JPS59205498A - Tin plated steel plate - Google Patents

Abstract

PURPOSE:To enhance coating property and to prevent the lowering in the close adhesiveness of a coating after drawing processing, in a tin plated steel plate, by specifying the alkali insoluble chromate amount in a chromate layer and the uniform degree of total chromate and tin oxide on the surface of the steel plate. CONSTITUTION:In a tin plated steel plate provided with a tin oxide layer and a chromate layer, the alkali insoluble chromate in the chromate layer is limited to 1-10mg/m<2> as a chromate amount while the uniform degree of total chromate and tin oxide on the surface of the steel plate is adjusted to 40% or more. In this case, it is pref. that chromate is amorphous. This steel plate is coated with an org. paint such as an epoxy urea paint in processing and excellent in the properties of a coating even in drawing processing after coating. In addition, the close adhesiveness of the coating is not lowered even in coating and drawing processing after storage and dry baking.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a tin-plated steel sheet, and more specifically to a tin-plated steel sheet that has excellent adhesive properties for organic coatings, and more specifically, has excellent drawing processability after application of an organic coating. Regarding tin-plated steel sheets.

Tin-plated steel sheets generally have beautiful surfaces, excellent corrosion resistance and solderability, and are non-toxic, so they have been used as materials for food cans and various other containers.

When tin-plated steel sheets are used as canning materials for various foods such as fish, meat, green peas, asparagus, etc., the adhesion of the coating film on the inside of the can may deteriorate, or trace amounts of tin-plated steel sheets may be removed from the food. There were problems such as discoloration on the inside of the can due to the hydrogen sulfide generated. In order to solve this problem, a proposal was made to conduct the reflow process in a non-oxidizing atmosphere when manufacturing tin-plated steel sheets (Japanese Patent Laid-Open No. 50-1091).
36), a proposal to remove the tin oxide film before chromate treatment (JP-A-52-103333), and the following 3.
There was a proposal (Japanese Unexamined Patent Publication No. 72742/1989) to use metal chromium plating with a resistance of 0.1 v/m" or more.

However, in recent years, many attempts have been made to manufacture packaging containers or packaging container members for foods, etc. by coating a tin-plated steel plate with a metal paint and then performing a drawing process. For example, the squeeze can for tuna oil pickling shown in Figure 1,
The upper part (1) of the container for beer and carbonated drinks shown in Figures (A) and 2 (B) and the upper part (4) of the container for beer shown in Figure 3 (CA) and Figure 3 (B) ) and the lower body (5) etc. can be mentioned as various examples. In the case of such containers or container parts, high-speed painting is possible because the painting is done on a flat plate before the drawing process, compared to the case where each molded product is painted and dried after the drawing process. Since the cost of coating can be reduced, there is an increasing demand for producing packaging containers or packaging container members by drawing after coating. However, when conventional tin-plated steel sheets were used for such purposes, the adhesion of the coating film after the drawing process was insufficient, and the sheets could not be used as packaging containers for foods, etc.

The present invention has excellent paint film performance in the drawing process after painting as described above, and it can also be applied to painting and drawing after long-term storage or dry baking on bamboo. The present invention provides a new tin-plated steel sheet that does not deteriorate.

The tin-plated steel sheet of the present invention is a tin-plated steel sheet having a tin oxide layer and chromate N, and the alkali-insoluble chromate in the chromate layer is 1-10% in terms of chromium content.
da/m”, preferably 1.5-3 yrg/m’
, most preferably 2 to 7 my/m", and the uniformity of total chromate and tin oxide on the steel sheet surface is 40% or more, preferably 50% or more, and most preferably 70% or more. Regarding the characteristic steel plate.

What is "alkali-insoluble chromate" in Kikiri 44+1 Blindness?
It is used to refer to chromate that is insoluble in a 7.5N aqueous sodium hydroxide solution at 90°C.

In addition, in this specification, "uniformity of total chromate and tin oxide on the surface of the steel sheet" means that the amount of chromium per total chromate is 5 to 1 lamp/lamp per all measurement points using the XfJ microanalyzer in the measurement case detailed later. m'' is used to express the percentage of the number of measurement points where tin oxide is 1 to 10 rn9/nL''.

