JPS58148759A - Barriering plastic laminated sheet for thermoforming, its manufacture and package using said manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a barrier plastic laminate sheet for molding. More specifically, it relates to a thermoformable barrier plastic laminate sheet as a packaging material for pharmaceutical products that require long-term quality maintenance.The thermoformable barrier plastic laminate sheet of the present invention is a thermoformable hard plastic. A vinylidene chloride-based copolymer resin emulsion is applied to the sheet, a vacuum-deposited film of an inorganic metal compound is provided on the surface, and then the two plastic sheets are stiffened and the surfaces of the vacuum-deposited inorganic metal compound are placed on the inside. This is a barrier plastic laminate sheet for thermoforming, in which molten polyethylene is laminated by extrusion lamination using a 1-die or by dry lamination with a polyethylene film interposed therebetween.

Conventionally, barrier packaging materials for pharmaceuticals, etc. are made by coating a plastic sheet with a copolymer resin emulsion based on hnyritene chloride.
After that, the side coated with the vinylidene chloride copolymer resin emulsion was placed on the inside of these two plastic sheets.
Molten polyethylene is laminated on that surface by extrusion lamination using a T-die, but P
It does not have sufficient performance as a TP packaging material, and there are limits to the long-term quality maintenance of the packaged items, and it cannot be said to be a barrier plastic laminate sheet for thermoforming that satisfies the barrier properties.

As a result of intensive studies to improve these shortcomings, we found that by applying a vacuum-deposited coating of an inorganic metal compound to a plastic sheet coated with a conventional vinylidene chloride copolymer resin emulsion, we were able to improve transparency and thermoformability. Sex, P
We have now discovered the new fact that it is possible to simultaneously improve the heat sealability, water vapor permeability, and oxygen permeability of the hard aluminum of the TP lid material coated with vinyl chloride, leading to the completion of the present invention.

That is, the present invention (1) Thermoformable hard plastic sheet.

A first vinylidene chloride copolymer resin layer, a first inorganic metal compound vapor deposited layer, a polyethylene layer, a second inorganic metal compound vapor deposited layer, a second vinylidene chloride copolymer resin layer, and a second thermoformable hard plastic. A barrier plastic laminate sheet for thermoforming, characterized in that the sheets are sequentially laminated, and each of the vinylidene chloride copolymer resin layers has a thickness of 15 to 60μ; (2) two thermoformable sheets; A vinylidene chloride copolymer resin emulsion is coated on one side of each hard plastic sheet and dried to form a vinylidene chloride copolymer resin layer, and then vapor deposited on the vinylidene chloride copolymer resin layer to form an inorganic metal compound vapor deposition layer. Then, the inorganic metal compound vapor-deposited layer side is turned inward, and molten polyethylene is extruded between them, laminated and fixed together, or dry laminated through a polyethylene film to be fixed together. Method of manufacturing a sheet and (3) first thermoformable rigid plastic sheet.

A first vinylidene chloride copolymer resin layer, a first inorganic metal compound vapor deposited layer, a polyethylene layer, a second inorganic metal compound vapor deposited layer, a second vinylidene chloride copolymer resin layer, and a second non-thermoformable hard plastic. The present invention relates to a PTP packaging body comprising a container thermoformed from a thermoformable barrier plastic laminated sheet formed by sequentially laminating sheets, and a sheet-like vinyl chloride-coated hard aluminum lid for sealing the container mouth.

