JPH0356695A - Composite plated steel sheet excellent in di workability - Google Patents

Abstract

PURPOSE:To produce a steel sheet for the beverage can excellent in drawability and squeezing property by providing each fluorinated hydrocarbon resin, tin based composite plating film alone or the composite of a base tin plating layer and a surface chemical conversion film on the surface of a steel sheet. CONSTITUTION:A steel sheet with the consumption of expensive Sn reduced is used to reduce the cost of the steel sheet as the base material, when a two- piece can as the container for beer, carbonated beverages, etc., is produced by high-degree drawing and squeezing. The Sn 3 contg. 0.1-20vol.% fluorinated hydrocarbon resin 4 having 0.5um grain diameter or the plating layer 2 of the fluorinated hydrocarbon resin-tin or fluorinated hydrocarbon resin-tin alloy consisting of the alloy 3 of Sn and Zn, Ni, Mn, Mo, Cu, etc., is formed at least on one side of a steel sheet 1 at 0.2-12.0g/m<2>. Alternatively, a thin Sn plating layer 5 is provided between the plating layer 2 and the base steel sheet 1, or a chromate film or the chemical conversion film 6 of zinc phosphate, etc., is formed on the fluorinated hydrocarbon resin-tin-based plating layer 2. Consequently, an inexpensive plated steel sheet for the beverage can with the consumption of expensive Sn reduced is obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a steel plate for can containers, especially DI cans, and in particular to a steel plate for DI cans.
¥! This invention relates to a double gold-plated steel sheet for cans with excellent cooling properties. In addition to DI cans, the steel plate of the present invention can also be used for DrD cans, body materials,
It can be applied as a material for can lids and 5 gallon cans.

[Conventional technology can containers can be classified from the perspective of the can body: canopy, bottom lid,
Cans are roughly divided into three-piece cans with an R-shaped ring, and two-piece cans with a top, a body, and a canopy.

Two-piece cans are currently available in Draw and
Redraw) can and DI (Draw and Ir)
oning) cans are widely used. Especially DI cans,
Used as beverage cans filled with beer, carbonated drinks, etc., and aerosol cans filled with antiperspirants, shaving cream, etc., containers are closely connected to daily life, and their production volume is increasing year by year.

The process of forming a steel plate into a DI can is called DI processing, and the DI cans currently in use mainly undergo two drawing processes (D
(rawing) and 2 to 3 times of ironing (Ironi
ng). The processing speed in DI processing is extremely high at 180 to 250 cans/min. In this DI processing, ironing processing (Ironir+g)
This is the most severe process, and the thickness of the workpiece is reduced by 50% or more after two or three ironing processes. In order for the material to withstand this severe DI processing, it is necessary that the material has good lubricating properties, especially in the portion that corresponds to the outer circumferential surface of the can. Continuously DI the material with insufficient lubricity on the outer circumferential surface of the can.
When processed, problems such as the occurrence of scratches called "galling" and excessive die wear occur.

"Scale" is a linear flaw that occurs when tin/iron alloy, iron, etc. adhere to the die during ironing, and this results in the processing of the outer peripheral surface of the can. As the number of processing cycles increases, non-lubricating substances build up on the die, and the "scalding" deepens accordingly, and eventually the can is torn off in the circumferential direction at the can body, resulting in a reduction in can productivity. decrease. Moreover, "scorch" deteriorates the appearance of the product.

As described above, the lubricity of the raw material that forms the outer periphery of the can is extremely important from various points of view, such as the productivity of DI cans, product appearance, and lifespan of ties. Currently, tin-plated aluminum and steel plates are used as materials for DI cans. The tin in the tin acts as a lubricant in DI processing.

Regarding tinplate, tin resources are being depleted, and the tin weight has been forced to decrease. D.I.
Materials for cans are no exception, and efforts have been made to reduce the basis weight, but as mentioned above, the lubricity of the portion of the material that forms the outer circumferential surface of the can is extremely important, so the tin basis weight has been reduced. There are limits. The tin plating thickness of the tin plate for DI cans currently used varies depending on the degree of DI processing, but
It is about 2.0 to 11.2 g/m2.

The reduction in the basis weight of tin as a material for DI cans has almost reached its limit, and there is a desire to develop a material for DI cans that has high productivity and low cost to replace tinplate.

