JPS6221428A - Manufacture of deep draw forming container - Google Patents

Abstract

PURPOSE:To improve the drawing form ability, and to prevent the generation of a wrinkle, ear breaking, etc. by providing a covering of a thermoplastic resin film on both faces of a steel foil or an iron foil, and executing the draw forming to a laminated body which has packed a film which becomes the inside surface side of a container, with an inorganic filler. CONSTITUTION:A surface treatment layer 2a and 2b are provided on both faces of a base body 1 of a steel foil and an iron foil, and on the side which becomes the inside surface of a container, a thermoplastic resin film inside surface layer 4 packed with an inorganic filler is provided through an adhesive agent layer 3a as necessary. Also, on the side which becomes the outside surface of the container, a thermoplastic film outside surface layer 5 is provided through an adhesive agent layer 3b as necessary. By using this laminated material, deep drawing forming is executed, and a deep draw forming container which does not generate a wrinkle, breaking of a foil, etc. is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing deep-drawn containers, and more particularly to a method for manufacturing deep-drawn containers from steel foil or iron foil. Furthermore, the present invention also relates to a method for producing deep-drawn containers that have excellent corrosion resistance and commercial value.

Prior Art and Technical Problems of the Invention Packaging materials used for containers and lids include various materials such as various metals, plastics, paper, glass, and ceramics, or composite materials of two or more of these materials. In terms of the combination of barrier properties against gases such as oxygen, carbon dioxide, and water vapor, and mechanical strength, metal materials are most suitable.

However, since metal cans and metal lids are difficult to dispose of by incineration, etc., there is a problem of so-called can pollution.As a packaging material that is easier to dispose of, a laminate made of metal foil and resin film is used. It has come to be widely used in the field of sealed containers and sealed lids. Almost all commercially available laminates for containers or lids are based on aluminum foil, but even though aluminum foil has excellent appearance characteristics and flexibility, its surface is Even when coated with organic resin, contents containing relatively high concentrations of salts such as common salt and contents containing organic acids can cause problems such as corrosion such as pitting and peeling of the coating layer. , resulting in defects such as leakage of contents and decreased shelf life.

As metal foils, those based on iron or steel, such as iron foil, steel foil, and tin foil, are also known, but when using these as packaging materials for foods, there are still problems. There are many issues that need to be addressed.

That is, iron and steel are metals that are extremely prone to rust, and rust can occur during the manufacturing process or storage of the package, which can significantly reduce its appearance and commercial value. In addition, iron elution and rust contamination can significantly reduce the flavor retention of the contents.
<to lower.

Furthermore, since iron or steel foil is significantly thinner than steel plate,
It has poor drawability and formability, and there are problems such as wrinkles occurring during drawing and the foil being cut, making it impossible to form a container. This drawback becomes more noticeable when a relatively thick organic resin coating is applied to the iron or steel foil for the purpose of improving its corrosion resistance and rust resistance.

Outline and Purpose of the Invention The present inventors provided a thermoplastic resin film coating on both sides of steel foil or iron foil, and at least filled the film on the inner surface of the container with an inorganic filler. When the laminate is subjected to heating, the laminate is 1. It has been found that deep drawing formability is significantly improved.

That is, the object of the present invention is to manufacture deep-drawn containers from steel foil or iron foil.1. We are here to provide you with a way to get it.

Another object of the present invention is to provide a method that can effectively prevent the occurrence of wrinkles, cutting of the foil, etc. during deep drawing of steel foil or iron foil into containers.

Still another object of the present invention is to provide a deep-drawn container made of steel foil or iron foil, which is effectively prevented from rusting, iron elution, etc., and which also has improved commercial value.

Structure of the Invention According to the present invention, a laminated material in which both sides of steel foil or iron foil are covered with thermoplastic resin films and at least the film layer on the inner surface of the container is filled with an inorganic filler is subjected to deep drawing. A method for manufacturing a deep-drawn container is provided.