The total amount of chromate in the steel sheet of the present invention is not particularly limited, but is generally preferably 3 to t21v/m'', and it is preferable that the chromate is non-quality. The oxide storage is not particularly limited, but is generally preferably 0.5 to 2 d.

On the other hand, in the steel sheet of the present invention, the alkali-insoluble chromate content is 1 Da/
If it is too small (less than m"), the growth of the tin oxide layer will be inhibited fb'
If the amount exceeds 10 da/m", it is not preferable because it increases the cost and there is no particular advantage.

f/c, book ~)', clearly) i, j lq, 04 &
'If': Total chromate mold tin oxidation of I '1λ uniform fiber 40 grooves and too low, j, +, force +
1- “The adhesion strength of the paint film on the can is reduced, so it is not recommended.
< jr 1. In addition, in the above definition of chromium resistance and uniformity, all chromates are chromium;
If there is less than m9/7n", the raw Ti of tin oxide In
- Because I can't suppress it, I'm going to squeeze it! ; Vi
This is not preferable because the strength decreases; on the other hand, 10+1 deg/m
If the amount of g is too high, peeling will occur at 7 chrome l.h old.', which is not desirable. Also, tin dodecide is tin poor 1 as l Triq / 711': ii + $
If the amount is too small (1111"1tf) occurs between the tin iride layer and the chromate layer, it is undesirable, and lO
If the amount exceeds Tψ/m1, peeling will occur within the tin oxide layer, which is not preferable.

During processing, the steel plate of the present invention is coated with an organic paint containing anti-corrosion gold on the surface that corresponds to the inner surface of the container.
Examples of major organic paints include epoxy paints, phenol paints, polyester paints, vinyl chloride/vinyl acetate copolymer paints, organosol paints, and acrylic paints. It is also used in ten combinations, among which epoxy/urea paint, epoxy phenol
- Ru-based paints are preferred.

The tin-plated steel sheet of the present invention can be manufactured by various methods.
I will now exemplify some preferred methods of doing so, but I am not intended to be apart of these illustrative methods.

(1) The surface of the copper plate is degreased, pickled, washed with water, tin-plated, and the tin-plated layer is remelted in a furnace by a conventional method. Completely remove the magnetic source, and then anodize to 2~12rr-y/
After producing a uniform tin oxide N, the tin oxide is produced by negative treatment in an aqueous solution containing hexavalent romium ion gold with a pH of 4 or less at a temperature of 60°C or higher and a current density of 1 to 3 A/d. Ro; I can do it.

(2) (grilled board) (1 surface is degreased, pickled,
After washing with water and tin plating 1~, remelting the tin plating layer in a non-oxidizing atmosphere] 1. After dissolving a part of the surface of the tin layer including the tin oxide layer in dilute acid, the melted width of the tin layer is 7 g.
Tin oxide layer in the following oxidizing atmosphere to 2-12~/1
After n9 is generated, it is heated in an aqueous solution containing hexavalent chromium ions with a pli of 3 or less at a temperature of 60°C or higher and a current density of 1 to 3 A.
/d m'' by cathodic treatment.

When the tin-plated metal plate of the present invention is drawn after applying the coating material, the adhesion strength of the coating film is extremely high.

This advantage d1 remains unchanged even if the steel plate is air-baked before being painted with paint, or even if the steel plate is stored for a period of time before being painted. As described above, the excellent feature of the tin-plated copper plate of the present invention is that the adhesive elasticity of the coating film on the flat plate before drawing is as good as the old one (Beer test) or slightly inferior (board grain test) compared to conventional products. This is extremely unconventional compared to the current situation, and furthermore, there is a literature that states that a chromate layer containing alkali-insoluble chromate tends to completely reduce the d' film resistance on flat plates (Takano et al. ``Influence of passive film on properties''; Summary of the 96th Iron and Steel Institute of Japan lecture [
It can be said that the above-mentioned features of the present invention are much more unexpected than those described in 1978], pp. 65-68).