For example, as disclosed in Japanese Patent Publication No. 53-42292, a steel plate having a crumpled phosphate film has been proposed as a material for DI cans based on a steel plate, but it does not have sufficient rust resistance. However, it has not yet been put into practical use.

[Problems to be Solved by the Invention] Lowering the basis weight of tin in the material for DI cans results in a thinner lubricating film, which causes problems such as the occurrence of "warming" and shortened die life. The present invention solves this problem and makes it possible to significantly reduce the basis weight of tin.
The purpose was to provide a low-cost material that has the same lubricity as tinplate, the current material for DI cans.

[Several Steps to Solve the Problems] The present invention is characterized by having a film in which a self-lubricating fluororesin is dispersed in a tin or tin-based alloy film.
It consists of the following F.

l. At least on one side of the steel plate, apply a fluororesin/tin composite plating film containing 0.1 to 20.0% by volume of fluororesin with a particle size of 0.5 μm or less at 0.2 to 12.0 g/+
A composite plated steel sheet with excellent DI workability characterized by n2if.

2. At least on one side of the steel plate, a fluororesin/tin-based alloy composite plating film containing 0.1 to 20.0% of fluororesin with a grain size of 0.5 μm or less in terms of volume ratio of 0.2 to 12.0 μm is applied.
A composite plated steel sheet with excellent DI workability, characterized by having a

However, the term "tin alloy" refers to a metal alloy or an alloy containing one or more of zinc, nickel, manganese, molybdenum, and copper.

3. A tin film is applied to at least one side of the steel plate, and the E layer is
Fluororesin with a particle size of 0.5 μm or less in a volume ratio of 0.1 to
Fluororesin/tin composite plating film containing 200%
．． DI characterized by the presence of 2 to 12.0 g/[n2
Composite plated steel sheet with excellent workability.

4. At least one side of the steel plate has a tin film, and the upper layer is
Fluororesin with a particle size of 0.5 μm or less in a volume ratio of 0.1 to
A composite plated steel sheet with excellent D1 workability, characterized by having a 200% fluororesin/tin alloy composite plated film of 0.2 to 12.0 g/+n2.

However, the term "tin-based alloy" refers to a metal alloy or an alloy containing one or more of zinc, nickel, manganese, molybdenum, and copper.

5. At least on one side of the steel plate, the grain size is 0.5 um or more
A fluororesin/tin composite plating film containing 0.1 to 20.0% by volume of fluororesin, 0.2 to 12.0 g/
A composite plated steel sheet with excellent DI workability, characterized by having a chromate film or a phosphate film on top of the chromate film.

6. At least on one side of the steel plate, a fluororesin/tin-based alloy composite plating skin containing 0.1 to 20.0% by volume of fluororesin with a particle size of 0.5 μm or less is applied to 0.2 to 12.
0 g/m' and further has a chromate film or a phosphate film on top of the chromate film or phosphate film, and has excellent DI workability.

However, the term "tin-based alloy" refers to a metal or alloy containing at least 2F4 or one of the following: tin alloy, nickel, manganese, molybdenum, and copper.

7. At least one side of the steel plate is coated with a tin film, and the upper layer is
Fluororesin with a particle size of 0.05 μm or less in a volume ratio of 0.1 to 2
Fluororesin/tin composite plating skin uq containing 0.0%,
0.2 ~ 12.037m2 Sara Nisononokami KIH
A composite plated steel sheet with excellent DI workability characterized by having a nichromate film or a phosphate film.

8. At least one side of the steel plate has a tin film, and its seven layers are
Fluororesin with a particle size of 0.5 μm or more at a volume ratio of 0.1
It has a fluororesin/tin-based alloy composite plating film containing ~20.0% of
A composite plated steel sheet with excellent DI workability, characterized by having a chromate film or a phosphate film in the layer.

However, the term "tin-based alloy" refers to a metal or alloy containing one or more of zinc, nickel, manganese, molybdenum, and copper.

The present invention will be explained in detail below.

