 1.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-13]
In embodiment No.1-13,, Phenylsulfonic acid implemented 5.6g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the tin on surface formed carried out after the investigation, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-14]
In embodiment No.1-14,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 9A/dm with non-electrolytic state dipping 1.5 seconds 2Handle and carry out catholyte.The energising amount is made as 1.7C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 50%.
[embodiment No.1-15]
In embodiment No.1-15,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 2.0A/dm with non-electrolytic state dipping 1.5 seconds 2Handle and carry out catholyte.The energising amount is made as 1.8C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 6mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 90%.
[embodiment No.1-16]
In embodiment No.1-16,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.2 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.2g/m 2Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 1.5C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-17]
In embodiment No.1-17,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.5 second, quenching in 80 ℃ warm water.The tin that has carried out alloying with iron through this processing is 0.5g/m 2Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 1.5C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[embodiment No.1-18]
In embodiment No.1-18,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is made as 3.0A/dm 2, the current density in the 2nd stage is made as 2.0A/dm 2In addition, total energising amount is made as 1.9C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 62%.
[embodiment No.1-19]
In embodiment No.1-19,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 3.0 seconds.In this catholyte is handled, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 2.3A/dm 2In addition, total energising amount is made as 1.5C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 78%.
[embodiment No.1-20]
In embodiment No.1-20,, methylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium bicarbonate aqueous solution of 20g/L, current density is made as 1A/dm 2, the catholyte that carried out 0.9 second is handled, and washes.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, the current density in the 1st stage is made as 4.8A/dm 2, the current density in the 2nd stage is made as 1.9A/dm 2In addition, total energising amount is made as 1.5C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 30%, divalent is that 38%, 4 valencys are 32%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-21]
In comparative example No.1-21,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 2.1A/dm 2, the current density in the 2nd stage is made as 0.5A/dm 2In addition, total energising amount is made as 0.5C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 2mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 19%, divalent is that 39%, 4 valencys are 42%.The area occupation ratio of chromic salt epithelium is 62%.
[comparative example No.1-22]
In comparative example No.1-22,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 4.9A/dm 2, the current density in the 2nd stage is made as 2.5A/dm 2In addition, total energising amount is made as 9.5C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 10mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 19%, divalent is that 42%, 4 valencys are 39%.The area occupation ratio of chromic salt epithelium is 78%.
[comparative example No.1-23]
In comparative example No.1-23,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 45g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, carry out the catholyte in 2 stages and handle.In this catholyte is handled, the current density in the 1st stage is made as 2.1A/dm 2, the current density in the 2nd stage is made as 0.5A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of chromic salt epithelium converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 10%, divalent is that 78%, 4 valencys are 12%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-24]
In comparative example No.1-24,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, the water vapor concentration in inside is 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, the sodium bicarbonate aqueous solution of 20g/L, current density is made as 7A/dm 2, the catholyte that carried out 1 second is handled, and washes.Then, handle at the catholyte that carries out 2 stages.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 2.1A/dm 2, the current density in the 2nd stage is made as 0.5A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 35%, divalent is that 40%, 4 valencys are 25%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-25]
In comparative example No.1-25,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, 5 quality % aqueous hydrochloric acids dipping 1.8 seconds and wash after, dry down at 220 ℃.Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 2.1A/dm 2, the current density in the 2nd stage is made as 0.5A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 8%, divalent is that 40%, 4 valencys are 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,, Phenylsulfonic acid implemented 0.9g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 25g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, in 50 ℃, 5 quality % aqueous hydrochloric acids dipping 2 seconds and wash after, dry down at 220 ℃.Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 2.1A/dm 2, the current density in the 2nd stage is made as 0.5A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the tin on surface formed carried out after the investigation, 0 valency is 20%, divalent is that 40%, 4 valencys are 40%.The area occupation ratio of chromic salt epithelium is 70%.
