JP2019199568A - Biomass plastic sheet and PTP sheet - Google Patents

Abstract

To provide a biomass plastic sheet having excellent transparency and blister moldability.SOLUTION: A biomass plastic sheet has a layer A containing a cyclic olefinic resin, a high-density polyethylene and a low-density polyethylene. In the whole sheet, the amount of biomass-derived resin is 25 wt.% or more.SELECTED DRAWING: None

Description

  The present invention relates to a biomass plastic sheet and a PTP sheet.

  The package that wraps the packaged items such as pharmaceuticals, foodstuffs, drinking water, etc. has contents preservation properties such as water vapor barrier properties and gas barrier properties, design properties such as transparency, operability such as content takeout properties, etc. It is required to have characteristics. In order to meet these demands, a single-layer sheet made of polyvinyl chloride (PVC) or polypropylene (PP), or a package in which a PVC layer or PP layer is laminated on both sides of polyethylene (PE) by a dry laminate method or a heat laminate method. Has been used.

  However, a package formed of a single layer sheet of PVC or PP has a problem that it is inferior in water vapor barrier properties. Moreover, although the laminated body of PE and PVC or PP was able to solve about water vapor | steam barrier property, there existed a problem about the moldability of a blister pack and the division | segmentation ease of the obtained blister pack. Furthermore, it is difficult to bond and laminate the PE layer and the PP layer by fusion, and there is a problem that it cannot be put to practical use.

The conventional package is made of a fossil resource-derived material, but in recent years, development of a package using plant-derived biomass plastic has become active in order to reduce the amount of fossil resource used. .
As a package using such a biomass plastic, Patent Document 1 describes a biomass plastic sheet having a central layer containing high-density polyethylene (HDPE), biomass HDPE, and a cyclic olefin resin.

JP 2014-226829 A

  Although the biomass plastic sheet described in Patent Document 1 is excellent in water vapor barrier properties, it has transparency and formability when forming a PTP (press through pack) sheet from the sheet (hereinafter referred to as “blister formability”). There was room for improvement.

  This invention is made | formed in view of the said problem, and makes it a subject to provide the biomass plastic sheet which is excellent in transparency and blister moldability.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a specific biomass plastic sheet, and have completed the present invention.
A configuration example of the present invention is as follows.

[1] A biomass plastic sheet having a layer A containing a cyclic olefin-based resin, high-density polyethylene and low-density polyethylene,
The amount of the resin derived from biomass in the entire sheet is 25% by weight or more,
Biomass plastic sheet.

[2] The biomass plastic sheet according to [1], having a first layer, a second layer, and a third layer in this order, wherein the second layer is the layer A.
[3] The biomass plastic sheet according to [2], which is a laminated sheet formed by a coextrusion method.

[4] The content of the cyclic olefin-based resin in the layer A is 1 to 75% by weight with respect to 100% by weight in total of the cyclic olefin-based resin, the high-density polyethylene, and the low-density polyethylene. [3] The biomass plastic sheet according to any one of [3].
[5] The content of the high-density polyethylene in the layer A is 1 to 98% by weight with respect to 100% by weight in total of the cyclic olefin resin, the high-density polyethylene, and the low-density polyethylene. 4]. The biomass plastic sheet according to any one of [4].
[6] The content of the low density polyethylene in the layer A is 1 to 98% by weight with respect to 100% by weight in total of the cyclic olefin-based resin, the high density polyethylene, and the low density polyethylene. [5] A biomass plastic sheet according to any one of [5].

[7] The biomass plastic sheet has a surface layer,
The biomass plastic sheet according to any one of [1] to [6], wherein the surface layer contains a propylene-based resin.
[8] The biomass plastic sheet has a surface layer,
The biomass plastic sheet according to any one of [1] to [7], wherein the surface layer contains linear low-density polyethylene.

  [9] A PTP sheet comprising the biomass plastic sheet according to any one of [1] to [8].

According to the present invention, a biomass plastic sheet excellent in transparency and blister moldability can be easily obtained.
Moreover, according to this invention, the biomass plastic sheet which is excellent also in water vapor | steam barrier property and the preservability of a to-be-packaged object can be obtained easily.