The inventors conducted research through experiments in order to solve the technical problem of reducing the tin or tin joint weight as much as possible and ensuring DI formability, especially the life of the tie. As a result of repeated efforts, it was discovered that by eutectoiding fluororesin into the tin film or tin-based alloy film layer on the surface of the steel sheet, the DI formability of the surface of the steel sheet could be improved and the life of the die could be extended, and the present invention was completed. Ta.

Below, the configuration of the present invention will be explained in more detail with reference to the drawings.

An embodiment of the structure of the present invention is shown in FIG. This surface-treated steel sheet has the following features on the surface of the steel sheet 1 obtained by cold rolling:
A fluororesin composite tin plating film or a fluororesin composite tin alloy plating film 2 of 0.2 to 12.0 g/+" is formed.

In the composite plated skin @2, fluororesin particles 4 with a particle size of 0.5 μm or less are contained in metal tin or tin-based alloy 3 at a volume ratio of 0.5 μm or less.
Present at 1-20.0%. Although FIG. 1 shows an embodiment in which the steel plate 1 has a plating layer on only one side, it is of course possible to have a plating layer on both sides of the steel plate.

Another embodiment of the invention is shown in FIG. This surface treatment JII!
The steel plate further has a tin film 5 below the fluororesin composite tin plating film or the fluororesin composite tin alloy plating film 2 . In the case of FIG. 2 as well, although the embodiment is different from the embodiment in which the plated layer is provided only on one side of the steel plate 1, it is possible to provide the plated layer on both sides of the steel plate.

Next, still another example of the present invention is shown in FIG.

This Table i treated steel sheet further has seven layers 6 of a fluororesin composite tin plating film or a fluororesin composite tin-based alloy plating film 2.
It has a chromate film or a phosphate film. still,
FIG. 3 shows an example in which a plating defect is present on only one side of a steel plate substrate, or it is also possible to form a plating layer on both sides of a steel plate substrate. Further, although FIG. 3 shows an example in which the coating shown in FIG. 1 is formed on one side of the steel plate l, the coating shown in FIG. 2 may be formed on one or both surfaces instead of this.

The surface-treated steel sheet in the present invention is constructed by dividing 0.1 to 20% by volume of fluororesin with a particle size of 0.5 μm or more in a tin plating layer or a tin-based alloy plating layer, , 2 to 12.0 g/m2, and has excellent DI processability.

The term "tin-based alloy" as used herein refers to an alloy consisting of one of zinc, nickel, manganese, molybdenum, and copper, or two or more of these.

Examples of the fluororesin to be dispersed in the plating layer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer,
Detrafluoroethylene-ethylene copolymer, chlorotridetrafluoroethylene-alkylene copolymer, vinylidene fluoride-hexafluorobrobylene, vinylidene fluoride-chlorotritetrafluoroethylene copolymer,
Examples include vinylidene fluoride-pentafluoropropylene copolymer, fluorinated ethylene brobyleno ether resin, and mixtures of two or more of these. Even when any of the above-mentioned fluororesins is used, a plating film having excellent DI lubricity and rust resistance can be obtained.

Next, when the particle size of the fluororesin exceeds 0.5 μm, the surface of the plating layer becomes rough and the appearance of the plating becomes ugly. Furthermore, when using a fluororesin with a particle size of more than 0.5 μm, 013
I was disappointed that the printability of the paint after molding was poor. In addition, D
Although it is not clear why the bottle printing performance deteriorates after a certain amount of molding, it is thought to be due to the effect of the oil and water repellency of the fluororesin. The above means that the particle size of fluororesin is 0.5 ul1
This is the reason why it is limited to 1 or less.

Lower limit of fluororesin serum in fluororesin composite tin plating film and fluororesin composite tin-based alloy plating film: 0. lvol wood is the minimum content at which the effect of fluororesin on DI appearance appears. At the upper limit of 20 vol'4 kA, the effect of the fluororesin on DI moldability is saturated. Preferably 1~
IOvol96 containing stars are good.

Furthermore, the lower limit value of 0.2 g/m2 for 1 model of fluororesin composite tin plating skin and fluororesin composite tin-based alloy plating film is D
I is the minimum thickness that can be molded. Upper limit value (7)12.
0g/n+2 is D if it exceeds 12.0g/l'I12
I The effect on formability is saturated. Preferably DI moldability,
Because of economy! ．． 5 to 6.0 g/m2 is good.