[comparative example No.1-27]
In comparative example No.1-27,, Phenylsulfonic acid implemented 2.8g/m in bathing 2Zinc-plated.Then, carrying out soft heat handles.In soft heat was handled, the water vapor concentration in inside was 15g/m 3The heating 5.6 seconds that heats up of electric heating device cathetus, with tin fusion 0.4 second, quenching in 80 ℃ warm water.The amount of having carried out the tin of alloying with iron through this processing is 0.4g/m 2Then, dipping 2 seconds and washing in 50 ℃, 5 quality % aqueous hydrochloric acids.Then, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.In this catholyte is handled, in 53 ℃, the sodium dichromate aqueous solutio of 28g/L, the current density in the 1st stage is made as 2.1A/dm 2, the current density in the 2nd stage is made as 0.5A/dm 2In addition, total energising amount is made as 2.1C/dm 2The amount of the chromic salt epithelium that forms converts with Metal Cr and counts 5mg/m 2In addition, the composition of the tin on surface carried out investigation after, 0 valency is 28%, divalent is that 32%, 4 valencys are 40%.The lining area occupation ratio of chromic salt epithelium is 70%.
Like this, made the sample of 27 kinds of tin plates.
Then, to each sample coating 8g/m 2Epoxy-phenol resin paint, down heating is after 10 minutes at 204 ℃, cool to room temperature is filmed thereby form.And then, at room temperature preserve more than 8 hours after, it is the cover moulding of 50mm that the mode that becomes jar internal surface with application face makes diameter.
Then, estimate following 3 specific characters of the cover of moulding.
[without the time boiling the handled adaptation of filming]
Cover is immersed in the heat treated of under 120 ℃, carrying out in 4 kinds of aqueous solution 90 minutes.This is handled with respect to the makers' heat-sterilization of can and handles.After the heat treated, wash at once and drying, then, the interval with 3mm on cover engraves 100 tessellated indentations that reach cold-rolled steel sheet (substrate), carries out tape stripping, estimates the adaptation of 10 grades through the revolution mark of filming.In this is estimated, be that 100% cover (cover of not peeling off) is designated as 10 fens, the revolution mark of filming is more than 90% and is lower than 100% be designated as 9 fens with the revolution mark of filming.And then the scope of the revolution mark of filming whenever departs from 10%, respectively mark is reduced by 1 fen, and the revolution mark of filming is more than 0% and is lower than 10% cover and is designated as 0 fen.Then, the cover more than 9 minutes is designated as qualified.In addition, in the test in 4 kinds of aqueous solution, qualified with all being that cover more than 7 minutes is designated as.
In addition, as the solute of 4 kinds of aqueous solution, (a)～(d) 4 kinds below using.
(a) 3 quality % acetate+2 quality %NaCl
(b) 1.1 quality % lactic acid
(c) 2 quality % Hydrocerol As+0.4 quality % xitix
(d) 0.056 quality % halfcystine HCl+0.4 quality %KH 2PO 4+ 0.81 quality %Na 2HPO 4
[through the time handle after the boiling adaptation of filming]
Each when making cover, before the coating epoxy-phenol resin paint, be that bale packing was so stored 7 days in anti-tarnish paper under the condition of 90%RH in humidity under 50 ℃ with the sample of tin plate.Then, as above-mentioned, make cover, carry out with [without the time boiling the handled adaptation of filming] same evaluation, in the test in 4 kinds of aqueous solution, with all reach cover more than 7 minutes be designated as qualified.
[evaluation of the composition of tin]
Use PHI corporate system Quantum2000 type XPS analysis device, analyze and resolve through above-mentioned method.
These results are shown in table 1.
Table 1
Figure BDA0000081086750000221
As shown in table 1, in embodiment No.1-1～No.1-20, no matter the kind of steeping fluid, through the time boiling before handling film adaptation and through the time boiling after the handling adaptation of filming good.The amount of having carried out the tin of alloying with iron is lower than 0.1g/m 2Embodiment No.1-9 in, the part that becomes of the outward appearance after the soft heat is inhomogeneous, but is enough to and can uses as the tin plate that tank body is used.
On the other hand, in the comparative example No.1-21 that the amount of chromic salt epithelium is lacked than scope of the present invention, the boiling adaptation of filming in comprising the steeping fluid of halfcystine (d) under the situation of dipping is low.This as a result teaching under the situation that the amount of chromic salt epithelium is lacked than scope of the present invention, low for the boiling of the content that the comprises halfcystine adaptation of filming.
