SURFACE-TREATED STEEL SHEET AND METHOD OF PRODUCING SAME

Description

TECHNICAL FIELD

The present disclosure relates to a surface-treated steel sheet, in particular, a surface-treated steel sheet with excellent sulfide staining resistance after painting, adhesion to the paint layer in wet environments, and appearance. The surface-treated steel sheet of the present disclosure can be suitably used in containers such as cans. The present disclosure also relates to a method of producing the surface-treated steel sheet.

BACKGROUND

A Sn-plated steel sheet (tinplate), one type of surface-treated steel sheet, is widely used as material for various metal cans such as bever age cans, food cans, pails, and 18-liter cans because of its excellent corrosion resistance, weldability, workability, bright and beautiful appearance, and ease of production.

Surface-treated steel sheets used for these applications are required to have excellent adhesion to paint along with excellent resistance (sulfide staining resistance) to discoloration (sulfide staining) caused by the reaction between sulfur and Sn from the can contents (especially protein). Therefore, it is common for Sn-plated steel sheets to be subjected to chromating treatment to improve the paint adhesion property and sulfide staining resistance.

Chromating treatment is one type of surface treatment using a coating solution containing a chromium compound, such as chromic acid or chromate. Typically, as the chromate treatment, a metal Cr layer and an Cr oxide layer are formed on the surface of the steel sheet by cathodic electrolysis in an electrolytic solution containing a hexavalent chromium compound, as described in Patent Literature (PTL) 1 to 3.

However, in recent years, increasing environmental awareness has led to a worldwide trend toward regulating the use of hexavalent chromium. Demand therefore exists for establishing a production method that does not use chromium in the field of surface-treated steel sheets used for containers and the like.

For example, in PTL 4, a surface-treated steel sheet with a coating containing a zirconium compound on the surface of a Sn-plated steel sheet is proposed.

Another method of producing a surface-treated steel sheet without the use of hexavalent chromium is the use of trivalent chromium. For example, PTL 5 proposes a method of forming a surface treatment layer composed of a metal Cr layer and a Cr oxide layer on the surface of a Sn-plated steel sheet by performing cathodic electrolysis in an electrolytic solution containing trivalent chromium ions.

CITATION LIST

Patent Literature

• PTL 1: JP S58-110695 A
• PTL 2: JP S55-134197 A
• PTL 3: JP S57-035699 A
• PTL 4: JP 2018-135569 A
• PTL 5: JP 7070823 B

SUMMARY

Technical Problem

However, the above-described conventional technology has the following problems.

For example, the surface-treated steel sheet proposed in PTL 4 can be formed without performing chromate treatment. According to PTL 4, the surface-treated steel sheet has excellent sulfide staining resistance and paint layer adhesion.

However, in PTL 4, the paint layer adhesion was evaluated under mild conditions compared to the actual environment of a can. In reality, the surface-treated steel sheet proposed in PTL 4 has insufficient adhesion to paint (hereinafter referred to as “paint secondary adhesion” (coating secondary adhesion)) in wet environments, which represent more severe conditions.

According to the method proposed in PTL 5, a surface treatment layer can be formed without using hexavalent chromium. According to PTL 5, the surface-treated steel sheet obtained by the above method has excellent paint secondary adhesion and sulfide staining resistance under severe conditions similar to the actual environment of a can.

However, the surface-treated steel sheet produced by the method proposed in PTL 5 has a poor appearance because the original bright and beautiful metallic luster of the tinplate is lost.

Thus, a surface-treated steel sheet that can be produced without the use of hexavalent chromium and that combines excellent sulfide staining resistance, paint secondary adhesion, and appearance has yet to be realized.

It is an aim of the present disclosure, conceived in light of the above circumstances, to provide a surface-treated steel sheet that can be produced without using hexavalent chromium and that has excellent sulfide staining resistance, paint secondary adhesion, and appearance.

Solution to Problem

As a result of intensive studies to achieve to above aim, we made the following discoveries (1) and (2).

(1) In a surface-treated steel sheet having a coating layer containing at least one of Zr oxide and Ti oxide on a Sn plating layer, controlling each of the water contact angle and the total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface of the steel sheet to all elements each to be within a specific range makes it possible to obtain a surface-treated steel sheet that has excellent sulfide staining resistance, paint secondary adhesion, and appearance.

(2) The aforementioned surface-treated steel sheet can be produced by performing surface conditioning under a predetermined set of conditions after coating formation, followed by a final water washing using water whose electrical conductivity is equal to or less than a predetermined value.

The present disclosure has been made based on these discoveries. We provide the following.

1. A surface-treated steel sheet including, on at least one side of a steel sheet,

• • a Sn plating layer; and
  • a coating layer disposed on the Sn plating layer and containing at least one of Zr oxide and Ti oxide, wherein
  • a water contact angle is 50° or less, and
  • a total atomic ratio of K, Na, Mg, and Ca adsorbed on a surface of the steel sheet to all elements is 5.0% or less.

2. The surface-treated steel sheet according to 1, wherein the Sn plating layer has a Sn coating weight of 0.1 g/m² to 20.0 g/m² per side of the steel sheet.

3. The surface-treated steel sheet according to 1 or 2, wherein a total coating weight of Zr oxide and Ti oxide in the coating layer is 0.3 mg/m² to 50.0 mg/m² per side of the steel sheet in terms of amount of metal Zr and amount of metal Ti.

4. The surface-treated steel sheet according to any one of 1 to 3, wherein the coating layer further contains P, and a P coating weight is 50.0 mg/m² or less per side of the steel sheet.

5. The surface-treated steel sheet according to any one of 1 to 4, wherein the coating layer further contains Mn, and a Mn coating weight is 50.0 mg/m² or less per side of the steel sheet.

6. The surface-treated steel sheet according to any one of 1 to 5, further including a Ni-containing layer disposed below the Sn plating layer.

7. The surface-treated steel sheet according to 6, wherein the Ni-containing layer has a Ni coating weight of 2 mg/m² to 2000 mg/m² per side of the steel sheet.

8. A method of producing a surface-treated steel sheet including, on at least one side of a steel sheet, a Sn plating layer, and a coating layer disposed on the Sn plating layer and containing at least one of Zr oxide and Ti oxide, the method including:

• • a coating formation process of treating a surface of a steel sheet having a Sn plating layer on at least one side with an aqueous solution containing at least one of Zr ions and Ti ions to form the coating layer on the Sn plating layer;
  • a surface conditioning process of holding the aqueous solution at over 30.0 g/m² to 60.0 g/m² or less on a surface of the coating layer for 0.1 seconds to 20.0 seconds; and
  • a water washing process of subjecting the steel sheet after the surface conditioning process to water washing at least once, wherein
  • in the water washing process,
    • water with an electrical conductivity of 100 uS/m or less is used at least in the last water washing.

9. The method of producing a surface-treated steel sheet according to 8, wherein the surface-treated steel sheet further includes a Ni-containing layer disposed below the Sn plating layer.

Advantageous Effect

According to the present disclosure, a surface-treated steel sheet that uses no hexavalent chromium and that combines excellent sulfide staining resistance, paint secondary adhesion, and appearance can be provided. The surface-treated steel sheet of the present disclosure can be suitably used as a material for containers and the like.

DETAILED DESCRIPTION

A method for carrying out the presently disclosed techniques will be described in detail below. The following description merely presents examples of preferred embodiments of the present disclosure, and the present disclosure is not limited to these embodiments.

A surface-treated steel sheet in an embodiment of the present disclosure includes, on at least one side of the steel sheet, a Sn plating layer and a coating layer disposed on the Sn plating layer, the coating layer containing at least one of Zr oxide and Ti oxide. In the present disclosure, it is important that the water contact angle be 50° or less, and that the total atomic ratio of K, Na, Mg, and Ca adsorbed on a surface of the steel sheet to all elements be 5.0% or less. The following is a description of each of the above constituent elements of the surface-treated steel sheet.

[Steel Sheet]

Any steel sheet can be used as the above steel sheet without any particular limitation, but a steel sheet for cans is preferred. For example, an ultra low carbon steel sheet or low carbon steel sheet can be used as the steel sheet. The method of producing the steel sheet is not limited, and a steel sheet produced by any method may be used, but it typically suffices to use a cold-rolled steel sheet. The cold-rolled steel sheet can be produced by general production processes, for example, hot rolling, pickling, cold rolling, annealing, and temper rolling.

The chemical composition of the steel sheet is not limited, but the steel sheet may contain C, Mn, Cr, P, S, Si, Cu, Ni, Mo, Al, and unavoidable impurities to the extent that the effects of the scope of the present disclosure are not impaired. In this case, a steel sheet with the chemical composition specified in ASTM A 623M-09, for example, can be suitably used as the steel sheet.

In one embodiment of the present disclosure, a steel sheet having a chemical composition containing, in mass %,

• • C: 0.0001% to 0.13%,
  • Si: 0% to 0.020%,
  • M n: 0.01% to 0.60%,
  • P: 0% to 0.020%,
  • S: 0% to 0.030%,
  • Al: 0% to 0.20%,
  • N: 0% to 0.040%,
  • Cu: 0% to 0.20%,
  • Ni: 0% to 0.15%,
  • Cr: 0% to 0.10%,
  • Mo: 0% to 0.05%,
  • Ti: 0% to 0.020%,
  • Nb: 0% to 0.020%,
  • B: 0% to 0.020%,
  • Ca: 0% to 0.020%,
  • Sn: 0% to 0.020%, and
  • Sb: 0% to 0.020%,
    with the balance being Fe and inevitable impurities, is preferably used. In the aforementioned chemical composition, Si, P, S, Al, and N are components whose content is more preferable the lower it is, and Cu, Ni, Cr, Mo, Ti, Nb, B, Ca, Sn, and Sb are components that can optionally be added.