7 - The fluororesin composite tin plating film and the fluorine resin composite tin-based alloy plating film have been explained, but furthermore,
As shown in FIG. 2, even if a tin layer exists under the fluororesin composite tin plating layer or the fluororesin composite tin-based alloy plating film, DI formability is good. In addition, in furiki, a heat treatment called reflow is sometimes performed to heat the steel plate above the melting point of tin in order to make it shiny or to eliminate holes in the tin film. However, it is well known that the tin-iron alloy layer formed by reflow deteriorates the DI formability, and even in the surface-treated steel sheet obtained by the present invention, the formation of the tin-iron alloy layer by heat treatment is It is desirable to reduce the insertion force.

Furthermore, as shown in FIG. 3 of the present invention, a chromate film or a phosphate film is added to the fluororesin composite tin plating film or the fluororesin composite tin alloy plating film to prevent rust. Gender increases by 1]].

In addition, only one side has a fluororesin composite tin plating film or a fluororesin composite tin-based alloy plating film shown in each example of the present invention, and the other side, which is the inner surface of the can, has a 50 series film or a tin-free/tin-free coating. By adopting a structure with a film known as a container material such as chromium type film M, organic film, Sn-based film, H-type film on tin-free steel/chromium type film, etc., it is possible to protect the contents from conventional materials. It is possible to create a container with a reliable inner surface coating. In addition, if-mechanical films mentioned here include vinyl, modified vinyl, epoxy, phenol, epoxyphenol, epoxyamino, acrylic, epoxyurea, vinylorcanosol, nylon, polyester, polycarbonate, polyethylene, polypropylene resin, and these. Examples include a film made of a mixture of two or more resins, and a film formed by laminating two or more layers of two or more of these resins.

Further, the Sn-based film refers to Sn or Sn alloy plating, or a film in which a chromate film or a phosphate film is further formed on these plating films.

Furthermore, the surface-treated steel sheet obtained by the present invention is used not only for DI cans, but also as DrD can body material, can lid material containing EOE, and 5-gallon can body and lid material.

[Example] This will be explained in detail in Examples below.

(Example 1) Using an electroplating bath having the composition shown below, plating was performed on both sides of a rolled steel sheet under the following conditions.

Bath composition: stannous sulfate 40 g/Q sulfuric acid 60 g/crossphenolsulfonic acid 40 g/u cationic surfactant 2 g/2 polytetrafluoroethylene particles (particle size 0.5 μm or less and average particle size 0.15
μII+) 10g/standing condition plating temperature 45℃ negative current density 4A/dm2 positive bar
High-purity tin plate stirring pump type (7 nights flow rate 220 m/+nin) plating in the clear air
1. Second plating film 11QN 2.0 g/m2 Volume of polytetrafluoroethylene deposited 10 vol% Outer layer Uniform white color Main 1: As the cationic activator 1, a perfnowoleoloalkylammonium salt was used.

(Example 2) An electroplating bath having the following composition 1 was used, and the following condition fE 1 was applied.
After plating on both sides of a cold-rolled steel sheet, using an electroplating bath with the following composition 2 on one side, and plating under the following conditions 2, using a chromate treatment bath with the following composition 3, Chromate treatment was performed on both sides of the plated steel sheet under Condition 3 below.

Bath composition 1 Stannous sulfate 40g/Q phenol sulfate gelatin β-naphthol conditions! Plating temperature Cathode current density Anode stirring Bomb type (fatiguing flow rate: Plating time Plating film I Il5! Thick appearance Bath composition 2 Tinnous chloride Nickel chloride Cuprous chloride Nl 148F2 NaF Additive 60g/2 40g/Q 2g/9 .lg/Q 45℃ 4A/dm2 High purity tin plate 20m/min) 4 seconds 0.9g/m2 Uniform white 50g/300g/1 15gQ 35g/Q 2Bg/Q 30g/1 Cation ten life world! Ancient agent 1 1g/
tAmpholytic surfactant 2g/tetrafluoroethylene-barfluoroalkylvinyl ether conjugate particles (average particle size 0.15μm compared with particle size 0.5μm or less) 15g, Qj condition 2 Plating quality 45°C jf
MiTH? a r Jri48/+Jm” anode
High-purity tin plate stirred pump type (7 nights waterfall speed: 20m/min) plating time
8 seconds plating film 2 Film thickness 1. 5g/m
2 alloy ready-made tin: 70”N, nickel: 15mm copper: 15t Polytetrafluoroethylene precipitation amount 10vol*Appearance
Uniform white color; perfluoroalkyltrimethylammonium was used as the cationic activator.

