JPH0398844A - Contracted or contracted-stroked can of laminated material and manufacture thereof - Google Patents

Abstract

PURPOSE:To prevent inner surface defects from generating by a method wherein anti-blocking agent particles are contained in a copolymer polyester film, and the anti-blocking agent particles are buried under the film surface. CONSTITUTION:A biaxially oriented film which is composed of a copolymer polyester film 4, of which main component is ethylene telephthalate unit and which contains a small quantity of other ester unit and of which melting point if 170 - 252 deg.C, and which also contains anti-blocking agent particles 5 is heat bonded at least on one side, which becomes the inner surface of a can, of a metallic base 2 directly or through a primer for bonding, and thus a laminated body 1 is manufactured. And at least the film surface of this laminated body 1 is heated to a temperature which is at or higher than the melting point of the copolymer polyester, and then quenched, and the anti-blocking agent particles 5 are buried under the film surface, and contracting or contracting-stroking process is applied to the laminated body 1 after the treatments. By doing this, inner surface layer defects such as pin hole crack, fracture, exfoliation, etc. can be prevented from generating.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a drawing or drawing-iron can made from a laminate material and a method for manufacturing the same. This article relates to a laminated drawn or drawn-sealed can that eliminates inner surface defects caused by king agent particles and has improved corrosion resistance, and a method for manufacturing the same. (Prior art) There have already been many proposals for producing drawn and ironed cans using a laminate material in which a thermoplastic resin film such as polyethylene terephthalate (PET) is laminated on the inner surface of a metallic can. It is being done. For example, JP-A-60-170532, JP-A-60
Publication No. 172637 discloses that a metal material in which an oriented thermoplastic resin film such as PET is adhered to at least the surface that is to become the inner surface of the container is squeezed between a punch and a die at an appropriate stretching temperature for the resin. Subjected to ironing process,
A method for producing a drawn and ironed can is described, which is characterized by imparting molecular orientation to the film layer. (Problems to be solved by the invention) These proposals improve the adhesion of the resin film to the inner surface of the can by actively imparting molecular orientation to the resin film during drawing and ironing of the metal material. be. However, according to the research conducted by the present inventors, it has been found that there are common and unavoidable major drawbacks when subjecting metal-resin film laminate materials to drawing and ironing processes. That is, stretched films such as PET generally contain particles of an anti-blocking agent such as silica in order to improve the processability and handling of the film and to eliminate the tendency for the films to adhere to each other. These anti-blocking agent particles protrude from the film surface and exist as minute protrusions, thereby exerting an anti-blocking effect. However, when a film laminate containing anti-blocking agent particles is subjected to ironing or advanced deep drawing, stress concentration occurs in the protruding anti-blocking agent particles, causing minute holes, cracks, or the like in the film. Furthermore, defects such as breakage occur. Therefore, drawn or drawn and ironed cans using this laminate material have a high enamel rate value, and cannot achieve the desired corrosion resistance and metal elution prevention performance. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a drawn or drawn and ironed can, which eliminates the above-mentioned drawbacks of conventional laminate drawn or drawn and ironed cans, and a method for manufacturing the same. Another object of the present invention is to provide a drawn or drawn-ironed can which prevents the occurrence of inner surface defects caused by anti-blocking agent particles and has excellent corrosion resistance and metal elution resistance, and a method for manufacturing the same. (Means for Solving the Problems) According to the present invention, a metal material and an ethylene terephthalate unit provided on at least the inside surface of the metal material directly or via an adhesive primer, and other Formed by drawing or drawing-ironing of a laminate with a copolyester film containing a small amount of ester units and having a melting point of 170 to 252°C, the copolyester film containing anti-blocking agent particles, There is provided a squeeze or squeeze-squeeze can characterized in that the anti-blocking agent particles are buried below the surface of the film. According to the present invention, a biaxially stretched film made of a copolyester mainly composed of ethylene terephthalate units and containing small amounts of other ester units and having a melting point of 170 to 252° C. and containing antiblocking agent particles is coated with at least one of the metal materials. A laminate is produced by thermally adhering it to the inner surface of the can either directly or via an adhesive primer, and at least the film surface of this laminate is heated to a temperature equal to or higher than the melting point of the copolymerized polyester, and then rapidly cooled to form an anti-block film. burying agent particles below the film surface,
There is provided a method for producing a drawn or drawn and ironed can, characterized in that the treated laminate is subjected to drawing or drawing and ironing processing. (Function) In the present invention, the use of a two-wheel stretched film containing an anti-blocking agent for lamination is indispensable in terms of film handling, lamination operation, coating layer thickness control, etc.; By heating at least the surface of the film laminated on the material to a temperature equal to or higher than its melting point, and then rapidly cooling, it becomes possible to bury the anti-blocking agent particles protruding from the surface below the film surface; This is based on the discovery that when a laminate material treated with embedded anti-blocking agent particles is subjected to deep drawing or drawing ironing, the occurrence of internal coating defects such as holes, cracks, breaks, and peeling is prevented. In the present invention, the film to be laminated on the metal material is a copolyester consisting mainly of ethylene terephthalate units, containing a small amount of other ester units, and having a melting point of 170 to 252°C, particularly 180 to 245°C. The first feature is that a two-wheel stretched film is used.