Next, the barrier plastic laminate sheet for thermoforming of the present invention will be explained with reference to the drawings. Figure 1 shows the Mat of the present invention.
1 is a schematic cross-section showing a preferred embodiment of a shaped barrier plastic laminate sheet. In FIG. 1, 1 is a first thermoformable hard plastic sheet, 2 is a first anchor coat layer, 3 is a first vinylidene chloride copolymer resin layer,
4 is the second anchor coat layer, 5 is the first inorganic metal compound vapor deposited layer, 6 is the third anchor coat layer, 7 is the Lt polyethylene layer, 8 is the fourth anchor coat layer)/1. It is the second inorganic metal compound vapor deposited layer, 10 is the fifth anchor coat layer, 11 is the second vinylidene chloride copolymer resin layer, 12 is the sixth anchor coat layer, and 13 is the second thermoformable layer. It is a hard plastic sheet.

first and second thermoformable rigid plastic sheets)
1. ．． Preferably, the material No. 13 is one that can be easily pressure-formed or vacuum-formed by contact heating or radiant heating, and has shape retention properties after bulk molding. From this point of view, for example, hard vinyl chloride sheets, unstretched polypropylene sheets, polystyrene sheets, cellulose acetate sheets, polycarbonate sheets, unstretched high-density polyethylene sheets, etc.
I can stay. In particular, hard vinyl chloride sheets are particularly preferably used because they have excellent heat sealability on the hard aluminum vinyl chloride coated surface for PTP river covers.

Although the thickness of the thermoformable hard plastic sheet is not particularly limited, it is usually preferably used that has a thickness of about 30 to 1000 microns.

The overall thickness of the laminated sheet is 1 considering the usage-L.
Laminated sheets of 50 to 2000 microns are chosen.

The first thermoformable hard plastic sheet 1 and the second thermoformable hard plastic seam 3 are usually constructed of the same material, but may be of different materials.

Desired printing may be applied to the front and/or back surfaces of the first and/or second thermoformable hard plastic sheet, thereby further displaying and decorative effects.

First and second vinylidene chloride copolymer resin layers 3, 1
As No. 1, it is preferable to use a material that has high barrier properties without impairing the thermoformability of the thermoformable hard plastic sheet. From this point of view, a vinylidene chloride-based copolymer resin having a copolymerization composition of 80 to 95% vinylidene chloride monomer (wt%, the same shall apply hereinafter) and 5 to 20% vinyl chloride monomer, etc. during copolymerization. An emulsion [for example, Saran Latex (trade name: Asahi Dow)] is applied directly to one side of the first and second thermoformable hard plastic sheets 1, 13 or to the first or sixth anchor coat layer 2,
It is formed by coating and drying through 12. The formation method is not limited in any way, and any conventional methods such as air knife foot method, gravure coating method, smoothing coating method, roll coating method, etc. can be adopted, but the vinylidene chloride copolymer resin layer has sufficient barrier properties. In order to demonstrate
After applying the vinylidene chloride copolymer resin emulsion to a thermoformable hard plastic sheet, it must be dried to evaporate the moisture and promote crystallization of the vinylidene chloride copolymer resin, but heat shrinkage etc. A temperature range must be selected that does not cause deformation due to heat. If the drying temperature is low, the vinylidene chloride copolymer resin emulsion will not be sufficiently dried, and the resulting vinylidene chloride IJ-dene copolymer resin layer will not crystallize. In this case, not only the barrier properties are not sufficiently exhibited, but also blocking occurs when the thermoformable hard plastic sheet is rolled up into a roll. Therefore, the drying temperature of the coater is 90
It is desirable to set the temperature to about -150°C. The thickness of the vinylidene chloride copolymer resin layer is usually selected from a range of 1.5 to 60 microns, preferably about 23 to 55 microns. Thickness is 1.5μ
If the thickness is less than 60μ, the barrier properties are poor, and even if the thickness is greater than 60μ, it is difficult to improve the barrier properties, so those thicker than 60μ are economically disadvantageous.

First and second inorganic metal compound vapor deposited layers 5,9LJ Examples: EVA silicon, aluminum, titanium, selenium.