No lower limit is placed on the thickness of the steel sheet, but the thickness is preferably 0.10 mm or more. No upper limit is placed on the thickness of the steel sheet either, but the thickness is preferably 0.60 mm or less. The term “steel sheet” as used here includes a “steel strip”.

[Sn Plating Layer]

The Sn plating layer need only be provided on at least one side of the steel sheet but may be provided on both sides. The Sn plating layer need only cover at least a portion of the steel sheet but may cover the entire side on which the Sn plating layer is provided. The Sn plating layer may be a continuous layer or a discontinuous layer. The discontinuous layer is, for example, a layer with an island-like structure.

The Sn plating layer includes the case of a portion of the Sn plating layer being alloyed. For example, the Sn plating layer includes the case in which a portion of the Sn plating layer is a Sn alloy layer due to hot melt treatment after Sn plating. Examples of the Sn alloy layer include an Fe—Sn alloy layer and an Fe—Sn—Ni alloy layer.

For example, by heating and melting Sn by electrical resistance heating or the like after Sn plating, a portion of the steel sheet side of the Sn plating layer can be made into an Fe—Sn alloy layer. In addition, by performing Sn plating on a steel sheet having a Ni-containing layer on the surface and further heating and melting the Sn by electrical resistance heating or the like, a portion of the steel sheet side of the Sn plating layer can be made into either or both of an Fe—Sn—Ni alloy layer and an Fe—Sn alloy layer.

The Sn coating weight in the Sn plating layer is not limited and can be any amount. However, from the perspective of further improving the appearance and corrosion resistance of the surface-treated steel sheet, the Sn coating weight is preferably set to 20.0 g/m² or less per side of the steel sheet.

From the same perspective, the Sn coating weight is preferably set to 0.1 g/m² or more and more preferably to 0.2 g/m² or more. From the perspective of further improving workability, the Sn coating weight is even more preferably set to 1.0 g/m² or more.

The Sn coating weight can be measured by the electrolytic stripping method specified in JIS G 3303.

The Sn plating layer can be formed by any method without limitation, including methods such as electroplating and hot dip coating. In the case of forming the Sn plating layer by electroplating, any plating bath can be used. Examples of plating baths that can be used include a phenolsulfonic acid Sn plating bath, a methanesulfonic acid Sn plating bath, and a halogen-based Sn plating bath.

After forming the Sn plating layer, reflow treatment may be performed. In the case of reflow treatment, the Sn plating layer is heated to a temperature at or above the melting point of Sn (231.9° C.) to form an alloy layer such as an Fe—Sn alloy layer on the bottom layer (steel sheet side) of the unalloyed Sn plating layer. If the reflow treatment is omitted, a Sn-plated steel sheet with an unalloyed Sn plating layer is obtained.

The surface side of the Sn plating layer may contain Sn oxide or may contain no Sn oxide at all. However, from the perspective of further improving the paint secondary adhesion and sulfide staining resistance, the surface side of the Sn plating layer preferably contains Sn oxide. Although Sn oxide can be formed by reflow treatment or by dissolved oxygen contained in water used in water washing after Sn plating, the amount of Sn oxide contained in the Sn plating layer is preferably controlled by the below-described pretreatment or the like.

[Ni-Containing Layer]

The surface-treated steel sheet can further optionally include a Ni-containing layer. For example, the surface-treated steel sheet according to an embodiment of the present disclosure can further include a Ni-containing layer disposed below the Sn plating layer. In other words, a surface-treated steel sheet in an embodiment of the present disclosure includes, on at least one side of the steel sheet, a Ni-containing layer, a Sn plating layer disposed on the Ni-containing layer, and a coating layer disposed on the Sn plating layer and containing at least one of Zr oxide and Ti oxide.

As the Ni-containing layer, any layer that contains nickel can be used. For example, one or both of a Ni layer and a Ni alloy layer can be used. The Ni layer is, for example, a Ni-coated or plated layer. The Ni alloy layer is, for example, a Ni—Fe alloy layer. By forming the Sn plating layer on the Ni-containing layer and then performing reflow treatment, an Fe—Sn—Ni alloy layer, an Fe—Sn alloy layer, or the like can be formed on the bottom layer (steel sheet side) of the unalloyed Sn plating layer.

The method of forming the Ni-containing layer is not limited, and any method, such as electroplating, can be used. In the case of forming a Ni—Fe alloy layer as a Ni-containing layer, the Ni—Fe alloy layer can be formed by forming a Ni layer on the steel sheet surface, by electroplating or another such method, and then annealing.

No limit is placed on the Ni coating weight of the Ni-containing layer, but from the perspective of further improving sulfide staining resistance, the Ni coating weight is preferably set to 2 mg/m² or more per side of the steel sheet. From a cost perspective, the Ni coating weight per side of the steel sheet is preferably set to 2000 mg/m² or less.

The Ni coating weight of the Ni-containing layer is measured by a calibration curve method using X-ray fluorescence. First, a plurality of steel sheets with known Ni coating weight are prepared, the X-ray fluorescence intensity derived from Ni is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the Ni coating weight is linearly approximated to yield a calibration curve. The X-ray fluorescence intensity derived from Ni in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the Ni coating weight of the Ni-containing layer.

[Coating Layer]

A coating layer containing at least one of Zr oxide and Ti oxide exists on the Sn plating layer. The inclusion of at least one of Zr oxide and Ti oxide in the coating layer is necessary to obtain excellent sulfide staining resistance, paint secondary adhesion, and appearance.

No lower limit is placed on the total coating weight of Zr oxide and Ti oxide in the coating layer. However, from the perspective of further improving sulfide staining resistance, the total coating weight of the Zr oxide and Ti oxide is preferably 0.3 mg/m² or more, more preferably 0.4 mg/m² or more, and even more preferably 0.5 mg/m² or more, per side of the steel sheet in terms of the amount of metal Zr and amount of metal Ti. No upper limit is placed on the total coating weight of Zr oxide and Ti oxide in the coating layer either. However, if the total coating weight of Zr oxide and Ti oxide is excessively high, the original bright and beautiful appearance of tinplate may be impaired and the paint secondary adhesion may be compromised due to cohesion failure of the coating layer. Therefore, from the perspective of ensuring more stable paint secondary adhesion, the total coating weight of the Zr oxide and Ti oxide is preferably 50.0 mg/m² or less, more preferably 45.0 mg/m² or less, and even more preferably 40.0 mg/m² or less, per side of the steel sheet in terms of the amount of metal Zr and amount of metal Ti. In calculating the total coating weight of Zr oxide and Ti oxide, the value yielded by conversion to the amount of metal Zr is used as the coating weight of Zr oxide, and the value yielded by conversion to the amount of metal Ti is used as the coating weight of Ti oxide.

The coating weight of Zr oxide in the coating layer is measured by a calibration curve method using X-ray fluorescence. First, a plurality of steel sheets with known Zr coating weight are prepared, the X-ray fluorescence intensity derived from Zr is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the coating weight as metal Zr is linearly approximated to yield a calibration curve. The X-ray fluorescence intensity derived from Zr in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of Zr oxide in the coating layer in terms of metal Zr.

The coating weight of Ti oxide in the coating layer is also measured by a calibration curve method using X-ray fluorescence. First, a plurality of steel sheets with known Ti coating weight are prepared, the X-ray fluorescence intensity derived from Ti is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the coating weight as metal Ti is linearly approximated to yield a calibration curve. The X-ray fluorescence intensity derived from Ti in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of Ti oxide in the coating layer in terms of metal Ti.

The coating layer may contain P from the perspective of further improving sulfide staining resistance. Although no upper limit is placed on the coating weight of P contained in the coating layer, the coating weight of P is preferably 50.0 mg/m² or less per side of the steel sheet, since paint secondary adhesion may be impaired due to cohesion failure of the coating layer. No lower limit is placed on the coating weight of P in the coating layer, and the coating weight of P may, for example, be 0.0 mg/m², i.e., no P whatsoever may be contained.

The coating weight of P in the coating layer is measured by a calibration curve method using X-ray fluorescence. First, a plurality of steel sheets with known P coating weight are prepared, the X-ray fluorescence intensity derived from P is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the P coating weight is linearly approximated to yield a calibration curve. The X-ray fluorescence intensity derived from P in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of P in the coating layer.

The coating layer may contain Min from the perspective of further improving sulfide staining resistance. Although no upper limit is placed on the coating weight of M n contained in the coating layer, the coating weight of Mn is preferably 50.0 mg/m² or less per side of the steel sheet, since paint secondary adhesion may be impaired due to cohesion failure of the coating layer. No lower limit is placed on the coating weight of Mn in the coating layer, and the coating weight of Mn may, for example, be 0.0 mg/m², i.e., no Mn whatsoever may be contained.

The coating weight of Mn in the coating layer is measured by a calibration curve method using X-ray fluorescence. First, a plurality of steel sheets with known Mn coating weight are prepared, the X-ray fluorescence intensity derived from Mn is measured for the plates in advance, and the relationship between the measured X-ray fluorescence intensity and the Mn coating weight is linearly approximated to yield a calibration curve. The X-ray fluorescence intensity derived from Mn in the surface-treated steel sheet can then be measured, and the above-described calibration curve can be used to determine the coating weight of Mn in the coating layer.

The aforementioned coating layer may contain Sn. No upper limit is placed on the Sn content in the coating layer. The coating layer need not contain Sn, i.e., the content may be 0.0 mg/m².

The aforementioned coating layer may contain C. No upper limit is placed on the C content in the coating layer. The coating layer need not contain C, i.e., the content may be 0.0 mg/m².