Since this copolyester mainly consists of ethylene terephthalate units, it has excellent mechanical strength and processability, and can be subjected to advanced drawing and drawing ironing processes while coated with metal. In addition, polyester mainly composed of ethylene terephthalate units has superior barrier properties against corrosive components compared to other polyesters, and cans coated with this film on the inside have the advantage of superior corrosion resistance. This copolyester may also contain small amounts of ester units other than ethylene terephthalate.
This is important in terms of laminating workability and embedding of anti-blocking agents. Polyester (PET) consisting of ethylene terephcrate alone generally has a melting point of 257°C, but by including a copolymerized ester component, the melting point of this film is lowered to the above range, and the film has a melting point of 257°C. Enables embedding of anti-blocking agent particles by thermal adhesion through partial fusion or by melting and rapid cooling. In addition, by introducing the copolymerized ester component, the ultimate crystallinity and crystallization rate can be lowered, and together with the fact that the melting point can be lowered, it is possible to lower the internal stress remaining in the laminate. ．． It is also important that the melting point of the copolyester used is within the above range; if the melting point of the copolyester is higher than the above range, defects may occur such as cracking of the film during drawing and ironing, and embedding of anti-blocking agent particles. It also tends to have drawbacks such as the inability to process smoothly. On the other hand, if it is lower than the above range, the enamelator value ( ERV) tends to increase. It is also important that this copolyester film is biaxially stretched. That is, by biaxially stretching a copolymerized polyester film, the stiffness of the film becomes stronger and the lamination operation becomes easier. In addition, because the polyester of the film is molecularly oriented in biaxial directions, lamellae (
It also has the advantage of being less likely to produce spherulites. The laminate material obtained by thermally adhering the above-mentioned two-wheel stretched film and the metal material directly or through an adhesive primer layer is heated to a temperature above the melting point of the copolymerized polyester at least on the surface of the film prior to drawing or drawing and ironing. The second feature is that it is heated so that it becomes , and then rapidly cooled. Through this heating and rapid cooling, the anti-blocking agent particles that were present protruding from the film surface are effectively buried below the surface due to the surface tension of the molten resin, and are then fixed in this buried state by rapid cooling. become. According to the results of observation using scanning electron micrographs, as shown in FIG. 3, in untreated biaxially stretched copolymerized polyester, the number of anti-blocking agent particles 5 protruding from the surface of the polyester film 4 per 100 μm square 1
However, after performing the burial treatment of the present invention, as shown in Figure 4, this number has decreased to zero to almost zero. In the present invention, also. Due to the heating and rapid cooling for this burial treatment, the copolymer film becomes an unoriented or non-quality state, and has excellent workability that can withstand deep drawing and drawing ironing.
(Preferred embodiment of the invention) In FIG. 1 showing an example of the laminate material used in the present invention, this laminate material l has the following properties: It consists of a metal material 2, an adhesive primer layer 3 provided on the side of the metal material that will become the inner surface of the can, and a copolymerized polyester film layer 4 provided via this primer layer.