The steel foil or iron foil used in the present invention may be provided with a surface treatment layer on its surface. As will be described in detail later, this surface treatment layer may be any surface treatment layer known per se formed by plating treatment, electrolytic treatment, chemical conversion treatment, chemical treatment, or the like.

As described in detail later, any thermoplastic resin film used for coating may be used as long as it is film-formable and water resistant. As the inorganic filler, any inorganic pigment or inorganic extender pigment can be used.

PREFERRED EMBODIMENTS OF THE INVENTION The invention will now be described in more detail with reference to the accompanying drawings, in which: FIG.

Laminated materials and effects The present invention, as described in section 7 above, when subjecting steel foil or iron foil to drawing forming, the steel foil or iron foil is laminated with thermoplastic resin films on both sides, and on the inner surface of the container. It is characterized in that it is used in the form of a laminate material in which the film layer is filled with an inorganic filler.

That is, the above-mentioned inorganic filler-filled film layers from 1 to 5 are
- By providing it on the inner surface of the container, drawing formability is significantly improved, problems such as wrinkles and edge breakage are eliminated, and the critical drawing ratio is significantly improved as shown in the example below. can be done.

The drawing ratio R is expressed by the formula R=D/d, where D is the diameter of the material to be drawn and d is the diameter of the punch used (the diameter of the bottom of the container), and this value is As the thickness increases, drawing becomes impossible due to breakage. The maximum value of H that can be formed is called the critical drawing ratio]7, meaning that the larger this value is, the deeper drawing is possible.

Due to the thickness effect of iron or steel foil, drawing workability and formability are significantly inferior to steel sheets. This is because wrinkles are generated during the drawing process, and even if the wrinkle-pressing force is increased to prevent wrinkles from occurring, the wrinkle-pressing force is not sufficiently transmitted to the foil surface through the organic film. Furthermore, if the wrinkle pressing force is increased too much, iron or steel foil has low strength and will break, making it impossible to form a container.

Since the inorganic filler in the organic resin coating hardens the organic resin coating 6 itself, it is thought that the wrinkle suppressing force is efficiently transmitted to the foil, thereby making it possible to form a wrinkle-free squeezed container.

Fourth, above 1. By using a coating containing an inorganic filler, the corrosion tendency of corrosive components such as iron or steel foil is significantly suppressed, and hydrogen generation, for example, is significantly suppressed and
．． The shelf life of the iron or steel foil is considerably extended, and even if rust occurs on the iron or steel foil during long-term storage, this rust is hidden and the appearance characteristics are maintained well over a long period of time.
Product value can be increased.

In FIG. 1 showing an example of the laminated material used in the present invention, surface treatment layers 2α and 2b are provided on both sides of a base 1 made of steel foil or iron foil.
An inorganic filler-filled thermoplastic resin film inner layer 4 is provided on the inner surface of the container (lower side in the figure) via an adhesive layer 6a (-) if necessary. On the side that becomes the outer surface of the container, a thermoplastic film outer surface layer 5 is also provided via an adhesive layer 6b if necessary.The outer surface layer 5 is of course a resin film layer not filled with an inorganic filler. However, it is generally preferable to use a film layer filled with an inorganic filler like the inner layer 4.

The reason why iron or steel foil is used in the present invention is that compared to aluminum foil, this foil has a significantly lower pitting rate against contents containing salt. can be,
This significantly improves the corrosion resistance of packaging materials and gas AIJ properties.1. I can meet you.

′! Furthermore, iron or steel foil has a Young's modulus that is about 2.5 times that of aluminum foil, and can provide sufficient strength and shape retention with a relatively thin thickness. Furthermore, iron or steel foil is available relatively cheaply compared to aluminum foil, and can also reduce the cost of the container.

This iron or steel foil has a thickness of 10 to 120 μm, especially 3
It is also important to have a thickness of 0 to 100 μm. If the thickness is less than the above range, it is difficult to obtain a foil without defects such as pinholes, and it is difficult to obtain sufficient barrier properties against various gases, water vapor, etc. Furthermore, if the above range is exceeded, it may become difficult to dispose of the final container, or
Alternatively, the economics or other advantages of using foil will be lost.