In addition; The ratio of comparative example No.1-22 that the amount of chromic salt epithelium is Duoed than scope of the present invention, the divalent Sn atom comparative example No.1-23 higher than scope of the present invention, and the ratio of the 4 valency Sn atoms comparative example No.1-25 higher than scope of the present invention in, the adaptation of filming of the boiling under the situation of during comprising the steeping fluid of acetate (a), flooding is low.This as a result teaching under the situation that the amount of chromic salt epithelium is Duoed than scope of the present invention, the ratio of divalent Sn atom than the high situation of scope of the present invention under, and the ratio of 4 valency Sn atoms than the high situation of scope of the present invention under, low for the boiling of the content that the comprises acetate adaptation of filming.Particularly in comparative example No.1-25, the ratio of 4 valency Sn atoms is high, therefore, produces stain, becomes the steel plate of the tin plate that can't use as tank body.
In addition, in the ratio of the 0 valency Sn atom comparative example No.1-24 higher than scope of the present invention, through the time boiling before the handling adaptation of filming good, but during comprising the steeping fluid of acetate (a) under the situation of dipping through the time boiling after the processing adaptation of filming low.
In addition; In the comparative example No.1-26 that tinned amount is lacked than scope of the present invention, the boiling in comprising the steeping fluid of acetate (a) under the situation of dipping film adaptation, comprising boiling under the situation of dipping in the steeping fluid (c) of Hydrocerol A film adaptation, and to comprise boiling under the situation of flooding in the steeping fluid (d) of the halfcystine adaptation of filming low.This as a result teaching under the situation that tinned amount is lacked than scope of the present invention, low for the boiling of the content that comprises acetate, Hydrocerol A or the halfcystine adaptation of filming.
In addition, in the comparative example No.1-27 that the ratio of divalent Sn atom lacks than scope of the present invention, through through the time change, no matter the kind of steeping fluid, the boiling adaptation of filming is low.This as a result teaching under the situation that the ratio of divalent Sn atom lacks than scope of the present invention, through the time after the boiling adaptation of filming low.
(the 2nd experiment)
In the 2nd experiment, be that the cold-rolled steel sheet of 0.20mm carries out electrolytic degreasing with the aqueous sodium hydroxide solution of 10 quality % also with thickness, wash then.Then, in the aqueous hydrochloric acid of 10 quality %, carry out dip pickling, and wash.Then, be described below, carry out zinc-plated under various conditions and chemical conversion processing etc.
[embodiment No.2-1]
In embodiment No.2-1,, Phenylsulfonic acid implemented 1.7g/mm in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere under soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[embodiment No.2-2]
In embodiment No.2-2,, methylsulfonic acid implemented 12.4g/mm in bathing 2Zinc-plated.Then, carry out the soft heat processing same, non-electrolytic dip treating with embodiment No.2-1, and catholyte handle.
[embodiment No.2-3]
In embodiment No.2-2,, Phenylsulfonic acid implemented 2.1g/m in bathing 2Zinc-plated.Then, carry out the soft heat processing same, non-electrolytic dip treating with embodiment No.2-1, and catholyte handle.
[embodiment No.2-4]
In embodiment No.2-4,, Phenylsulfonic acid implemented 3.8g/m in bathing 2Zinc-plated.Then, carry out the soft heat processing same, non-electrolytic dip treating with embodiment No.2-1, and catholyte handle.
[embodiment No.2-5]
In embodiment No.2-5,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.12 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.0 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.04 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 2.2A/dm 2Carrying out the catholyte in 0.40 second the 2nd stage handles.In addition, total energising amount is made as 1.03C/dm 2
[embodiment No.2-6]
In embodiment No.2-6,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 35g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.68 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.10 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 1.00 seconds the 2nd stage handles.In addition, total energising amount is made as 2.17C/dm 2
[embodiment No.2-7]
In embodiment No.2-7,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 35g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.6 second.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[embodiment No.2-8]
In embodiment No.2-8,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.65 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 3.7 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carry out the catholyte in 0.15 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.1A/dm 2Carrying out the catholyte in 0.15 second the 2nd stage handles.In addition, total energising amount is made as 1.92C/dm 2
[embodiment No.2-9]
In embodiment No.2-9,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.8 second.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[embodiment No.2-10]
In embodiment No.2-10,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 10g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.65 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.8 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.10 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 1.00 seconds the 2nd stage handles.In addition, total energising amount is made as 2.17C/dm 2
[embodiment No.2-11]
In embodiment No.2-11,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 0.3A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.10C/dm 2
[embodiment No.2-12]
In embodiment No.2-12,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 9.0A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.62C/dm 2
[embodiment No.2-13]
In embodiment No.2-13,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 4.6A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.36C/dm 2
[embodiment No.2-14]
In embodiment No.2-14,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.60 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 0.3A/dm 2Carrying out the catholyte in 0.06 second the 2nd stage handles.In addition, total energising amount is made as 2.24C/dm 2
