CN106460192B - Steel plate for container - Google Patents
Steel plate for container Download PDFInfo
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- CN106460192B CN106460192B CN201580025043.8A CN201580025043A CN106460192B CN 106460192 B CN106460192 B CN 106460192B CN 201580025043 A CN201580025043 A CN 201580025043A CN 106460192 B CN106460192 B CN 106460192B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The present invention provides the steel plate for container of excellent corrosion resistance after corrosion resistance and coating after film attaches.Said vesse has the envelope of the plated steel sheet and configuration of the coating comprising Sn layers on the surface of the above-mentioned coating side of above-mentioned plated steel sheet at least part on the surface of steel plate with steel plate, wherein, above-mentioned envelope contains Ti, and the adhesion amount of the Ti conversion of the above-mentioned every single side of plated steel sheet is 1.0mg/m2More than and less than 60.0mg/m2, and specifically A value defined in formula (1) is 30 hereinafter, the atomic ratio (F/Ti) of the F and Ti of the most surface of above-mentioned envelope are greater than 0.00 and less than 0.10, the state ratio (OH/MO) of the O in above-mentioned envelope is preferably smaller than 0.70.
Description
Technical field
The present invention relates to steel plate for container.
Background technique
As the steel plate (steel plate for container) for containers such as tanks, for example, Patent Document 1 discloses: " a kind of tank or
Cover handles metal plate with resin clad surface, is to be formed with the surface treatment based on inorganic constituents in metal sheet surface
The resin clad surface that organic resin clad is formed on layer and the at the surface at least single side of reason layer handles metal plate,
It is characterized in that, above-mentioned inorganic surface treatment layer is intermittently to implement catholyte and formed, and by not phosphorus-containing acid ion but contains F
It is constituted with the oxide of the Ti or Ti of hydroxyl and Zr, contained by the most surface in above-mentioned inorganic surface treatment layer, O and Ti's
Atomic ratio is that the atomic ratio of 1 < O/Ti < 5, F and M (wherein, M is Ti or Ti and Zr) are 0.1 < F/M < 2.5, the weight of Ti
Film thickness is 5~300mg/m2" (claim 1).
Existing technical literature
Patent document
Patent document 1: No. 4487651 bulletins of Japanese Patent No.
Summary of the invention
Problem to be solved by the invention
The present inventors has studied PET film for the steel plate for container (surface treated steel plate) recorded in patent document 1
Adhesiveness (hereinafter also referred to " film adhesiveness ") and adhesiveness (hereinafter also referred to " coating adhesion ") to coating, as a result send out
It is existing: the corrosion resistance (hereinafter also referred to " corrosion resistance after film attaches ") that is pasted in the state of PET film sometimes and to be coated with
Corrosion resistance (hereinafter also referred to " corrosion resistance after coating ") under coating state is insufficient.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide resistance to after corrosion resistance after film attaching and coating
The excellent steel plate for container of corrosivity.
The method for solving problem
The present inventors has made intensive studies to achieve the goals above, as a result, it has been found that: by making the envelope containing Ti
Meet specific condition, the excellent corrosion resistance for being thus pasted with the state of PET film and being coated in the state of coating, thus
Complete the present invention.
That is, the present invention provides following (I)~(VI).
(I) a kind of steel plate for container has the coating comprising Sn layers at least part on the surface of steel plate
The envelope of plated steel sheet and configuration on the surface of the above-mentioned coating side of above-mentioned plated steel sheet, wherein above-mentioned envelope contains Ti, on
The adhesion amount for stating the Ti conversion of the every single side of plated steel sheet is 1.0mg/m2More than and less than 60.0mg/m2, also, following formula (1) institute
The A value of definition is 30 hereinafter, the atomic ratio (F/Ti) of the F and Ti of the most surface of above-mentioned envelope are greater than 0.00 and less than 0.10.
A=[(Ti0-TiA)/Ti0]×100…(1)
(in formula (1), Ti0Indicate the adhesion amount (unit: mg/ of the Ti conversion of the every single side of above-mentioned plated steel sheet of above-mentioned envelope
m2), TiAIndicate the above-mentioned plated steel sheet that above-mentioned envelope after ten minutes is impregnated in 50 DEG C of 1mol/L sodium hydrate aqueous solution
Adhesion amount (the unit: mg/m of the Ti conversion of every single side2)。)
(II) steel plate for container as described in above-mentioned (I), wherein will be present in above-mentioned as the O for constituting hydroxide
The ratio (unit: %) of O in envelope is recorded as OH, will be present in the O in above-mentioned envelope as the O for constituting metal oxide
Ratio (unit: %) be recorded as MO in the case where, the ratio indicated with OH/MO is less than 0.70.
(III) steel plate for container as described in above-mentioned (I) or (II), wherein the surface free energy of above-mentioned envelope is 40mN/
M or more.
(IV) steel plate for container as described in any one of above-mentioned (I)~(III), wherein above-mentioned envelope contains Ni, above-mentioned
The adhesion amount of the Ni conversion of the every single side of plated steel sheet is 0.1~3.0mg/m2。
(V) steel plate for container as described in any one of above-mentioned (I)~(IV), wherein above-mentioned coating also include selected from by
At least one layer in group that Ni layers, Ni-Fe alloy-layer, Fe-Sn alloy-layer and Fe-Sn-Ni alloy-layer form.
(VI) steel plate for container as described in any one of above-mentioned (I)~(V), wherein in above-mentioned coating and above-mentioned envelope
Between have the tin oxide film containing tin-oxide, electricity needed for the reduction of above-mentioned tin-oxide be 2.0~5.0mC/cm2。
Invention effect
In accordance with the invention it is possible to provide the steel plate for container of excellent corrosion resistance after corrosion resistance and coating after film attaches.
Specific embodiment
[steel plate for container]
In summary, steel plate for container of the invention has plated steel sheet and configuration on the surface of the coating side of plated steel sheet
On specific envelope.
The film adhesiveness and coating adhesion (hereinafter also referred to collectively as " adhesiveness ") of steel plate for container of the invention be excellent, simultaneously
And film attach after after corrosion resistance and coating corrosion resistance (hereafter referred to collectively as " corrosion resistance ") it is excellent.
Firstly, the concrete mode of plated steel sheet and envelope is described in detail below.
[plated steel sheet]
Plated steel sheet has at least part of coating on the surface of covering steel plate, and coating includes at least Sn layers.
As the steel plate of raw material, the steel plate of general tank can be used.Coating can be pantostrat, may be not
Continuous island.In addition, at least single side of steel plate is arranged in coating, also can be set two-sided.The formation of coating can be with
It is carried out according to contained metallic element by well known method.