≪Biomass plastic sheet≫
The biomass plastic sheet according to the present invention (hereinafter also referred to as “the present sheet”) is a biomass plastic sheet having a layer A containing a cyclic olefin-based resin, high-density polyethylene and low-density polyethylene,
The amount of biomass-derived resin in the entire sheet is 25% by weight or more.
Since this sheet has the layer A, even if the amount of the resin derived from biomass is 25% by weight or more, it is excellent in transparency and blister moldability, and also in the water vapor barrier property and the preservability of the package. Excellent.
Moreover, this sheet | seat can reduce the usage-amount of a fossil resource significantly compared with the past, and it contributes to suppression of the raise of the carbon dioxide density | concentration in air | atmosphere, and contributes to reducing environmental impact.

  The use of this sheet is not particularly limited, and examples thereof include a packaging sheet for packaging an article to be packaged such as a pharmaceutical product, a food product, and drinking water, and more preferably used for a PTP sheet for packaging a pharmaceutical product.

<Cyclic olefin resin>
The cyclic olefin resin contained in the layer A is not particularly limited as long as it is a (co) polymer containing a structural unit derived from a cyclic olefin.
When the layer A contains a cyclic olefin-based resin, a sheet excellent in water vapor barrier properties, blister moldability, transparency, smoothness, and the like can be easily obtained, and further, this sheet containing the cyclic olefin-based resin is used. Thus, it is possible to obtain a PTP sheet that is excellent in splitting ease (PTP sheet use evaluation).
The cyclic olefin resin contained in the layer A may be one type or two or more types.

Cyclic olefin resins include cyclic olefin ring-opening (co) polymers, cyclic olefin addition (co) polymers, hydrogenated products of these (co) polymers, the (co) polymers or hydrogenated products thereof. And graft modified products in which is modified with an unsaturated carboxylic acid or a derivative thereof.
Among these, a copolymer of a cyclic olefin and a monomer copolymerizable with the olefin, particularly an α-olefin such as ethylene or propylene is preferable.

  The cyclic olefin is not particularly limited, and examples thereof include norbornene, 6-methylnorbornene, 6-ethylnorbornene, 5-propylnorbornene, 6-n-butylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,6- Norbornene compounds such as dimethylnorbornene, 5-phenylnorbornene and 5-benzylnorbornene; 8-methyltetracyclo-3-dodecene, 8-ethyltetracyclo-3-dodecene, 5,10-dimethyltetracyclo-3-dodecene, etc. Tetracyclododecene compounds: cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-te Rahidoro 4,7-methano -1H- indene cycloalkene compounds such as; the compounds described in 2005-263287 JP 2001-199175, and the like.

  Examples of the monomer copolymerizable with the cyclic olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3- An α-olefin having 2 to 20 carbon atoms such as ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadiene; , Non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene.

  Examples of the cyclic olefin resin include, for example, JP-A-60-168708, JP-A-61-115916, JP-A-61-271308, JP-A-3-14882, and JP-A-3-122137. The resin manufactured according to the well-known resin described in gazette and Unexamined-Japanese-Patent No. 2005-263287, a well-known method, etc. can be mentioned.

  Commercially available products may be used as the cyclic olefin-based resin. Examples of the commercially available products include “ZEONOR” series (manufactured by ZEON Corporation), “Apel” series (manufactured by Mitsui Chemicals, Inc.), and “TOPAS”. Series (manufactured by Polyplastics Co., Ltd.).

The melt volume rate (MVR) measured according to ISO 1133 (190 ° C., 2.16 kg) of the cyclic olefin resin is the fluidity of the other layer when the sheet is a laminate of layer A and the other layer. However, it is preferably 0.5 to ⁵ cm 3/10 minutes, more preferably 1 to ³ cm 3/10 minutes.

  The content of the cyclic olefin-based resin in the layer A is such that a sheet excellent in water vapor barrier properties, blister moldability, transparency and smoothness can be easily obtained. And preferably 1 to 75% by weight, more preferably 3 to 60% by weight, still more preferably 5 to 40% by weight, and particularly preferably 10 to 30% by weight based on 100% by weight of the low density polyethylene.

