JPS6132134B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoformable barrier plastic laminate sheet formed by laminating plastic sheets. More specifically, it relates to a thermoformable barrier plastic laminate sheet as a packaging material for pharmaceutical products that require long-term quality maintenance, and the thermoformable barrier plastic laminate sheet referred to in the present invention is a thermoformable hard plastic. A vinylidene chloride 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 coated with the surface of the vacuum-deposited inorganic metal compound on the inside. This is a barrier plastic laminate sheet for thermoforming, which is made by laminating molten polyethylene by extrusion lamination using a T-die or by dry lamination with a polyethylene film interposed therebetween. Conventionally, barrier packaging materials for pharmaceuticals, etc. have been made by coating a plastic sheet with a vinylidene chloride copolymer resin emulsion, and then placing these two plastic sheets with the sides coated with the vinylidene chloride copolymer resin emulsion on the inside. Although molten polyethylene is laminated by extrusion lamination using a T-die, its performance as a PTP packaging material is insufficient and there are limits to the long-term quality maintenance of the packaged items. This 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 succeeded in improving transparency and thermoforming. We discovered a new fact that it is possible to simultaneously improve the properties, heat sealability of the PTP lid material with the vinyl chloride coated surface of hard aluminum, water vapor permeability, and oxygen permeability, leading to the completion of the present invention. That is, the present invention provides (1) a first thermoformable hard plastic sheet, a first vinylidene chloride copolymer resin layer, a first
An 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 sheet are sequentially laminated,
and a thermoformable barrier plastic laminate sheet, characterized in that each vinylidene chloride copolymer resin layer has a thickness of 1.5 to 60μ; (2) on one side of each of two thermoformable hard plastic sheets; A vinylidene chloride copolymer resin emulsion is applied and dried to form a vinylidene chloride copolymer resin layer, and an inorganic metal compound vapor deposited layer is formed by vapor deposition on the vinylidene chloride copolymer resin layer, and then the inorganic metal compound vapor deposited layer side is (3) A method for producing a barrier plastic laminated sheet for thermoforming, characterized in that the sheets are made to face inward, and molten polyethylene is extruded and laminated between them, or dry laminated and fixed together through a polyethylene film, and (3) a first thermoformable rigid plastic sheet; a first vinylidene chloride copolymer resin layer;
A thermoformable barrier formed by sequentially laminating an inorganic metal compound deposited layer, a polyethylene layer, a second inorganic metal compound deposited layer, a second vinylidene chloride copolymer resin layer, and a second thermoformable hard plastic sheet. The present invention relates to a PTP package consisting of a container thermoformed from a plastic laminate sheet and a sheet-like vinyl chloride-coated hard aluminum lid for sealing the container opening. Next, the thermoformable barrier plastic laminate sheet of the present invention will be explained with reference to the drawings. FIG. 1 is a schematic cross-section showing a preferred embodiment of the thermoformable barrier plastic laminate sheet of the present invention. 1st
In the figure, 1 is a first thermoformable hard plastic sheet, 2 is a first anchor coat layer, 3 is a first vinylidene chloride copolymer resin layer, and 4 is a second thermoformable hard plastic sheet.
5 is the first inorganic metal compound vapor deposited layer, 6 is the third anchor coat layer, 7 is the polyethylene layer, 8 is the fourth anchor coat layer, 9 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, 1
3 is a second thermoformable rigid plastic sheet. The first and second thermoformable hard plastic sheets 1 and 13 are preferably those that can be easily pressure-formed or vacuum-formed by contact heating or radiation heating, and that have shape retention properties after molding. From this point of view, for example, hard vinyl chloride sheets, unstretched polypropylene sheets, polystyrene sheets, cellulose acetate sheets, polycarbonate sheets, and unstretched high-density polyethylene sheets are used. In particular, hard vinyl chloride sheets are particularly preferably used because they have excellent heat sealability with the vinyl chloride coated surface of hard aluminum, which is the lid material for PTP. The thickness of the thermoformable rigid plastic sheet is not particularly limited, but is usually 30 to 1000μ.
It is preferable to use one with a certain thickness. Considering the usage, the overall thickness of the laminated sheet is 150 mm.
~2000μ laminated sheets are chosen. First thermoformable rigid plastic sheet 1
and a second thermoformable rigid plastic sheet 1
3 is usually made of the same material, but may be made of a different material. The front and/or back sides of the first and/or second thermoformable rigid plastic sheets may be provided with desired printing, thereby providing even greater display and decorative effects. The first and second vinylidene chloride copolymer resin layers 3 and 11 are preferably those having high barrier properties without impairing the thermoformability of the thermoformable hard plastic sheet. From this point of view, during copolymerization, vinylidene chloride monomer accounts for 80 to 95%.