Note 2 = NNN Trial Kill N as a hermaphrodite surface active sentence
Carboxyalkyl ammonium hetaine was used.

Bath composition 3 Dichromate sorter 25g/QpH
4.5 Condition 3 Bath temperature 45℃ Immersion time
After applying for 2 seconds and washing with water, the plated film was dried with hot air. Film thickness: 2 mg/m2 (Example 3) Using the electroplating bath of the following bath set or 1, one side of a cold-rolled steel plate was coated under the following conditions 1. Then, on the other side, use the electroplating bath of the following bath set or 2 and perform plating under the following conditions 2, then use the phosphate-treated γ plate of the following set or 3, and then apply the following plating bath: Under Condition 3, the fluororesin composite tin plating was subjected to phosphate treatment. Furthermore, a polyethylene terephthalate film was laminated on the chrome plated surface.

Bath composition 1 Chromic anhydride sulfuric acid conditions! Plating temperature Cathode current density Anodic stirring Bomb type (Plating time Plating skin 11 parts! Membrane JtJ Bath composition 2 Metal tin Metal zinc TT machine Carphonic acid Conductive agent Cationic surfactant Nonionic active agent Detrough 2 Reoloethylene liquid Flow rate 200g/4 2g/2 50℃: lOA/dm2 Lead-tin alloy plate, 20m/min) 2 seconds 100mg/m2 40g/L 16g/2 1 2 0g/9. 80g/Q Ig/Q 0.5g/9. Hexafluoropropylene copolymer particles (average particle size 0.2 μm) 5 g
/Q tetrafluoroethylene-ethylene copolymer particles: IZ(
Average particle size 0.2um) 5g/Q condition 2 Plating temperature 35℃ Cathode current density 5A/dm2 Anode
High purity tin plate stirring pump type (liquid flow rate: 60o+/min) plating time
5 seconds plating film 2 Membrane 1.0) (/m
2 alloy combinations Tin: 6096, Zinc: 40t Total precipitation of tetrafluoroethylene-hexafluoropropylene copolymer and tetrafluoroethylene-ethylene copolymer 5 vol! jAppearance
Uniform grayish white Note 1: Perfluoroalkyltrimethylammonium salt was used as the cationic activator.

Note 2: A barfluoroalkyl ethylene oxide adduct was used as the nonionic activator.

Shaosei 3 Zinc phosphate 10g/Calcium phosphate 2g/2 Condition 3 Hot air dried plated skin 1 after spray coating 3 Film thickness 3mg/m2 (
Comparative Example 1) Using an electroplating bath having the following composition 1, plating was performed on both sides of a cold rolled steel sheet under conditions 1 described in F to obtain a plating film 1. Using a chromate treatment bath having the following composition 2, Under condition 2 below, both sides of the plated steel sheet were subjected to chromate treatment to achieve a plating skin JI5! I got 2.

Bath composition 1 Stannous sulfate 40g/Q sulfuric acid 60g/Q phenolsulfonic acid 40g/(1 Ceramic β-naphthol Condition 1 Plating temperature Cathode current density Anodic stirring Bomb type (Rin flow rate plating time Plating skin; 1 Membrane Thick appearance Bath composition 2 Sodium dichromate pH Condition 2 Bath temperature Immersion time After immersion and washing with water, hot air dry plating film 2 Film thickness 2g/Q 1g/Q 45℃ 4^/dm2 High purity tin plate: 20m/IIIin) 12 Second 2.8 g/m' Uniform = Uniform white 25 g/cross 4.5 45°C 2 mg/m2 DI workability was evaluated for the tempered steel plates obtained in Examples 1 to 3 and Comparative Example 1.Example The plated steel sheets produced in 1 to 3 were formed so that the fluororesin composite tin plating or fluororesin composite tin-based alloy plating surface became the outer surface of the DI can.Workability was evaluated by a continuous DI processing test of 200,000 cans. The occurrence of galling and the degree of wear of the ironing die were evaluated.The evaluation results are shown in Table 1.