Molded products made of the rivet sheet metal of the present invention after painting and drawing processing are as follows.
Parts of electric appliances such as the shade of lighting equipment, handbags this month 1, lead press cutting: 'i, parts of furniture and fixtures (t) of furniture and fixtures (meters, time dials, axles of bicycle chain cases, etc.) There are parts parts, toy parts, etc., and it is the first chemical 32 container.
- Squeeze can shown in Figure 2- Upper body of packaging container shown in Figure 2 (A) and Figure 2 (B) (1), Figure 13- L4) Polishing, +3-11
There is a packaging container upper body (4) and an anti-mold body (5) of <B>. The drawn cans shown in the drawings w and l are formed by drawing 1 to 3 times and are used, for example, for pickling tuna in oil. Figure 2 (, 4) and Figure 2 (73) are used as containers for beer, carbonated drinks, etc., and their lower bodies (
2) is formed by drawing and ironing, and the upper body (1) and lower body (2) formed by drawing are bonded (3).
It is glued using an adhesive or the like.

Figure 3 (, 4) and Figure 3 () 3) are used as containers for beer, etc., with an upper body (4) and a lower body (5).
) 11 are both formed by drawing process 9,
The upper body (4) and the lower body (5) are bonded to each other at an adhesive portion (6) using an adhesive or the like.

The measurement method used in this specification is as follows: [Measurement method for alkali-insoluble chromate powder] A disk-shaped sample with a diameter of 5 mm is used, and 7.5N hydroxide is added to the IJ solution.
Soak for 5 minutes at ℃ f? Afterwards, using a fluorescent X-ray analyzer, the characteristic The sialic alkali-insoluble chromate needle is determined by measuring with an optical X-ray device and subtracting this value from the initial value.

It is shown as the arithmetic mean value of 5 tests.

[Method for measuring uniformity of total chromate and tin oxide on tin-plated steel sheet surface]

The entire chromate layer and tin oxide layer, which had been reinforced in advance with a carbon evaporated film, were coated using the mercury amalgam method (Toyo Kohan; Bushikito Tin Free Steel, revised 2nd edition, p.

166, (1974, Agne Co., Ltd.)) was taken out from a tin-plated steel plate and used as a sample.

Using an X-ray micrometer and analyzer, the diameter is 10 to 50.
38x38 sample improvement using 0 nm electron beam globe
The characteristic X-ray intensities of chromium and tin are measured at 400 points every 2 pm on the μm surface $R, and the amount of chromium in the total chromate and the tin thread in the tin oxide are determined by the calibration curve method.

The amount of chromium in the total chromate for all measurement points is 5.
i 0 tng / yn" and the percentage of the number of measurement points where tin 2 in the tin oxide is 1 to 1 omp/m" is defined as the uniformity of the total chromate and tin oxide on the surface of the tin-plated steel sheet. It is shown as the arithmetic mean value of 10 tests.

[411j method after full chromate on tin-plated steel plate]
Using a disc-shaped sample with a surface diameter of 5 ttn, the specific X-ray curve of chromium was measured using a fluorescent X-ray analyzer for 1 minute, and the amount of chromium was determined by the test result. Next, the sample was immersed in 7.5 AI sodium hydroxide (6 liquids) at 90°C for 5 minutes at 14F, and then subjected to anodic electrolysis and cathodic electrolysis in a 1-1:1 solution of sodium hydroxide and sodium phosphorus mixed water. After removing the chromate on the surface of the sample, perform 611] again using the fluorescent X-ray device d, and subtract this 1 section from the initial value to find the total amount of chromate on the tin-plated steel plate.Number of tests It is shown as the arithmetic mean value of 5.

[Measurement method of tin oxide amount]

[Tinplate and Tin Free Steel JP, 216 Toyo Kohan, revised 2nd edition (1974, Agne Publishing Co., Ltd.) Measured based on the method for measuring the surface oxide film of electroplated brushes, and the reduction per unit area. Expressed as the amount of electricity required. It is shown as the arithmetic mean value of 5 tests.

[Measurement method of flat plate paint adhesion]

(1)-i T-type peel strength epoxy/phenolic paint with thickness sotngldm”
Length locm, width 5nuR from the sample coated and baked on
It was cut out and used as an adhesive test piece. The painted surfaces are bonded together using a nylon adhesive, and then "T-peel" is performed using a tensile tester to measure the strength at that time. It is shown as the arithmetic mean value of the number of tests io.