The aforementioned coating layer may contain elements other than Zr, Ti, O, Sn, Mn, P, Ni, and C, along with the below-described K, Na, Mg, and Ca. Elements other than those described above include metallic impurities such as Cu, Zn, and Fe, and elements such as S, N, F, Cl, Br, and Si, contained in the aqueous solution used in the coating formation process described below. However, an excessive presence of elements other than Zr, Ti, O, Sn, Mn, P, Ni, C, K, Na, Mg, and Ca may reduce sulfide staining resistance or adhesion. Therefore, the total content of elements other than Zr, Ti, O, Sn, Mn, P, Ni, C, K, Na, Mg, and Ca in the coating layer is preferably 30% or less, and more preferably 20% or less, in atomic ratio. The coating layer need not contain elements other than Zr, Ti, O, Sn, Mn, P, Ni, C, K, Na, Mg, and Ca, i.e., the content may be 0% in atomic ratio. The content of the above elements can be measured by XPS (X-ray photoelectron spectroscopy).

[Water Contact Angle]

In the present disclosure, it is important that the water contact angle on the surface-treated steel sheet be 50° or less. By highly hydrophilizing the surface of the surface-treated steel sheet so that the water contact angle is 50° or less, firm hydrogen bonds are formed between the resin in the paint and the surface-treated steel sheet, resulting in high adhesion even in wet environments. From the perspective of further improving paint secondary adhesion, the water contact angle is preferably set to 48° or less, and even more preferably to 45° or less. No lower limit is placed on the water contact angle, and the water contact angle may be 0°, because a lower contact angle is preferable from the perspective of improving adhesion. However, from the perspective of ease of production and the like, the contact angle of ethylene glycol may be 5° or more, or 8° or more.

Furthermore, the surface of the surface-treated steel sheet in the present disclosure, i.e., the surface of the coating layer containing at least one of Zr oxide and Ti oxide, is stable with regard to heat. For example, the water contact angle does not change significantly after heat treatment equivalent to paint baking. It is assumed that such thermal stability of the surface state also contributes to improved adhesion. Therefore, the water contact angle on the surface-treated steel sheet after heat treatment equivalent to painting is also preferably 50° or less, more preferably 48° or less, and even more preferably 45° or less. No lower limit is placed on the water contact angle of the surface-treated steel sheet after heat treatment equivalent to painting, and the water contact angle may be 0°, but the water contact angle may be 5° or more, or 8° or more. The conditions of the heat treatment equivalent to painting are set to a maximum temperature of 200° C. and a holding time at the maximum temperature of 10 minutes.

Although the mechanism by which the surface of the surface-treated steel sheet becomes hydrophilic is not clear, it is believed that a high degree of hydrophilicity is imparted by adjustment of the surface micro-roughness in the surface conditioning process described below. In a case in which the surface conditioning process described below is not performed, the surface of the surface-treated steel sheet cannot be fixed in a hydrophilic state, and the water contact angle exceeds 50°, even if the surface is hydrophilic immediately after production.

The water contact angle can be measured by the θ/2 method. In the measurement, the temperature of the surface-treated steel sheet to be measured is set to 20° C., and distilled water at a temperature of 20° C. is dropped onto the surface of the surface-treated steel sheet. The contact angle after 1 second from dropping is calculated by the θ/2 method. More specifically, measurement can be made by the method described in the Examples. Here, the surface of the surface-treated steel sheet may be coated with an anti-rust oil such as CSO (Cottonseed Oil), DOS (Dioctyl Sebacate), and ATBC (Acetyl Tributyl Citrate). In a case in which the surface-treated steel sheet is painted with oil, the water contact angle measured by the method described in the Examples after vaporizing the painted oil by the heat treatment equivalent to painting is taken as the water contact angle of the surface-treated steel sheet after painting with oil. As described above, the surface-treated steel sheet of the present disclosure is stable with respect to heat treatment. Therefore, if the water contact angle measured after the aforementioned heat treatment and the atomic ratio of the adsorbed elements described below satisfy the conditions of the present disclosure, the surface-treated steel sheet before the aforementioned heat treatment is also considered to achieve the effects of the present disclosure. Although additives such as rust inhibitors contained in the painted oil may remain on the surface of the surface-treated steel sheet after heat treatment equivalent to painting, the amount thereof is so small that it does not affect the above-described water contact angle and atomic ratio of adsorbed elements.

In a surface-treated steel sheet produced using a conventional hexavalent chromium bath as proposed in PTL 1 to 3, it has been reported that the composition of the chromium hydrated oxide layer on the surface layer significantly affects the adhesion to paint or film in wet environments. In wet environments, water that has penetrated the paint layer or film inhibits adhesion at the interface between the paint layer or film and the chromium hydrated oxide layer. It was thus believed that when numerous OH groups, which are hydrophilic, are present in the chromium hydrated oxide layer, expansion of moisture from water at the interface is promoted, resulting in reduced adhesive strength. In a conventional surface-treated steel sheet, reducing the number of OH groups through the progression of oxidation of chromium hydrated oxide, i.e., making the surface hydrophobic, therefore improves adhesion to paint or film in wet environments.

In contrast, in the present disclosure, a high degree of hydrophilicity is developed by the action of the minute irregularities on the surface of the coating layer formed in the surface conditioning process described below, allowing a paint to penetrate into the fine irregularities and form firm mechanical bonds at the interface between the paint layer and the surface treated steel sheet by the anchor effect, thereby maintaining high adhesion even under wet conditions.

[a Tomic Ratio of Adsorbed Elements]

As described above, the surface-treated steel sheet of the present disclosure has high hydrophilicity, with a water contact angle of 50° or less, and the surface is chemically active. Therefore, cations of elements such as K, Na, Mg, and Ca are easily adsorbed on the surface of the surface-treated steel sheet. We discovered that simply setting the water contact angle to 50° or less does not achieve the intended adhesion, due to the effect of the adsorbed cations. By reducing the amount of the cations adsorbed on the surface of the surface-treated steel sheet, the present disclosure improves adhesion to the resin and achieves excellent paint secondary adhesion, while also exhibiting firm barrier properties against sulfur penetration, thus achieving excellent sulfide staining resistance.

Specifically, the total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet to all elements is 5.0% or less, preferably 3.0% or less, and more preferably 1.0% or less. The lower the total atomic ratio, the better; hence, no lower limit is established, and the total atomic ratio may be 0.0%. The total atomic ratio can be measured by XPS. In the measurement, it suffices to determine the atomic ratios of K, Na, Mg, and Ca to all elements from the integrated intensity of the narrow spectra of K₂p, Na1s, Ca2p, and Mg1s at the top surface of the surface-treated steel sheet, using the relative sensitivity factor method. More specifically, measurement can be made by the method described in the Examples. In a case in which the surface-treated steel sheet is painted with oil, the atomic ratio measured by the method described in the Examples after vaporizing the painted oil by the heat treatment equivalent to painting is taken as the atomic ratio of the elements adsorbed to the surface-treated steel sheet after painting with oil.

[Production Method]

In the method of producing a surface-treated steel sheet in an embodiment of the present disclosure, a surface-treated steel sheet with the aforementioned characteristics can be produced by the method described below.

A method of producing a surface-treated steel sheet in an embodiment of the present disclosure is a method of producing a surface-treated steel sheet that includes, on at least one side of the steel sheet, a Sn plating layer and a coating layer disposed on the Sn plating layer, and the method includes the following processes (1) to (3). Each process is described below.

• • (1) Coating formation process
  • (2) Surface conditioning process
  • (3) Water washing process

The surface-treated steel sheet in an embodiment of the present disclosure can further include a Ni-containing layer disposed below the Sn plating layer. In the case of producing a surface-treated steel sheet with a Ni-containing layer, it suffices to subject a steel sheet having a Ni-containing layer on at least one side and a Sn plating layer disposed on the Ni-containing layer to the coating formation process.

[Coating Formation Process]

In the aforementioned coating formation process, the surface of a steel sheet having a Sn plating layer on at least one side is treated with an aqueous solution containing at least one of Zr ions and Ti ions to form a coating layer on the Sn plating layer. The formed coating layer is a coating layer containing at least one of Zr oxide and Ti oxide.

The treatment with an aqueous solution is not limited and may be performed by any method. The treatment can, for example, be performed by electrolysis. In a case in which the treatment is performed by electrolysis, the steel sheet with the Sn plating layer is preferably subjected to cathodic electrolysis in the aqueous solution. Conventional equipment used for chromating treatment or the like can be used as is for the cathodic electrolysis.

Therefore, from the perspective of equipment cost reduction, the coating layer is preferably formed by cathodic electrolysis.

The method of preparing the aqueous solution is not limited. For example, the aqueous solution can be prepared by dissolving one or both of a Zr-containing compound as a Zr ion source and a Ti-containing compound as a Ti ion source in water. Distilled water or deionized water can be used as the water, but these examples are not limiting, and any water can be used.

Any compounds that can provide Zr ions and Ti ions can be used as the Zr-containing compound and Ti-containing compound, respectively. For example, Zr salts such as ZrF₄ or Zr complexes such as H₂ZrF₆ and K₂ZrF₆ are preferably used as the Zr-containing compound. As the pH rises on the cathode surface, Zr ions become Zr oxide and form a coating. For example, Ti salts such as TiF₄ or Ti complexes such as H₂TiF₆ and K₂TiF₆ are preferably used as the Ti-containing compound. As the pH rises on the cathode surface, Ti ions become Ti oxide and form a coating.

The aqueous solution may further contain at least one selected from the group consisting of fluorine ions, nitrate ions, ammonium ions, phosphate ions, Mn ions, and sulfate ions. In a case in which the aqueous solution contains both nitrate ions and ammonium ions, the treatment can be performed in a short time, from several seconds to several tens of seconds, which is extremely advantageous from an industrial standpoint. The aqueous solution therefore preferably contains both nitrate ions and ammonium ions in addition to at least one of Zr ions and Ti ions. Hereafter, the unit of ionic concentration “ppm” refers to parts per million unless otherwise specified.