Magnesium, barium, indium, calcium, zirconium, thorium, thallium, tantalum, zinc, etc.
Alternatively, a transparent inorganic metal compound containing a single substance or a mixture of these oxides, halides, nitrides, etc. is used as the first and second vinylidene chloride copolymer resin layer 3.
, 11 either directly or by vapor deposition via the second and fifth anchor coat layers 4.10. The method of forming the same is not limited at all, and includes vacuum evaporation method 2 reactive evaporation method.

Any of the usual methods such as sputtering method 2 reactive sputtering method, ion blating method 2 reactive ion blating method, etc. can be employed.

The thickness of the inorganic metal compound vapor-deposited layer is usually 100 to 5000;
,, preferably from a range of about 300 to 800λ. If the thickness is less than 100λ, the barrier properties are poor, and even if it is thicker than 5000λ, the barrier properties are difficult to improve, so anything thicker than 5000X is economically disadvantageous.

A polyethylene layer 7 is formed between the first and second inorganic metal compound vapor deposited layers 5 and 9 at 280 to 330°C.
This involves extruding a certain amount of molten polyethylene and simultaneously laminating and fixing the two together. Prior to lamination, the surface of the inorganic metal compound vapor deposited layer may be subjected to anchor treatment. The thickness of the polyethylene layer depends on the thickness of the thermoformable hard plastic sheet to be laminated, but is usually selected from a range of about 20 to 70/l, preferably from about 30 to 50 μm.

If the thickness of the polyethylene layer is less than 20μ, sufficient lamination strength cannot be obtained, and if it is thicker than 70μ, even if the molten polyethylene is cooled after being extruded from the This is undesirable because the thermoformable hard plastic sheet that is used in the process shrinks and deforms due to the heat of melting the polyethylene, resulting in wavy wrinkles in the product. The thickness of the polyethylene film in the dry lamination method is usually 20 to 70 μm, preferably 30 to 50 μm, as in the extrusion lamination method using a T-die.
Selected from a range of about μ. If the thickness of the polyethylene film is less than 20 μm, it is not preferable because the cushioning effect against impact is small and wrinkles are likely to occur in the polyethylene film during dry lamination processing. Also 70/l
If it is thicker, it is difficult to slit by perforation in FTP packaging.

In the present invention, a polyethylene layer with a thickness of 20 to 70 IT is provided between the thick thermoformable hard plastic sheets, so that it has a shock-absorbing effect and can also be used between the thick thermoformable hard plastic sheets. It also exhibits sufficient adhesive strength for adhesion.

Anchor coat layer 2, 4, 6, 8, 10. ] 2 is between the thermoformable hard plastic sheet and the vinylidene chloride-based copolymer resin layer, between the vinylidene chloride-based copolymer resin layer and the inorganic metal compound vapor-deposited layer, or between the inorganic metal compound vapor-deposited layer and the polyethylene layer. Provided when the adhesion is poor.

Examples of anchor coating agents include those based on alkyl titanates, polyisocyanates, and polyalkyleneimines. Its thickness is usually about 01 to 2 μm. Furthermore, instead of providing an anchor coat layer, corona discharge treatment, plasma etching treatment, etc. may be applied, and the anchor coat and corona discharge treatment, plasma etching treatment, etc. may be used together.

FIG. 2 is a partially cutaway perspective view showing a preferred embodiment of a package using the thermoformable barrier plastic laminate sheet of the present invention. In FIG. 2, A is a container obtained by aging the thermoformable barrier plastic laminate sheet of the present invention into an L shape, and B is a lid material made of sheet-like vinyl chloride coated hard aluminum.

The barrier plastic sheet for thermoforming thus obtained has barrier properties such as water vapor permeability and gas permeability compared to conventional plastic sheets coated with a hnylidene chloride copolymer resin emulsion. It has been further improved, and has a bent vinyl chloride layer of a sheet made of hard aluminum coated with polyvinyl chloride, which has been conventionally used as a lid material in FTP packaging as a drug packaging material.
The thermoformable barrier sheet according to the present invention can be easily heat-sealed and has better barrier properties as a drug packaging material.