(1) -2nd gob test Apply epoxy/phenol paint to a thickness of 50 cm/dm and bake it on the sample. Cut the coated film into io0 pieces of 1° Omm. was applied, the tape was completely peeled off, and the coating area was evaluated as follows based on the percent fraction of the peeled coating.

Rating 5: No abnormality #4: 1-5% of the paint film peeled off.

13: 6~25chi 1 12026~60%' / 1: 60~100chi Adhesion production d-, epoxy on both sides of the sample stored at room temperature for 1 year.
50 strokes of phenolic paint/d m"L'J SAK
III Next application, ・Akatsuki was applied. After that, first paint (
A can with a diameter of 53 mm and a height of 40 mm was made by punching II' (diameter 112 d) into a mold with the 7-sided surface being the inner surface and drawing force 0 (drawing ratio 21). An adhesive test piece was cut out inside the can.The inner surfaces of the can were adhered to each other using a nylon adhesive, and the strength was measured by performing "T-peel" using a tensile tester.

Test H: Shown as the average value of i7 number 10.

(21-2 Paint adhesion after drawing of sample painted after dry baking Regarding sample baked at 200℃ for 10 minutes, (2)-1
(21-3 Deterioration of paint film due to drawing process (2+) During the drawing process prepared in the same way as the -1 test, ,
hO? A DC voltage of 5 V was applied for 30 seconds using the folded aperture as the cathode and the carbon rod as the anode, and the percentage of the peeled coating area was evaluated as follows.

Rating S: 3'i Always No #4: Area of 1 to 5 inches of paint and kudzu peeling off.

13: 6-25% I #2: 26-60% f 11: 60-100% I [Actual can storage test 1. Measurement method of size] Fill a can with 1 −1 holes (usually σ) with the favorite food, and heat sterilize at 116° C. for 90 minutes after tightening. After that, the cans were stored at 37° C., and the number of perforation breaks that occurred within one year is shown.The number of test breaks was 100 cans.

f3) -2 Inner surface state of can 13+ After opening the storage can shown in -1, visually check the occurrence state of the blood path inside the can, changes in the coating film, etc.

(31-3 Vacuum degree inside the can (3) Regarding the storage cans shown in -1 without perforation, the vacuum degree inside the can was measured.

Examples of specific embodiments of the present invention will be explained below using Examples (and Comparative Examples).

Examples 1 to 4 (corresponding to manufacturing method (1) described in the main text of the specification) A cold rolled steel plate with a thickness of 0.23 ran was electrolytically degreased, washed with water, pickled, and washed with water again by a conventional method, and then one side was This p5.
After applying 6f/m” tin plating to both sides and washing with water,
The tl was remelted at 280° C. by current flow resistance heating. Then the temperature is 50℃ and the concentration is 25? After performing cathodic electrolysis treatment for 2 seconds in a charcoal C sodium aqueous solution of /l at a current density a A / d m'', washing with water, immediately anodic electrolysis in a boric acid aqueous solution with a concentration of 52/l under the conditions shown in Detailed Table 1. It was treated, washed with water, and then subjected to implicit electrolytic treatment in an aqueous solution with a hexavalent ROM ion concentration of xOy7t at pH 3.5 and temperature of 60°C.The properties of the obtained tin-plated steel sheets are summarized in Clone-3 ( The same applies to the following Examples and Comparative Examples).

Comparative Example 1 A tin-plated steel sheet was obtained by manufacturing under the same conditions as Examples 1 to 4, except that anodic electrolysis and cathodic electrolysis were performed under the conditions shown in Table 1.

Comparative Example 2 Anodic electrolytic treatment was performed under the conditions of Cloth-1 below, except that electroless immersion treatment for 6 seconds in a water bath solution with a hexavalent chromium ion concentration of 102/l was performed instead of cathodic electrolytic treatment. Example 1~
A tin-plated steel sheet was obtained by manufacturing under the same conditions as in No. 4.

Comparative Example 3 (Trace of Example 1 of %Kasho 53-72742) After the thick plates used in Examples 1 to 4 were pretreated, tin plated, and melted in the same manner as Examples 1 to 4, the concentration was 25t/
1. After cathodic electrolysis treatment for 0.3 seconds at a current density of 1A/drn in an aqueous sodium pentate solution at a temperature of 50°C, washing with water, followed by chromic anhydride 801/1. sulfuric acid o,
5y7t, electric δ1 in an aqueous solution at a temperature of 50°C, and wisdom j4(1
A tin-plated copper plate was obtained by cathodic electrolytic treatment at 0 A/dm'' for 1 second.