An emulsion of a vinylidene chloride copolymer resin having a copolymerization composition of 5% to 20% (by weight, same hereinafter) and a vinyl chloride monomer (for example, Saran Latex (trade name of Asahi Dow Co., Ltd.)) the first and second thermoformable rigid plastic sheets 1,1;
It is formed by coating and drying directly or through the first or sixth anchor coat layer 2, 12 on one side of the anchor coat layer 3. The formation method is not limited in any way, and conventional methods such as air knife coating, gravure coating, smoothing coating, and roll coating can be adopted, but vinylidene chloride copolymer resin layers have sufficient barrier properties. In order to achieve this, it is necessary to apply a vinylidene chloride copolymer resin emulsion to a thermoformable hard plastic sheet and then dry it to evaporate the water and promote crystallization of the vinylidene chloride copolymer resin. However, a temperature range must be selected that does not cause thermal deformation such as thermal contraction. If the drying temperature is low, the vinylidene chloride copolymer resin emulsion will not be sufficiently dried, and the resulting vinylidene chloride 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 preferably about 90 to 150°C. The thickness of the vinylidene chloride copolymer resin layer is usually selected from a range of 1.5 to 60μ, preferably about 23 to 55μ. If the thickness is less than 1.5μ, the barrier properties are poor, and if the thickness is greater than 60μ, the barrier properties will not improve, so anything thicker than 60μ is economically disadvantageous. First and second inorganic metal compound vapor deposited layers 5, 9
For example, silicon, aluminum, titanium, selenium,
A transparent inorganic metal compound mainly consisting of magnesium, barium, indium, calcium, zirconium, thorium, thallium, tantalum, zinc, etc., or an oxide, halide, nitride, etc. of these, alone or in a mixture thereof, is used as the first and second material. It is formed by vapor deposition on the surfaces of the second vinylidene chloride copolymer resin layers 3 and 11 directly or via the second and fifth anchor coat layers 4 and 10. The formation method is not limited at all, and any conventional method such as a vacuum deposition method, a reactive deposition method, a sputtering method, a reactive sputtering method, an ion plating method, or a reactive ion plating method can be employed. The thickness of the inorganic metal compound vapor deposited layer is 100 mm
It is selected from the range of about 5000 Å, preferably about 300 to 800 Å. If the thickness is less than 100 Å, the barrier properties are poor, and even if the thickness is greater than 5000 Å, the barrier properties are difficult to improve, so anything thicker than 5000 Å is economically disadvantageous. A polyethylene layer 7 is formed between the first and second inorganic metal compound vapor deposited layers 5 and 9 from a T-die.
Molten polyethylene at a temperature of about 280 to 330°C is extruded and formed, and at the same time, both are laminated and fixed 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 rigid plastic sheet to be laminated, but is usually 20-70μ, preferably 30μ.
Selected from the range of ~50μ. 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 extruded from the T-die and cooled, it will not be completely cooled and the lamination will fail. This is undesirable because the thermoformable hard plastic sheet that is being molded shrinks and deforms due to the melting heat of the polyethylene, resulting in wavy wrinkles in the product. The thickness of polyethylene film in dry lamination method is T-
Usually similar to die extrusion lamination method
It is selected from a range of about 20 to 70μ, preferably about 30 to 50μ. If the thickness of the polyethylene film is less than 20 μm, it is not preferable because it has little impact cushioning effect and wrinkles are likely to occur in the polyethylene film during dry lamination processing. Also 70μ
If it is thicker, it is difficult to slit the perforations in PTP packaging. In the present invention, a polyethylene layer with a thickness of 20 to 70 μm is provided between the thick thermoformable hard plastic sheets, so that it acts as a shock absorber. It also exhibits sufficient adhesive strength for adhesion. Anchor coat layer 2, 4, 6, 8, 10, 12
is the adhesion between a thermoformable hard plastic sheet and a vinylidene chloride-based copolymer resin layer, between a vinylidene chloride-based copolymer resin layer and an inorganic metal compound vapor-deposited layer, or between an inorganic metal compound vapor-deposited layer and a polyethylene layer. It is set when the quality is bad. Examples of anchor coating agents include those based on alkyl titanates, polyisocyanates, and polyalkyleneimines. Its thickness is usually about 0.1 to 2 microns. 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 thermoforming the thermoformable barrier plastic laminate sheet of the present invention, and B is a lid material made of sheet-like vinyl chloride coated hard aluminum. The barrier plastic sheet for thermoforming thus obtained has better barrier properties such as water vapor permeability and gas permeability than conventional plastic sheets coated with vinylidene chloride copolymer resin emulsion. The polyvinyl chloride layer of a sheet made of hard aluminum coated with polyvinyl chloride, which has been further improved as a lid material in PTP packaging as a drug packaging material, and the thermoformable barrier sheet according to the present invention. It can be easily heat-sealed and has better barrier properties as a drug packaging material. Example 1 100 μ of hard vinyl chloride sheet (Sumilite VSS-8142ZUV manufactured by Sumitomo Bakelite Co., Ltd.)