In FIG. 2 showing another example of the laminate material used in the present invention, the laminated material 1 is composed of a metal material 2 and a copolymerized polyester film layer 4 directly thermally bonded to the metal material. In this copolyester film layer 4, only the very surface layer 4a in contact with the metal material 1 is melted and bonded, and most of the remaining layer 4b
In this case, the molecular orientation due to biaxial stretching is maintained as it was when purchased. In the present invention, various surface-treated steel plates and light metal plates such as aluminum are used as the metal materials. Surface-treated steel sheets include cold-rolled steel sheets that are annealed and then subjected to secondary cold rolling, and subjected to one or more surface treatments such as zinc plating, tin plating, nickel plating, electrolytic chromic acid treatment, and chromic acid treatment. It can be used. It is also possible to perform different plating or surface treatments on the front and back sides of the plate. An example of a suitable surface-treated steel sheet is an electrolytic chromic acid treated steel sheet, particularly 1
It is equipped with a metal chromium layer of 0 to 200 mg/m2 and a chromium oxide layer of 1 to 500 g/II12 (metal chromium equivalent), and has excellent paint film adhesion and corrosion resistance. Excellent combination of Other examples of surface-treated steel sheets include 0.1 to o. It is a tin plate with a tin plating amount of 2 g/m2. This tin plate is preferably subjected to dichromic acid treatment, chromic acid treatment, or chromic acid/phosphoric acid treatment such that the amount of chromium is 1 to 30 mg/m2 in terms of metallic chromium.

As the light metal plate, an aluminum alloy plate is used in addition to a so-called pure aluminum plate. An aluminum-based alloy plate excellent in corrosion resistance and workability is Mn:O. O to 1.5
Weight %, Mg: 0. O to 5% by weight, Zn: 0.0
1 to 0.3% by weight, Cu: 0.01 to 0.25
, and Cr: 0.01 to 0.25% by weight, the balance being A1. These light metal plates also
It is desirable to perform surface treatment from the viewpoint of paint film or film adhesion and corrosion resistance, and these surface treatments include chromium treatment, zirconium treatment, phosphoric acid treatment, alumite treatment, acrylic acid treatment, etc. Among these, it is desirable that chromic acid treatment or chromic acid/phosphoric acid treatment is performed such that the amount of chromium is 5 to 300 B/tm in terms of metallic chromium. Base thickness of metal plate (A) varies depending on the type of metal, the purpose of the container, and the size, but generally ranges from 0.IO to 0.0.
It is preferable to have a thickness of 50 mm, within which the thickness is 0.10 to 0.40 mm in the case of surface-treated steel sheets, and 0.10 to 0.40 mm in the case of light metal sheets. It is preferable to have a thickness of l5 to 0.50+wm. The copolymerized polyester used is mainly composed of ethylene terephrate units and contains small amounts of other ester units. In general, 7 of the dibasic acid components in copolymerized polyester
0 mol % or more, especially 75 mol % or more of the terephthalic acid component, 70 mol % or more, especially 75 mol % or more of the dihydric acid component consists of ethylene glycol, and the dibasic acid component and/or the terephthalic acid component consists of ethylene glycol. 1 to 30 mol%, especially 5 to 25 mol% of the components are dibasic acid components other than terephthalic acid and/or
Or, it is preferable that it consists of a diol component other than ethylene glycol. Dibasic acids other than terephthalic acid include isophthalic acid,
Aromatic dicarboxylic acids such as phthalic acid and naphthalene dicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and Aliphatic dicarboxylic acids such as succinic acid, adibic acid, sebacic acid, and dodecanedioic acid. Combinations of the above may be mentioned, and dioxylic components other than ethylene glycol include propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexylene glycol, cyclohexanedimethanol, and ethylene oxide addition of bisphenol A. Examples include one or more types of things. Of course, the combination of these comonomers must be such that the melting point of the copolyester falls within the above range. The copolyester used should have a molecular weight sufficient to form a film, for which it should have an intrinsic viscosity (1.V.) of 0.55 to t. 9 dl/
g, preferably in the range of 0.65 to 1.4 dl/g. This copolyester film contains an anti-blocking agent which is known per se.
Examples of anti-blocking agents include amorphous silica,
Inorganic particles such as zeolite, non-quality alumina silica, etc. are used, with particle sizes ranging from 0.05 to 10μ, especially 0.1
Those in the range of 5μ to 5μ apex are used. The content of the anti-blocking agent is generally 100% of the copolymerized polyester.
It is within the range of 0.01 to 065 parts by weight, particularly 0.03 to 0.1 parts by weight. It is important that the copolyester film is biaxially stretched. The degree of biaxial orientation can be confirmed by polarized fluorescence method, birefringence method, density gradient tube method, etc. In the present invention, the copolyester film has a density of 1.345 g/cm" to 1.3 g/cm".