Comparative Example 4 (Trace of Example 4 of JP-A-52-103333) The thick plates used in Examples 1 to 4 were treated in the same manner as in Examples 1 to 4, Pretreatment 1: lying tin plating, remelting, Then pHa, s
After cathodic electrolysis treatment for 1 second at a current density of 5 A/d in saline solution of 30 l/l, washing with water, then 209 l/l
Current density a A /
A tin-plated steel plate was obtained by cathodic electrolytic treatment at d m''' for 1 second.

Examples 5 to 8 (corresponding to manufacturing method (2) described in the main text of the specification) A cold-rolled plate with a thickness of 0.23 trm was degreased at a fixed angle 1, washed with water, pickled, and washed with water again by a conventional method. After that, tin plating was applied to both sides at a rate of F) 2.8 W/m'' on one side and washed with water.Next, by direct current reverse resistance heating in a nitrogen gas atmosphere.
1 liter was remelted at 1280°C. After that, it was immersed in 0.5N sulfuric acid for 1 second, washed with water, and then oxidized in air according to the conditions shown in Table 2 below.
A tin-plated steel sheet was obtained by cathodic treatment in an aqueous solution of pH 30 and temperature of 60°C.

Comparative Example 5 The same thick plate used in Examples 5 to 8 was pretreated, tin plated, and remelted in the same manner as in Examples 5 to 8, and then
Hexavalent Romuio 71141i in an aqueous solution of 15 t/l, pH 3.0, temperature 60°C, current density "A/d"
A tin-plated steel plate was obtained by cathodic electrolytic treatment at mF for 0.5 seconds.

Comparative Example 6 The same thick plate used in actual hI・l15-8 was placed on the fruiting mountain side 5.
After pretreatment and tin plating in the same manner as in ~8,
It was remelted at 9280° C. by direct current resistance heating in nitrogen atmosphere.

Thereafter, in an aqueous solution with a hexavalent ROM ion concentration of 15 t/l, the pH was 3.0, the temperature was 60°C, and the current was 1.4/d.
A tin-plated steel sheet was obtained by cathodic electrolytic treatment for 0.6 seconds.

Comparative Example 7 (JP-A-5O-109136 (7) Example 2
(trace) The same thick plates used in Examples 5 to 8 were pretreated and tin plated in the same manner as in Examples 5 to 8, and then melted at 270°C by direct current resistance heating in nitrogen gas and immediately submerged in water. It was immersed in water, rapidly cooled, and then placed at pH 4.5 and temperature 45°C at '15.5? /l dichromium aqueous solution, current retention 2
．． A tin-plated steel sheet was obtained by cathodic electrolysis treatment at 1/cl m' for L9 seconds.

543- From the data in Table 3, the following can be seen: Example 1
~4. Comparative Example 1.2, 1. The uniformity of the total chromate and tin oxide on the surface of the tin-plated copper plate was investigated in a relatively narrow range of 67 to 80 inches. Yes, when the alkali-insoluble chromate a becomes less than 1, the adhesion of the paint after the drawing process of the sample painted after storage, the coating density strength after the drawing process of the sample painted after baking (9) Due to processing, all properties such as deterioration of ifi+!-1: deteriorated significantly, and even in the storage test results of actual cans fully filled with highly corrosive tuna and soy sauce flavored contents, there were holes and a coating film on the can body. It can be seen that these characteristics are unrelated to the total chromate content and tin oxidation '4'J T<, which have been conventionally used to characterize tin-plated steel sheets.

Comparative Example 3 is a tin-plated copper plate containing a large amount of metallic chromium in chromate m, and although the flat plate paint adhesion is excellent, each property after drawing is inferior to that of the tin-plated steel plate of the present invention. Inferior.