Example 1 An isocyanate-based anchor coating agent (Coronet, manufactured by Nippon Polyurethane Industries, Ltd.) I, -75 was applied to a 100 μ thick sheet of hard vinyl chloride sheet (Sumitomo Bakelite Co., Ltd., Sumilite VSS-8142ZUV) using a gravure coating method. ) was coated and dried, then a vinylidene chloride copolymer resin emulsion (Saran Latex L-400 manufactured by Asahi Dow Co., Ltd.) was coated six times using the air knife coating method to form a vinylidene chloride copolymer resin layer with a thickness of 49μ. Then, two vinyl chloride sheets coated with a vinylidene chloride copolymer resin layer were wound into a roll and a polyurethane anchor coating agent (AD- manufactured by Toyo Morton Co., Ltd. 5
27,) by gravure coating method and after drying, At203
A vacuum-deposited film of 30OA was continuously deposited on the powder under a vacuum of 10-4 Torr, and polyethyleneimine (BORIMIN P manufactured by BASF Corporation) was applied as an anchor coating agent on the surfaces of the two vacuum-deposited films using a gravure coating method and dried. , Extrude polyethylene to a thickness of 35 μm from an extruder T-die and laminate the vacuum-deposited coating surfaces of two rolls together via an anchor coating agent to obtain a thermoformable barrier plastic laminate sheet with a total thickness of approximately 337 μm. Obtained. Barrier properties, thermoformability, heat sealability, etc. were as shown in the attached table.

Example 2 An isocyanate-based anchor coating agent (Coronet, manufactured by Nippon Polyurethane Industries, Ltd.) L-75 was applied to a 100 μ thick sheet of hard vinyl chloride sheet (Sumito Bakelite Co., Ltd., Sumilite VSS-8142Z [JV) by gravure coating. ) was coated and after drying, a vinylidene chloride copolymer resin emulsion (Saran Latex L-400 manufactured by Asahi Dow Co., Ltd.) was coated three times using the air knife coating method to form a vinylidene chloride copolymer resin layer with a thickness of 18μ. Two vinyl chloride sheets coated with a vinylidene chloride copolymer resin emulsion were wound into rolls. A polyurethane anchor coating agent (AD-527 manufactured by Toyo Morton Co., Ltd.) is applied to the surface of this vinylidene chloride-based resin layer using a gravure coating method and dried.
t20. powder at 700″ under a vacuum of 1O-4 Torr.
The vacuum-deposited film A was continuously deposited. Polyethyleneimine (BA) was applied as an anchor coating agent to the two vacuum-deposited film surfaces.
Borimin P (manufactured by SF Co., Ltd.) was coated and dried using the gravure coating method, and polyethylene was coated with a thickness of 60 μm using the extruder T-die.
The vacuum-deposited coating surfaces of two rolls were extruded and laminated together via an anchor coating agent to obtain a thermoformable barrier plastic laminate sheet with a total thickness of about 300 μm. The heat sealability of hard aluminum, which is the Ti material for PTp, with the vinyl chloride coating was as shown in the attached table.

Comparative Example 1 A biaxially stretched nylon film with a thickness of 25μ was coated with an equimolar mixture of silicon and silicon dioxide using a high-frequency induction heating continuous vapor deposition machine as a raw material, and the degree of vacuum was I x 10-' to 2.
X ] O-' Torr te'r 1
, 500; and then extrusion laminated with low density polyethylene to a thickness of 70 μm under normal conditions. Hard aluminum coated with vinyl chloride, which has barrier properties, thermoformability, and is a lid material for PTP. The heat sealability etc. with is shown in the attached table.

This film cannot be thermoformed as a packaging material for PTP, and the heat sealing strength between the polyethylene layer and the vinyl chloride layer coated on the hard aluminum of the lid material is low, and the barrier properties are also insufficient.