Hereinafter, the preferred embodiment of steel plate and coating is described in detail.
< steel plate >
The type of steel plate is not particularly limited, be able to use be typically used as container material steel plate (for example, low carbon steel plate,
Ultra-low carbon steel plate).Manufacturing method, material of the steel plate etc. are also not particularly limited, by common steel disc manufacturing process through overheating
It rolls, pickling, cold rolling, annealing, the processes such as temper rolling manufacture.
Steel plate can according to need using being formed on its surface the steel plate of nickeliferous (Ni) layer, can on the layer containing Ni shape
At it is aftermentioned include Sn layers of coating.It include island thereby, it is possible to be formed by using having the steel plate containing Ni layers to implement plating Sn
The coating of Sn, weldability improve.
It as containing Ni layers, as long as containing nickel, such as can enumerate: plating Ni layers of (Ni layers), Ni-Fe alloy-layer etc..
The methods of steel plate imparting is not particularly limited containing Ni layers of method, such as can enumerate well known plating.In addition,
In the case where assigning Ni-Fe alloy-layer as containing Ni layers, anneal after assigning Ni on surface of steel plate by plating etc., by
This is coordinated Ni diffusion layer, is capable of forming Ni-Fe alloy-layer.
It is not particularly limited containing the Ni adhesion amount in Ni layers, as the W metal conversion amount of every single side, preferably 50~
2000mg/m2.It is also advantageous in terms of cost when in above range.
It should be noted that Ni adhesion amount can carry out surface analysis by fluorescent X-ray to measure.In this case,
Adhere to sample using Ni known to Ni adhesion amount, predefines the calibration curve in relation to Ni adhesion amount, use the calibration curve phase
Ni adhesion amount is determined over the ground.
But in the case where aftermentioned envelope contains Ni, it is difficult to only by the surface analysis using above-mentioned fluorescent X-ray
Measurement is containing the Ni adhesion amount in Ni layers.It in this case, can be from being found out by fluorescent X-ray containing Ni adhesion amount in Ni layers
Ni adhesion amount subtracts Ni adhesion amount contained in aftermentioned envelope to acquire.
< coating >
Plated steel sheet has the coating comprising Sn layers at least part of surface of steel plate.Steel plate is arranged in extremely in the coating
Few single side, also can be set two-sided.In addition, coating is at least part of layer covered on surface of steel plate, Ke Yiwei
Pantostrat, or discontinuous island.
The Sn adhesion amount of the every single side of the steel plate of coating is preferably 0.1~15.0g/m2.When Sn adhesion amount is in above range,
The appearance characteristics and excellent corrosion resistance of steel plate for container.Especially from these characteristics it is more excellent from the aspect of, more preferably
0.2~15.0g/m2, from the aspect of excellent processability, further preferably 1.0~15.0g/m2。
It should be noted that Sn adhesion amount can carry out surface analysis by fluorescent X-ray to measure.Fluorescent X-ray
In the case of, using Sn adhesion amount sample known to Sn amount, the calibration curve of related Sn amount is predefined, the calibration curve phase is used
Sn amount is determined over the ground.
As coating, other than the Sn layers of coating constituted obtained by plating Sn, can also enumerate after plating Sn by logical
Electric heating etc. makes to be partially formed with Fe-Sn conjunction obtained from Sn heating melting, in Sn layers of the bottoms (Sn layers/steel plate interface)
The coating of layer gold.
In addition, can also be enumerated as coating: on surface there is the steel plate containing Ni layers to carry out plating Sn and then by logical
Electric heating etc. makes to be partially formed with Fe-Sn- obtained from Sn heating melting, in Sn layers of the bottoms (Sn layers/steel plate interface)
The coating of Ni alloy-layer, Fe-Sn alloy-layer etc..
It should be noted that in the present invention, above-mentioned be also regarded as containing Ni layers (Ni layers, Ni-Fe alloy-layer) is included in plating
It applies in the coating of steel plate.
As the manufacturing method of coating, can enumerate well known method (for example, galvanoplastic or be immersed in the Sn of melting into
The method of row plating).
For example, being with the adhesion amount of every single side using phenol sulfonic acid Sn plating bath, Loprazolam Sn plating bath or halogen Sn plating bath
Specified amount (such as 2.8g/m2) mode after Sn is electroplated in surface of steel plate temperature more than the fusing point (231.9 DEG C) of Sn carry out
Heating melting processing, thus, it is possible to the bottoms (Sn layers/steel plate interface) for manufacturing in Sn simple substance coating (Sn layers) to be formed with Fe-Sn
The coating of alloy-layer.In the case where omitting heating melting processing, Sn simple substance coating (Sn layers) can be manufactured.
In addition, in the case that steel plate has on the surface thereof containing Ni layers, if it is molten to carry out heating after plating Sn on layer containing Ni
Melt processing, then forms Fe-Sn-Ni alloy-layer at the bottom of Sn simple substance coating (Sn layers) (Sn layers/steel plate interface), Fe-Sn is closed
Layer gold etc..
[envelope]
Then, envelope of the configuration on the surface of the coating side of above-mentioned plated steel sheet is illustrated.In summary, envelope
It is the envelope containing Ti (titanium elements) as its ingredient, is formed using aftermentioned treatment fluid (treatment fluid of the invention).It needs
It is bright, hexafluorotitanic acid radical ion (TiF is contained in treatment fluid of the invention6 2-), therefore, F may also be contained in envelope.
The adhesion amount (hereinafter also referred to " Ti adhesion amount ") of the Ti conversion of the every single side of the plated steel sheet of envelope is 1.0mg/m2
More than and less than 60mg/m2.Ti adhesion amount is less than 1.0mg/m2It or is 60mg/m2When above, adhesiveness and poor corrosion resistance.From
Adhesiveness and the more excellent reason of corrosion resistance are set out, and Ti adhesion amount is preferably 3~30mg/m2, more preferably 5~20mg/m2。
In addition, the adhesion amount of the Ni conversion of the every single side of the plated steel sheet of envelope is (following to be also referred to as in the case that envelope contains Ni
For " Ni adhesion amount ") it is preferably 0.1~3.0mg/m2.When Ni adhesion amount is in above range, steel plate for container of the invention
Adhesiveness and corrosion resistance are more excellent.
Ti adhesion amount and Ni adhesion amount using the surface analysis of fluorescent X-ray by being measured.
Ti and Ni in envelope are contained in the form of various Ti oxides and Ni oxide respectively, the kind of these compounds
Class, form are not particularly limited.