In a case in which the aqueous solution contains Zr ions, no lower limit is placed on the concentration of the Zr ions, but the concentration is preferably set to 100 ppm or more. No upper limit is placed on the concentration of the Zr ions either, but the concentration is preferably set to 4000 ppm or less. Similarly, in a case in which the aqueous solution contains Ti ions, no lower limit is placed on the concentration of the Ti ions, but the concentration is preferably set to 100 ppm or more. No upper limit is placed on the concentration of the Ti ions either, but the concentration is preferably set to 4000 ppm or less.

In a case in which the aqueous solution contains fluorine ions, no lower limit is placed on the concentration of the fluorine ions, but the concentration is preferably set to 120 ppm or more. No upper limit is placed on the concentration of the fluorine ions either, but the concentration is preferably set to 4000 ppm or less. In a case in which the aqueous solution contains phosphate ions, no lower limit is placed on the concentration of the phosphate ions, but the concentration is preferably set to 50 ppm or more. No upper limit is placed on the concentration of the phosphate ions either, but the concentration is preferably set to 5000 ppm or less. In a case in which the aqueous solution contains Mn ions, no lower limit is placed on the concentration of the Mn ions, but the concentration is preferably set to 50 ppm or more. No upper limit is placed on the concentration of the Mn ions either, but the concentration is preferably set to 5000 ppm or less. In a case in which the aqueous solution contains ammonium ions, no lower limit is placed on the concentration of the ammonium ions, and the concentration may be 0 ppm. No upper limit is placed on the concentration of the ammonium ions either, but the concentration is preferably set to 20000 ppm or less. In a case in which the aqueous solution contains nitrate ions, no lower limit is placed on the concentration of the nitrate ions, and the concentration may be 0 ppm. No upper limit is placed on the concentration of the nitrate ions either, but the concentration is preferably set to 20000 ppm or less. In a case in which the aqueous solution contains sulfate ions, no lower limit is placed on the concentration of the sulfate ions, and the concentration may be 0 ppm. No upper limit is placed on the concentration of the sulfate ions either, but the concentration is preferably set to 20000 ppm or less.

No upper limit is placed on the temperature of the aqueous solution during cathodic electrolysis, but the temperature is preferably set to 50° C. or lower, for example. Cathodic electrolysis at temperatures of 50° C. or lower enables the formation of a dense, uniform coating microstructure constituted by very fine particles. By setting the temperature of the aqueous solution to 50° C. or lower, the occurrence of defects, cracks, microcracks, and the like in the coating layer to be formed can be suppressed, and the paint layer adhesion can be further improved. No lower limit is placed on the temperature of the aqueous solution during cathodic electrolysis either, but the temperature is preferably set to 10° C. or higher, for example. By setting the temperature of the aqueous solution to 10° C. or higher, the efficiency of coating formation can be increased. In addition, if the temperature of the aqueous solution is 10° C. or higher, cooling of the solution is not necessary even when the outside temperature is high, such as during the summer, which is economical.

No lower limit is placed on the pH of the aqueous solution, but the pH is preferably set to 3 or higher. If the pH is 3 or higher, the formation efficiency of Zr oxide or Ti oxide can be further improved. No upper limit is placed on the pH of the aqueous solution either, but the pH is preferably set to 5 or less. A pH of 5 or less prevents the formation of large amounts of precipitation in the aqueous solution and can achieve good continuous productivity.

Nitric acid, ammonia water, or the like, for example, may be added to the aqueous solution for the purpose of adjusting pH and improving electrolytic efficiency.

No lower limit is placed on the current density for cathodic electrolysis, but the current density is, for example, preferably set to 0.05 A/dm² or higher, more preferably 1 A/dm² or higher. If the current density is 0.05 A/dm² or higher, the formation efficiency of Zr oxide or Ti oxide is improved. As a result, a more stable coating layer containing Zr oxide or Ti oxide can be generated, further improving sulfide staining resistance and anti-yellowing property. No upper limit is placed on the current density during cathodic electrolysis, but the current density is, for example, preferably set to 50 A/dm² or less, more preferably 10 A/dm² or less. If the current density is 50 A/dm² or less, the efficiency of generating Zr oxides or Ti oxides can be made appropriate, and the generation of coarse Zr oxide or Ti oxide with poor adhesion can be suppressed.

No limit is placed on the electrolysis time in the aforementioned cathodic electrolysis, and it suffices to adjust the electrolysis time according to the current density to obtain the Zr coating weight and Ti coating weight described above.

The current pattern in the aforementioned cathodic electrolysis may be continuous current passage or intermittent current passage. The relationship between the aqueous solution and the steel sheet during the aforementioned cathodic electrolysis is not limited, and the solution may be relatively stationary or moving. However, from the perspective of promoting the reaction and improving uniformity, cathodic electrolysis is preferably conducted while the steel sheet and the aqueous solution are moved relative to each other. For example, cathodic electrolysis can be performed continuously while passing a steel sheet through a treatment tank housing an aqueous solution containing at least one of Zr ions and Ti ions, so that the steel sheet and the aqueous solution are moved relative to each other.

When cathodic electrolysis is performed while moving the steel sheet and the aqueous solution relative to each other, the relative flow speed between the aqueous solution and the steel sheet is preferably 50 m/min or more. If the relative flow speed is 50 m/min or more, the pH of the steel sheet surface where hydrogen is generated together with current passage can be made more uniform, effectively suppressing the formation of coarse Zr oxide or Ti oxide. No upper limit is placed on the relative flow speed.

[Surface Conditioning Process]

Next, surface conditioning is performed on the coating layer obtained in the coating formation process. Specifically, the aqueous solution is held at over 30.0 g/m² to 60.0 g/m² or less on a surface of the coating layer for 0.1 seconds to 20.0 seconds. By performing surface conditioning under the above conditions, the coating layer can be fixed in a highly hydrophilic state.

The mechanism by which the surface conditioning process can fix the coating layer in a highly hydrophilic state is not clear but is thought to be as follows. By bringing the coating layer into contact with the aqueous solution, the surface of the coating layer is slightly etched, forming minute irregularities on the surface of the coating layer. The action of these minute irregularities results in a high degree of hydrophilicity. This hydrophilicity is different from the hydrophilicity resulting from the presence of hydrophilic functional groups, such as OH groups, and is due to the physical structure provided by the surface roughness, which also has excellent stability with respect to heat.

Although the state of existence of the aqueous solution on the surface of the coating layer is not limited, the aqueous solution is preferably in the form of a liquid film from the perspective of ensuring uniform progress of etching.

A Mount of Aqueous Solution: Over 30.0 g/m² to 60.0 g/m² or Less

If the amount of aqueous solution used for surface conditioning is 30.0 g/m² or less, etching does not proceed sufficiently, resulting in a water contact angle that is greater than 50°. The amount of the aqueous solution is therefore set to over 30.0 g/m², preferably 32.0 g/m² or more, and more preferably 35.0 g/m² or more. On the other hand, if the amount of aqueous solution exceeds 60.0 g/m², etching in fact does not proceed and the desired hydrophilicity cannot be obtained. This is thought to be because the progress of etching depends on the amount of dissolved oxygen present near the interface between the coating layer and the aqueous solution. In other words, if the amount of aqueous solution is excessive, the thickness of the layer formed by the aqueous solution increases, causing an insufficient supply of oxygen to the interface, which results in insufficient progress of etching. The amount of the aqueous solution is therefore set to 60.0 g/m² or less, preferably 58.0 g/m² or less, and more preferably 55.0 g/m² or less.

Holding Time: 0.1 Seconds to 20.0 Seconds

If the holding time in the surface conditioning is less than 0.1 seconds, etching does not proceed sufficiently, resulting in a water contact angle that is greater than 50°. The holding time is therefore set to 0.1 seconds or longer, preferably 0.2 seconds or longer, and more preferably 0.3 seconds or longer. On the other hand, the water contact angle is also greater than 50° in a case in which the holding time exceeds 20.0 seconds. This is thought to be due to excessive etching, leading to deviation from surface conditions suitable for the development of hydrophilicity. The holding time is therefore set to 20.0 seconds or shorter, preferably 18.0 seconds or shorter, and more preferably 15.0 seconds or shorter.

The amount of the aforementioned aqueous solution can be measured by a moisture meter using a filter-type infrared absorption method. Specifically, the absorbance at the surface is measured by a moisture meter using a filter-type infrared absorption method, and the amount of aqueous solution is determined from the absorbance using a previously determined calibration curve. The calibration curve can be prepared by the following procedures. First, a steel sheet with the above coating layer is placed on an electronic balance. The aqueous solution is dropped by pipette onto the steel sheet having the coating layer to form a liquid film over the entire surface of the steel sheet having the coating layer. The weight of the aqueous solution present on the steel sheet having the coating layer is determined from the weight of the steel sheet having the coating layer before the aqueous solution is dropped and the weight of the steel sheet having the coating layer after the aqueous solution is dropped. The resulting weight of the aqueous solution is divided by the area of the steel sheet having the coating layer to obtain the amount of aqueous solution per unit area. At the same time, the absorbance on the surface of the steel sheet having the coating layer is measured by a moisture meter using a filter-type infrared absorption method. The above measurements are performed multiple times while varying the amount of aqueous solution, and a calibration curve representing the correlation between the amount of aqueous solution and absorbance is created. A linear approximation of the correlation between the amount of aqueous solution and absorbance can be used as the calibration curve.