It is desirable that the molecules are oriented to have a density in the range of 95 g/c1. In addition, the thickness of the film is 5 to 50 μ-, especially l2
It is desirable that the thickness be between 40 μm and 40 μm. In order to improve the adhesion of the film, it is generally desirable to subject the surface of the biaxially oriented copolyester film to a corona discharge treatment. The degree of corona discharge treatment is preferably such that the wetting tension is 4 4 dyne/c@ or more. In addition, it is also possible to perform adhesion-improving surface treatments known per se such as plasma treatment and flame treatment on the film, or adhesion-improving coating treatments such as urethane resin-based or modified polyester resin-based coatings. When directly thermally bonding a film and a metal material, the metal material is preheated to a temperature near or above the melting point of the copolyester, and the heated metal material and film are laminated and pressure bonded. rear. This is rapidly cooled and laminated. It is also possible to thermally bond the two using an adhesive primer. The adhesive primer used in the present invention exhibits excellent adhesion to both the metal material and the copolyester film. Typical primer paints with excellent adhesion and corrosion resistance are phenol-epoxy paints, which are made of resol-type phenol-aldehyde resins derived from various phenols and formaldehyde, and bisphenol-type epoxy resins. Yes, especially phenol resin and epoxy resin in a weight ratio of 50:50 to 5:95, especially 4
It is a paint containing a weight ratio of 0:60 to 10:90. The adhesive primer layer generally has a thickness of 0.3 to 5
It is best to provide it at a thickness of 1 μm. According to the present invention, at least the surface of the film of the laminate is heated to a temperature equal to or higher than the melting point of the copolyester and then rapidly cooled to embed the anti-blocking agent particles.
Since the embedding treatment of the anti-blocking agent particles is carried out almost during the g1 period at the same time as the surface layer of the film is melted, a very short treatment time is sufficient. The temperature of the film is
The melting point of the copolyester is m. When closed, m, +l
O0°C, especially m, +5°C to m. , +80°C is suitable, and the heating time is 0.1 to 600 seconds, especially 0.1 to 600 seconds.
A range of 1 to 60 seconds is appropriate. Furthermore, the fact that the film is in a molten state at the free interface is effective in embedding the anti-blocking agent particles. Heating of the film can be performed using a hot air circulation furnace, an infrared kneading furnace, resistance heating, high frequency induction heating, etc., and rapid cooling after heating can be performed using water cooling, air cooling, cooling with liquid nitrogen, dry ice, etc. It can be carried out. The rapid cooling is preferably carried out so that the molten copolymerized polyester passes through the polyester crystallization temperature range (100 to 200°C) within 30 seconds, particularly within 10 seconds. Drawing and ironing The laminate material that has been immersed as described above is subjected to drawing or drawing-ironing by means known per se, but in this case. It is preferable to use the following conditions. First, drawing or drawing and ironing is preferably carried out at an appropriate stretching temperature for the copolyester, particularly at a temperature of 30 to 80°C, most preferably at a temperature of 40 to 70°C. That is, in this temperature range, the copolymerized polyester undergoes plastic flow during squeezing, effectively oriented the molecules in the axial direction, and is effectively thinned during squeezing. In addition, the drawing or drawing-iron process is performed using a combination of a punch and a die, and the punch has an average roughness (Ra) of 0.01 to 3μ, especially 0.1 to 2μ.
