PTP packaging sheets

Abstract

To provide a PTP packaging sheet excellent in dispersibility of barium sulfate and excellent in imaging properties.SOLUTION: It is a PTP packaging sheet containing a resin and barium sulfate having an average particle size of 0.05 to 1.5 μm as measured by a laser diffraction / scattering method, the content of barium sulfate per unit area of the surface perpendicular to the thickness direction of the PTP package sheet is 40 g / m2 or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a PTP packaging sheet. [Background technology]

[0002] Pharmaceuticals and foods in the form of tablets, capsules, etc. are typically distributed as PTP packaging by forming a pocket (deep-drawn section) of a predetermined depth in a transparent plastic sheet called a press-through pack packaging sheet (hereinafter referred to as "PTP packaging sheet"). The pharmaceuticals or foods are placed in this pocket, and the opening is sealed with a sealing material (lid material) such as aluminum foil. The pharmaceuticals or foods placed in the pocket can then be taken out from the sealing material side, for example, by pressing the pocket with a finger.

[0003] In PTP packaging, there are usually many connected compartments, each containing a single pocket for a drug or food product, which can be separated individually by perforations or half-cuts. When removing a drug or food product from such PTP packaging, it is common to separate the connected compartments one by one before removing the product. When separating multiple interconnected storage compartments one by one to remove the contents, there is a risk of accidentally ingesting the entire PTP packaging (hereinafter also referred to as "accidental ingestion").

[0004] When accidental ingestion occurs as described above, the PTP packaging can injure not only the esophagus but also the stomach and intestines, so it is necessary to remove the PTP packaging from the body as soon as possible. However, conventional PTP packaging is difficult to detect with hospital X-rays, and can only be found with CT scans or endoscopy, which has led to delays in detection and subsequent serious complications. Therefore, as a countermeasure against such accidental ingestion, there is a need for the development of PTP packaging that can be visualized with X-rays.

[0005] Examples of PTP packaging that can be visualized with X-rays include the PTP packaging described in Patent Documents 1 and 2. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-235790 [Patent Document 2] Japanese Patent Publication No. 2000-286 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, conventional PTP packaging sheets used in X-ray-enhanced PTP packaging were not sufficiently X-ray-enhanced and had room for improvement. Furthermore, it was found that when attempting to improve the contrast properties of the PTP packaging sheet used in conventional X-ray contrast-enhanced PTP packaging, a decrease in the dispersibility of the X-ray contrast agent leads to a decrease in productivity.

[0008] The present invention has been made in view of the above, and aims to provide a PTP packaging sheet that has excellent dispersibility of barium sulfate and excellent contrast imaging properties. [Means for solving the problem]

[0009] The inventors of this invention conducted diligent research to solve the aforementioned problems and, as a result, found that the problems can be solved according to the following configuration example, thus completing the present invention. An example of the configuration of the present invention is as follows.

[0010] [1] A PTP packaging sheet comprising a resin and barium sulfate having an average particle size of 0.05 to 1.5 μm as measured by laser diffraction and scattering method, The barium sulfate content per unit area of ​​the surface perpendicular to the thickness direction of the sheet is 40 g / m². 2 That concludes the PTP packaging sheet.

[0011] [2] The PTP packaging sheet is a single-layer sheet consisting only of layer A containing the resin and the barium sulfate, or the PTP packaging sheet is a multi-layer sheet containing the layer A, where the concentration of barium sulfate in the layer A is 7 to 35% by mass, the PTP packaging sheet according to [1].

[0012] [3] The PTP packaging sheet according to [1] or [2], having a thickness of 50 to 600 μm.

[0013] [4] The PTP packaging sheet according to any one of [1] to [3], wherein the resin is at least one selected from vinyl chloride resins, ethylene resins, and propylene resins.

[0014] [5] The PTP packaging sheet according to any one of [1] to [4], having a haze value of 80% or less.

[0015] [6] The PTP packaging sheet according to any one of [1] to [5], wherein the PTP packaging sheet is a sheet that can be imaged even when present in the body.

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a PTP packaging sheet having excellent dispersibility of barium sulfate and excellent imaging properties, particularly a PTP packaging sheet that can be imaged even when present in the body. Further, according to the present invention, it is possible to provide a PTP packaging sheet having excellent safety and excellent formability of the PTP package.