The method of adjusting the amount of aqueous solution present on the surface of the coating layer is not limited, and any method can be used. For example, the amount of the aqueous solution on the surface of the steel sheet can be adjusted by wringing out the solution with a wringer roll or by wiping.

Prior to the coating formation process, the steel sheet having a Sn plating layer can optionally be pretreated. The pretreatment can, for example, remove a natural oxide film present on the surface of the Sn plating layer. By removal of the natural oxide film, the amount of Sn oxide can be adjusted and the surface can be activated.

Although the method of the pretreatment is not limited and any method can be used, one or both of electrolytic treatment in an alkaline aqueous solution and immersion treatment in an alkaline aqueous solution are preferably performed as the pretreatment. One or both of cathodic electrolysis and anodic electrolysis can be used as the electrolysis. Any of treatments (1) to (4) below is preferably performed as the pretreatment.

• • (1) Cathodic electrolysis in an alkaline aqueous solution
  • (2) Immersion treatment in an alkaline aqueous solution
  • (3) Cathodic electrolysis in an alkaline aqueous solution and subsequent anodic electrolysis in an alkaline aqueous solution
  • (4) A nodic electrolysis in an alkaline aqueous solution

The alkaline aqueous solution may contain one or more optional electrolytes. Any electrolyte may be used without limitation. Carbonate, for example, is preferably used as the electrolyte, and sodium bicarbonate is more preferably used. No lower limit is placed on the concentration of the alkaline aqueous solution, but the concentration is preferably set to 1 g/L or higher, more preferably 5 g/L or higher. No upper limit is placed on the concentration of the alkaline aqueous solution either, but the concentration is preferably set to 30 g/L or lower, more preferably 20 g/L or lower.

No lower limit is placed on the temperature of the alkaline aqueous solution, but the temperature is preferably set to 10° C. or higher, more preferably 15° C. or higher. No upper limit is placed on the temperature of the alkaline aqueous solution either, but the temperature is preferably set to 70° C. or lower, more preferably 60° C. or lower.

In the case of performing cathodic electrolysis as the pretreatment, no lower limit is placed on the electrolytic density in the cathodic electrolysis, but the electrolytic density is preferably set to 0.5 C/dm² or higher, more preferably 1.0 C/dm² or higher. No upper limit is placed on the electrolytic density of the cathodic electrolysis either, but the electrolytic density is preferably set to 10.0 C/dm² or less because an excessively high electrolytic density will saturate the effect of the pretreatment.

In the case of performing immersion treatment as the pretreatment, no lower limit is placed on the immersion time in the immersion treatment, but the immersion time is preferably set to 0.1 seconds or longer, more preferably 0.5 seconds or longer. No upper limit is placed on the immersion time either, but the immersion time is preferably set to 10 seconds or shorter, since an excessively long immersion time will saturate the effect of the pretreatment.

In the case of performing anodic electrolysis as the pretreatment, no lower limit is placed on the electrolytic density in the anodic electrolysis, but the electrolytic density is preferably set to 0.5 C/dm² or higher, more preferably 1.0 C/dm² or higher. No upper limit is placed on the electrolytic density of the anodic electrolysis either, but the electrolytic density is preferably set to 10.0 C/dm² or less because an excessively high electrolytic density will saturate the effect of the pretreatment.

After the pretreatment, water washing is preferably performed from the perspective of removing any pretreatment solution adhering to the surface. When forming the Sn plating layer on the surface of the base steel

sheet, pretreatment is preferably performed on the base steel sheet. Although any of the above pretreatments can be performed, at least one of degreasing, pickling, and water washing is preferably performed.

Degreasing removes rolling oil, anti-rust oil, and the like from the steel sheet. The degreasing is not limited and can be performed by any method.

After degreasing, water washing is preferably performed to remove any degreasing treatment solution adhering to the steel sheet surface.

Pickling removes the natural oxide film present on the surface of the steel sheet and activates the surface. The pickling is not limited and can be performed by any method. After pickling, water washing is preferably performed to remove any pickling treatment solution adhering to the steel sheet surface.

[Water Washing Process]

Next, the steel sheet after the surface conditioning process is subjected to water washing at least once. Water washing removes any residual aqueous solution from the surface of the steel sheet. The water washing is not limited and may be performed by any method. For example, a water washing tank can be installed downstream from the tank for coating formation, and the steel sheet after the coating formation process can be continuously immersed in water. Water washing may also be performed by spraying water on the steel sheet after the coating formation process.

The number of times the water washing is performed is not limited and may be one or more. However, to avoid an excessively large number of water washing tanks, the number of times water washing is performed is preferably five or less. In the case of performing water washing treatment two or more times, each water washing may be performed in the same or a different manner.

In the present disclosure, it is important to use water with an electrical conductivity of 100 μS/m or less at least in the last water washing of the water washing process. This reduces the amount of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet and thereby improves adhesion. Water with an electrical conductivity of 100 μS/m or less can be produced by any method. The water with an electrical conductivity of 100 μS/m or less may, for example, be reverse osmosis water, ion-exchanged water, or distilled water. The electrical conductivity of the water used for water washing can be measured using a conductivity meter.

When water washing is performed two or more times in the water washing process, any water can be used for the water washing other than the last water washing, since the above-described effect can be obtained by using water with an electrical conductivity of 100 μS/m or less for the last water washing. Water with an electrical conductivity of 100 μS/m or less may also be used for water washing other than the last water washing. However, from the perspective of cost reduction, water with an electrical conductivity of 100 μS/m or less is preferably used only for the last water washing, with normal water such as tap water or industrial water being used for water washing other than the last water washing.

From the perspective of further reducing the amount of K, Na, Mg, and Ca adsorbed on the surface of surface-treated steel sheet, the electrical conductivity of the water used for the last water washing is preferably set to 50 μS/m or less, more preferably 30 μS/m or less. On the other hand, no lower limit is placed on the electrical conductivity, and the electrical conductivity may be 0 μS/m. However, from the perspective of cost reduction, the electrical conductivity is preferably set to 1 μS/m or more.

The temperature of water used for the water washing treatment is not limited and may be any temperature. However, since excessively high temperatures place an excessive burden on the water washing equipment, the temperature of the water used for water washing is preferably set to 95° C. or lower. No lower limit is placed on the temperature of water used for water washing either, but the temperature is preferably θ° C. or higher. The temperature of the water used in the water washing may be room temperature.

No limit is placed on the water washing time per water washing treatment, but from the perspective of increasing the effectiveness of the water washing treatment, the water washing time is preferably 0.1 seconds or longer, more preferably 0.2 seconds or longer. No upper limit is placed on the water washing time per water washing treatment either, but in the case of production on a continuous line, the water washing time is preferably 10 seconds or less, more preferably 8 seconds or less, because a longer water washing time reduces the line speed and lowers productivity.

Drying may optionally be performed after the water washing process. The drying method is not limited, and ordinary dryers or electric furnace drying methods, for example, can be applied. The temperature during the drying process is preferably 100° C. or lower. Within the aforementioned range, the transformation of the surface-treatment coating can be suppressed. Although no lower limit is placed on the temperature, the lower limit is typically around room temperature.

Applications of the surface-treated steel sheet of the present disclosure are not limited, but the surface-treated steel sheet is particularly suitable as a surface-treated steel sheet for containers used in the production of various types of containers, such as food cans, beverage cans, pails, and 18-liter cans, for example.

Examples

To determine the effects of the present disclosure, surface-treated steel sheets were produced by the following procedures, and their properties were evaluated. The present disclosure is not, however, limited to the following examples.

(Sn Plating)

First, steel sheets were sequentially subjected to electrolytic degreasing, water washing, pickling by immersion in dilute sulfuric acid, and water washing, followed by Sn electroplating using a phenol sulfonic acid bath to form an Sn plating layer on both sides of the steel sheets. The Sn coating weight of the Sn plating layer was set at this time to the values illustrated in Tables 2 and 3 by changing the current passage time. For some of the Examples, prior to the Sn electroplating, the steel sheets were subjected to Ni electroplating using a Watts bath to form a Ni plating layer as a Ni-containing layer on both sides of the steel sheets. The Ni coating weight of the Ni plating layer was set at this time to the values illustrated in Tables 2 and 3 by changing the current passage time and the current density. The Sn coating weight of the Sn plating layer was measured by the electrolytic stripping method specified in JIS G 3303. The Ni coating weight of the Ni plating layer was measured by the above-described calibration curve method using X-ray fluorescence.

Furthermore, some of the Examples were subjected to reflow treatment after the Sn plating layer was formed. In the reflow treatment, the steel sheet was heated at a heating rate of 50° C./see by a direct current heating method for 5 seconds and then introduced into water for rapid cooling.

A steel sheet for cans (T4 blank sheet) with a thickness of 0.17 mm was used as the steel sheet.

(Pretreatment for Sn-Plated Steel Sheet)

The resulting Sn-plated steel sheets were then subjected to the pretreatment indicated in Tables 2 and 3. “C” indicates cathodic electrolysis, “A” indicates anodic electrolysis, “D” indicates immersion treatment, and “C→A” indicates further anodic electrolysis after cathodic electrolysis. A sodium bicarbonate solution with a concentration of 10 g/L was used for the cathodic electrolysis, anodic electrolysis, and soaking treatment in the above pretreatment, and the temperature of the aqueous sodium bicarbonate solution was room temperature. The electrolytic density during the cathodic electrolysis was 2.0 C/dm² and the anodic electrolysis was 4.0 C/dm². The immersion time during the immersion treatment was 1 second. For comparison, no pretreatment was performed on some of the Examples.