<High density polyethylene>
Since the layer A contains high-density polyethylene (hereinafter also referred to as “HDPE”), a sheet excellent in strength, transparency, water vapor barrier property, ease of taking out contents, and the like can be obtained.
The HDPE contained in the layer A may be one type or two or more types.

The density measured according to JIS K 7112 of HDPE is 0.942 g / cm ³ or more, and preferably 0.945 to 0.970 g from the viewpoint that a sheet having a high water vapor barrier property can be easily obtained. / Cm ³ , more preferably 0.95 to 0.967 g / cm ³ .

  The MFR measured according to HDPE JIS K 7210 is preferably from 0.1 to 10 g / 10 min, more preferably from the viewpoint that a sheet having good pocket formability can be easily obtained by blister molding. 0.5 to 6 g / 10 min.

HDPE is not only a homopolymer of ethylene, but also a copolymer of ethylene and an α-olefin such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Good.
HDPE can be obtained by synthesis by a conventionally known method. Moreover, as HDPE, you may use a commercial item.

The HDPE may be a biomass-derived HDPE from the viewpoint of suppressing an increase in the amount of CO ₂ in the atmosphere and leading to saving of petroleum resources.

  The biomass is not particularly limited, but sugarcane (including bagasse), corn, starch, castor oil, crushed tatami (used waste tatami), wood chips, wood flour, sawdust, paper waste, grass sorghum, sugar beet squeezed Examples include grass, rice straw, and other vegetation, coniferous materials, hardwood materials, non-tree materials, and wastes of these materials.

The biomass-derived HDPE is not particularly limited as long as it is an HDPE obtained using biomass-derived ethylene as a raw material. Specifically, a plant using ethylene synthesized using an alcohol obtained by fermenting a plant as a raw material is used. HDPE of origin is mentioned.
More specifically, a sugar solution or starch obtained from the biomass is fermented by a microorganism such as yeast by a conventionally known method to produce bioethanol, which is heated in the presence of a catalyst, and subjected to an intramolecular dehydration reaction. In the presence of a conventional catalyst in the same manner as the synthesis of fossil fuel-derived HDPE, using ethylene obtained by equalization and optionally α-olefin (eg 1-butene, 1-hexene) as a copolymerization monomer And HDPE obtained by (co) polymerization with (1).
As the copolymerization monomer, in addition to the α-olefin derived from biomass, a comonomer derived from fossil fuel generally used in the synthesis of conventional high-density polyethylene may be used.

  A commercial product may be used as the HDPE derived from biomass.

  The content of HDPE in the layer A is such that a sheet excellent in strength, transparency, water vapor barrier property, and ease of taking out the contents can be easily obtained. And it is preferably 1 to 98% by weight, more preferably 5 to 90% by weight, further preferably 10 to 80% by weight, and particularly preferably 30 to 75% by weight with respect to 100% by weight of the low density polyethylene.

<Low density polyethylene>
Since the layer A contains low density polyethylene (hereinafter also referred to as “LDPE”), a sheet having excellent transparency and blister moldability can be obtained.
The LDPE contained in the layer A may be one type or two or more types.

The density measured according to ASTM D 1505 of LDPE is preferably 0.910 to 0.930 g / cm ³ , more preferably 0.915, from the viewpoint that a sheet excellent in transparency can be easily obtained. ˜0.924 g / cm ³ .

  The MFR measured according to ASTM D 1238 of LDPE is preferably 0.1 to 10 g / 10 min, more preferably from the viewpoint that a sheet having good pocket formability can be easily obtained by blister molding. 0.5 to 6 g / 10 min.

  As LDPE, a commercial item may be used and it may synthesize | combine and obtain by a conventionally well-known method.

  The LDPE may be a homopolymer of ethylene, or may be a low density polyethylene obtained by polymerizing in the presence of a metallocene catalyst or the like using ethylene as a main component and α-olefin as a subcomponent. . As the α-olefin, one or more of α-olefins having 3 to 40 carbon atoms, preferably 4 to 35 carbon atoms, more preferably 4 to 30 carbon atoms are used, for example, α-olefins having 3 to 8 carbon atoms. And an α-olefin having 10 to 26 carbon atoms can be used in combination. When the low density polyethylene is a copolymer, the content of α-olefin is preferably 3 to 15 mol% with respect to the copolymer.