As the foil substrate, iron foil is used when flexibility or pliability is required, and steel foil is used when rigidity and mechanical strength necessary for shape retention are required.

The iron foil and the cathode and the electrolyte mainly composed of ferrous chloride, ferrous sulfate, etc. It is obtained by electrodepositing on the surface of a metal substrate and peeling the formed film from the surface of the substrate, and has extremely high purity (CF, 9997').
It also has excellent corrosion resistance and is softer than steel foil. Further, steel foil has a structure in which crystal grains are elongated in the rolling direction, whereas iron foil has a columnar crystal structure in which crystals grow in the thickness direction.

As steel foil, soft one (ductiLg) is also available.
A hard material (full hard) is also used. The former type involves secondary cold rolling (after annealing the cold rolled steel plate).
~, re-annealed, galvanized, tin plated if necessary,
It can be obtained by performing one or more of the following post-treatments: nickel plating, electrolytic chromic acid treatment, and chromic acid treatment. In the latter type, cold-rolled steel sheets are annealed and then subjected to secondary cold rolling (7. If necessary, post-treatment such as zinc plating, tin plating, nickel plating, electrolytic chromic acid treatment, chromic acid treatment, etc.) A fully hard-type steel sheet with a metal plating layer, which is made of metal, is also produced by annealing a cold-rolled steel plate and then tempering it. is also manufactured.

An example of the mechanical properties of soft steel foil, hard steel foil, and iron foil is as follows.

Tensile strength and elongation are generally 30 each for soft steel foil.
~50Kg/nJ, 15-55 inches, and 40-60 for hard steel foil, 9/mJI, 1-15 inches, respectively.

Iron foil: 60-50 KglomR, 2-10 respectively
It is within the range of Generally, it is desirable to use steel foil.

In the present invention, the iron or steel foil 1 is preferably provided with a surface treatment layer consisting of a metal plating layer or a chromate layer thereon from the viewpoint of corrosion resistance and adhesion of the organic resin coating. - Yes. Organic resin coating is effective in preventing direct contact between contents and iron or steel foil.
However, the resin coating has the property that it does not allow hydrogen ions from organic acids contained in highly corrosive contents to pass through to a large extent, but it does allow anions such as chloride ions contained in salts to pass through to a small extent. ．． I'm here. For this reason, the coating tends to peel off at the interface between the organic resin coating and the foil.
, Fl When such peeling occurs, corrosion such as rust generation, iron elution, and pitting corrosion easily progresses in this part.

According to a preferred embodiment of the present invention, a surface treatment layer consisting of a gold plating layer or a chromate layer is provided on the iron or steel foil, so that the metal plating layer has 1.1 resistance to the above-mentioned corrosive components. 1. In effect 1~, it further acts to improve the adhesion with the organic resin coating layer. At this time, when a chromate layer is provided on the metal plating layer, the adhesion with the organic resin coating is further improved.

Typical metal plating layers include metals that are softer than iron and have anti-corrosion effects, such as N+
, Sn, Zn, A1, etc. are advantageously used. The plating layer made of these metals not only has an excellent anti-corrosion effect but also has good drawing formability, and when cutting iron or steel foil, the plating layer metal flows to the cut edge and the cut edge (7) Shows an unexpected and novel effect of suppressing the occurrence of rust from the cut edge.

The fact that the plating layer metal flows and exists at the cut edge of the iron or steel foil with the plating layer is confirmed by the presence of the plating layer metal when the cut edge is observed with an X-ray microanalyzer. be done.