(Coating Formation Process)

Next, the surface of the Sn-plated steel sheet was treated with an aqueous solution to form a coating layer on the Sn plating layer. Specifically, an aqueous solution with the composition illustrated in Table 1 was used as the aqueous solution, and the coating layer was formed by performing cathodic electrolysis in the aqueous solution. The temperature of the aqueous solution was set to 35° C., and the pH was adjusted to be between 3 and 5. The Zr coating weight and Ti coating weight were controlled by adjusting the electrical density. Zirconium fluoride (ZrF₄) was used as the Zr-containing compound and titanium fluoride (TiF 4) as the Ti-containing compound. The aqueous solution was prepared by adjusting the concentration of each ion through use of additional compounds other than the Zr-containing compound and the Ti-containing compound for the aqueous solution to have the compositions illustrated in Table 1.

(Surface Conditioning Process)

After the coating formation process, surface conditioning was performed under the set of conditions illustrated in Tables 2 and 3. Specifically, at the end of the coating formation process, the steel sheet having the aqueous solution adhering to its surface was squeezed with a wringer roll to adjust the amount of aqueous solution present on the surface of the coating layer to the amounts listed in Tables 2 and 3. The amount of aqueous solution was measured by a moisture meter using a filter-type infrared absorption method, as described above. The steel sheets were then held for the holding time illustrated in Tables 2 and 3. In other words, the aqueous solution used in the surface conditioning process is the same as that used in the aforementioned coating formation process.

(Water Washing Process)

Next, water washing treatment was applied to the steel sheets after the aforementioned surface preparation process. The water washing treatment was performed 1 to 5 times under the set of conditions illustrated in Tables 2 and 3. The method of each water washing and the electrical conductivity of the water used are illustrated in Tables 2 and 3. For the times when the water washing method was “immersion”, water washing was performed by immersing the steel plate in water. For the times when the water washing method was “spray”, on the other hand, water washing was performed by spraying water onto the steel sheet. The electrical conductivity was measured using a conductivity meter.

For comparison, in Comparative Example No. 78, the surface-treated steel sheet was produced under the same conditions as in Example No. 4 in PTL 5. That is, after cathodic electrolysis of a Sn-plated steel sheet in a chromium sulfate aqueous solution, water washing was performed twice.

The coating weight of Zr oxide, the coating weight of Ti oxide, the P coating weight, and the Mn coating weight in the coating layer were measured for each of the obtained surface-treated steel sheets. The measurements were performed by the above-described calibration curve method using X-ray fluorescence. The measurement results are listed in Tables 4 and 5. In Tables 4 and 5, the coating weight for Zr oxide and Ti oxide are listed as the amount of metal Zr and amount of metal Ti, respectively.

The water contact angle and the atomic ratios of adsorbed elements were measured by the following procedures for each of the obtained surface-treated steel sheets. The measurement results are listed in Tables 4 and 5.

(Water contact angle)

The water contact angle was measured using an automatic contact angle meter, model CA-VP, produced by K yowa Interface Science Co., Ltd. The surface temperature of the surface treated steel sheet was 20° C.±1° C., and distilled water at 20° C.±1° C. was used. A 2 μl drop of distilled water was dropped onto the surface of the surface-treated steel sheet, and the contact angle was measured 1 second later by the θ/2 method. The arithmetic mean value of the contact angles of 5 drops was used as the water contact angle.

To confirm the change in contact angle due to heat, the contact angle was also measured after the surface-treated steel sheet was subjected to heat treatment at 200° C. for 10 minutes. The measurement conditions were the same as above. As a result, the contact angle values were substantially the same before and after heat treatment for the surface-treated steel sheets meeting the conditions of the present disclosure. In contrast, some of the surface-treated steel sheets that did not meet the conditions of the present disclosure exhibited significant changes in contact angle values due to heat treatment.

(Atomic Ratio of Adsorbed Elements)

The total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet to all elements was measured by XPS. No sputtering was performed in the measurements. From the integrated intensity of the narrow spectra of K₂p, Na1s, Ca2p, and Mg1s at the top surface of the sample, the detected atomic ratios to all elements were quantified using the relative sensitivity factor method and calculated as (K atomic ratio+Na atomic ratio+Ca atomic ratio+M g atomic ratio). For the XPS measurement, the scanning X-ray photoelectron spectrometer PHI X-tool, produced by ULVAC-PHI, was used, with the X-ray source being a monochrome AIK a beam, the voltage being 15 kV, the beam diameter being 100 μm ø, and the take-off angle being 45°.

Furthermore, the obtained surface-treated steel sheets were evaluated for sulfide staining resistance, paint secondary adhesion, and appearance by the following methods. The evaluation results are listed in Tables 4 and 5.

(Sulfide Staining Resistance)

On the surface of a surface-treated steel sheet prepared by the above-described method, a commercial epoxy resin paint for cans was applied at a dry mass of 60 mg/dm², subsequently baked at 200° C. for 10 minutes, and then left at room temperature for 24 hours. The resulting steel sheet was then cut to a predetermined size. An aqueous solution containing anhydrous disodium hydrogen phosphate: 7.1 g/L, anhydrous sodium dihydrogen phosphate: 3.0 g/L, and L-cysteine hydrochloride: 6.0 g/L was prepared and boiled for 1 hour, after which the reduction in volume by evaporation was compensated for by adding pure water. The resulting aqueous solution was poured into a pressure-resistant, heat-resistant container made of Teflon® (Teflon is a registered trademark in Japan, other countries, or both). The steel sheet cut to the predetermined size was immersed in the aqueous solution, and the lid of the container was closed and sealed. The sealed container was subjected to retort treatment at a temperature of 131° C. for 60 minutes.

The sulfide staining resistance was evaluated based on the appearance of the steel sheet after the retort treatment. No change whatsoever in the appearance before and after the test was evaluated as “1”, the occurrence of blackening in 10% by area or less was evaluated as “2”, the occurrence of blackening in 20% or less by area and more than 10% by area was evaluated as “3”, and the occurrence of blackening in more than 20% by area was evaluated as “4”. A rating of 1 to 3 indicates excellent sulfide staining resistance in practical use and was thus considered passing.

(Paint Secondary Adhesion)

The surface of the resulting surface-treated steel sheet was coated with an epoxy phenolic paint and baked at 210° C. for 10 minutes to produce a prepainted steel sheet. The coating weight of the paint was 50 mg/dm².

Two prepainted steel sheets made under the same conditions were stacked so that the coated surfaces faced each other with a nylon adhesive film therebetween and were then pressure bonded under a set of conditions including a pressure of 2.94×10⁵ Pa, a temperature of 190° C., and a pressure bonding time of 30 seconds. The bonded steel sheets were then divided into 5 mm wide test pieces. The divided test pieces were immersed for 168 hours in a 55° C. test solution consisting of a mixed aqueous solution containing 1.5 mass % citric acid and 1.5 mass % common salt. After immersion and subsequent washing and drying, the two steel sheets of the divided test pieces were pulled apart in a tensile tester, and the tensile strength at the time of separation was measured. The average of three test pieces was evaluated at the following four levels. For practical purposes, a result of 1 to 3 can be evaluated as excellent paint secondary adhesion.

• • 1:2.5 kgf or more 2:2.0 kgf or more but less than 2.5 kgf 3:1.5 kgf or more but less than 2.0 kgf 4: Less than 1.5 kgf

(Appearance)

The L-value was measured for surface-treated steel sheets prepared by the above-described method and for Sn-plated steel sheets before the coating formation process. The L value was measured using the spectrophotometer SQ-2000 produced by Nippon Denshoku Industries, with a measurement diameter of 30 mm ø, and the SCI (Specular Component Include: including positive reflection) value was used. The difference in L-value, ΔL, was then calculated using the formula (L-value of Sn-plated steel sheet before coating formation process)-(L-value of resulting surface-treated steel sheet). The L value represents the brightness of the color, and a larger ΔL represents greater degradation in the original bright and beautiful appearance of tinplate. AL was evaluated at the following four levels. For practical purposes, a result of 1 to 3 can be evaluated as excellent in appearance.

• • 1: Less than 1.0
  • 2:1.0 or more but less than 3.0
  • 3:3.0 or more but less than 5.0
  • 4:5.0 or more

As is clear from Table 5, No. 78, which simulates Example No. 4 in PTL 5, obtained excellent sulfide staining resistance and paint secondary adhesion, but had an inferior appearance. On the other hand, as is clear from Tables 4 and 5, all of the surface-treated steel sheets that met the conditions of the present disclosure combined excellent sulfide staining resistance, paint secondary adhesion, and appearance.