Comparative Example 2 A silicon compound having a thickness of 200 mm was vacuum-deposited on a polyester film having a thickness of 12 μm using silicon monoxide as a raw material in the same manner as in Comparative Example 1, and the film was laminated. This film cannot be thermoformed and is not suitable as a drug packaging material for PTI), and also cannot provide any heat sealability between the polyethylene layer and hard aluminum coated with vinyl chloride, which is the lid material.

The results are shown in the attached table.

Comparative Example 3 An isocyanate-based anchor coating agent was applied to a 100μ hard vinyl chloride sheet using a gravure coating method, and after drying, a vinylidene chloride-based copolymer resin emulsion was applied six times using an air knife coating method to coat vinylidene chloride and copolymer resin. Two vinyl chloride sheets coated with a vinylidene chloride copolymer resin layer were prepared by forming a polymer resin layer to a thickness of 49 μm and winding it into a roll. The vinylidene chloride copolymer resin layer of this sheet is treated with an anchor coating agent based on Isoshane-1 using the gravure coating method, and polyethylene is extruded from a T-die to a thickness of 35 μm and two rolls are laminated and thermoformed. The thermoformability and heat sealability with the vinyl chloride surface of hard aluminum coated with vinyl chloride, which is the lid material for PTP, are the same as in the examples, but the barrier properties were not tested. It has not yet reached the level of the barrier plastic laminate sheet for thermoforming.

Comparative Example 4 100 μ of hard vinyl chloride sheet used in Example 1
Apply At203 powder to 1O-4 Tor on one side of a thick sheet.
Two rolls were prepared on which a vacuum-deposited film of 500^ was continuously deposited under a vacuum of r. An isocyanate-based anchor coating agent is applied to the opposite side of the vacuum-deposited coating surface of these two rolls, that is, the hard vinyl chloride sheet surface, and after drying, a vinylidene chloride-based copolymer resin emulsion is applied six times to coat the vinylidene chloride-based copolymer resin emulsion. A copolymer resin layer was formed to a thickness of 49 μm and wound into a roll. A polyethylene imine anchor treatment agent was applied to the surface of this vinylidene chloride copolymer resin layer, and after drying, polyethylene was applied to the extruder T-die to a thickness of 30 μm.
The vinylithine chloride copolymer resin layers of two rolls were extruded and laminated together via an anchor coating agent to obtain a sheet with a total thickness of 332μ.The obtained sheet I was used for thermoforming according to the present invention. Compared to barrier sheets, the surface of the vacuum-deposited coating comes into direct contact with the mold during thermoforming, so the vacuum-deposited coating peels off from the hard vinyl chloride sheet, resulting in PTP.
It is also impossible to heat seal the aluminum cover with a vinyl chloride coating.

Comparative Example 5 100 μ of hard vinyl chloride sheet used in Example 1
An isocyanate-based anchor coating agent is coated on one side of a thick sheet using the gravure coating method. After drying, a vinylidene chloride-based copolymer resin emulsion is applied and dried to form a vinylidene chloride-based copolymer resin layer with a thickness of 12 μm, and then rolled. Two vinyl chloride sheets coated with a vinylidene chloride copolymer resin layer were wound up into a shape, and thereafter they were processed in the same manner as described in Example 2 and thermoformed to a total thickness of about 266 μm. Obtain a barrier plastic sheet for use. This thermoformable plastic sheet has thermoformability and heat sealability with vinyl chloride, which is made of hard aluminum coated with vinyl chloride, which is the lid material for PTP, and is equivalent to the thermoformable barrier plastic sheet according to the present invention. Since the coating amount of the vinylidene chloride copolymer resin emulsion is small, the barrier properties are poor and the object of the present invention is not met.