Table 1 From the results in Table 1, it can be seen that the surface-treated steel sheet of the present invention has excellent DI workability and has little wear on the ironing die.

[Effects of the Invention] According to the present invention, a surface-treated steel sheet with excellent DI formability can be obtained, and the life of ironing dies can be extended. Moreover, the surface-treated steel sheet of the present invention can be used not only for DI cans but also for DrD cans.
It is also used as can body material, can lid material containing EOE, and 5-gallon can body and lid material, and has a wide range of applications.

[Brief explanation of drawings]

FIG. 1, FIG. 2, and FIG. 3 are diagrams showing each example of the configuration of the present invention. DESCRIPTION OF SYMBOLS 1... Steel plate, 2... Fluororesin composite tin plating film or fluororesin composite tin-based alloy film, 3... Metal tin or tin-based alloy, 4... Fluororesin, 5... Tin film, 6
...upper layer

Claims (1)

[Scope of Claims] 1. A fluororesin/tin composite plating film containing 0.1 to 20.0% by volume of fluororesin with a particle size of 0.5 μm or less on at least one side of the steel plate; ~12.0g/m
A composite plated steel sheet with excellent DI workability, characterized by having ^2. 2. At least on one side of the steel plate, apply a fluororesin/tin-based alloy composite plating film containing 0.1 to 20.0% by volume of fluororesin with a particle size of 0.5 μm or less.
Composite plated steel sheet with excellent DI workability, characterized by having g/m^2. However, the term "tin-based alloy" refers to a metal or alloy containing one or more of zinc, nickel, manganese, molybdenum, and copper. 3. At least one side of the steel plate has a tin film, and the upper layer has a tin film,
Fluororesin with a particle size of 0.5 μm or less in a volume ratio of 0.1 to
Fluororesin/tin composite plating film containing 20.0%,
D characterized by having 0.2 to 12.0 g/m^2
Composite plated steel sheet with excellent workability. 4. At least one side of the steel plate has a tin film on the top layer,
Fluororesin with a particle size of 0.5 μm or less in a volume ratio of 0.1 to
A composite plated steel sheet with excellent DI workability, characterized by having a fluororesin/tin-based alloy composite plating film containing 20.0% of 0.2 to 12.0 g/m^2. However, the term "tin-based alloy" refers to a metal or alloy containing one or more of zinc, nickel, manganese, molybdenum, and copper. 5. At least on one side of the steel plate, apply a fluororesin/tin composite plating film containing 0.1 to 20.0% by volume of fluororesin with a particle size of 0.5 μm or less at 0.2 to 12.0 g/m
A composite plated steel sheet with excellent DI workability, characterized in that it has a chromate film or a phosphate film on top of the chromate film. 6. At least on one side of the steel plate, apply a fluororesin/tin-based alloy composite plating film containing 0.1 to 20.0% by volume of fluororesin with a particle size of 0.5 μm or less at 0.2 to 12.0 μm.
g/m^2 and further has a chromate film or a phosphate film on top of the chromate film or phosphate film, and has excellent DI workability. However, the term "tin alloy" refers to a metal or alloy containing one or more of zinc, nickel, manganese, molybdenum, and copper. 7. At least one side of the steel plate has a tin film, and the upper layer has a tin film,
Fluororesin with a particle size of 0.5 μm or less in a volume ratio of 0.1 to
Fluororesin/tin composite plating film containing 20.0%,
0.2 to 12.0 g/m^2 and further has a chromate film or a phosphate film on the upper layer.
Composite plated steel sheet with excellent workability. 8. At least one side of the steel plate has a tin film, and the upper layer has a tin film,
Fluororesin with a particle size of 0.5 μm or less in a volume ratio of 0.1 to
DI processing characterized by having a fluororesin/tin-based alloy composite plating film containing 20.0%, 0.2 to 12.0 g/m^2, and further having a chromate film or phosphate film on the upper layer. Composite plated steel sheet with excellent properties. However, the term "tin-based alloy" refers to a metal or alloy containing one or more of zinc, nickel, manganese, molybdenum, and copper.