Generally, the hardness of the metal plating layer is Vickers hardness//
11500 or less, more preferably (~(is HU40 (:) or less metal is 0.1 to 15f/r&, especially 0.2 to 12
It is preferably present in a coverage of v/-. That is, if the metal has a hardness exceeding the above range, the plating layer metal will not flow to the cut edge when cutting iron or steel foil, and the rust prevention effect at the cut edge will not be obtained. Also, the amount of metal plating is
At the end of the above range, the effect of blocking corrosive components or preventing corrosion is unsatisfactory, and in particular, the effect of preventing rust from forming on cut edges cannot be obtained. Providing a warped, plated layer beyond the above range is economically disadvantageous and offsets the advantages of using iron or steel foil.

A nickel plating layer has a particularly excellent shielding effect against corrosive components, and it is also compatible with easily available plated iron or steel foil.
For example, tin plated foil, that is, tin foil can be mentioned. In this tin foil, sufficient corrosion resistance and adhesion of the organic film can be obtained even when the amount of tin coated is relatively small, for example, in the range of 0.5 to 10 P/m. In this case, the tin layer is bonded to the metallic tin layer. (It may be present in ~, but in terms of resin adhesion, Sn
/Ft It is preferably present in the form of a tin-iron alloy layer with a metal atomic ratio in the range of 2 to 1.

Examples of the chromate layer include a chromium oxide layer mainly composed of water-use chromium oxide with a coating amount of Cr in the range of 1 to 50 WLg/m'', particularly 6 to 65 μ/m. The above-mentioned plating layer 1 can be formed by a chemical conversion treatment and/or a chemical treatment which are known per se.

In the present invention, in the case of a container in which rust formation at the cut edge part is not a problem, for example, a draw-formed container with curled edges, the plating layer is a metallic chromium layer, and moreover, a nine-layered container having a chromate layer thereon is used. It may also be a free steel foil.

This gold chromium layer is 0.06 to 0.59/n? , especially 0.05 to 0.39/n? It is preferable that the metal plating layer be present in a coating amount of 0. Furthermore, the metal plating layer is not limited to being composed of a single metal layer, but can also be composed of a plurality of different types of metal layers. For example, the base plating layer is the above-mentioned soft metal layer such as nickel, the top plating layer is a chromium metal layer formed by electrolytic chromic acid treatment, and further has a chromium oxide layer thereon. good.

In the present invention, an organic resin coating is provided on both sides of the above-mentioned iron or steel foil, and in this case, at least the resin layer on the inner surface of the container, preferably the resin Im on both sides, is filled with an inorganic filler.

The inorganic filler and 1 to 1 include inorganic white pigments such as rutile or anatase titanium dioxide, zinc white, and cross white; pallite, precipitated pallite sulfate, calcium carbonate,
White body pigments such as gypsum, precipitated silica, aerosil, talc, fired or unfired ray, barium carbonate, alumina white, synthetic or natural mica, synthetic calcium silicate, magnesium carbonate, barium carbonate; carbon black, magnetite, etc. red pigments such as red pigment; yellow pigments such as red pigment; and blue pigments such as ultramarine blue and cobalt blue. However, the inorganic fillers that can be used in the present invention are not limited to those exemplified above.

These inorganic fillers can be easily dispersed into the resin.
In order to ensure uniformity, the average particle size is preferably in the range of 0.05 to 20 μm (and, in terms of drawability, it is desirable that the specific gravity is in the range of 2.0 to 90). I7.Furthermore, in terms of concealment and barrier properties, TRS K-
It is desirable that the hiding power of 5101 is 50 cd/or more.

Inorganic fillers particularly suitable for the purposes of the invention include titanium dioxide, especially rutile titanium dioxide. This titanium dioxide has the greatest anticorrosion effect among various pigments against the corrosion of steel foil caused by corrosive components, and also has excellent hiding power, making it possible to maintain the white color of packaging containers permanently. It becomes possible.

Suitable examples of organic thermoplastic resins include, but are not limited to:

(α) Polyolefins; polypropylene, polyethylene, polybutene-1, propylene-ethylene copolymer,
Propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ionically crosslinked olefin copolymer (ionomer).