It is preferable to use a punch with side surfaces of Generally, a dot-like (dimple-like) roughness pattern is preferred. Furthermore, it is preferable that the lubricant used has as low a viscosity as possible, and in general, lubricants of 100 to 400 SUS (Saybolt Universal Seconds) (40°C) are advantageously used in terms of ease of removal. The can body of the present invention is manufactured by a method known per se, except for using the laminate material described above. That is, the laminate is sheared into a shape such as a disk, and subjected to one-stage or multi-stage drawing between a drawing punch and a drawing die. Drawing forming can also be performed by deep drawing forming into a large diameter shallow cup and deep drawing forming into a small diameter deep drawn cup.In this deep drawing process, the upper part of the cup side wall is drawn to make the wall thickness uniform. It is also possible to apply a slight strain to the material, or to apply tensile force in the axial direction by selecting a drawing die such as Girasias. In the case of deep-drawn cans, the drawing process can be performed in one stage or in multiple stages, and is expressed by the following formula D R o = d where D is the diameter of the laminate material cut in front, and d is the diameter of the punch. It is preferable that the aperture ratio R0 defined by R0 is in the range of 1.2 to 2.5 for one stage. The ironing process can be performed in one stage or in multiple stages, and the following formula io is used. The ironing rate defined by (R.l is preferably 20 to 40% in one stage ironing process.In the case of multi-stage ironing, set the ironing rate as high as possible in the first ironing process, and It is better to set the ironing rate in the final ironing ring in the range of 3 to 20% from the viewpoint of the ease with which the cup can be pulled out afterwards.After the resulting drawing or drawing cup goes through processes such as trimming and washing as necessary, A can body that can be tightened with a can lid by netting and flanging processing. (Effects of the invention) According to the present invention, a biaxially stretched film of a specific copolyester polyester laminated on a metal material is produced. Heating to a temperature at least above the surface and its melting point, followed by rapid cooling, makes it possible to bury the anti-blocking agent particles that have been protruding from the surface below the film surface; By subjecting the treated laminate to deep drawing or drawing and ironing, the occurrence of internal coating defects such as bottle holes, cracks, breaks, and peeling was prevented. (Example 1) Primer' Bisphenol 8% by weight 75%. A mixed phenol consisting of 25% P-cresol and formaldehyde were reacted in the presence of a base catalyst. Purification. A solution of resol type phenol formaldehyde resin was produced by dissolving it in a solvent. Bisphenol A type epoxy resin (Ebicoat 1009)
．． Average molecular weight 3750. An adhesive primer paint was prepared by mixing the epoxy equivalent (2650) solution and the above resol type phenol formaldehyde resin solution at a solid content weight ratio of 70:30 and precondensing btt. - Meat 1゛thickness 25μm two-wheel stretched polyethylene terephthalate/
The solid content of the adhesive primer paint is 10 on one side of an isophthalate (ethylene isophthalate mole fraction 20%, melting point 216°C) copolyester film.
a+g/da" and dried at 120°C. Both sides of a cold-rolled steel plate with a thickness of 0.30 mm and a temper of T-2.5 were coated with 2.8 g/7 m" of tin using a known method. 7.0 by plating and cathodic treatment of the upper layer in dichromic acid.
A film consisting of a chromium permanent oxide layer with a concentration of 1.0 mg/m" was formed. This surface-treated steel plate was heated to 215°C and supplied so that one side of the copolyester film faced the adhesive primer-coated side of the copolyester film. The laminated material was then heated to 226°C and immediately cooled with water to obtain a coated steel plate in which the anti-blocking agent particles in the copolyester film were buried under the surface of the film. .Migamishiugama 1 The obtained polyester resin-coated steel plate was drawn and ironed under the following forming conditions so that the inner surface of the DI can was coated with polyester resin. Punch out a disc of
According to the usual method, the inner diameter between the drawing punch and the drawing die is approximately 87mm.
Shape into m■ cup shape. The dimensions of this can body, which was then ironed using a combination of an ironing punch with a dimple-shaped surface (depth lum) and an ironing die (making speed of 230 cans per minute), are shown below. Body wall thickness 0. 105-11 Can body inner diameter
65.71 Can body height 124mm Degrease the obtained DI can. After cleaning, drying, and printing on the outside, bake at 195℃, then neck. The flanging process was performed and the following items were evaluated. The results are shown in Table 1. ■Evaluation of metal exposure inside the can The above DI can was used with 1% saline as the electrolyte, and the inside of the can was used as an anode and a stainless steel plate as the counter electrode. During this time, a voltage of 6.30 volts was applied, and the current flowing after 4 seconds was measured. The degree of metal exposure was evaluated. Measurements were carried out for each n = 20 cans. ■Evaluation of the number of anti-blocking agent particles protruding from the surface After lamination, an electron micrograph of the polyester resin surface (magnification
1000) was taken in 1O field, and the average number of particles protruding from the surface per 100 μm square was evaluated from these photographs. ■Actual can bag test Fill with carbonated beverage (commercially available Sprite), tighten the aluminum lid according to the usual method, store at 37℃ for 3 months, then cut the tightened part with a can opening machine and remove the lid from the can body. The state of corrosion on the inner surface of the can and the presence or absence of pitting corrosion were observed. (Example 2) A DI can was molded in the same manner as in Example 1, except that the laminate surface of cold-rolled 14@ was plated with 0.5 g/m'' of tin, and the same evaluation was carried out. The results are shown in Table 1. (Comparative Example 1) A laminate material was produced in the same manner as in Example 1. However, heating was not performed after embedding the anti-blocking agent particles. A DI can was formed using the material and the same evaluation was carried out.The obtained results are shown in Table 1. (Example 3) A cold rolled steel plate with a thickness of 0.30 mm and a temper of T-2.5. A film is formed on the laminate surface by a well-known electrolytic chromic acid treatment, consisting of an upper layer of a chromium hydrated oxide layer with a chromium content of 20B7m" and a lower layer of a metallic chromium layer with a chromium content of 10B7m". 2.8g/ by a known method on the surface
This surface-treated steel sheet was heated to 215°C.