It should be noted that x-ray fluorescence analysis is for example implemented based on following conditions.
Device: the fluorescent x-ray analyzer System3270 of Rigaku company manufacture
Measure diameter: 30mm
Measure atmosphere: vacuum
Spectrogram: Ti-K α, Ni-K α
Slit: COARSE
Light splitting crystallization: TAP
Using based on the peak of the Ti-K α of the x-ray fluorescence analysis for the surface treatment capsule that above-mentioned condition measures, Ni-K α
Number quantity.Using standard sample known to adhesion amount, the calibration curve in relation to Ti adhesion amount and Ni adhesion amount is predefined, is used
The calibration curve relatively finds out Ti adhesion amount and Ni adhesion amount.
But in the case where coating contains Ni, it is difficult to only measure quilt using the surface analysis of fluorescent X-ray by above-mentioned
Ni adhesion amount contained in film.
In this case, by and with using scanning electron microscope (Scanning Electron Microscope:
SEM), the cross-section observation and glow discharge of transmission electron microscope (Transmission Electron Microscope:TEM)
Spectrum analysis can differentiate Ni amount contained in Ni adhesion amount and coating contained in envelope.
Specifically, revealing the section of envelope and coating by focused ion beam (Focused Ion Beam:FIB) processing
Out, the thickness of envelope is calculated by the cross-section observation using SEM or TEM.Then, the sputtering based on Glow Discharge Spectrometry is found out
The relationship of depth and sputtering time.Then, the glow discharge optical emission spectrometry point until the sputtering time for corresponding to film thickness is found out
The luminometer scalar product score value based on Ni element of analysis.According to the luminometer scalar product score value based on Ni element, using finding out in advance
Calibration curve, Ni adhesion amount can be found out.
Here, calibration curve is made by following methods.
Firstly, carrying out brightness with the different multiple samples of the envelope containing Ni, Ni adhesion amount on the coating without Ni
The analysis of light discharge spectrum finds out the counting integral until the sputtering time that can not detect the luminous counting based on Ni element
Value.Then, the Ni adhesion amount of these samples is found out by the surface analysis using fluorescent X-ray.In this way, producing based on aura
The Ni of discharge spectrum analysis counts the calibration curve of integrated value and Ni adhesion amount.
Think that envelope contains the Ti oxide with crosslinking as Ti-O-Ti key, but the present inventors has found, if by
The crosslinking progress of film and molecular weight carries out, then the surface free energy of envelope increases, the interaction of envelope and film and coating
Enhancing, adhesiveness improve, and the corrosion of steel plate is difficult to carry out as a result, the excellent corrosion resistance after film attaches and after coating.Also,
The present inventors has found the index by the state ratio (OH/MO) of aftermentioned A value, atomic ratio (F/Ti) and O as crosslink density.
< A value >
A value defined in the following formula (1) of envelope is 30 or less.
A=[(Ti0-TiA)/Ti0]×100…(1)
In formula (1), Ti0Indicate the Ti adhesion amount (unit: mg/m of envelope2), it is measured by fluorescent X-ray.In addition, TiA
Indicate Ti0Steel plate for container is impregnated to Ti adhesion amount after ten minutes after measurement in 50 DEG C of 1mol/L sodium hydrate aqueous solution
(unit: mg/m2), it is measured by fluorescent X-ray.
A value defined in formula (1) is to indicate the index of the crosslink density of envelope.That is, steel plate for container is impregnated into
In the case where stating in sodium hydrate aqueous solution, it is fragment if the crosslinking of envelope is insufficient, dissolves out a large amount of Ti and A from envelope
Value increases, and on the other hand, if crosslinking promotes, the molecular weight of envelope is promoted, and Ti the amount of dissolution reduces and A value reduces.
Therefore, from the viewpoint of adhesiveness and corrosion resistance, in the present invention, A value is set as 30 or less.From adherency
Property and the more excellent reason of corrosion resistance set out, A value is preferably 20 or less, more preferably 15 or less.
< atomic ratio (F/Ti) >
In addition, envelope is 0.00 < F/Ti in the atomic ratio (F/Ti) of the F and Ti of the most surface with coating side opposite side
< 0.10.
Envelope is formed using aftermentioned treatment fluid (treatment fluid of the invention), specifically, hexafluoro contained in treatment fluid
Metatitanic acid radical ion (TiF6 2-) because of the OH of the Surface Creation in plated steel sheet-And by hydrolysis, become Ti (OH)nF6-n 2-(n
=0~6 integer) after be adsorbed on the surface of plated steel sheet, dehydration condensation carries out, and envelope is consequently formed.Think to lead at this time
Cross efficiently removing Ti (OH)nF6-n 2-F, formed as a result, largely because of Ti-O-Ti key obtained by dehydrating condensation, the crosslinking of envelope
It is promoted, thus molecular weight.That is, needing to reduce the remaining F in envelope for the molecular weight of envelope.Cause
This promotes for the envelope of molecular weight crosslinking, and the value of above-mentioned atomic ratio (F/Ti) is opposite to be reduced.
That is, above-mentioned atomic ratio (F/Ti) is also the index for indicating the crosslink density of envelope.From adhesiveness and corrosion resistance
Viewpoint is set out, and in the present invention, above-mentioned atomic ratio (F/Ti) is set greater than 0.00 and less than 0.10.From adhesiveness and corrosion resistant
The more excellent reason of corrosion is set out, and above-mentioned atomic ratio (F/Ti) is preferably set to 0.03 or less.
It should be noted that above-mentioned atomic ratio can be by measuring Fl by X-ray photoelectron spectroscopy (XPS) respectivelysWith
The peak of Ti3d simultaneously finds out value obtained by atomic concentration by analysis software to measure.Here, the x-ray source as XPS, uses list
The AlK α (hv:1486.6eV) of color.When measurement, directly the envelope most surface of steel plate for container is analyzed.
State ratio (OH/MO) > of < O
In the present invention, (single in the ratio for the O being present in above-mentioned envelope as the O for constituting hydroxide
Position: %) it is recorded as OH, remembers the ratio (unit: %) for the O being present in above-mentioned envelope as the O for constituting metal oxide
It carries in the case where being MO, the ratio that is indicated with OH/MO (in this specification, also referred to as " the state ratio (OH/MO) of O " or is referred to as " shape
State ratio (OH/MO) ") it is preferably smaller than 0.70.
It should be noted that " OH " and " MO " is to be present in the O in above-mentioned envelope as the O for being constituted hydroxide
Amount (unit: atom %) and it is present in O amount (unit: atom %) in above-mentioned envelope as the O for constituting metal oxide
On the basis of total amount (hereinafter also referred to " total O amount ") (unit: atom %).