(b) Polyamides; especially general formula % formula % (11 In the formula, the number is 3 to 13, m is the number 4 to 11. Polyamides consisting of repeating units represented by

For example, poly-ω-aminocaproic acid, poly-ω-aminohebutanoic acid, poly-ω-aminocaprylic acid, poly-ω
-aminoberatic acid, poly-ω-aminodecanoic acid, poly-ω-minoundecanoic acid, poly-ω-aminododecanoic acid, poly-ω-aminotridecanoic acid, polysamethylene adipamide, polyhexane Methylene dodecamide, polyhexamethylene dodecamide, Bo11 hexamethylene tridecamide, polydecamethylene adipamide, polydecamethylene apamide, polydecamethylene dodecamide, polydecamethylene tridecamide, polydodecamethylene adipamide Mido, polydecamethylene adipamide, polydodecamethylene dodecamide, polydodecamethylene tridecaodo, polydidecamethylene adipamide, polytridecamethylene dodecamide, polytridecamethylene dodecamide, polytridecamethylene tridecamide mido, polydecamethylene adipamide,
Polydecamethylene adipamide, polydecamethylene adipamide, boritridecamethylene azeramide or copolyamides thereof.

(C) Polyesters; in particular, from the repeating unit represented by the general formula % (4) where R5 is an alkylene group having 2 to 6 carbon atoms, R1 is an alkylene group having 2 to 24 carbon atoms, or an arylene group Made of polyester.

For example, polyethylene terephthalate, polyethylene terephthalate/isophthalate, polytetramethylene terephthalate, polyethylene/tetramethylene terephthalate, polytetramethylene terephthalate/isophthalate, polyethylene terephthalate/isophthalate, polytetramethylene/ethylene terephthalate, polyethylene/tetramethylene terephthalate/iso Phthalates, polyethylene/oxybenzoates, or blends thereof.

(d) Polycarbonates; especially those with the general formula % (5
) A polycarbonate represented by the formula in which R8 is a hydrocarbon group having 8 to 15 carbon atoms.

For example, poly P-xylene glycol biscarbonate, poly-dioxydiphenyl-methane carbonate,
Poly-dioxydiphenylethane carbonate, poly-
Dioxydiphenyl 2,2-propane carbonate, poly-dioxydiphenyl 1,1-ethane carbonate.

(1) Polyvinyl chloride, vinyl chloride-butadiene
t[Coalescence, vinyl chloride resin such as vinyl chloride-styrene-butadiene copolymer.

(1) Vinylidene chloride resins such as vinylidene chloride-vinylidene chloride copolymer and vinylidene chloride-vinylpyridine copolymer.

(q) High nitrile resins such as high nitrile content acrylonitrile-butadiene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-styrene-butadiene copolymers, etc.

(A) Polystyrene resin, styrene-butadiene copolymer, styrene-acrylonide 11l copolymer, AB
S resin etc.

These resins are generally formed into a film shape and adhered to the aforementioned steel foil by thermal fusion or bonded using an adhesive. An excellent adhesive for this is a urethane adhesive, and for a polyolefin film, an acid-modified olefin resin grafted with ethylenically unsaturated carboxylic acid or its anhydride can be used. A low melting point copolyamide can be used as an adhesive for polyamide film, and a low melting point copolyamide can be used as an adhesive for polyester film.

Furthermore, as an adhesive undercoat, an epoxy-phenol paint containing an adhesion promoter such as an acid-modified olefin resin may be applied (1-1) and the film layer may be thermally bonded through this undercoat layer.

The thickness of the thermoplastic resin film layer is generally 10 to 150 mm.
The thickness is preferably in the range of 30 to 100 μm, and if it is thinner than this range, the resin film tends to lose its coating effect against corrosion, and if it is thicker than this range, the drawability is reduced.

The amount of inorganic filler packed into the resin varies somewhat depending on the thickness of the film, etc., but it is 2 to 50 parts per resin.
%, particularly preferably in the range of 5 to 60% by weight. If the filling amount is lower than the above range, the effect of improving the rigidity of the film layer and suppressing the occurrence of wrinkles will be unsatisfactory, and the corrosion resistance and hiding effect will likely be unsatisfactory as well. On the other hand, if the amount exceeds the above range, the properties of the film will become brittle, and pinholes, cracks, tears, and peeling will occur in the film during drawing forming.]
7 easy.