TABLE 1
Aqueous	Composition (ppm)

solution	Zr4+	Ti4+	Mn4+	PO43−	F−	NO33−	NH4+

A	3000	—	—	—	4000	—	—
B	1500	—	—	—	2000	3000	2000
C	2000	—	—	950	2000	1600	1000
D	2000	—	—	950	2000	7000	2500
E	2000	2000	—	950	2000	7000	2500
F	—	1500	—	—	2000	3000	2000
G	—	2000	—	950	2000	1600	1000
H	—	2000	—	950	2000	7000	2500
I	2000	2000	2000	950	2000	7000	2500

	TABLE 2
	Production conditions

Surface conditioning

Coating

process

Water washing treatment

Sn plating layer

formation

Amount of

First time

		Ni coating	Sn coating		process	aqueous			Electrical
	Reflow	weight	weight		Aqueous	solution	Holding		conductivity
No.	treatment	[mg/m2]	[g/m2]	Pretreatment	solution	[g/m2]	time [sec]	Method	[μS/m]
1	yes	—	5.6	C	A	38.5	0.8	immersion	21
2	yes	—	2.8	C	B	43.2	11.2	spray	17
3	yes	—	5.6	C	C	48.3	2.3	spray	100
4	yes	—	2.8	C	D	31.3	6.5	spray	61
5	yes	—	5.6	C	E	51.9	1.8	spray	9
6	yes	—	2.8	C	F	37.5	0.5	immersion	15
7	yes	—	5.6	C	G	40.3	13.8	spray	98
8	yes	—	2.8	C	H	41.3	2.6	immersion	12
9	yes	—	5.6	C	I	41.8	7.2	immersion	21
10	yes	—	2.8	C	A	42.0	13.6	immersion	121
11	yes	—	8.4	C	B	53.9	8.0	immersion	14
12	yes	—	11.2	C	C	47.4	13.2	immersion	73
13	yes	—	5.6	C	D	45.0	5.3	immersion	118
14	yes	—	0.7	C	E	37.4	4.5	immersion	123
15	yes	—	0.9	C	F	39.5	11.5	immersion	67
16	no	—	2.8	C	G	49.5	9.9	immersion	31
17	no	—	5.6	C	H	51.8	4.1	immersion	19
18	no	—	8.4	C	I	38.6	2.3	immersion	21
19	no	—	11.2	C	A	37.7	1.0	immersion	13
20	no	—	0.8	C	B	45.3	2.6	spray	29
21	yes	3	1.1	C	C	48.5	10.3	immersion	14
22	yes	6	1.0	C	D	43.2	1.1	immersion	89
23	yes	11	0.7	C	E	35.8	3.5	immersion	98
24	yes	41	0.7	C	F	51.2	12.3	immersion	93
25	yes	102	0.9	C	G	45.6	9.2	immersion	32
26	no	2	1.2	C	H	41.3	11.9	immersion	49
27	no	5	0.8	C	I	38.4	13.2	immersion	216
28	no	13	1.1	C	A	47.1	12.6	immersion	12
29	no	35	1.2	C	B	42.0	11.8	immersion	160
30	no	98	1.0	C	C	36.5	1.5	immersion	23
31	yes	—	2.8	D	D	41.6	8.7	immersion	20
32	no	—	2.8	D	E	48.9	5.6	immersion	16
33	yes	3	0.9	D	F	53.7	13.2	immersion	113
34	no	2	1.0	D	G	35.8	11.5	immersion	29
35	yes	—	2.8	C→A	H	46.5	11.3	immersion	32
36	no	—	2.8	C→A	I	53.0	8.2	immersion	15
37	yes	3	1.0	C→A	A	37.4	14.6	immersion	111
38	no	3	1.1	C→A	B	39.0	6.7	immersion	29
39	yes	—	2.8	A	C	46.5	3.2	immersion	13
40	no	—	2.8	A	D	49.2	0.7	immersion	15

	Production conditions
	Water washing treatment

Second time

Third time

Fourth time

Fifth time

		Electrical		Electrical		Electrical		Electrical
		conductivity		conductivity		conductivity		conductivity
No.	Method	[μS/m]	Method	[μS/m]	Method	[μS/m]	Method	[μS/m]	Notes
1	—	—	—	—	—	—	—	—	Example
2	—	—	—	—	—	—	—	—	Example
3	immersion	15	—	—	—	—	—	—	Example
4	spray	12	—	—	—	—	—	—	Example
5	immersion	30	immersion	15	—	—	—	—	Example
6	immersion	6	spray	8	—	—	—	—	Example
7	immersion	43	immersion	106	immersion	27	—	—	Example
8	immersion	59	spray	262	spray	9	—	—	Example
9	immersion	213	immersion	103	immersion	31	immersion	13	Example
10	spray	63	spray	25	immersion	191	spray	18	Example
11	immersion	194	spray	15	—	—	—	—	Example
12	spray	101	spray	22	—	—	—	—	Example
13	immersion	76	immersion	17	—	—	—	—	Example
14	spray	63	spray	29	—	—	—	—	Example
15	immersion	40	spray	13	—	—	—	—	Example
16	immersion	94	immersion	8	—	—	—	—	Example
17	immersion	51	spray	24	—	—	—	—	Example
18	immersion	14	immersion	19	—	—	—	—	Example
19	immersion	171	spray	18	—	—	—	—	Example
20	immersion	36	immersion	6	—	—	—	—	Example
21	immersion	211	spray	8	—	—	—	—	Example
22	immersion	109	spray	7	—	—	—	—	Example
23	immersion	104	immersion	26	—	—	—	—	Example
24	immersion	66	spray	13	—	—	—	—	Example
25	immersion	37	spray	11	—	—	—	—	Example
26	immersion	93	immersion	10	—	—	—	—	Example
27	immersion	68	spray	9	—	—	—	—	Example
28	immersion	50	immersion	13	—	—	—	—	Example
29	immersion	13	spray	16	—	—	—	—	Example
30	immersion	24	immersion	22	—	—	—	—	Example
31	immersion	69	spray	13	—	—	—	—	Example
32	spray	225	immersion	28	—	—	—	—	Example
33	immersion	13	spray	18	—	—	—	—	Example
34	immersion	33	immersion	11	—	—	—	—	Example
35	immersion	52	spray	16	—	—	—	—	Example
36	immersion	43	immersion	24	—	—	—	—	Example
37	immersion	16	spray	9	—	—	—	—	Example
38	immersion	186	immersion	13	—	—	—	—	Example
39	immersion	16	spray	21	—	—	—	—	Example
40	immersion	32	immersion	26	—	—	—	—	Example

	TABLE 3
	Production conditions

Surface conditioning

Water washing treatment

Sn plating layer

Coating

process

Ni

Sn

formation

Amount of

First time

		coating	coating		process	aqueous	Holding		Electrical
	Reflow	weight	weight		Aqueous	solution	time		conductivity	Second time
No.	treatment	[mg/m2]	[g/m2]	Pretreatment	solution	[g/m2]	[sec]	Method	[μS/m]	Method
41	yes	2	0.8	A	E	51.9	1.3	immersion	11	immersion
42	no	4	1.0	A	F	45.6	3.5	immersion	12	immersion
43	yes	—	2.8	none	G	38.3	2.8	immersion	26	immersion
44	no	—	2.8	none	H	52.4	0.8	immersion	53	immersion
45	yes	3	0.8	none	I	53.0	5.4	immersion	19	immersion
46	no	2	0.9	none	A	47.3	3.2	immersion	89	immersion
47	yes	—	2.8	C	H	39.5	2.8	immersion	24	immersion
48	yes	—	2.8	C	I	46.3	11.2	immersion	86	immersion
49	yes	—	2.8	C	B	52.6	13.2	immersion	16	immersion
50	yes	—	2.8	C	C	41.6	11.2	immersion	20	immersion
51	yes	—	2.8	C	D	56.2	8.9	immersion	9	immersion
52	yes	—	2.8	C	E	59.3	6.8	immersion	21	immersion
53	yes	—	2.8	C	F	63.0	7.8	immersion	106	immersion
54	yes	—	2.8	C	G	33.6	4.5	immersion	89	immersion
55	yes	—	2.8	C	H	30.8	1.5	immersion	154	immersion
56	yes	—	2.8	C	I	29.2	0.9	immersion	135	immersion
57	yes	—	2.8	C	A	40.3	16.1	immersion	101	immersion
58	yes	—	2.8	C	B	37.2	19.4	immersion	116	immersion
59	yes	—	2.8	C	C	36.5	20.8	immersion	132	immersion
60	yes	—	2.8	C	D	38.6	0.2	immersion	16	immersion
61	yes	—	2.8	C	E	42.3	0.1	immersion	19	immersion
62	yes	—	2.8	C	F	52.9	0.05	immersion	109	immersion
63	yes	—	2.8	C	G	39.3	11.3	spray	43	—
64	yes	—	2.8	C	H	40.6	13.5	immersion	83	—
65	yes	—	2.8	C	I	37.2	10.0	immersion	151	—
66	yes	—	2.8	C	A	52.2	2.5	immersion	105	immersion
67	yes	—	2.8	C	B	53.6	3.3	immersion	11	spray
68	yes	—	2.8	C	C	50.9	12.1	immersion	9	immersion
69	yes	—	2.8	C	D	43.2	7.4	immersion	106	immersion
70	yes	—	2.8	C	E	48.5	5.0	immersion	13	immersion
71	yes	—	2.8	C	F	44.4	1.5	immersion	21	immersion
72	yes	—	2.8	C	G	39.5	1.6	immersion	38	immersion
73	yes	—	2.8	C	H	36.1	2.6	immersion	109	immersion
74	yes	—	2.8	C	I	42.1	7.9	immersion	121	immersion
75	yes	—	2.8	C	A	49.2	10.5	immersion	13	immersion
76	yes	—	2.8	C	B	44.1	11.5	immersion	119	immersion
77	yes	—	2.8	C	C	52.3	1.9	immersion	125	immersion