That is, " OH " refers to as the O for constituting hydroxide and is present in O amount (unit: atom %) phase in above-mentioned envelope
For the ratio (unit: %) of total O amount (unit: atom %).
Equally, " MO " refers to as the O for constituting metal oxide and is present in the (unit: former of the O amount in above-mentioned envelope
Sub- %) ratio relative to total O amount (unit: atom %).
Here, being illustrated to the meaning of the state ratio (OH/MO) of the O (oxygen element) in envelope.
Firstly, as defined above, above-mentioned state ratio (OH/MO) refer to as the O for constituting hydroxide and be present in by
The ratio (OH) of O in film be present in as the O for constituting metal oxide O in envelope ratio (in other words, as
The ratio between the O (M-O-M) that is bonded with metallic element and the ratio for being present in the O in envelope) (MO).
Therefore, above-mentioned state ratio (OH/MO) indicates hexafluorotitanic acid radical ion (TiF6 2-) Ti that is generated by hydrolysis
(OH)nF6-n 2-(integers of n=0~6) and the Ti-O-Ti key that is formed by dehydration condensation there are ratio, envelope
Crosslinking promotes in the case where forming the envelope of the molecular weight of a large amount of Ti-O-Ti keys, and the value of OH/MO is opposite to be reduced.
That is, above-mentioned state ratio (OH/MO) is also the index for indicating the crosslink density of envelope.
From the viewpoint of adhesiveness and corrosion resistance, above-mentioned state ratio (OH/MO) is preferably smaller than 0.70, from corrosion resistance
More excellent reason is set out, and more preferably 0.40 or less.
It should be noted that the lower limit value of above-mentioned state ratio (OH/MO) is not particularly limited, preferably 0.05 or more, more
Preferably 0.15 or more.
As the method for finding out above-mentioned state ratio (OH/MO), radiating light etc. can be used for example and be measured, in the present invention
In, using the method found out by the state for measuring oxygen using XPS.Specifically, using the AlK α of monochromatization as X-ray
Source, measure the peak oxygen Ols, peak be separated into bond energy be located at 529.5~532.8eV range as composition metal oxide O (with
The O of metallic element bonding) and existing O and bond energy are located at the O as composition hydroxide of the range of 530.9~532.8eV
And existing O, integrated intensity ratio is calculated by analysis software, finds out the value of state ratio (OH/MO).Measurement area is 100 μm of φ
It is above.When measurement, directly the envelope most surface of steel plate for container is analyzed.
It should be noted that as described later, with A value as described above, atomic ratio (F/Ti) and state ratio (OH/MO)
Envelope pass through the electrolytic current density for having when handling catholyte be set as high current density envelope formation process and/or
Afterwards the manufacturing method of the present invention of dipping process and obtain.
< surface free energy >
As described above, the surface free energy (γ s) of envelope increases if the crosslinking propulsion of envelope and molecular weight promote
Greatly, adhesiveness and excellent corrosion resistance.
Therefore, in the present invention, envelope is preferably 40mN/m with the surface free energy on the surface of coating side opposite side
More than.More preferably 60mN/m or more.
It should be noted that being described later for the measuring method of surface free energy.
[tin oxide film]
Steel plate for container of the invention has the tin containing tin-oxide preferably between envelope and the coating of plated steel sheet
Oxidation film.Also, electricity needed for the reduction of the tin-oxide of the tin oxide film (hereinafter also referred to " reduction electricity ") is 2.0~
5.0mC/cm2。
Steel plate for container of the invention is by being able to suppress the coloring of envelope, good appearance with such tin oxide film.
It is thought that because are as follows: by tin oxide film, it is suppressed from impurity (mainly Sn) doping of the coating into envelope, as a result, by
The diminution of the band gap of Ti oxide in film is suppressed, it is seen that light absorption reduces, and therefore, the colour developing of tea system color is improved.
But tin oxide film it is excessive when, envelope have interference colours, instead sometimes appearance be deteriorated, therefore, by tin oxide film
Reduction electricity is set as 5.0mC/cm2Below.
In addition, the reduction electricity of tin oxide film is greater than 5.0mC/cm2When, the cohesion generated in tin oxide film sometimes destroys,
Film adhesiveness and coating adhesion reduce, and therefore, the reduction electricity of tin oxide film are also set as 5.0mC/cm2Below.
The reason more excellent from the appearance of steel plate for container, the reduction electricity of tin oxide film is preferably 3.0~
5.0mC/cm2, more preferably 3.6~5.0mC/cm2。
Electricity needed for the reduction of tin-oxide can be found out according to potential-time curve, and the potential-time curve is
With 0.05mA/cm in the hydrobromic acid aqueous solution for the 0.001mol/L that the methods of the bubbling by nitrogen eliminates dissolved oxygen2's
Constant current carries out catholyte to steel plate for container and obtains.
It should be noted that hydrogen coexists in above-mentioned constant current anodizing process and generates electric current in the case where envelope contains Ni, it cannot
Directly measure the reduction current of tin-oxide.It therefore, can be from the current potential pair from dipping current potential to -0.7V (vs.Ag/AgCl)
First time reduction current curve that current potential obtains during being scanned with later equally from dipping current potential to -0.7V
(vs.Ag/AgCl) electricity corresponding to the difference for second of reduction current curve that current potential is scanned current potential is found out.
[manufacturing method of steel plate for container]
Then, to the method (hereinafter also referred to " the manufacturing method of the present invention ") of the steel plate for container of manufacture aforementioned present invention
It is illustrated.The manufacturing method of the present invention, which at least has, uses aftermentioned treatment fluid (hereinafter also referred to " treatment fluid of the invention ")
Form the envelope formation process of above-mentioned envelope.
[envelope formation process]
Envelope formation process is the process that above-mentioned envelope is formed on the surface of the coating side of plated steel sheet, is by plating steel
Plate is impregnated into (impregnation) in aftermentioned treatment fluid of the invention or implements at catholyte to the plated steel sheet after dipping
The process of reason.
Compared with impregnation, in catholyte processing, the surface OH of plated steel sheet-Concentration further increases, hexafluoro titanium
Acid ion (TiF6 2-) hydrolysis further promoted, the crosslinking of envelope caused by dehydrating condensation later carries out quilt
Further promote, for that reason preferably.It should be noted that alternately catholyte processing and anode also can be implemented
The alternating electrolysis of electrolysis processing.
The condition etc. of used treatment fluid of the invention, catholyte processing is described in detail below.