[embodiment No.2-15]
In embodiment No.2-15,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carry out the catholyte in 0.60 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 9.0A/dm 2Carrying out the catholyte in 0.06 second the 2nd stage handles.In addition, total energising amount is made as 1.62C/dm 2
[embodiment No.2-16]
In embodiment No.2-16,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 4.6A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 2.98C/dm 2
[embodiment No.2-17]
In embodiment No.2-17,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.1A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 0.88C/dm 2
[embodiment No.2-18]
In embodiment No.2-18,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.65 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 4.5A/dm 2Carry out the catholyte in 0.15 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carrying out the catholyte in 1.50 seconds the 2nd stage handles.In addition, total energising amount is made as 6.23C/dm 2
[embodiment No.2-19]
In embodiment No.2-19,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.65 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.4A/dm 2Carry out the catholyte in 0.10 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.4A/dm 2Carrying out the catholyte in 1.00 seconds the 2nd stage handles.In addition, total energising amount is made as 3.74C/dm 2
[embodiment No.2-20]
In embodiment No.2-20,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 42 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 42 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 42 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[embodiment No.2-21]
In embodiment No.2-21,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 53 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 53 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 53 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[embodiment No.2-22]
In embodiment No.2-22,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 22g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 22g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 22g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[embodiment No.2-23]
In embodiment No.2-23,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 28g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 28g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 28g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[embodiment No.2-24]
In embodiment No.2-24,, methylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.26C/dm 2
[embodiment No.2-25]
In embodiment No.2-25,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 2.2A/dm with non-electrolytic state dipping 1.5 seconds 2And the catholyte that carried out 0.60 second is handled.The energising amount is made as 1.32C/dm 2
[embodiment No.2-26]
In embodiment No.2-26,, Phenylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 0.1A/dm with non-electrolytic state dipping 1.5 seconds 2And the catholyte that carried out 11.00 seconds is handled.The energising amount is made as 1.10C/dm 2
[embodiment No.2-27]
In embodiment No.2-27,, methylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 35g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 12.0A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.5A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.62C/dm 2
[embodiment No.2-28]
In embodiment No.2-28,, methylsulfonic acid implemented 2.6g/m in bathing 2Zinc-plated.Then, through being 46g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.42 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[comparative example No.2-31]
In comparative example No.2-31,, Phenylsulfonic acid implemented 1.1g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.36 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.0 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[comparative example No.2-32]
In comparative example No.2-32,, Phenylsulfonic acid implemented 2.7g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.07 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.04 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.40 second the 2nd stage handles.In addition, total energising amount is made as 0.87C/dm 2
[comparative example No.2-33]
In comparative example No.2-33,, Phenylsulfonic acid implemented 2.7g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.73 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.0A/dm 2Carry out the catholyte in 0.15 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.1A/dm 2Carrying out the catholyte in 1.50 seconds the 2nd stage handles.In addition, total energising amount is made as 2.10C/dm 2
[comparative example No.2-34]
In comparative example No.2-34,, Phenylsulfonic acid implemented 2.7g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.36 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.3 second.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 3.7A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 1.8A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 1.30C/dm 2
[comparative example No.2-35]
In comparative example No.2-35,, Phenylsulfonic acid implemented 2.7g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.36 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 0.7 second.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 0.9A/dm 2Carry out the catholyte in 0.06 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 0.9A/dm 2Carrying out the catholyte in 0.60 second the 2nd stage handles.In addition, total energising amount is made as 0.59C/dm 2
[comparative example No.2-36]
In comparative example No.2-36,, Phenylsulfonic acid implemented 2.7g/m in bathing 2Zinc-plated.Then, through being 25g/m at water vapor concentration 3Atmosphere in soft heat handle with the tin fusion quenching in 80 ℃ warm water.The fusion time of tin was made as 0.65 second.Then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L,, then, carry out the catholyte in 2 stages and handle with non-electrolytic state dipping 1.5 seconds.That is, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 4.2A/dm 2Carry out the catholyte in 0.15 second the 1st stage and handle, then, in 50 ℃, the sodium dichromate aqueous solutio of 25g/L, current density is made as 4.2A/dm 2Carrying out the catholyte in 1.50 seconds the 2nd stage handles.In addition, total energising amount is made as 6.93C/dm 2
So, made the sample of 34 kinds of tin plates.In addition, creating conditions of they is shown in Table 2.