The LDPE may be a biomass-derived LDPE from the viewpoint of suppressing an increase in the amount of CO ₂ in the atmosphere and leading to saving of petroleum resources.
Biomass-derived LDPE can be synthesized according to a conventionally known method for synthesizing LDPE using the biomass-derived raw materials listed in the HDPE column.
Moreover, you may use a commercial item as LDPE derived from biomass.

  The content of LDPE in the layer A is a cyclic olefin from the viewpoint that a sheet excellent in transparency and blister formability can be easily obtained while being excellent in water vapor barrier properties and preservability of the package. 1 to 98% by weight, more preferably 5 to 90% by weight, still more preferably 10 to 80% by weight, and particularly preferably 15 to 60% by weight based on the total of 100% by weight of the resin, high density polyethylene and low density polyethylene. % By weight, more preferably 30 to 60% by weight.

<Other ingredients>
The layer A is preferably a layer composed of the cyclic olefin-based resin, HDPE, and LDPE in consideration of using the sheet as a package for packaging an article to be packaged such as pharmaceuticals, foodstuffs, and drinking water. However, if necessary, other components other than the cyclic olefin-based resin, HDPE, and LDPE may be included within a range not impairing the effects of the present invention.

  Examples of the other components include colorants, various fillers, heat stabilizers, neutralizers, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, and nucleating agents.

  Examples of the coloring pigment include azo pigments, pearl pigments such as quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica. Examples of the filler include talc, calcium carbonate, silica, alumina, carbon black, zinc oxide, zeolite, hydrotalcite, glass fiber, paper powder, and wood powder. Examples of the heat stabilizer include hindered phenols, sulfurs, and phosphorus compounds. Examples of the neutralizing agent include stearic acid metal salts and hydrotalcite. Examples of the ultraviolet absorber include benzotriazole, benzoate, benzophenone, and benzotriazine compounds. Examples of the light stabilizer include hindered amine compounds. Examples of the lubricant include hydrocarbons, fatty acids, fatty acid amides, metal soaps, esters, and fluorine compounds. Examples of the nucleating agent include sorbitol compounds.

<Method for producing layer A>
The layer A can be produced, for example, by (dry) blending the cyclic olefin resin, HDPE, LDPE and other components as necessary, and molding the sheet into a sheet by a known method such as a melt molding method. it can.

<Structure of biomass plastic sheet>
The sheet is not particularly limited as long as it includes the layer A, and may be a sheet composed of a single layer A, but is more suitable as a package for packaging an article to be packaged such as pharmaceuticals, foodstuffs, and drinking water. The first layer, the second layer, and the third layer are in this order from the viewpoint of being excellent in the moldability when producing the sheet and the blister formability when producing the PTP sheet from the sheet. And the second layer is preferably a laminated sheet which is the layer A, and more preferably a laminated sheet comprising a first layer, a second layer and a third layer. In the case of a laminated sheet composed of these three layers, the first layer and / or the third layer is the surface layer of the sheet. That is, in the present invention, at least one of the outermost layers in the sheet is referred to as a surface layer.
Further, if necessary, a multilayer sheet in which a layer such as a gas barrier layer such as an oxygen barrier layer, a gas absorption layer, a moisture proof layer, a light shielding layer, a bleed out prevention layer is laminated on one side or both sides of the laminated sheet may be used. Good.

<Second layer>
The second layer is the layer A.
By using the layer A as the second layer of the laminated sheet, the water vapor barrier property, the preservability of the package, the transparency and the blister moldability are excellent in balance, and the package such as pharmaceuticals, foods, and drinking water can be used. A biomass plastic sheet suitably used as a package to be packaged can be easily obtained.

The thickness of the second layer may be appropriately selected according to the use of the sheet, but is preferably 50 to 480 μm, more preferably 100 to 350 μm from the viewpoint that the effect of the layer A is more exhibited. .
Moreover, the ratio of the thickness of the 2nd layer in the lamination sheet which consists of a 1st layer, a 2nd layer, and a 3rd layer becomes like this. Preferably it is 50 to 90%, More preferably, it is 60 to 80%.