< treatment fluid >
Treatment fluid of the invention contains for the Ti ingredient (Ti compound) to above-mentioned envelope supply Ti (titanium elements).As
The Ti ingredient, can enumerate fluotitanic acid (H2TiF6) and/or its salt.It should be noted that the concrete example of the salt as fluotitanic acid,
Hexafluorotitanic acid potassium (K can be enumerated2TiF6), hexafluorotitanic acid sodium (Na2TiF6), ammonium hexa-fluorotitanate ((NH4)2TiF6) etc..
The content of Ti ingredient in treatment fluid of the invention is not particularly limited, the case where using fluotitanic acid and/or its salt
Under, it is converted into hexafluorotitanic acid radical ion (TiF6 2-) amount be preferably 0.004~0.4mol/L, more preferably 0.02~0.2mol/
L。
In addition, treatment fluid of the invention contains for above-mentioned in the case where containing Ni (nickel element) in above-mentioned envelope
Envelope supplies the Ni ingredient (Ni compound) of Ni (nickel element).
It as the Ni ingredient, is not particularly limited, nickel sulfate (NiSO can be enumerated4), nickel sulfate hexahydrate close object, nickel chloride
(NiCl2), nickel chloride hexahydrate etc..
The content of Ni ingredient in treatment fluid of the invention is not particularly limited, and is converted into Ni ion (Ni2+) amount it is preferred
For 0.002~0.04mol/L, more preferably 0.004~0.02mol/L.
Organic solvent also can be used together usually using water as the solvent in treatment fluid of the invention.
The pH for the treatment of fluid of the invention is not particularly limited, preferably pH2.0~5.0.When within the scope of this, place can be shortened
It manages the time, and the excellent in stability for the treatment of fluid.Well known sour component can be used in the adjustment of pH (for example, phosphoric acid, sulphur
Acid), alkali composition (for example, sodium hydroxide, ammonium hydroxide).
In addition, can according to need in treatment fluid of the invention living containing surfaces such as lauryl sodium sulfate, acetylenediols
Property agent.In addition, from the viewpoint of the ageing stability of attachment characteristic phosphorus can be condensed containing pyrophosphate etc. in treatment fluid
Hydrochlorate.
The liquid temperature for the treatment of fluid is preferably 20~80 DEG C, and more preferably 40~60 DEG C.
< catholyte handles >
As one of the method for envelope for obtaining above-mentioned molecular weight, in envelope formation process, yin will be implemented
Electrolytic current density when the electrolysis processing of pole is set as high current density.By improving current density when catholyte processing,
The surface OH of plated steel sheet-Concentration increases, TiF6 2-Hydrolysis be promoted, the friendship of the envelope by dehydrating condensation later
Connection carries out, the envelope of available molecular weight.In addition, by being set as high current density, additionally it is possible to expect to inhibit envelope
Ni adhesion amount become excessive effect.Specifically, electrolytic current density is preferably greater than 20.0A/dm2And 100.0A/dm2
Hereinafter, more preferably 25.0~100.0A/dm2, further preferably 30.0~100.0A/dm2。
But in the case where the manufacturing method of the present invention has aftermentioned rear dipping process, high current density is not must
Must, as electrolytic current density, such as 1.0~20.0A/dm can be enumerated2。
It should be noted that the conduction time of catholyte processing is preferably 0.1~5 second, more preferably 0.3~2 second.Separately
Outside, electric quantity density is the product of current density and conduction time, is suitably set.
[rear dipping process]
In addition, other methods as the envelope for obtaining above-mentioned molecular weight, the manufacturing method of the present invention is in quilt
Having after impregnation or catholyte processing in film formation process impregnates plated steel sheet in acid bath 0.1 second or more
Rear dipping process.Thus the dipping process after such is adsorbed on the Ti (OH) on the surface of plated steel sheetnF6-n 2-F quilt
It efficiently removes, forms the Ti-O-Ti key largely obtained by dehydrating condensation, the crosslinking of envelope promotes, available high molecular weight
The envelope of change.
Dip time in acid bath is not particularly limited as long as being 0.1 second or more, and preferably 0.5 second or more, more
Preferably 1.0~3.0 seconds.
The pH of acid bath can for example be enumerated as 5.0 hereinafter, pH adjusting in can be used well known sour component (for example,
Phosphoric acid, sulfuric acid, nitric acid etc.).
It should be noted that above-mentioned treatment fluid (pH=2.0~5.0) of the invention can be used as acid bath.
That is, the degree of the molecular weight of presumption envelope not will receive the influence of ion contained in acid bath.
As the temperature of acid bath, such as 60~100 DEG C can be enumerated.
But in above-mentioned envelope formation process, electrolytic current density when catholyte is handled is set as high current
Density (is greater than 20.0A/dm2And 100.0A/dm2In the case where below), the manufacturing method of the present invention impregnates after may not possess
Process.
It should be noted that by cathode electricity after rear dipping process or without rear dipping process
Electrolytic current density when solution processing is set as after the envelope formation process of high current density, miscellaneous contained in envelope from reducing
The reasons why matter, sets out, and preferably carries out washing process to obtained steel plate.
The method of washing process is not particularly limited, such as can enumerate the case where being manufactured using tinuous production
Under after film process tank be arranged water washing tank and method etc. in water is continuously impregnated after film process.In washing process
The temperature of used water is preferably 40~90 DEG C.
At this point, the reason more excellent from the effect obtained by washing process, washing time is preferably greater than 0.5 second,
Preferably 1.0~5.0 seconds.
In addition, can also be dried instead of washing process or after washing process.Temperature and mode when dry
It is not particularly limited, such as common drier, electric furnace drying mode can be applied.As temperature when being dried, preferably
It is 100 DEG C or less.When in above range, it is able to suppress the oxidation of envelope, keeps the stability of envelope composition.It needs to illustrate
It is that lower limit is not particularly limited, usually near room temperature.
[pretreatment process]
The manufacturing method of the present invention preferably has pretreatment process before above-mentioned envelope formation process.Pretreatment process is
By plated steel sheet is immersed in the pretreatment fluid containing oxidant or carbonate or in above-mentioned pretreatment fluid carry out sun
Pole electrolysis handles the process that above-mentioned tin oxide film is thus formed on the surface of the coating side of plated steel sheet.
By the way that plated steel sheet is immersed in above-mentioned pretreatment fluid or is carried out at anode electrolysis in above-mentioned pretreatment fluid
Reason, the possessed a part comprising Sn layers of coating of plated steel sheet are pretreated oxidant or carbonate oxidation in liquid, shape
At the tin oxide film containing tin-oxide.