Comparative Example 4 is a trace of the example of JP-A-52-103333, but the amount of alkali-insoluble chromate is 0.3
The uniformity of the total chromate and tin oxide film on the surface of the tin-plated steel sheet is as low as 1R9/m”, and the uniformity of the total chromate and tin oxide film on the surface of the tin-plated steel plate is as low as 35 cm.The flat plate paint adhesion is the same as the product of the present invention, but the paint adhesion after drawing is significantly lower. Inferior.

In Examples 5 to 8 and Comparative Examples 5.6, the amount of alkali-insoluble chromate was within a relatively narrow range of 4.2 to 4.5, and the effect of uniformity of tin oxide and the overall mate on the surface of the tin-plated steel sheet was evaluated. This is a study on camellia.If the uniformity is less than 40%, the paint density after drawing process, holes in the actual can storage test,
It can be seen that the condition of the inner surface of the can deteriorates.

Comparative Example 7 is a trace of the example of JP-A-50-109136, but the alkali-insoluble chromium is 0.8~/m
The uniformity of total chromate and tin oxide on the surface of the tin-plated steel plate is as low as 15 cm, and although it is slightly superior to the product of the present invention in flat plate paint adhesion, the paint layer density and tin oxide after drawing process are low. The actual can storage test results were significantly inferior to the product of the present invention.

Example 9 (Application example) Using the tin-plated copper plate of Example 1, epoxy was applied to the inner and outer surfaces.
After applying and baking the urea-based paint so that the total coating film amount is 150 da/d, 60 da/d, it is punched into a 94 m# disc and molded using normal press processing. The inner diameter of the edge of the joint is 64.5+am.
Then, a container upper body like 1 in FIG. 2(A) having a spout with a diameter of 25 mm in the center was prepared.

On the other hand, the material thickness is 0.30. A tin-plated steel plate manufactured in the same manner as in Example 1 was heated to about 142. Punch to a diameter of a+ and draw #) Form into a kelp shape with an inner diameter of about 85s* between a punch and a drawing die. Next, this pot-shaped molded product was subjected to a reproofing process, and then subjected to a hardening process using a 66-inch diameter ironing punch and die.

The outer surface is coated with modified epoxy paint with a coating amount of 60q/
After coating with a mandrel coater so that the color is d m", it is baked, and the inner surface is coated with 1 coat of epoxy urea paint.
After spray coating and baking to give a coating thickness of 50 da/dra", neck-in processing is performed to form the lower part of the container, as shown in 2 in Figure 2 (A), where the outer circumference of the circumferential edge is 64.4 am. The body was created.

Approximately 411 points on the outer surface side of the entire edge of this lower body
A polyester adhesive was applied to a width of 0I and a width of about 2M on the inner side. The upper body thus obtained and the lower body coated with adhesive were fitted together, and the lower joint was heated with high frequency to melt the adhesive, which was then cooled and solidified to join the upper body and lower body. We made a metal container with a capacity of about 500 go. See Figure 2 (B).

After filling this container with cola, seal the spout tightly and heat to 50°C.
When a storage test was conducted for 6 months, the adhesive strength of the joint was 2.
．． Strong iron elution amount of 4 Kf/4 rtan width is 0.5
ppm, and no perforation or leakage of contents is observed during storage, indicating that a jointed container with an upper body manufactured by drawing using an uninvented tin-plated steel plate exhibits excellent container performance. I understand.

Example 10 (Application example) Epoxy urea thread paint and vinyl paint were applied to the inner and outer surfaces of the tin-plated steel plate of Example 5, with a total coating amount of 150% each.
■ / d tn'', 60 ~ / d Go, coated and baked, the wheat was punched into a disk with a diameter of 250 cm, and drawn by normal press processing, and the edge of the joint was A container upper body having an inner diameter of 110.6 m and a spout with a diameter of 30 y*m in the center as shown in 4 in FIG. 3 CA) was prepared.

On the other hand, the same painted board F) 250 rI! An inner plate having a diameter of m was punched out and drawn by press working to produce a container lower body as shown in Figure 3 CA) 5 having an outer diameter of 110.611111 mm at the edge of the joint.

Over the entire circumference of the edge of this lower body, its outer surface 5.5
A polyester thread adhesive was applied with a simple cloth and a 1.5 rope width on the inner side. The thus obtained upper body and the lower body coated with adhesive were fitted together, and the mating part was heated with high frequency to melt the adhesive, which was then cooled and solidified to join the upper body and the lower body. A container with a capacity of about 2 tons was produced. See Figure 3 CB).