<First layer and third layer>
The first layer and the third layer may be appropriately selected according to the use of the sheet, but have a good appearance (surface smoothness) and a package that wraps an article to be packaged such as pharmaceuticals, foodstuffs, and drinking water. It is preferable to include a propylene-based resin from the standpoint that a biomass plastic sheet suitably used as can be easily obtained, etc., and a biomass plastic sheet superior in adhesiveness with the second layer can be easily obtained. In view of the above, it is preferable to include linear low density polyethylene (hereinafter also referred to as “LLDPE”).
The first layer and the third layer may be different layers, but are preferably the same layer from the viewpoint of ease of production, production cost, and the like of the sheet.

  The thicknesses of the first layer and the third layer may be appropriately selected according to the use of the sheet, but from the standpoint that the effect of the layer A is more exerted, the thickness of the first layer in the laminated sheet is preferable. The thickness is such that the ratio of the thickness of the two layers falls within the above range, more preferably 5 to 100 μm, and more preferably 10 to 50 μm.

The propylene-based resin is not particularly limited, and examples thereof include a propylene homopolymer, a copolymer of propylene and ethylene and at least one selected from ethylene and an α-olefin having 4 or more carbon atoms. The copolymer may be a random copolymer or a block copolymer.
Examples of the α-olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4, 4 -Dimethylpentene-1 etc. are mentioned.
The proportion of structural units derived from propylene in the copolymer is preferably 80% by weight or more, more preferably 85% by weight or more.

The MFR measured according to JIS K 7210 (230 ° C.) of the propylene-based resin is preferably 0.1 to 10 g / 10 minutes, more preferably 0.5 to 7 g / 10 minutes.
It is preferable to use a propylene-based resin having an MFR in the above range because the moldability at the time of producing the sheet is excellent.

  As a propylene-type resin, a commercial item may be used and you may synthesize | combine and obtain by a conventionally well-known method.

  The amount of the propylene-based resin contained in each of the first layer and the third layer is preferably 50 to 98% by weight with respect to 100% by weight of each layer from the viewpoint that the physical properties of the propylene-based resin are more exhibited. %, More preferably 70 to 90% by weight.

In addition to the propylene-based resin, the first layer and the third layer may contain other polymers, the other components, and the like as necessary.
As the other polymer, a biomass-derived resin may be used.

The laminated sheet is a laminated sheet in which the first layer and the third layer are laminated via the second layer, and the second layer containing a cyclic olefin resin, HDPE and LDPE, and a propylene resin. When the first layer and the third layer containing are bonded without using an adhesive layer, interlayer adhesion tends to be insufficient.
In order to more suitably use this sheet as a package for packaging articles such as pharmaceuticals, foodstuffs, and drinking water, it is preferable not to include an adhesive layer, and from the viewpoint of manufacturing cost, manufacturing equipment, and the like. However, it is preferable not to use an adhesive layer.
When laminating the first layer and the third layer containing a propylene-based resin via the second layer without using an adhesive layer, it is possible to easily obtain a laminated sheet having superior interlayer adhesion. Therefore, it is preferable to use LLDPE as the other polymer.

LLDPE may be an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. In addition, the copolymer may be a random copolymer or a block copolymer.
Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene and 1-decene. These α-olefins may be one kind or two or more kinds.

The density measured according to JIS K 7112 of LLDPE is preferably 0.900 to 0.920 g from the viewpoint of obtaining a laminated sheet that is superior in impact strength, crack resistance, tear strength, transparency, low temperature sealability, and the like. / Cm ³ , more preferably 0.900 to 0.910 g / cm ³ .

The MFR measured according to JIS K 7210 of LLDPE is preferably 0.1 to 10 g / 10 minutes, more preferably 0.5 to 7 g / 10 minutes.
It is preferable that the MFR is in the above range because the moldability of the laminated sheet is more excellent.

  As LLDPE, a commercially available product may be used, or it may be obtained by synthesis by a conventionally known method.