Deep drawing according to the present invention can be easily carried out by using the above-mentioned laminated material as a raw material. That is,
In FIG. 2 for explaining the deep drawing method, the above (
- A material 10 obtained by shearing a laminated material into a predetermined size and shape is press-worked between a punch 12 and a die 16 that are relatively movable in the axial direction, with the head pressed by a wrinkle presser 11. and form it into the shape of a seamless cup with a bottom.

In this case, according to the method of the present invention, since the inorganic filler-filled film layer is located at least on the side of the wrinkle presser 11, the generation of wrinkles is effectively suppressed, and the formula R= 1)/ It is a remarkable feature that the aperture ratio defined by d can be obtained in a high range of 1-1, usually from 1.5 to 1.
The limiting aperture ratio of about 2.0 can be increased to about 2.4. Generally, one stage of drawing operation is sufficient, but two or more stages of drawing operation may be performed as desired.

For drawing forming, ordinary metal punches can be used for the punches 12 and 1-7, but a metal core 14 and a rubber active side wall 15 surrounding it as shown in FIG.
Punch 12' (Patent No. 1130414)
By using No. 1), the occurrence of wrinkles can be further suppressed.

FIG. 4 shows an example of a deep-drawn container according to the present invention. It consists of a side wall portion 22 that extends vertically or upwardly and widens toward the end, and a flange portion 26 provided at the upper end of the side wall portion.

There is a cut edge 24 on the outside of this flange portion 26, but as already mentioned, the occurrence of rust is suppressed by covering the steel foil or iron foil with a plated metal layer. In addition, iron or steel foils have sharp cut edges that can easily cause damage to fingers or the like if touched. This has completely eliminated the dangers associated with this, making it possible to establish the safety of packaging materials using iron or steel foil. ○Figure 5 showing another example of the deep-drawn container according to the present invention 4, this container is formed from a bottom portion 21, a side wall portion 22, and a flange portion 26, but the outermost edge of the flange portion 26 is formed by rolling a laminated material. A curl portion 25 is provided.

The bottom shape of these containers can be any shape such as circle, oval, square, rectangle, hexagon, hexagon, etc! .

It should be understood that what you get is:

Furthermore, it should be understood that by using a heat-sealable resin film as the inner material resin, sealing with the lid material can be easily achieved by heat-sealing.

The invention is illustrated by the following example.

Example 1 Both sides of a 75μ thick steel foil were treated with an electrolytic chromic acid treatment bath (an aqueous solution of chromic anhydride 60 fl/l, sulfuric acid C1,2'//l, and sodium silicofluoride 0.2 r//). Cathodic electrolysis is carried out inside the
Thickness rl, 1f/lr? Metallic chromium and 15q/lr?
After providing a surface treatment layer of chromate layer, a 70 μ thick polypropylene film filled with 5 If・t% of rutile titanium dioxide was applied to the inner surface of the container using a urethane adhesive, and a 70 μm thick polypropylene film filled with 5 If・t% of rutile titanium dioxide was applied to the outer surface of the container. A polypropylene film with a thickness of 30 μm without filler filling (7) was laminated on the plate.

This 1. The critical drawing ratio and the appearance of the container were evaluated using the method shown in FIG. 2.

In addition, for evaluating the corrosion resistance of the container, a cylindrical container 7 with a bottom diameter of 66 wr IR 1 and a height of 321111 was used as shown in Fig. 5.
Forming a deep-drawn cup with a flange (,7).
Watt bath (nickel sulfate 240f/
nickel chloride 45 fl/l, nickel chloride 45 fl/l, ferric acid 309/l aqueous solution) to a thickness of 2. Of//lr/plating, then cathodically electrolyzed in the above electrolytic chromic acid treatment bath,
Thickness 0. After surface treatment of metallic chromium and IEl/- chromate layer of []5r/m”, one side is coated with epoxy.
The phenolic paint was baked to a thickness of 5 μm, and a 50 μm thick polypropylene film was laminated on the other side using a urethane adhesive. The material obtained in this way was punched out into a circular shape with a diameter of 70 m to create a heat-sealed lid.