After filling this container with orange juice at 90℃,
When the spout was sealed and a storage test was conducted at 50℃ for 6 months, the adhesive strength of the joint was as strong as Z7Kf/&5an even after storage, and the amount of iron eluted was as low as 0, a ppm. Since no holes or leakage of contents were observed, it can be seen that the joined container with the upper and lower bodies manufactured by drawing using all the tin-plated copper plates of the present invention exhibits excellent container performance. .

[Brief explanation of the drawing]

Figure 1 shows the size of a can made using the tin-plated steel sheet of the present invention.
! Figure 1i111, Figure 2 (, () and (B) are cross-sectional views of a container using the tin-plated steel plate of the present invention for the upper body, Figure 3 CA) and CB) are the entire upper body of the tin-plated steel plate of the present invention. and a sectional view of a container used for the lower body. Procedural amendment written by two other persons (voluntary) June 30, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1. Indication of case: 1982 Patent Application No. 79434 2. Title of invention: Tin-plated steel plate 3. Amendments made. Related to Nagisa Incident T Patent Applicant Address: 26 (Name) Kishimoto Sho 4, 4439 Kamaritani-cho, Kanazawa-ku, Yokohama, Kanagawa Prefecture; Agent: 107; and 2 others who volunteered. As per the attachment ■, the statement in the claim column of the specification is corrected as follows: "λ Claim 1: A tin-plated steel sheet having a tin oxide layer and a chromate layer, the chromate layer comprising: A steel plate characterized in that the amount of alkali-insoluble chromate therein is 1 to 10 tv/rd, and the uniformity of the total chromate and tin oxide on the surface of the steel plate is 40 cm or more.2. 3. The steel plate according to claim 1, which is for coating with an organic paint.
Steel plate described in section. 4. The steel plate according to claim 3, wherein the organic paint is an epoxy-urea paint, an epoxy-phenol paint, or an organosol paint. 5. The steel plate according to any one of claims 1 to 4, which is used for drawing processing. 6. A tin-plated steel sheet having each of the A molded product manufactured by painting and drawing a steel plate of 40 inches or more. 7. The molded article according to claim 6, which is a container or a member of a container. 8. The molded article according to claim 6, which is a cap. ” B. The statement in the detailed description of the invention column of the specification is corrected as follows. (1) The 5th line of page 5 and the 5th line from the bottom of page 6 of the specification indicate “
"Tin oxide layer" should be corrected to "Tin oxide layer." (2) Add “or adhesion” between “corrosion prevention” and “intended for” on the second line from the bottom of page 7. (3) Page 18, line 7, page 21, line 3 and 5 lines from the bottom, page 22, line 4, page 24, lines 2 and 9, page 25, line 1 Correct the line that says ``thick plate'' to i ``original plate.'' (4) Replace Table 3 on page 26 with Table 3 below. (0% of the value (ch) of column 5 "uniformity of total chromate and tin oxide on the surface of tin-plated steel sheet" of Comparative Example 6 was somewhat unclear, so this 0% is clearly shown in Table 3. replaced)

Claims (1)

[Scope of Claims] 1. The tin oxide layer and the chromate layer are tin-plated with gold.
The uniformity of all chromate and tin oxide on the M plate surface is 40≠
The above results are 'F(fg) steel &. 2. Chromate is amorphous. Copper plate as described in item 1 or 2 of the scope of demand for Denru material. 4. 'T'J made by Takeki Kenryo with epoxy/urea paint, epoxy/phenol head material or merganosol) I/m material. '
, lf□' 1 stroke of steel plate according to item 3 of box 41B. 5. A steel plate according to any one of Claims 1 to 4, which can be used for drawing. 6. A tin-plated steel sheet having a tin oxide layer and a chromate layer, in which the amount of alkali-insoluble chromate in 1 m of chromate is 1 to 10 to /77+,'', and the total chromate and tin oxide on the surface of the steel sheet The uniformity of
A molded product produced by painting and drawing a steel plate having a modulus of 0 or more. 7. A molded product according to claim 6 made of a container or a member of a container. 86 Molded products described in scope item 6.