Brief Description of the Drawings

[0017] [Figure 1] FIG. 1 is an X-ray contrast photograph of the PTP packaging sheet produced in Example 4. [Figure 2] FIG. 2 is an X-ray contrast photograph of the PTP packaging sheet produced in Example 5.​​​​​Figure 4 is an X-ray contrast photograph of the PTP packaging sheet produced in Example 10. [Figure 5] Figure 5 is an X-ray contrast photograph of the PTP packaging sheet produced in Comparative Example 2.

Mode for Carrying Out the Invention

[0018] ≪PTP Packaging Sheet≫ The PTP packaging sheet according to the present invention (hereinafter also referred to as "this sheet") contains a resin and barium sulfate having an average particle diameter measured by the laser diffraction / scattering method of 0.05 to 1.5 μm. The content of barium sulfate per unit area of the surface orthogonal to the thickness direction of this sheet is 40 g / m 2 or more.

[0019] This sheet may be a single-layer sheet consisting only of a layer containing the resin and the barium sulfate (hereinafter also referred to as "layer A"), or may be a multi-layer sheet containing layer A. In the case of the multi-layer sheet, it may contain two or more layers of layer A, or may contain two or more layers of a layer other than layer A (hereinafter also referred to as "layer B"). When this sheet contains two or more layers of layer A, the two or more layers of layer A may be the same layer or different layers. When this sheet contains two or more layers of layer B, the two or more layers of layer B may be the same layer or different layers. Examples of the layer B include a layer containing a resin and not containing barium sulfate.

[0020] Preferable examples of this sheet include a single-layer sheet consisting only of layer A, a laminated sheet in which layer B, layer A, and layer B are laminated in this order, a laminated sheet in which layer B, layer B, layer A, layer B, and layer B are laminated in this order, and a laminated sheet in which layer B, layer A, layer B, layer A, and layer B are laminated in this order. A single-layer sheet consisting only of layer A and a laminated sheet in which layer B, layer A, and layer B are laminated in this order are more preferable. Furthermore, the sheet may be a multilayer sheet in which layers such as an oxygen barrier layer, a gas barrier layer, a gas absorption layer, a moisture barrier layer, a light shielding layer, or a bleed-out prevention layer are laminated on one or both sides of the single-layer sheet or laminated sheet as needed.

[0021] The barium sulfate content per unit area of ​​the surface perpendicular to the thickness direction of this sheet (the surface with the largest surface area of ​​this sheet) (hereinafter also simply referred to as "barium sulfate content per unit area") is 40 g / m². 2 The above is preferable, preferably 40-130 g / m² 2 Comfortable 55-100g / m 2 That is the case. When the barium sulfate content per unit area is within the aforementioned range, a PTP packaging sheet with excellent contrast-enhancing properties can be obtained, particularly one that is capable of contrast imaging even when present in the body.

[0022] The barium sulfate content per unit area can be calculated by multiplying the density of the sheet, the thickness of layer A, and the concentration of barium sulfate in layer A. For example, if the sheet contains layer A1 with a thickness a1 (m) and a barium sulfate concentration of c1 (mass%), and layer A2 with a thickness a2 (m) and a barium sulfate concentration of c2 (mass%), the barium sulfate content per unit area can be calculated by multiplying the density of the sheet (g / m²). 3 It can be calculated as ) × (a1 × c1 / 100 + a2 × c2 / 100). The same applies if this sheet contains three or more layers A.

[0023] The thickness of this sheet is not particularly limited, but it is preferably 50 to 600 μm, more preferably 100 to 400 μm, and even more preferably 150 to 300 μm, from the standpoint of excellent pocket formability when manufacturing PTP packaging from this sheet. If the sheet is a single-layer sheet, the thickness of layer A is the same as the thickness of the sheet. On the other hand, if the sheet is a laminated sheet, the total thickness of layer A in the sheet should be selected such that the barium sulfate content per unit area falls within the above range, but preferably it is 50 to 300 μm, more preferably 85 to 250 μm. In this specification, there is no particular distinction made between film and sheet.

[0024] The shape of this sheet is not particularly restricted and can be appropriately selected according to the intended use of the PTP packaging.

[0025] The haze value of this sheet is preferably 80% or less, more preferably 50% or less, from the standpoint of easily obtaining a sheet with excellent visibility of the contents contained in the PTP packaging. There is no particular lower limit to the haze value; the smaller the better. The haze value can be measured specifically by the method described in the following examples.