A biaxially oriented polyethylene terephthalate/sebacate copolyester film (mol fraction of ethylene sebacate component 23%, melting point 220°C) with a thickness of 25 μm was placed on one side of the film so as to face the side having the electrolytic chromic acid treatment layer. Then, this laminate material was heated to 235°C and immediately cooled with water to obtain a coated steel plate in which the anti-blocking agent particles in the copolyester film were buried under the surface of the film. A drawn and ironed can was made from this RFI steel plate under the same forming conditions as in Example 1, and the same evaluation was performed. The results are shown in Table 1. (Actual Journey Example 4) In Example 3, a film was formed on a steel plate by electrolytic chromic acid treatment, in which the upper layer was a chromium permanent oxide layer with a chromium content of 20 B7m", and the lower layer was a metallic chromium layer with a chromium content of ioIlg/m". A DI can was molded in the same manner as in Example 3, except for the following points, and the same evaluation was performed. The results are shown in Table 1. (Example 5) In Example 3, the laminate side surface of the cold-rolled steel sheet was coated with 0.0% by a known method. Nickel plating of 1g/*" was applied, followed by tin plating of 0.5g/m", and the upper layer was treated with a known electrolytic chromic acid treatment to reduce the amount of chromium to 20 rag.
/rs'' chromium permanent oxide layer, the lower layer is a 20mg/rs'' metal chromium layer, and biaxially oriented polyethylene terephthalate/isophthalate (ethylene isophthalate mole fraction 14%. melting point 225). ℃
) DI cans were molded in the same manner as in Example 3, except that a copolymerized polyester film was used, and the same tests were conducted. The results are shown in Table 1. (Example 6) Aluminum alloy plate heated to 235°C (thickness 0.32
on. Material name: A3RO 04H 3 9 material. The amount of chromium treated with chromic acid phosphoric acid on the surface is 20 trrg/ra.
A biaxially oriented polyethylene terephthalate/isophthalate (mol fraction of ethylene isophthalate component: 10%, melting point: 240°C) copolyester film having a film thickness of 15 μm was laminated onto the plate (2) using a primer in the same manner as in Example 1. The film was then heated to 250°C and cooled with water to produce a coated aluminum alloy plate in which the anti-blocking agent particles in the copolyester film were buried beneath the surface of the film.
Aluminum DI cans were molded from this material under the molding conditions shown below, and similar tests were conducted. The results are shown in Table I. 0 Forming Conditions Punch an aluminum laminate plate into a disc with a diameter of approximately 140 + w + w, and form it into a cup shape with an inner diameter of approximately 87 mm between a drawing punch and a drawing die according to the usual method. Next, ironing was performed using a combination of an ironing punch with a dimple-shaped surface (depth 1 μm) and an ironing die. The dimensions of this can body are shown below. Body wall thickness: 0.125aui Can body inner diameter
65.7 ma + can body height 124 mm (Comparative Example 2) The same aluminum alloy plate as in Example 6 was heated to 255°C, and a biaxially stretched polyethylene terephthalate film was placed on one side of the plate so that the aluminum alloy plate and the surface coated with the adhesive primer faced each other. The material was supplied in such a manner as to be hot and press-bonded, and after lamination, it was cooled with water. Next, this laminate material was heated to 275°C and immediately cooled with water. A DI can molding test was conducted using this material in the same manner as in Example 6, but the subsequent tests were discontinued due to poor release properties and scratches on the inner surface. (Comparative Example 3) In Example 1, the surface treatment of the punch used in the second drawing process and the final ironing process was changed from cross-surface finish to mirror finish (Ra
A molding test of a DI can was carried out in the same manner as in Example 1, except that the molding temperature was 0.1 or less), but the subsequent tests were discontinued due to poor release properties and scratches on the inner surface. (Comparative Example 4) In Example 6, the surface treatment of the punch used in the second process drawing process and final ironing process was changed from cross-surface finish to mirror finish (Ra
A molding test of a DI can was carried out in the same manner as in Example 6, except that the molding temperature was 0.1 or less), but the subsequent tests were discontinued due to poor release properties and scratches on the inner surface. (Example 7) Tinplate heated to 195°C (plate thickness 0.20 mm. Tempered T-2.5. Tempered T-2.8 on both sides of a cold-rolled steel plate by a known method.