78	yes	—	2.8	C	PTL 5, Example No. 4	spray	62	spray

	Production conditions
	Water washing treatment

Second time

Third time

Fourth time

Fifth time

	Electrical		Electrical		Electrical		Electrical
	conductivity		conductivity		conductivity		conductivity
No.	[μS/m]	Method	[μS/m]	Method	[μS/m]	Method	[μS/m]	Notes
41	16	immersion	18	—	—	—	—	Example
42	174	spray	15	—	—	—	—	Example
43	39	immersion	26	—	—	—	—	Example
44	151	spray	15	—	—	—	—	Example
45	74	immersion	19	—	—	—	—	Example
46	19	spray	16	—	—	—	—	Example
47	16	immersion	14	—	—	—	—	Example
48	22	spray	13	—	—	—	—	Example
49	151	spray	17	—	—	—	—	Example
50	13	spray	20	—	—	—	—	Example
51	136	spray	11	—	—	—	—	Example
52	209	spray	18	—	—	—	—	Example
53	168	spray	13	—	—	—	—	Comparative example
54	13	spray	16	—	—	—	—	Example
55	22	spray	18	—	—	—	—	Example
56	9	spray	6	—	—	—	—	Comparative example
57	14	spray	25	—	—	—	—	Example
58	69	spray	11	—	—	—	—	Example
59	89	spray	10	—	—	—	—	Comparative example
60	163	spray	29	—	—	—	—	Example
61	117	spray	20	—	—	—	—	Example
62	105	spray	13	—	—	—	—	Comparative example
63	—	—	—	—	—	—	—	Example
64	—	—	—	—	—	—	—	Example
65	—	—	—	—	—	—	—	Comparative example
66	36	—	—	—	—	—	—	Example
67	78	—	—	—	—	—	—	Example
68	205	—	—	—	—	—	—	Comparative example
69	132	spray	47	—	—	—	—	Example
70	16	immersion	68	—	—	—	—	Example
71	9	spray	112	—	—	—	—	Comparative example
72	153	spray	22	immersion	40	—	—	Example
73	12	immersion	105	spray	53	—	—	Example
74	165	spray	13	immersion	101	—	—	Comparative example
75	80	spray	199	immersion	103	spray	38	Example
76	74	immersion	106	immersion	79	immersion	93	Example
77	39	spray	51	immersion	83	spray	261	Comparative example
78	11	—	—	—	—	—	—	Comparative example

	TABLE 4
	Measurement results

Coating layer

Atomic

Zr oxide and Ti oxide

ratio of

Evaluation

	Zr coating	Ti coating		P coating	Mn coating	Water	adsorbed	Sulfide	Paint
	weight	weight	Total	weight	weight	contact	elements	staining	secondary
No.	[mg/m2]	[mg/m2]	[mg/m2]	[mg/m2]	[mg/m2]	angle [°]	[%]	resistance	adhesion	Appearance	Notes

1	5.8	0.0	5.8	0.0	0.0	22.3	0.3	1	1	1	Example
2	3.2	0.0	3.2	0.0	0.0	42.3	0.0	1	1	1	Example
3	16.3	0.0	16.3	22.1	0.0	33.1	0.0	1	1	1	Example
4	7.8	0.0	7.8	10.3	0.0	9.3	0.0	1	1	1	Example
5	11.5	3.2	14.7	8.6	0.0	6.8	0.0	1	1	1	Example
6	0.0	15.6	15.6	0.0	0.0	13.5	0.0	1	1	1	Example
7	0.0	2.8	2.8	33.9	0.0	11.3	0.0	1	1	1	Example
8	0.0	13.5	13.5	47.3	0.0	17.3	0.0	1	1	1	Example
9	9.3	1.2	10.5	8.2	12.3	11.3	0.5	1	1	1	Example
10	2.1	0.0	2.1	0.0	0.0	22.5	0.2	1	1	1	Example
11	15.3	0.0	15.3	0.0	0.0	36.3	0.0	1	1	1	Example
12	32.5	0.0	32.5	13.8	0.0	7.6	0.7	1	1	1	Example
13	39.4	0.0	39.4	3.7	0.0	41.9	0.1	1	1	1	Example
14	12.5	11.3	23.8	9.3	0.0	30.3	0.0	1	1	1	Example
15	0.0	20.4	20.4	0.0	0.0	18.3	0.0	1	1	1	Example
16	0.0	16.8	16.8	28.5	0.0	20.6	0.0	1	1	1	Example
17	0.0	25.6	25.6	16.7	0.0	44.5	0.0	1	1	1	Example
18	6.9	0.8	7.7	12.6	32.1	39.6	0.0	1	1	1	Example
19	13.6	0.0	13.6	0.0	0.0	13.2	0.0	1	1	1	Example
20	22.9	0.0	22.9	0.0	0.0	22.5	0.0	1	1	1	Example
21	32.3	0.0	32.3	31.6	0.0	26.3	0.0	1	1	1	Example
22	16.9	0.0	16.9	16.9	0.0	34.5	0.0	1	1	1	Example
23	22.5	11.6	34.1	7.2	0.0	28.4	0.6	1	1	1	Example
24	0.0	16.5	16.5	0.0	0.0	16.6	0.0	1	1	1	Example
25	0.0	32.8	32.8	41.3	0.0	9.2	0.0	1	1	1	Example
26	0.0	22.3	22.3	39.4	0.0	19.7	0.0	1	1	1	Example
27	4.2	16.5	20.7	24.6	18.5	25.5	0.0	1	1	1	Example
28	16.3	0.0	16.3	0.0	0.0	23.4	0.0	1	1	1	Example
29	11.2	0.0	11.2	0.0	0.0	15.6	0.0	1	1	1	Example
30	9.8	0.0	9.8	32.4	0.0	13.8	0.0	1	1	1	Example
31	7.6	0.0	7.6	16.8	0.0	13.5	0.2	1	1	1	Example
32	4.8	3.7	8.5	17.2	0.0	24.3	0.0	1	1	1	Example
33	0.0	3.6	3.6	0.0	0.0	19.3	0.0	1	1	1	Example
34	0.0	9.8	9.8	10.6	0.0	22.6	0.0	1	1	1	Example
35	0.0	12.6	12.6	0.4	0.0	32.6	0.0	1	1	1	Example
36	24.6	14.3	38.9	3.2	48.3	18.6	0.1	1	1	1	Example
37	33.6	0.0	33.6	0.0	0.0	24.2	0.0	1	1	1	Example
38	16.2	0.0	16.2	0.0	0.0	19.6	0.0	1	1	1	Example
39	13.5	0.0	13.5	16.3	0.0	9.8	0.0	1	1	1	Example
40	19.3	0.0	19.3	2.7	0.0	12.6	0.6	1	1	1	Example

	TABLE 5
	Measurement results

Coating layer

Atomic

Zr oxide and Ti oxide

Water

ratio of

Evaluation

	Zr coating	Ti coating		P coating	Mn coating	contact	adsorbed	Sulfide	Paint
	weight	weight	Total	weight	weight	angle	elements	staining	secondary
No.	[mg/m2]	[mg/m2]	[mg/m2]	[mg/m2]	[mg/m2]	[°]	[%]	resistance	adhesion	Appearance	Notes

41	0.7	7.8	8.5	22.8	0.0	14.3	0.0	1	1	1	Example
42	0.0	12.1	12.1	0.0	0.0	19.6	0.0	1	1	1	Example
43	14.6	0.0	14.6	12.6	0.0	10.3	0.1	1	1	1	Example
44	17.6	0.0	17.6	3.8	0.0	26.1	0.0	1	1	1	Example
45	0.8	7.3	8.1	21.5	0.0	19.3	0.0	1	1	1	Example
46	0.0	11.1	11.1	0.0	0.0	31.5	0.0	1	1	1	Example
47	0.0	47.9	47.9	11.3	0.0	41.5	0.0	2	2	2	Example
48	36.3	22.0	58.3	17.5	7.5	16.3	0.0	3	3	3	Example
49	0.3	0.0	0.3	0.0	0.0	25.3	0.0	2	2	1	Example
50	0.2	0.0	0.2	34.1	0.0	19.2	0.0	3	3	1	Example
51	3.6	0.0	3.6	9.1	0.0	46.2	0.0	2	2	1	Example
52	1.2	34.5	35.7	22.7	0.0	48.9	0.0	3	3	1	Example
53	0.0	16.2	16.2	0.0	0.0	53.3	0.0	4	4	1	Comparative example
54	0.0	11.2	11.2	39.6	0.0	45.6	0.0	2	2	1	Example
55	0.0	4.3	4.3	11.2	0.0	49.3	0.2	3	3	1	Example
56	21.6	9.8	31.4	16.8	16.3	68.6	0.0	4	4	1	Comparative example
57	8.3	0.0	8.3	0.0	0.0	45.2	0.0	2	2	1	Example
58	15.5	0.0	15.5	0.0	0.0	48.3	0.0	3	3	1	Example
59	13.6	0.0	13.6	13.8	0.0	54.6	0.0	4	4	1	Comparative example
60	12.3	0.0	12.3	7.5	0.0	47.6	0.1	2	2	1	Example
61	6.3	4.2	10.5	5.2	0.0	49.9	0.0	3	3	1	Example
62	0.0	15.6	15.6	0.0	0.0	73.6	0.0	4	4	1	Comparative example
63	0.0	24.1	24.1	13.4	0.0	16.2	1.2	2	2	1	Example
64	0.0	16.3	16.3	12.8	0.0	13.8	3.6	3	3	1	Example
65	22.5	1.3	23.8	1.9	8.2	22.8	5.3	4	4	1	Comparative example
66	22.1	0.0	22.1	0.0	0.0	41.3	2.1	2	2	1	Example
67	16.2	0.0	16.2	0.0	0.0	31.4	4.6	3	3	1	Example
68	32.5	0.0	32.5	3.7	0.0	36.9	6.9	4	4	1	Comparative example
69	16.3	0.0	16.3	16.2	0.0	13.2	1.8	2	2	1	Example
70	11.2	26.5	37.7	17.9	0.0	8.9	3.3	3	3	1	Example
71	0.0	29.8	29.8	0.0	0.0	29.8	7.2	4	4	1	Comparative example
72	0.0	10.5	10.5	6.4	0.0	16.4	2.3	2	2	1	Example
73	0.0	12.3	12.3	4.8	0.0	11.9	3.9	3	3	1	Example
74	1.8	2.9	4.7	18.5	29.8	10.0	5.8	4	4	1	Comparative example
75	16.2	0.0	16.2	0.0	0.0	12.6	1.1	2	2	1	Example
76	13.2	0.0	13.2	0.0	0.0	38.2	4.3	3	3	1	Example
77	9.0	0.0	9.0	16.4	0.0	34.5	6.2	4	4	1	Comparative example

78		PTL 5, Example No. 4	41.6	0.0	1	1	4	Comparative example