  The amount of LLDPE contained in each of the first layer and the third layer is preferably 2 to 50% by weight with respect to 100% by weight of each layer from the standpoint that a laminated sheet excellent in interlayer adhesion can be easily obtained. More preferably, it is 10 to 30% by weight.

<Physical properties of biomass plastic sheet>
In this sheet, the amount of biomass-derived resin (biomass plasticity) in 100% by weight of the entire sheet is 25% by weight or more, preferably 25 to 90% by weight, and more preferably 25 to 80% by weight.
That the biomass plasticity is within the above range means that the amount of fossil resources used can be greatly reduced compared to the conventional case, contributing to the suppression of the increase in the concentration of carbon dioxide in the atmosphere and reducing the environmental burden. Contributes to reducing.
From the viewpoint of reducing the amount of fossil resources used, the upper limit of the biomass plasticity is better, but considering the cost of the obtained sheet, the upper limit is preferably in the above range.

The biomass plasticity can be calculated from the raw material of each layer, specifically from the following formula (1).
Biomass plastic degree = weight of resin derived from biomass used for production of this sheet × biomass degree of the resin (%) / total weight of resin used for production of this sheet (1)

In addition, the mass of the resin derived from biomass and the mass of the resin derived from fossil fuel can be distinguished by the ratio of ¹⁴ C contained, and specifically, can be distinguished by ASTM-D6866-12. Is possible.
Moreover, when using a commercial item as resin derived from biomass, since the biomass degree in this commercial item is displayed, what is necessary is just to use the value.

  The haze value measured in accordance with JIS K 7136 of this sheet is a sheet having excellent transparency, and a PTP sheet having excellent transparency in the pocket part (acquisition part for pharmaceuticals and the like) and excellent visibility of contents can be easily obtained. From the standpoint of being able to do so, it is preferably 80% or less, more preferably 50% or less. The smaller the haze value, the better. However, the lower limit of the haze value is, for example, 10%.

The thickness of the sheet may be appropriately selected depending on the desired application, but is preferably 100 to 500 μm, more preferably 200 to 400 μm.
If it is such thickness, a PTP sheet can be manufactured from this sheet with good moldability.

<Manufacturing method of biomass plastic sheet>
In particular, the laminated sheet and the multilayer sheet can be produced by the same method as a conventionally known laminated body producing method. For example, the laminated sheet or the multi-layer sheet may be heat-sealed after the sheets forming the first layer and the third layer are superposed on both sides of the layer A, or the sheet forming each layer may be bonded to the adhesive layer. You may manufacture by adhering via these.
Here, in order to improve the interlayer adhesion of the obtained laminated sheet or the multilayer sheet, the surface of any layer forming the laminated sheet or the multilayer sheet is previously subjected to corona treatment, low temperature plasma treatment, ion bombardment. You may pre-process by methods, such as a process, a chemical | medical agent process, and a solvent process.

In addition, the laminated sheet and the multilayer sheet use raw materials for forming the layers, and if necessary, use a material obtained by blending the raw materials for forming the layers in advance, and perform coextrusion such as a multilayer T-die method and a multilayer inflation method. It can also be produced by a general multilayer sheet molding method such as a method, extrusion coating, dry lamination, heat lamination, a casting method such as a wet casting method or a dry casting method, or a calendar method.
Among these, the co-extrusion method is preferable from the viewpoints that productivity can be increased by eliminating the laminating process and use of an organic solvent can be eliminated.

The temperature at the time of co-extrusion may be appropriately selected according to the raw material to be used, but is preferably 160 to 300 ° C, more preferably 180 to 250 ° C.
For example, the temperature at the time of extruding the first layer and the third layer may be different from the temperature at the time of extruding the second layer.

≪PTP sheet≫
The PTP sheet according to the present invention includes the main sheet, and can be manufactured using the main sheet.
Since the PTP sheet includes the main sheet, the PTP sheet moldability, in particular, the temperature range in which a PTP sheet having a desired shape can be formed is widened, the degree of manufacturing freedom of the PTP sheet is increased, and the transparency is excellent. A sheet can be easily obtained.

  A method for producing a PTP sheet from this sheet is not particularly limited. For example, pockets are formed by a known molding method, and packages such as pharmaceuticals are loaded in each pocket, and the loaded packages are sealed. Thus, a PTP sheet can be manufactured by bonding this sheet and a sealing material (lid material).