As in Example 1, a film consisting of a chromium hydrated oxide layer of 70 g/m was formed on the top layer by a known cathodic treatment in dichromic acid. A 12 μm thick biaxially oriented polyethylene terephthalate/sebacate copolyester film (mol fraction of ethylene sebacate component: 30%, melting point 200°C) coated with a primer of
After heating to 5°C and cooling with water, a coated steel plate was prepared in which the anti-blocking agent particles in the copolyester film were buried under the surface of the film. A polyester paint containing titanium dioxide was applied to the non-laminated tin surface of this laminated material using a roll coater to a dry film thickness of 8 μm.
After baking at 90°C for 10 minutes, paraffin wax was applied to both sides at a rate of 1 a+g/d, and a circular Taber can was manufactured using the method described below, and the same test as in Example 1 was conducted. (however,
The contents of the actual can test were grape jelly (sterilized in hot water at 85°C for 30 minutes) and the results are shown in Table 1. A circular Taber can was made using a three-stage drawing method so that the polyester film surface of the Taber was on the inside of the can. +11 1st stage drawing process Bottom diameter 60.3mm, opening diameter 73.7mm, height 16
．． Squeeze into a 0mm cup. (2) Second stage drawing process bottom diameter 60. 3mm, opening diameter 70. Squeeze into a cup 4mm wide and 26.7mm high. (3) 3rd stage drawing process bottom diameter 60.3m++m. Opening diameter 74.211!1,
A circular Taber cup with a step 5 ms+ below the opening with a height of 33.0+ am was molded.

Trim the open end of this circular Taber cup using the usual method. A circular Taber can with steps was manufactured by reflanging. (Example 8) Both sides of a cold-rolled steel sheet were plated with 1.0 g/+" of tin by a known method, and then the upper layer was coated on both sides with a chromium content of 20 o+g/m" by a known electrolytic chromic acid treatment. A film was formed consisting of a chromium hydrated oxide layer and a 20 B/+" metallic chromium layer as the lower layer.
A two-wheel stretched polyethylene terephthalate/sebacate (mole fraction of ethylene sebacate component: 23%, melting point 220°C) copolyester film with a thickness of 12 μm was laminated thereon, and this laminate material was then heated at 230°C.
After heating, it was cooled in water. This material was coated on the outside in the same manner as in Example 7, and circular Taber cans were manufactured and the same tests were conducted.

The results are shown in Table 1. (Example 9) Both sides of a cold-rolled steel sheet were treated with electrolytic chromic acid using a known method to form a chromium hydrated oxide layer with an upper layer having a chromium content of 20 rag/1, and a lower layer with a chromium content of 100 tag/ra''. A film consisting of a metallic chromium layer was formed.This material was
A 12 μm thick biaxially oriented polyethylene terephthalate/isophthalate (ethylene isophthalate mole fraction: 8
%, melting point 245°C) copolymerized polyester film was laminated and then heated to 260°C. Similar to Example 7,
After painting the outside, circular Taber cans were manufactured and similar tests were conducted. The results are shown in Table I.

(Comparative Example 5) A laminate material was made in the same manner as in Example 7. However, heating was not performed after embedding the anti-blocking agent particles5.
A circular Taber can was manufactured in the same manner as in Example 7, and the same test was conducted. The results are shown in Table 1. (Comparative Example 6) In Example 7, a biaxially oriented polyethylene terephthalate/isophthalate copolymer polyester film (ethylene isophthalate mole fraction 32%, melting point 165°C)
was laminated onto a surface-treated steel plate heated to 160°C.