Comparative Example 6 100 μ of hard vinyl chloride sheet used in Example 1
Apply an isocyanate-based anchor coating agent to one side of a thick sheet using the gravure coating method. After drying, apply vinylidene chloride copolymer resin emulsion 10 times to a thickness of 77 μm.
Two vinyl chloride sheets coated with the vinylidene chloride copolymer resin layer were prepared and wound into a roll. Thereafter, processing was carried out as described in Example 2 to obtain a thermoforming barrier plastic laminate sheet with a total thickness of approximately 418μ.This thermoforming barrier plastic laminate sheet was coated with hard aluminum, which is the i-material for PTP. Heat sealability with vinyl chloride coated vinyl chloride.

The barrier properties are almost the same as the barrier plastic laminate sheet for thermoforming according to the present invention, but because the vinylidene chloride copolymer resin layer is too thick during thermoforming, foaming occurs between the layers, resulting in poor appearance and functionality. This also does not meet the purpose of the present invention.

Comparative Example 7 One side of the hard vinyl chloride sheet described in Example 1 was treated with an anchor coat, a vinylidene chloride copolymer resin layer was provided on the anchor coat treated side, and an anchor coat was applied on the surface of the hycoritene chloride copolymer resin layer, and the treatment Two rolls having vacuum-deposited coatings deposited on their surfaces were obtained.The vacuum-deposited coating surfaces of these two rolls were treated with a polyalkyleneimine-based anchor coating agent and a polyisocyanate-based anchor coating as an anchor coating treatment.11. An argyl titanate anchor coating agent, etc. is applied independently, and molten polypropylene is extruded to a thickness of 30 μm from an extruder T-Gui, and the vacuum-deposited coating surfaces of the two rolls are laminated together via the anchor coating agent. However, polypropylene had no adhesion between the surfaces of the vacuum-deposited coatings, and a laminate that could be used as a barrier plastic laminate sheet for thermoforming according to the present invention could not be obtained.

Regarding the thermoformability listed in the attached table, molding was performed using a maturing molding machine manufactured by Fuse Vacuum Co., Ltd. (model TM-4PW), and the molded product was not broken after thermoforming the plastic sheet, and the mold reproducibility with a thermoforming mold was evaluated. If the molded product is observed to be broken, it is marked with an
Those with no breakage were marked with an ○ mark.

Regarding the heat sealability of the hynyl chloride layer, which is heat-sealed to hard aluminum used as a lid material for PTP, use a regular heat sealer to
Heat seals at 80°C2 pressure 2.1kg/α2° time 1 second, heat sealing strength is 1.0 i, which has no problem in practical use
cq/ 15 en width or more is marked with ○, 10 is 9715m+
The width less than n is indicated by an X mark.

Water vapor transmission rate is measured according to JISZO208 and is 0.2
9/m2・24hr or more meets the objective of the present invention. Less than 2 hours/m''/24 hours is indicated by a circle.