Figure BDA0000081086750000341
Then, likewise carry out the film evaluation of characteristics such as adaptation of boiling with the 1st experiment.This result is shown in Table 3.
Table 3
Figure BDA0000081086750000351
As shown in table 3, in embodiment No.2-1～No.2-28, no matter the kind of steeping fluid, through the time boiling before handling film adaptation and through the time boiling after the handling adaptation of filming good.In embodiment No.2-5, though seldom there is the low part of gloss,, be enough to be used as the tin plate that tank body is used.
On the other hand; In the comparative example No.2-31 that zinc-plated amount is lacked than scope of the present invention, the boiling in comprising the steeping fluid of acetate (a) under the situation of dipping film adaptation, comprising boiling under the situation of dipping in the steeping fluid (c) of Hydrocerol A film adaptation, and to comprise boiling under the situation of flooding in the steeping fluid (d) of the halfcystine adaptation of filming low.This as a result teaching under the situation that zinc-plated amount is lacked than scope of the present invention, low for the boiling of the content that comprises acetate, Hydrocerol A or the halfcystine adaptation of filming.
In addition, in the comparative example No.2-32 of the fusion time of tin than scope weak point of the present invention, soft heat is handled insufficient, and part obtains lusterless outward appearance, therefore is designated as defective.
In addition, fusion time of tin than the long comparative example No.2-33 of scope of the present invention in, the adaptation of filming of the boiling under the situation of during comprising the steeping fluid of acetate (a), flooding significantly reduces.This as a result teaching fusion time of tin than the long situation of scope of the present invention under, significantly reduce for the boiling of the content that the comprises acetate adaptation of filming.
In addition, the time of immersion in sodium dichromate aqueous solutio than the short comparative example No.2-34 of scope of the present invention in, the also significantly reduction of adaptation of filming of the boiling during comprising the steeping fluid of acetate (a) under the situation of dipping.This as a result teaching time of immersion than the short situation of scope of the present invention under, significantly reduce for the boiling of the content that the comprises acetate adaptation of filming.
In addition, among the few comparative example No.2-35 of the logical electricity ratio scope of the present invention in chemical conversion is handled, the adaptation of filming of the boiling under the situation of during comprising the steeping fluid of halfcystine (d), flooding is low.This as a result teaching under the few situation of logical electricity ratio scope of the present invention, low for the boiling of the content that the comprises halfcystine adaptation of filming.
In addition, among the many comparative example No.2-36 of the logical electricity ratio scope of the present invention in chemical conversion is handled, the adaptation of filming of the boiling under the situation of during comprising the steeping fluid of acetate (a), flooding is low.This as a result teaching under the many situation of logical electricity ratio scope of the present invention, low for the boiling of the content that the comprises acetate adaptation of filming.
More than preferred embodiment be illustrated of the present invention, but the present invention is not limited to these, scope of the present invention is as putting down in writing in claims.
Utilizability on the industry
The present invention for example can be used for the manufacturing industry of tin plate and utilize industry.

Claims (16)

1. tin plate is characterized in that it has:
Steel plate,
On a surface of said steel plate with 1.2g/m 2The tin-plated coating film that more than forms,
The tin that between said steel plate and said tin-plated coating film, forms through the alloying of said steel plate and said tin-plated coating film and the alloy film of iron and
3mg/m is counted in converting with chromium metal of on said tin-plated coating film, forming 2More than and 8mg/m 2Following chromic salt epithelium,
Surface at said tin-plated coating film; The divalent tin atom is more than 35% and is lower than 75% with respect to the ratio of the total amount of tin atom; It is below 30% with respect to the ratio of the total amount of tin atom that 4 valency tin atoms are lower than 50%, 0 valency tin atom with respect to the ratio of the total amount of tin atom.
2. tin plate according to claim 1 is characterized in that, contained tin amount is 0.1mg/m in the said alloy film 2More than and 0.56g/m 2Below.
3. tin plate according to claim 1 is characterized in that, the area occupation ratio with 60%～80% on said tin-plated coating film is formed with said chromic salt epithelium.
4. tin plate according to claim 2 is characterized in that, the area occupation ratio with 60%～80% on said tin-plated coating film is formed with said chromic salt epithelium.