Next, this laminate material was heated to 175°C, and Example 7 was prepared.
Similarly, a circular Taber can is manufactured. A similar test was conducted. The results are shown in Table 1.

(Example 10) The upper layer is a chromium permanent oxide layer with a chromium content of 15 mg/m", and the lower layer is a metallic chromium layer with a chromium content of 100 mg/s". The plate thickness is [1.1851111. Temper DR-8
A 30 μm thick biaxially oriented polyethylene terephthalate/isophthalate (ethylene isophthalate mole fraction 20%, melting point 216°C) copolymer polyester was prepared by applying a primer to an electrolytic chromic acid treated cold rolled steel sheet in the same manner as in Example 1. The film is laminated and then heated to a temperature above the melting point 2
It was heated to 26°C and immediately quenched to make a laminate.
A polyester paint was applied to the non-laminated TFS surface of this laminate material using a roll coater so that the dry film thickness was 5 μm, and baked at 190°C for 10 minutes. During squeezing, a tensile force was applied in the axial direction to reduce the thickness of the cup side wall. prevent the increase,
Furthermore, we manufactured deep-drawn cans with reduced thickness compared to the original plate thickness. A test similar to that in Example 1 was conducted and the results are shown in Table 1. A deep-drawn can was produced using a three-stage forming method so that the polyester film surface was on the inside of the can. +11 1st stage process (drawing) Can body outer diameter 111.5wn. Squeeze into a cup with a height of 41.4 mm. (2) Second stage process (first stage re-drawing) Can body outer diameter 84.5 mm, height 70. Squeeze into a 1mm cup. (3) Third stage process (second stage re-drawing) Can body outer diameter 65. Narrow it down to a cup with I3mm and height 101.6+am. Form the bottom of this cup according to the conventional method. The open end was trimmed to produce a deep drawn can.

The side wall thickness of this can is. 6 (Example 11) The same surface treated steel plate as in Example 1O was heated to 210°C,
Copolymerized polyester film was directly laminated. This laminate material was heated to 226°C and immediately quenched to produce a laminate material. A deep-drawn can was formed using this material in the same manner as in Example 10, and the same evaluation was performed. The results obtained are shown in Table 1. (Comparative Example 7) A laminate material was made in the same manner as in Example 10. However, no heating was performed after embedding the anti-blocking agent particles. Similar to Example IO, a deep drawn can was produced in which a tensile force was applied in the axial direction during drawing to prevent the cup side wall thickness from increasing, and the thickness was further reduced from the original thickness, and similar tests were conducted. The results are shown in Table 1.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing the cross-sectional structure of one example of the laminate used in the present invention, FIG. 2 is a cross-sectional view showing the cross-sectional structure of another example of the laminated body used in the present invention, and FIG. FIG. 4 is a scanning electron microscope sketch (top view) of the polyester surface of an untreated laminate, and FIG. 4 is a scanning electron microscope sketch of the polyester surface of a laminate treated according to the present invention. 1 is a laminate, 2 is a metal substrate, 4 is a copolyester layer, and 5 is an anti-blocking agent particle.

Claims (2)

[Claims] (1) A metal material and a copolymer with a melting point of 170 to 252°C, which is mainly composed of ethylene terephthalate units and contains a small amount of other ester units, provided directly or via an adhesive primer on at least the inner surface of the metal material. It is formed by drawing or drawing-iron forming a laminate with a polymerized polyester film, and the copolymerized polyester film is a film containing anti-blocking agent particles, and the anti-blocking agent particles are buried below the surface of the film. A squeezing or squeezing can characterized by the fact that (2) A biaxially stretched film made of a copolyester containing mainly ethylene terephthalate units and a small amount of other ester units and having a melting point of 170 to 252°C and containing anti-blocking agent particles is used as at least the inner surface of the metal can. A laminate is produced by thermally adhering the anti-blocking agent particles to the side directly or via an adhesive primer, and at least the film surface of this laminate is heated to a temperature higher than the melting point of the copolyester, and then rapidly cooled to bond the anti-blocking agent particles to the film. buried below the surface,
A method for producing a drawn or drawn-ironed can, characterized in that the treated laminate is subjected to drawing or drawn-ironed processing.