The oxygen permeability was measured by the isobaric method at 23°C and was 0.4.
CC/ 2nd and 24th TLR, ATM and above wo X mark,
0.4 cc/No. 2-2 which meets the purpose of the present invention
Less than 4 hr, atm is indicated by a circle.If all or all of these characteristics are marked with a circle, they are financially satisfactory, and if there are any negative or X marks, they do not meet the purpose of the present invention. Therefore, Examples 11 and 2 fully meet the purpose as thermoformable barrier plastic sheets according to the present invention.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the barrier plastic laminate sheet for thermoforming of the present invention, and FIG. 2 shows the barrier glass laminated sheet for thermoforming of the invention. FIG. 2 is a partially cutaway perspective view showing an advantageous embodiment of the package used. 1. First thermoformable hard plastic sheet 1 and 2
...First anchor coat layer...First vinylidene chloride copolymer resin layer 4...
Second anchor coat layer 5...First inorganic metal compound vapor deposited layer 6...Front anchor coat layer 7...Polyethylene layer 8...Fourth anchor coat layer? ...Second inorganic metal compound vapor deposited layer 10...Fifth anchor coat layer 11...Second ring-stopping vinylidene copolymer resin layer 12...
・・Sixth anchor coat layer 1・・Second thermoformable plastic seal ・A
...Container B...Continued from page 1 of Month M, 72 Inventor Toshihiko Suzuki 2102-1 Osuna, Bold Hiratsuka, Ageo City Japan Polyflex Kogyo Co., Ltd. 71 Applicant Asahi Dow Co., Ltd. Tokyo 1-1-2 Yurakucho, Chiyoda-ku Proceedings Amendment Written April 20, 1980 Commissioner of the Japan Patent Office Shima 1) Tono Haruki 1 Indication of the case Patent application Sho F+7-31699 No. 2 Name of the invention Barrier properties for thermoforming Plastic laminated sheet, its manufacturing method and it? Package used 3 ・Relationship with the Calendar Incident Patent applicant: 1-1-2 Yurakucho, Chiyoda-ku, Tokyo Nichifu Polyflex Industry Co., Ltd. Representative: Fuka Hori 1-1-2 Yurakucho, Chiyoda-ku, Tokyo No. (046,) Asahi Dow Taishiki Company Representative Kado 1) Yoshi Yu 4, Agent Room 204, Sanshin Building, 1-4-1 Yurakucho, Chiyoda-ku, Tokyo" Tail Story 501-2138 "
Column 6 of ``Detailed Description of the Invention'', Oke-oh's Contents Specification, page 6, 14th column, ``Unable to be aged'' is corrected to ``Able to be aged.''

Claims (1)

[Claims] 1. A first thermoformable rigid plastic sheet. A first vinylidene chloride copolymer resin layer, a first inorganic metal compound vapor deposited layer, a polyethylene layer, a second inorganic metal compound vapor deposited layer, a second vinylidene chloride copolymer resin layer, and a second thermoformable A barrier plastic laminate sheet for thermoforming, characterized in that hard plastic sheets are successively laminated, and each vinylidene chloride copolymer resin layer has a thickness of 1.5 to 60 μm. 2. The barrier plastic laminate sheet for thermoforming according to claim 1, wherein the laminate has a total thickness of 150 to 2000μ. 3 The hard plastic sheet that can be aged is 30 mm thick.
Thermoformable barrier plastic laminate sheet 04 according to claim 1 or 2, which is a hard vinyl chloride sheet with a thickness of ~1000μ, wherein the inorganic metal compound vapor-deposited layer is
The barrier plastic laminate sheet for thermoforming according to claim 1 or 2, which is a vapor-deposited aluminum oxide layer having a thickness of 100 to 5000 mm. 5. The barrier plastic laminate sheet for thermoforming according to claim 1 or 2, wherein the polyethylene layer has a thickness of 20 to 70 μm. A vinylidene chloride copolymer resin emulsion was coated on one side of each of 62 thermoformable hard plastic sheets and dried to form a vinylidene chloride copolymer resin layer, and then a vinylidene chloride copolymer resin layer was formed on the vinyl IJ chloride copolymer resin layer. An inorganic metal compound vapor deposited layer is formed by vapor deposition, and then the sides of the inorganic metal compound vapor deposited layers are turned inward, and molten polyethylene is extruded between them and laminated to fix them together, or by dry lamination through a polyethylene film to fix them together. A method for producing a thermoformable barrier plastic laminated notebook characterized by the following: Z first thermoformable rigid plastic sheet. A first vinylidene chloride copolymer resin layer, a first inorganic metal compound vapor deposited layer, a polyethylene layer, a second inorganic metal compound vapor deposited layer, a second vinylidene chloride copolymer resin layer, and a second thermoformable A PTP consisting of a container thermoformed from a thermoformable barrier plastic laminated sheet made of hard plastic sheets laminated in sequence, and a sheet-like vinyl chloride-coated hard aluminum sheet sealing the container mouth.
packaging for