Oxidant contained in pretreatment fluid or carbonate are not particularly limited.
As oxidant, known oxidant can be used, can enumerate for example: chlorine dioxide；Perchloric acid, high iodine
The contour hydracid of acid；The high Chlorates such as sodium perchlorate, potassium hyperchlorate, ammonium perchlorate；The chlorites such as sodium chlorite, potassium chlorite
Class；Sodium hypochlorite, calcium hypochlorite grade Chlorates；The bromic acids salt such as sodium bromate, potassium bromate；The acid iodide such as sodium iodate, Potassiumiodate
Salt；The high iodates such as sodium metaperiodate, potassium metaperiodate；Sodium peroxide, potassium peroxide, peromag, calper calcium peroxide, peroxidating
The peroxide of the alkali or alkaline earth metals such as barium；Hydrogen peroxide such as hydrogen peroxide, SODIUM PERCARBONATE or derivatives thereof；Deng.
In addition, known water soluble carbonate can be used as carbonate, such as sodium carbonate, carbon can be enumerated
The carbonate of the alkali metal such as sour potassium.
Wherein, from the reasons why can be continuous on the steel plate and tin oxide film densely be formed, as oxidant, preferably
Perchloric acid salt, the peroxide of alkali or alkaline earth metal, hydrogen peroxide or derivatives thereof, as carbonate, preferably carbonic acid
Sodium.
In addition, the oxygen from the reasons why can be continuous on the steel plate and tin oxide film densely be formed, in pretreatment fluid
Agent or the content of carbonate are preferably 5~30g/L, more preferably 10~20g/L.
From be formed by tin oxide film amount be it is appropriate, the reasons why tone variations of envelope can be further suppressed, in advance
The liquid temperature for the treatment of fluid is preferably 20~80 DEG C, more preferably 40~60 DEG C.
From the same reason, the dip time in pretreatment fluid is preferably 0.1~5 second, more preferably 0.2~2
Second.After impregnating in pretreatment fluid, implementation washing process can according to need.
About the electrolytic condition in pretreatment fluid, from the same reason, electricity is carried out in the way of anode by steel plate side
Solution, electrolytic current density is preferably 1.0~10.0A/dm2, more preferably 3.0~6.0A/dm2.In addition, conduction time is preferably
0.1~5 second, more preferably 0.2~2 second.It can according to need implementation washing process after electrolysis processing in pretreatment fluid.
The steel plate for container of the invention that manufacturing method through the invention obtains can be used in manufacture DI tank, food cans,
The various containers such as beverage can.
Embodiment
The present invention is concretely demonstrated hereinafter, enumerating embodiment.But present invention is not limited to this.
The manufacture > of < plated steel sheet
Plated steel sheet is manufactured by following methods.
Firstly, the steel plate (T4 raw sheet) to plate thickness 0.22mm carries out electrolytic degreasing, bathed using watt with every shown in the 5th table
The Ni adhesion amount of single side is in two-sided formation nickel coating.Then, in 10 volume %H2+ 90 volume %N2It is moved back in atmosphere at 700 DEG C
Fire makes nickel coating scattering and permeating, thus two-sided formation Ni-Fe alloy-layer (containing Ni layers) (showing Ni adhesion amount in the 5th table).
Then, using Sn plating bath, there is the steel plate containing Ni layers with the Sn of every single side shown in the 5th table on surface layer to above-mentioned
Adhesion amount is at two-sided formation Sn layers.Then, implement heating melting processing more than the fusing point of Sn, plated in the two-sided formation of T4 raw sheet
Layer.In this way, foring from lower layer side two-sided successively by Ni-Fe alloy-layer/Fe-Sn-Ni alloy-layer/Sn layers of coating constituted.
The production > of the test material of < steel plate for container
As described below, the test material in the tunicate steel plate for container of two-sided formation of plated steel sheet is produced.
" pretreatment process "
The plated steel sheet of manufacture is washed, using the pretreatment fluid (solvent: water) of composition shown in the 1st table, according to the 4th
(current density is led to for immersion condition (dip time) shown in treatment fluid temperature and the 4th table shown in table or anode electrolysis condition
The electric time), in two-sided formation tin oxide film.It should be noted that in the feelings for not forming tin oxide film by pretreatment process
Under condition, "-" is recorded as in the 4th table.
" envelope formation process "
Then, it will be washed after pretreatment process or without the plated steel sheet of pretreatment process, using by pH
It is adjusted to the treatment fluid (solvent: water) formed shown in 4.0 the 2nd table, treatment fluid temperature and electrolytic condition shown in the 4th table
Implement catholyte processing under (current density, conduction time, electric quantity density).
" rear dipping process "
To part test material, after envelope formation process, using the acid bath of composition shown in the 3rd table, in the 4th table institute
It is impregnated at the treatment fluid temperature and dip time shown.It should be noted that in the case where not through dipping process later,
"-" is recorded as in 4th table.
It should be noted that being formed after rear dipping process or in the case where dipping process after no warp in envelope
After process, obtained steel plate is subjected to washing process, is dried using blower in room temperature.
Then, for the test material of the steel plate for container of production, by following methods, to film adhesiveness, clagging
Property, film attach after after corrosion resistance, coating corrosion resistance and appearance evaluated.It shows the results of the evaluation in following 5th tables.
The reduction electricity of tin oxide film and Ti adhesion amount, Ni adhesion amount, A value, atomic ratio (F/Ti) and the state of envelope
It is measured or calculates by the above method than (OH/MO).In addition, measuring the surface free energy of envelope by following methods.It will
All results are shown in following 5th tables.
But in the case where not forming tin oxide film by pretreatment process, in the column of the reduction electricity of the 5th table
It is recorded as "-".It should be noted that in fact, being determined to reduction electricity, as a result respectively less than 1.0mC/cm2。
< surface free energy (γ s) >
Contact angle when liquid is added dropwise to test material surface is set as θ, by the surface free energy on test material surface
Dispersion force is at being divided into γ sd, by its polar forces at being divided into γ shAnd the surface free energy of liquid is set as γ l, by its point
Power is dissipated at being divided into γ ld, by its polar forces at being divided into γ lhWhen, meet following relationships.