An isocyanate-based anchor coating agent (Coronate L-75 manufactured by Nippon Polyurethane Industries Co., Ltd.) was coated on a thick sheet using the gravure coating method, and after drying, vinylidene chloride-based copolymer resin emulsion (Saran Latex L- manufactured by Asahi Dow Co., Ltd.) was applied. 400) was coated six times using the air knife coating method to form a vinylidene chloride copolymer resin layer with a thickness of 49μ, and the vinyl chloride sheet coated with the vinylidene chloride copolymer resin layer was wound into a roll. A polyurethane anchor coating agent (AD-527, manufactured by Toyo Morton Co., Ltd.) was coated on the vinylidene chloride copolymer resin layer surface of two sheets prepared using the gravure coating method. After drying, Al ₂ O ₃ powder was applied at 10 ^-4 Torr. A 300 Å vacuum-deposited film was continuously deposited under the vacuum of Polyethylene was extruded to a thickness of 35μ and the vacuum-deposited coating surfaces of the two rolls were laminated together via an anchor coating agent to obtain a thermoformable barrier plastic laminate sheet having a total thickness of about 337μ. barrier properties,
Thermoformability, heat sheet properties, etc. were as shown in the attached table. Example 2 100μ of hard vinyl chloride sheet (Sumilite VSS-8142ZUV manufactured by Sumitomo Bakelite Co., Ltd.)
An isocyanate-based anchor coating agent (Coronate L-75 manufactured by Nippon Polyurethane Industries Co., Ltd.) was applied to a thick sheet using the gravure coating method. After drying, vinylidene chloride-based copolymer resin emulsion (Saran Latex L- manufactured by Asahi Dow Co., Ltd.) was applied. 400) three times using the air knife coating method to form a vinylidene chloride copolymer resin layer with a thickness of 18μ, and then wound two vinyl chloride sheets coated with vinylidene chloride copolymer resin emulsion into a roll. Created. A polyurethane anchor coating agent (AD-527 manufactured by Toyo Morton Co., Ltd.) was applied to the surface of this vinylidene chloride copolymer resin layer using a gravure coating method. After drying, Al ₂ O ₃ powder was applied under a vacuum of 10 ^-4 Torr to 700 Å. Vapor deposition films were continuously deposited. Polyethyleneimine (Polymin P manufactured by BASF Corporation) was applied as an anchor coating agent to the two vacuum-deposited film surfaces using the gravure coating method, dried, extruded the polyethylene to a thickness of 60μ from an extruder T-die, and then vacuum-coated the two rolls. The vapor-deposited coatings were laminated together via an anchor coating agent to obtain a thermoformable barrier plastic laminated sheet with a total thickness of approximately 300μ. The heat sealability with the vinyl chloride coated surface was as shown in the attached table. Comparative Example 1 A biaxially stretched nylon film with a thickness of 25 μm was coated with an equimolar mixture of silicon and silicon dioxide using a high-frequency induction heating continuous vapor deposition machine at a vacuum degree of 1×.
Barrier properties and thermoformability made by depositing a silicon compound to a thickness of 1500 Å at 10 ^-4 to 2 x 10 ^-4 Torr, and then extrusion laminating a low density polyethylene layer to a thickness of 70 μ under normal conditions. The heat sealability with vinyl chloride-coated hard aluminum, which is the lid material for PTP, is shown in the attached table. This film cannot be thermoformed as a packaging material for PTP, and the strength of the heat seal between the vinyl chloride layer coated on the hard aluminum of the lid material and the polyethylene layer is low, and its barrier properties are also insufficient. Comparative Example 2 In the same manner as in Comparative Example 1, a silicon compound was vacuum-deposited to a thickness of 200 Å on a polyester film having a thickness of 12 μm using silicon monoxide as a thick material, and the film was laminated. This film cannot be thermoformed and is not suitable as a drug packaging material for PTP, and it also cannot provide any heat sealability between the polyethylene layer and the 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 using an air knife coating method.