Here, specific examples of the method for forming a pocket in the sheet include the following methods.
・ Hot and compressed air forming method: The sheet is sandwiched between a lower mold having holes for supplying high-temperature and high-pressure air and an upper mold having pocket-shaped concave portions, and air is supplied while softening by heating and pockets are formed. Method of forming Preheater flat plate pressure forming method: After heating and softening the sheet, the sheet is sandwiched between a lower mold having holes to which high-pressure air is supplied and an upper mold having pocket-shaped recesses, Method of forming pockets by supplying air ・ Drum type vacuum forming method: After this sheet is partially heated and softened by a heating drum having pocket-shaped recesses, the recesses are vacuumed to form pockets. Method ・ Pin forming method: Heating and softening the sheet, then crimping it with a pocket-shaped concavo-convex mold ・ Preheater plug assist pressure forming method: Heating and softening the sheet, and then high-pressure air Is a method of forming a pocket by inserting air between a lower mold having a hole to which a hole is supplied and an upper mold having a pocket-shaped concave portion, and forming a pocket at the time of molding. How to raise and lower to aid molding

  Among these, since the present sheet does not cause molding defects not only by the vacuum forming method but also by the pressure forming method, it can be formed by a pressure forming method such as a flat plate type pressure forming method or a plug assist pressure forming method.

  In addition, the shape, size, depth, number, arrangement, etc. of the pocket portion of the PTP sheet can be appropriately selected depending on the shape and application of the medicine.

  As the sealing material (lid material), a material having a heat-sealable resin layer is preferable since the loaded package can be sealed by heat sealing (heating adhesion). The heat-sealable resin layer is not particularly limited as long as the heat-sealable resin layer is a layer that is fused to the sheet loaded with an article to be packaged such as pharmaceuticals, foods, and drinking water. (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), ethylene / acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMA), ethylene / methyl acrylate copolymer (EMAA), ethylene / ethyl acrylate copolymer (EEA), ethylene / methyl methacrylic acid copolymer (EMMA) And a layer containing one or more ionomers (IO) and the like.

  Moreover, it is preferable that a sealing material (cover material) has metal vapor deposition film layers, such as an aluminum layer, and a metal foil layer from the point that gas-barrier property is favorable.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited by these.

[Example 1]
As the second layer forming material, the following HDPE1 (20 wt%), HDPE2 (50 wt%), LDPE (20 wt%) and COC (10 wt%) were dry blended, and then using a φ65 mm twin screw extruder. After melt-kneading at 200 ° C. and dry blending the following PP (85 wt%) and LLDPE (15 wt%) as the first and third layer forming materials, 215 ° C. using a φ65 mm single screw extruder The mixture was melt-kneaded and coextruded at a die temperature of 210 ° C. from a two-kind, three-layer multi-manifold die.
At this time, the discharge amount of the molten resin was adjusted so that the thicknesses of the respective layers were 30 μm for the first layer, 190 μm for the second layer, and 30 μm for the third layer. Subsequently, this co-extruded sheet was cooled with a cast roll to produce a biomass plastic sheet as a multilayer sheet.

[Examples 2 to 4 and Comparative Examples 1 to 2]
A biomass plastic sheet was produced in the same manner as in Example 1 except that the materials forming each layer and the contents thereof were changed to the materials and contents shown in Table 1.
The material (commercially available product) for forming each layer is shown below.

<First and third layer forming materials>
PP (homopolypropylene): MFR (JIS K 7210, 230 ° C.); 3.0 g / 10 min
LLDPE (linear low density polyethylene): density (JIS K 7112); 0.903 g / cm ³ , MFR (JIS K 7210); 1.2 g / 10 min