γl(1+cosθ)/2×(rlh)1/2
=(γ sd)1/2×(γld)1/2/(γlh)1/2+(γsh)1/2
Accordingly, with respect to surface free energy, known (γ l, γ l are usedh、γldIt is known) five kinds of liquid (water, glycerol, formyls
Amine, ethylene glycol, diethylene glycol), static contact angle is found out using contact angle instrument (the CA-D type of consonance interface science company manufacture)
(relative humidity: 55~66%, 20 DEG C of temperature).In above-mentioned formula, the contact angle θ measured respectively to above-mentioned five kinds of liquid and each is substituted into
γ l, the γ l of kind liquidh、γldValue, by least square method fitting find out γ sd、γsh, calculating surface free energy γ s (=
γsd+γsh) (unit: mN/m).It should be noted that the surface free energy of five kinds of liquid used in measurement is shown in the 6th
In table.
< film adhesiveness >
4kg/cm is pressurised into roller2, plate travelling speed is 40mpm, the surface temperature of plate after roller passes through is 160 DEG C item
So that commercially available PET film (Melinex850, E.I.Du Pont Company's manufacture) is heat fused in the surface of made steel plate for container under part, connects
, heating (being kept for 120 seconds in the case where reaching plate temperature and being 210 DEG C), makes laminate steel after carrying out in batch furnace.
To the laminate steel (width 50mm × length 50mm) of production, using the formed punch of 3/16 inch of R of front end diameter, make 1kg
Hammer from 25cm height fall, with post the surface side of film become convex mode carry out Du Pont impact processing.Produce four this
The processing experiment piece of sample, is placed in steaming plant in a manner of upward by convex surface, and 30 points are kept under 130 DEG C of boiling environment
Clock then takes out, and is evaluated according to following 5 stages the degree of the film stripping of processing department by visual observation, is tested using 4
The average value (retaining one after decimal point) of piece, evaluates film adhesiveness.It, can when result is 3.0 or more on practical
Evaluate the sample excellent as film adhesiveness.
5: without removing
4: processing department area it is peeling-off less than 5%
3: 5% in the area of processing department is peeling-off more than and less than 20%
2: 20% in the area of processing department is peeling-off more than and less than 50%
1: 50% or more in the area of processing department is peeling-off
< coating adhesion >
On the surface of the steel plate for container (width 100mm × length 150mm) of production, it is coated with epoxy novolac class coating,
210 DEG C be sintered within 10 minutes, and implementation adhesion amount is 50mg/dm2Coating.It then, will be identical with above-mentioned implementation coating
Under the conditions of the two panels steel plate for container that makes clip nylon tacky film and be laminated in such a way that coating surface faces, be then in pressure
2.94×105It is bonded under the conditions of the crimping that Pa, temperature are 190 DEG C, the crimping time is 30 seconds.Then, it is divided into 5mm
The test film of width.The steel plate for container of the two panels test film of segmentation is peeled away using cupping machine, when measurement is removed
Tensile strength.It is evaluated with average value of following benchmark to two split-plot experiment pieces.On practical, when result is zero or △, energy
Enough evaluations sample excellent as coating adhesion.
◎: 2.0kgf or more (same with chromic acid salt treatment material)
Zero: 1.0kgf more than and less than 2.0kgf
×: less than 1.0kgf
Corrosion resistance > after < film attaches
4kg/cm is pressurised into roller2, plate travelling speed is 40mpm, the surface temperature of plate after roller passes through is 160 DEG C item
So that commercially available PET film (Melinex850, E.I.Du Pont Company's manufacture) is heat fused in the surface of made steel plate for container under part, connects
, heating (being kept for 120 seconds in the case where reaching plate temperature and being 210 DEG C), makes laminate steel after carrying out in batch furnace.
Then, it is imported using cutter in the film surface of the laminate steel (width 70mm × length 40mm) of production and reaches base steel
The cross-cut of the depth of (steel plate).The laminate steel of cross-cut will have been imported by containing 1.5 mass % citric acids and 1.5
It is impregnated 96 hours in 55 DEG C of the experimental liquid that the mixed aqueous solution of quality % salt is constituted.It after dipping, cleaned, dried, so
The adhesive tape removing for attaching glassine paper adhesive tape in film surface and being removed is carried out afterwards.To the 10mm from the cross part of cross-cut
Within 4 Site Determination film stripping width (total width of the left and right spread from cutting part), find out being averaged for 4 positions
Value.Using the average value of film stripping width as Erosion Width, evaluated with following benchmark.On practical, when result is ◎ or zero,
The sample as excellent corrosion resistance can be evaluated.
◎: Erosion Width is less than 0.8mm
Zero: Erosion Width is 0.8mm more than and less than 1.5mm
△: Erosion Width is 1.5mm more than and less than 2.0mm
×: Erosion Width is 2.0mm or more
Corrosion resistance > after < coating
It is coated with epoxy novolac class coating on the surface of the steel plate for container (width 70mm × length 40mm) of production, is then existed
210 DEG C be sintered within 10 minutes, and implementing adhesion amount is 50mg/dm2Coating.
Then, it is imported using cutter in the coating surface of the above-mentioned steel plate for container (coated steel plate) for implementing coating and reaches steel
The cross-cut of the depth of base (steel plate).Cross-cut coated steel plate will have been imported by containing 1.5 mass % citric acids and 1.5
It is impregnated 96 hours in 55 DEG C of the experimental liquid that the mixed aqueous solution of quality % salt is constituted.It after dipping, cleaned, dried, so
The adhesive tape removing for attaching glassine paper adhesive tape in film and being removed is carried out afterwards.To the 10mm from the cross part of cross-cut
Within 4 Site Determination film stripping width (total width of the left and right spread from cutting part), find out being averaged for 4 positions
Value.Using the average value of film stripping width as Erosion Width, evaluated with following benchmark.On practical, when result is ◎ or zero,
The sample as excellent corrosion resistance can be evaluated.
◎: Erosion Width is less than 0.2mm
Zero: Erosion Width is 0.2mm more than and less than 0.6mm
△: Erosion Width is 0.6mm more than and less than 1.0mm
×: Erosion Width is 1.0mm or more
< appearance >
For the steel plate for container after rigid production (after production within 60 points), the colour developing of the tea system color of envelope is commented
Valence.Specifically, the L value of the SQ-2000 measurement envelope manufactured using electricity Se industrial group of Japan, is commented with following benchmark
Valence.When for ◎ or zero, it can evaluate as inhibiting the coloring of envelope, the sample of good appearance.
◎: L value is 75 or more
Zero: L value is 70 more than and less than 75
△: L value is 60 more than and less than 70
×: L value is less than 60
[table 1]
1st table
[table 2]
2nd table
[table 3]
3rd table
[table 4]
4th table
[table 5]
5th table
[table 6]
6th table
The result as shown in above-mentioned 1st~5 table it will be apparent that, the film adhesiveness of example (test material No.1~40) and
Corrosion resistance is excellent after corrosion resistance and coating after coating adhesion and film attach.