Next, the deep-drawn cup was filled with tuna dressing, the lid was heat-sealed, and then heat sterilized at 116C for 40 minutes.

After storage for 6 months at '57C, the inner and outer conditions of the squeeze cup container and lid were observed, and the amount of hydrogen generated in the head space was measured. The results are shown in Table-1.

Examples 2 and 6 The content of titanium dioxide in the inner film was 1, respectively.
Tests and evaluations were carried out in the same manner as in Example 1, except that the titanium dioxide was 0 wt % and 60 ωt %, and that the outer film also contained 10 wt % titanium dioxide. The results are shown in Table-1.

Comparative Example 1゜Thickness 70μ and 60μ without filler on inner and outer surfaces
Tests and evaluations 1 to 1 were carried out in the same manner as in Example 1, except that a μ polypropylene film was used, and the results are shown in Table 1.

Comparative Example 2.6゜Inner side film contains 01% titanium dioxide 6Q with a thickness of 70μ and titanium dioxide 10W with a thickness of 160μ, respectively.
Tests and evaluations were carried out in the same manner as in Example 1, except that the polypropylene film was 60μ thick and contained 1001% titanium dioxide (the results are shown in Table 1). Shown below.

Example 4, 5, 6゜The inner side film was a polypropylene film having a thickness of 40μ and containing 1% titanium dioxide iQ, and a thickness of 7.
-4 is a polypropylene film containing titanium dioxide iQ + gt% with a thickness of 0μ, a medium density polyethylene film with a thickness of 70μ and containing 2001% of titanium dioxide, and -4 is a polypropylene film with a thickness of 40μ and containing titanium dioxide 1 ('Jwt%).
The results are shown in Table 1 in the same manner as in Example 1, except that the containing polypropylene films, -5 and 6, were unstretched nylon films with a thickness of 40 μm.

Example Z 1. Same as Example 1 except that polypropylene films with thicknesses of 70 μm and 40 μm filled with 30 tut% zinc white were used as the inner and outer films. The results of the test measurements are shown in Table 1.

Example 8 Tests and evaluations were carried out in the same manner as in Example 1, except that polypropylene films with thicknesses of 70 μm and 40 μm filled with 30111 t% Palite at 1° were used as the inner and outer films. The results are shown in Table 1.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of the laminated material used in the present invention, and FIG.
3 is a cross-sectional view of a forming punch; FIG. 4 is a view showing an example of a deep-drawn container according to the present invention; FIG. 5 is a cross-sectional view of a deep-drawn container according to the present invention. It is a figure showing an example of a molded container. 1 is a base of steel foil or iron foil, 2α and 2b are surface treatment layers,
6α and 3b adhesive layer, 4 is inorganic filler-filled thermoplastic resin film, 5 #i outer thermoplastic resin film, 1
0 is a laminated material, 11 is 1. Holder, 12 is a punch, 13 is a die, 14 is a metal core of the punch, 15 is a rubber band, 20 is the entire container, 21 is a bottom of the container, 22 is a side wall, 23 is a flange, 24 is a cut edge, 25 is a curled portion shows.

Claims (3)

[Claims] (1) Deep drawing characterized by subjecting a laminated material in which both sides of steel foil or iron foil are covered with thermoplastic resin films and at least the film layer on the inner surface of the container is filled with an inorganic filler to deep drawing. Manufacturing method for draw-molded containers. (2) The method according to claim 1, wherein the inorganic filler is contained in an amount of 2 to 50% by weight based on the thermoplastic resin. (3) The method according to claim 1, wherein the steel foil or iron foil is provided with a surface treatment layer consisting of a metal plating layer and/or a chromate layer.