Apply multiple coats to increase the thickness of the vinylidene chloride copolymer resin layer.
Two vinyl chloride sheets coated with a vinylidene chloride copolymer resin layer were prepared, each having a thickness of 49μ and wound into a roll. An isocyanate-based anchor coating agent is applied to the vinylidene chloride-based copolymer resin layer of this sheet by gravure coating, and T
- Extrude polyethylene from the die to a thickness of 35μ 2
A plastic sheet for thermoforming was obtained by laminating rolls of books, and its thermoformability and heat sealability with the vinyl chloride surface of hard aluminum, which is the lid material for PTP, coated with vinyl chloride, are the same as in the examples. However, the barrier properties have not reached the level of the barrier plastic laminate sheets for thermoforming of Examples. Comparative Example 4 The hard vinyl chloride sheet used in Example 1
Al ₂ O ₃ powder on one side of a 100μ thick sheet
Two rolls were prepared on which a 500 Å vacuum-deposited film was continuously deposited under a vacuum of 10 ^-4 Torr. An isocyanate-based anchor coating agent is applied to the surface opposite to the vacuum-deposited coating surface of these two rolls, that is, the surface of the hard vinyl chloride sheet, and after drying, 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 polyethyleneimine anchor coating agent is applied to the surface of the vinylidene chloride copolymer resin layer, and after drying, polyethylene is extruded to a thickness of 30μ from an extruder T-die, and the vinylidene chloride copolymer resin layer surfaces of the two rolls are coated together through the anchor coating agent. The resulting sheet was laminated to obtain a sheet with a total thickness of 332μ.Compared to the barrier sheet for thermoforming according to the present invention, the surface of the vacuum-deposited coating was in direct contact with the mold during thermoforming. As a result, the vacuum-deposited coating peels off from the hard vinyl chloride sheet surface, making it impossible to heat-seal the vinyl chloride-coated surface of the hard aluminum of the PTP lid material. Comparative Example 5 The hard vinyl chloride sheet used in Example 1
Apply an isocyanate-based anchor coating agent on one side of a 100 μ thick sheet using the gravure coating method. After drying, apply a vinylidene chloride-based copolymer resin emulsion and dry.
After creating two vinyl chloride sheets coated with a vinylidene chloride copolymer resin layer formed into a 1.2μ film and wound into a roll, the entire film was processed in the same manner as described in Example 2. Thickness is approximately 266μ
A barrier plastic sheet for thermoforming was obtained. This plastic sheet for thermoforming has thermoformability and heat sealability with vinyl chloride coated on hard aluminum, which is the PTP lid material, as the barrier plastic sheet for thermoforming 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 present invention is not suitable and does not meet the purpose of the present invention. Comparative Example 6 The hard vinyl chloride sheet used in Example 1
Apply an isocyanate-based anchor coating agent to one side of a 100 μ thick sheet using the gravure coating method. After drying, apply a 10% vinylidene chloride copolymer resin emulsion.
A vinylidene chloride copolymer resin layer with a thickness of 77 μm was applied by repeated coating, and two vinyl chloride sheets coated with the vinylidene chloride copolymer resin layer were wound into rolls. Thereafter, processing was carried out as described in Example 2 to obtain a thermoformable barrier plastic laminate sheet having a total thickness of approximately 418μ.This thermoformable barrier plastic laminate sheet was made of PTP.
The heat sealing properties and barrier properties of vinyl chloride coated on hard aluminum, which is the lid material, are almost the same as the barrier plastic laminated sheet for thermoforming according to the present invention, but during thermoforming, the chloride Since the vinylidene copolymer resin layer is too thick, foaming occurs between the layers, which does not meet the objectives of the present invention both in terms of appearance and functionality. 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 used on the anchor coat treated side, the vinylidene chloride copolymer resin layer was treated with an anchor coat, and the Two rolls were obtained with vacuum-deposited coatings deposited on the treated surfaces. A polyalkylene imine anchor coating agent, a polyisocyanate anchor coating agent, an alkyl titanate anchor coating agent, etc. are individually coated on the vacuum-deposited film surfaces of these two rolls as an anchor coating treatment, and the extruder T- Extrude molten polypropylene from a die to a thickness of 30μ,
An attempt was made to laminate the vacuum-deposited coating surfaces of two rolls together using an anchor coating agent, but polypropylene had no adhesive force between the vacuum-deposited coating surfaces at all, and the barrier plastic laminate sheet for thermoforming according to the present invention could not be used. No laminate product could be obtained. Regarding the thermoformability listed in the attached table, molding was performed using a thermoforming machine manufactured by Fuse Vacuum Co., Ltd. (model TM-4PW).