5. the method for manufacture of a tin plate is characterized in that, it has following operation:
On a surface of steel plate, form 1.2g/m 2The operation of above tin-plated coating film,
Through soft heat handle the operation make said tin-plated coating film and said steel plate alloying form alloy film and
On said tin-plated coating film, form the operation of chromic salt epithelium,
Will said soft heat handle described in the tin-plated coating film fused time be made as more than 0.1 second and below 0.7 second,
The operation of said formation chromic salt epithelium has following operation:
With said steel plate in sodium dichromate aqueous solutio, flood more than 0.5 second with non-electrolytic mode and the operation below 4.0 seconds and
Then, for said steel plate in sodium dichromate aqueous solutio with 0.8C/dm 2More than and 6.5C/dm 2The operation that following energising amount enforcement utilizes the chemical conversion of catholyte to handle.
6. the method for manufacture of tin plate according to claim 5 is characterized in that, it is 0g/m that said soft heat is handled at water vapor concentration 3More than and 40g/m 3Carry out in the following atmosphere.
7. the method for manufacture of tin plate according to claim 5 is characterized in that, the current density when said chemical conversion is handled is made as 0.1A/dm 2More than and 10.0A/dm 2Below.
8. the method for manufacture of tin plate according to claim 6 is characterized in that, the current density when said chemical conversion is handled is made as 0.1A/dm 2More than and 10.0A/dm 2Below.
9. the method for manufacture of tin plate according to claim 5 is characterized in that, said operation of carrying out the chemical conversion processing has following operation:
With 2.0A/dm 2More than and 10.0A/dm 2Below current density carry out more than 0.001 second and below 0.2 second electrolytic operation and
Then, with 0.1A/dm 2More than and 5.0A/dm 2Following current density is carried out more than 0.01 second and 2.0 seconds electrolytic operation.
10. the method for manufacture of tin plate according to claim 6 is characterized in that, said operation of carrying out the chemical conversion processing has following operation:
With 2.0A/dm 2More than and 10.0A/dm 2Below current density carry out more than 0.001 second and below 0.2 second electrolytic operation and
Then, with 0.1A/dm 2More than and 5.0A/dm 2Following current density is carried out more than 0.01 second and 2.0 seconds electrolytic operation.
11. the method for manufacture of a tin plate is characterized in that, it has following operation:
On a surface of steel plate, form 1.2g/m 2The operation of above tin-plated coating film,
Through soft heat handle the operation make said tin-plated coating film and said steel plate alloying form alloy film and
On said tin-plated coating film, form with the chromium metal conversion and count 3mg/m 2More than and 8mg/m 2The operation of following chromic salt epithelium.
12. the method for manufacture of tin plate according to claim 11 is characterized in that, it is 0g/m that said soft heat is handled at water vapor concentration 3More than and 40g/m 3Carry out in the following atmosphere.
13. the method for manufacture of tin plate according to claim 11 is characterized in that, the current density when said chemical conversion is handled is made as 0.1A/dm 2More than and 10.0A/dm 2Below.
14. the method for manufacture of tin plate according to claim 12 is characterized in that, the current density when said chemical conversion is handled is made as 0.1A/dm 2More than and 10.0A/dm 2Below.
15. the method for manufacture of tin plate according to claim 11 is characterized in that, said operation of carrying out the chemical conversion processing has following operation:
With 2.0A/dm 2More than and 10.0A/dm 2Below current density carry out more than 0.001 second and below 0.2 second electrolytic operation and
Then, with 0.1A/dm 2More than and 5.0A/dm 2Following current density is carried out more than 0.01 second and 2.0 seconds electrolytic operation.
16. the method for manufacture of tin plate according to claim 12 is characterized in that, said operation of carrying out the chemical conversion processing has following operation:
With 2.0A/dm 2More than and 10.0A/dm 2Below current density carry out more than 0.001 second and below 0.2 second electrolytic operation and
Then, with 0.1A/dm 2More than and 5.0A/dm 2Following current density is carried out more than 0.01 second and 2.0 seconds electrolytic operation.
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CN106133206A (en) * 2014-04-16 2016-11-16 杰富意钢铁株式会社 Electrolytic chromate processes the manufacture method of steel plate
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CN106133206A (en) * 2014-04-16 2016-11-16 杰富意钢铁株式会社 Electrolytic chromate processes the manufacture method of steel plate
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