<Second layer forming material>
HDPE1 (biomass high density polyethylene): density (ASTM D 792); 0.952 g / cm ³ , MFR (ASTM D 1238); 2.0 g / 10 min, degree of biomass (ASTM D 6866); 96%
HDPE2 (high density polyethylene): density (JIS K 7112); 0.958 g / cm ³ , MFR (JIS K 7210); 1 g / 10 min
HDPE3 (biomass high density polyethylene): density (ASTM D 792); 0.959 g / cm ³ , MFR (ASTM D 1238); 7.2 g / 10 min, degree of biomass (ASTM D 6866); 94.5%
HDPE4 (high density polyethylene): density (JIS K 7112); 0.964 g / cm ³ , MFR (JIS K 7210); 5.2 g / 10 min
LDPE (low density polyethylene): density (ASTM D 1505); 0.923 g / cm ³ , MFR (ASTM D 1238); 2.7 g / 10 min, degree of biomass (ASTM D 6866); 95%
· COC (cyclic olefin resin): MVR (ISO 1133,190 ℃, 2.16kg); 2.0cm 3 / 10min

<Transparency (haze value)>
Using the biomass plastic sheets obtained in Examples and Comparative Examples, the transparency (haze value) of the sheets was measured based on JIS K 7136. The results are shown in Table 1.

<Blister formability (moldable temperature)>
Using the biomass plastic sheets obtained in Examples and Comparative Examples, the moldability when molding PTP sheets was evaluated by the following methods.
The blister moldability is φ11.0 at each temperature in the range of 100 to 150 ° C. using a pinpoint heating plate with a biomass plastic sheet in a PTP molding machine (CBP Co., Ltd., FBP-M2). X Molding using 4.0 tablet model (diameter 11 mmφ, depth 4.0 mm) and a plug assist mechanism was performed, and the mold followability to the mold (tablet mold) of the obtained sheet at each temperature was evaluated. In addition, the mold followability evaluated the external appearance nonuniformity of the pocket top part, the corner part, and the side part by visual observation.
Table 1 shows the temperature range in which a sheet having no appearance irregularities at the pocket top, corner and side portions can be obtained.

<Blister formability (PTP sheet use evaluation)>
The lid material aluminum foil is heat-sealed with respect to the PTP sheet obtained by the blister formability at a sealing temperature of 220 ° C., and then a dividing line from a 10-tablet sheet to a 2-tablet sheet called a slit is formed at a slit forming temperature of 120. The film was formed under the conditions of ° C and a slit forming speed of 2.8 m / min. The slit portion was bent at 90 °, the two tablet sheets were cut off, and visually evaluated based on the following criteria.
In addition, when PTP sheet use evaluation is x, it shows that blister moldability is not enough.
○: During separation, the center layer (second layer) and the surface layer (the layer on the opposite side of the second layer in contact with the tablet [first layer]) were separated ×: Delamination during separation Could be split without any problem

Claims (9)

A biomass plastic sheet having a layer A containing a cyclic olefin-based resin, high-density polyethylene and low-density polyethylene,
The amount of the resin derived from biomass in the entire sheet is 25% by weight or more,
Biomass plastic sheet.   The biomass plastic sheet according to claim 1, comprising a first layer, a second layer, and a third layer in this order, wherein the second layer is the layer A.   The biomass plastic sheet according to claim 2, which is a laminated sheet formed by a coextrusion method.   Any of Claims 1-3 whose content of the cyclic olefin resin in the said layer A is 1 to 75 weight% with respect to a total of 100 weight% of the said cyclic olefin resin, a high density polyethylene, and a low density polyethylene. The biomass plastic sheet according to claim 1.   The content of the high-density polyethylene in the layer A is 1 to 98% by weight with respect to a total of 100% by weight of the cyclic olefin-based resin, the high-density polyethylene, and the low-density polyethylene. The biomass plastic sheet according to item 1.   The content of the low density polyethylene in the layer A is 1 to 98% by weight with respect to a total of 100% by weight of the cyclic olefin resin, the high density polyethylene, and the low density polyethylene. The biomass plastic sheet according to item 1. The biomass plastic sheet has a surface layer;
The biomass plastic sheet according to any one of claims 1 to 6, wherein the surface layer contains a propylene-based resin. The biomass plastic sheet has a surface layer;
The biomass plastic sheet according to any one of claims 1 to 7, wherein the surface layer comprises linear low-density polyethylene.   The PTP sheet containing the biomass plastic sheet of any one of Claims 1-8.