Breakage of the molded product after thermoforming the plastic sheet,
When observing the mold reproducibility using a thermoforming mold, molded products with cracks were marked with an x mark, and molded products with no cracks were marked with an ○ mark. Heat-sealability with the vinyl chloride layer, which is made of hard aluminum coated with vinyl chloride used as a lid material for PTP, was performed using a regular heat sealer at a temperature of 180℃, a pressure of 2.1Kg/cm ² , and a time of 1 second. If the heat sealing strength is 1.0Kg/15mm width or more, which does not affect practical use, mark ○, 1.0Kg/
Widths less than 15 mm are indicated by an x mark. Water vapor transmission rate is measured according to JISZ0208 and is 0.2
g/m ² ·24 hr or more is represented by an x mark, and less than 0.2 g/m ² ·24 hr, which meets the purpose of the present invention, is represented by an ○ mark. The oxygen permeability was measured using the isobaric method at 23°C and was 0.4.
cc/m ² ·24 hr · atm or more is represented by an x mark, and less than 0.4 cc/m ² ·24 hr · atm, which meets the purpose of the present invention, is represented by an ○ mark. If all of these characteristics are marked with an O mark, the material is comprehensively satisfied, and if even one property is marked with an X mark, the object of the present invention is not met. Therefore, Examples 1 and 2 sufficiently fulfill the purpose as thermoformable barrier plastic sheets according to the present invention. 【table】

[Brief explanation of the drawing]

FIG. 1 is a schematic sectional view showing a preferred embodiment of the barrier plastic laminate sheet for thermoforming of the present invention, and FIG. 2 is a schematic sectional view showing a preferred embodiment of a package using the barrier plastic laminate sheet for thermoforming of the present invention. FIG. DESCRIPTION OF SYMBOLS 1... First thermoformable hard plastic sheet, 2... First anchor coat layer, 3... First vinylidene chloride copolymer resin layer, 4... Second
Anchor coat layer, 5... first inorganic metal compound vapor deposited layer, 6... third anchor coat layer, 7...
...Polyethylene layer, 8...Fourth anchor coat layer, 9...Second inorganic metal compound vapor deposition layer, 10...
...Fifth anchor coat layer, 11...Second vinylidene chloride copolymer resin layer, 12...Sixth anchor coat layer, 13...Second thermoformable plastic sheet, A...Container, B... Lid material.

Claims (1)

[Scope of Claims] 1. A first thermoformable hard plastic sheet, a first vinylidene chloride copolymer resin layer, a first
inorganic metal compound vapor deposited layer, polyethylene layer, second
an inorganic metal compound vapor-deposited layer, a second vinylidene chloride copolymer resin layer, and a second thermoformable hard plastic sheet are sequentially laminated, and
The thickness of each vinylidene chloride copolymer resin layer is
A thermoformable barrier plastic laminate sheet having a thickness of 1.5 to 60μ. 2. The barrier plastic laminate sheet for thermoforming according to claim 1, wherein the total thickness of the laminate is 150 to 2000μ. 3. The thermoformable barrier plastic laminate sheet according to claim 1 or 2, wherein the thermoformable hard plastic sheet is a hard vinyl chloride sheet having a thickness of 30 to 1000 μm. 4. The barrier plastic laminate sheet for thermoforming according to claim 1 or 2, wherein the inorganic metal compound vapor-deposited layer is an aluminum oxide vapor-deposited layer having a thickness of 100 to 500 Å. 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. 6. A vinylidene chloride copolymer resin emulsion is coated on one side of each of two thermoformable hard plastic sheets and dried to form a vinylidene chloride copolymer resin layer, and an inorganic resin layer is formed on the vinylidene chloride copolymer resin layer. A metal compound vapor-deposited layer is formed by vapor deposition, and then the inorganic metal compound vapor-deposited layer side is turned inward, and molten polyethylene is extruded between them and laminated to fix them together, or by dry lamination through a polyethylene film. A method for producing a thermoformable barrier plastic laminated sheet characterized by fixation. 7 First thermoformable hard plastic sheet, first vinylidene chloride copolymer resin layer, first
inorganic metal compound vapor deposited layer, polyethylene layer, second
A container obtained by thermoforming a thermoformable barrier plastic laminate sheet in which an inorganic metal compound vapor-deposited layer, a second vinylidene chloride copolymer resin layer, and a second thermoformable hard plastic sheet are sequentially laminated; Consists of a sheet-like vinyl chloride-coated hard aluminum lid that seals the container mouth.
Packaging for PTP.