In addition we know, having reduction electricity is 2.0~5.0mC/cm2Tin oxide film example (test material No.29
~40) appearance is more excellent.
In contrast, A value is not 30 or less and atomic ratio (F/Ti) is not less than 0.10, furthermore state ratio (OH/MO)
Be not less than 0.70 comparative example (test material No.41 and 42) film attach after poor corrosion resistance after corrosion resistance and coating.
In addition, the Ti adhesion amount of envelope is not 1.0mg/m2More than and less than 60.0mg/m2Comparative example (test material
Poor corrosion resistance after corrosion resistance and coating after No.43 and film adhesiveness and coating adhesion 44) and film attach.
In addition, Ni adhesion amount is not 0.1~3.0mg/m2, furthermore A value be not that 30 or less, atomic ratio (F/Ti) is not less than
0.10 and state ratio (OH/MO) be not less than 0.70 comparative example (test material No.45) film adhesiveness and clagging
Property and film attach after poor corrosion resistance after corrosion resistance and coating.
Claims (6)
1. a kind of steel plate for container has the plating steel of the coating comprising Sn layers at least part on the surface of steel plate
The envelope of plate and configuration on the surface of the coating side of the plated steel sheet, wherein
The envelope contains Ti, and the adhesion amount of the Ti conversion of the every single side of plated steel sheet is 1.0mg/m2More than and less than
60.0mg/m2, also, A value defined in following formula (1) be 30 hereinafter,
Atomic ratio, the i.e. F/Ti of the F and Ti of the most surface of the envelope are greater than 0.00 and less than 0.10,
A=[(Ti0-TiA)/Ti0]×100…(1)
In formula (1), Ti0Indicate the adhesion amount of the Ti conversion of the every single side of the plated steel sheet of the envelope, unit mg/m2,
TiAIndicate the every list of the plated steel sheet that the envelope after ten minutes is impregnated in 50 DEG C of 1mol/L sodium hydrate aqueous solution
The adhesion amount of the Ti conversion in face, unit mg/m2。
2. steel plate for container as described in claim 1, wherein the envelope will be present in as the O for constituting hydroxide
In the ratio of O be recorded as OH, be recorded as the ratio of O being present in the envelope as the O for constituting metal oxide
In the case where MO, for the ratio indicated with OH/MO less than 0.70, the unit of aforementioned proportion is %.
3. steel plate for container as claimed in claim 1 or 2, wherein the surface free energy of the envelope is 40mN/m or more.
4. steel plate for container as claimed in claim 1 or 2, wherein the envelope contains Ni, the every single side of plated steel sheet
The adhesion amount of Ni conversion is 0.1~3.0mg/m2。
5. steel plate for container as claimed in claim 1 or 2, wherein the coating also includes selected from by Ni layers, Ni-Fe alloy
At least one layer in the group of layer, Fe-Sn alloy-layer and Fe-Sn-Ni alloy-layer composition.
6. steel plate for container as claimed in claim 1 or 2, wherein have between the coating and the envelope and contain tin
The tin oxide film of oxide, electricity needed for the reduction of the tin-oxide are 2.0~5.0mC/cm2。
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014101391 | 2014-05-15 | ||
| JP2014-101391 | 2014-05-15 | ||
| JP2014-259985 | 2014-12-24 | ||
| JP2014259985A JP5842988B2 (en) | 2014-05-15 | 2014-12-24 | Steel plate for containers |
| PCT/JP2015/061458 WO2015174190A1 (en) | 2014-05-15 | 2015-04-14 | Steel plate for container |
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| Publication Number | Publication Date |
|---|---|
| CN106460192A CN106460192A (en) | 2017-02-22 |
| CN106460192B true CN106460192B (en) | 2018-12-14 |
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| JP (1) | JP5842988B2 (en) |
| KR (1) | KR101791374B1 (en) |
| CN (1) | CN106460192B (en) |
| MY (1) | MY176527A (en) |
| PH (1) | PH12016502097B1 (en) |
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| JP7435924B1 (en) | 2022-11-24 | 2024-02-21 | Ｊｆｅスチール株式会社 | Surface treated steel sheet and its manufacturing method |
| JP7460035B1 (en) | 2022-11-24 | 2024-04-02 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and its manufacturing method |
| JP7401039B1 (en) * | 2022-11-24 | 2023-12-19 | Ｊｆｅスチール株式会社 | Surface treated steel sheet and its manufacturing method |
| JP7435925B1 (en) | 2022-11-24 | 2024-02-21 | Ｊｆｅスチール株式会社 | Surface treated steel sheet and its manufacturing method |
| WO2024111156A1 (en) * | 2022-11-24 | 2024-05-30 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and production method therefor |
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| JP4487651B2 (en) * | 2004-06-22 | 2010-06-23 | 東洋製罐株式会社 | Surface-treated metal material and surface treatment method thereof, resin-coated metal material, metal can, metal lid |
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| JP5218505B2 (en) * | 2010-09-15 | 2013-06-26 | Ｊｆｅスチール株式会社 | Steel plate continuous electrolytic treatment apparatus and surface-treated steel plate manufacturing method using the same |
| JP5994495B2 (en) * | 2011-09-05 | 2016-09-21 | Ｊｆｅスチール株式会社 | Steel plate for containers |
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|---|---|---|---|---|
| CN101010452A (en) * | 2004-06-22 | 2007-08-01 | 东洋制罐株式会社 | Surface-treated metal materials, method of treating the surfaces thereof, resin-coated metal materials, cans and can lids |
| JP2010255065A (en) * | 2009-04-28 | 2010-11-11 | Jfe Steel Corp | Surface treated steel sheet and method of manufacturing the same |
| JP2011231404A (en) * | 2011-04-27 | 2011-11-17 | Toyo Seikan Kaisha Ltd | Surface-treated metallic plate, surface treatment method of the same, resin-coated metallic plate, can, and can lid |
Also Published As
| Publication number | Publication date |
|---|---|
| PH12016502097A1 (en) | 2017-01-09 |
| TW201545861A (en) | 2015-12-16 |
| JP5842988B2 (en) | 2016-01-13 |
| CN106460192A (en) | 2017-02-22 |
| MY176527A (en) | 2020-08-13 |
| WO2015174190A1 (en) | 2015-11-19 |
| KR101791374B1 (en) | 2017-10-27 |
| KR20160140867A (en) | 2016-12-07 |
| JP2015232169A (en) | 2015-12-24 |
| TWI552863B (en) | 2016-10-11 |
| PH12016502097B1 (en) | 2017-01-09 |
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