[0026] <Resin> The aforementioned resin is not particularly limited, and any conventionally known resin used in PTP packaging sheets can be used without restriction. The resin contained in layer A may be one type or two or more types. If layer B contains resin, the resin contained in layer B may also be one type or two or more types.

[0027] The resin content in layer A is preferably 65 to 93% by mass, more preferably 70 to 84% by mass, and even more preferably 74 to 84% by mass, from the viewpoint that a sheet with excellent strength, transparency, water vapor barrier properties, and preservation properties of the contents can be easily obtained.

[0028] Examples of the aforementioned resins include ester resins (polyesters) such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene, polypropylene, polybutene, ethylene-propylene copolymer and ethylene-butene copolymer, polystyrene, polyamide, vinyl chloride resin (PVC), polycarbonate, polyacrylonitrile, and polyimide. The aforementioned resin may be a resin obtained by a conventionally known method of synthesis, or it may be a commercially available product.

[0029] Among these, it is preferable that at least one is selected from vinyl chloride resins and olefin resins, and more preferably at least one is selected from vinyl chloride resins, ethylene resins and propylene resins, in order to easily obtain a sheet that can be suitably used in PTP packaging. Furthermore, if the resin is an ethylene-based resin or a propylene-based resin, it is preferable that the sheet be a laminated sheet, as this offers superior moldability and pocket moldability during the manufacturing process.

[0030] [Vinyl chloride resin] Vinyl chloride resin can be used as the resin for layer A and layer B. When the sheet is a single-layer sheet, a vinyl chloride resin is preferred as the resin used for layer A.

[0031] The vinyl chloride resin is not particularly limited as long as it is a resin obtained from vinyl chloride as a raw material, and examples include a homopolymer of vinyl chloride or a copolymer of vinyl chloride and another monomer.

[0032] The aforementioned other monomers are not particularly limited, but include, for example, olefins such as ethylene, propylene, and isobutene or their chlorinated derivatives, dienes such as isoprene and butadiene, vinyl compounds such as acrylonitrile, methacrylonitrile, and vinyl acetate, maleic acid or its esters or acid anhydrides, acrylic acid or its esters, methacrylic acid or its esters, and vinylidene chloride.

[0033] Furthermore, the vinyl chloride resin may be a resin in which the homopolymer or copolymer is partially crosslinked. Alternatively, a polymer blend of vinyl chloride resins, such as a polymer blend consisting of vinyl chloride resin and polyvinylidene chloride, may be used. Of these, homopolymers of vinyl chloride are preferred.

[0034] The average degree of polymerization of the vinyl chloride resin, as measured according to JIS K 6720-2, is preferably 500 to 5000, and more preferably 500 to 2000, in order to obtain a sheet with excellent thermal stability and moldability.

[0035] [Ethylene-based resin] Ethylene-based resins can be used as the resins for layer A and layer B. In particular, when this sheet is the laminated sheet described above, it is preferable that layer A contains an ethylene-based resin, as it has excellent transparency and can be suitably used as a PTP packaging for packaging contents such as pharmaceuticals and food products.

[0036] The ethylene-based resin is not particularly limited and examples include high-density polyethylene (hereinafter also referred to as "HDPE"), medium-density polyethylene, low-density polyethylene (hereinafter also referred to as "LDPE"), and linear low-density polyethylene (hereinafter also referred to as "LLDPE").

[0037] The aforementioned layer A preferably contains HDPE, as it allows for the easy acquisition of a sheet with excellent strength, transparency, water vapor barrier properties, and ease of removal of contents.

[0038] The MFR, measured according to JIS K 7210 for HDPE (190°C, 2.16 kg load), is preferably 0.1 to 10 g / 10 min, more preferably 0.5 to 6 g / 10 min, as it allows for easy acquisition of sheets with good pocket moldability.

[0039] HDPE may be not only a homopolymer of ethylene, but also a copolymer of ethylene with α-olefins such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

[0040] HDPE may be biomass-derived HDPE, as it helps to suppress the increase in CO2 in the atmosphere and also contributes to the conservation of petroleum resources.

[0041] The aforementioned biomass is not particularly limited, but examples include sugarcane (including bagasse), corn, starch, castor oil, crushed tatami mats (used waste tatami mats), wood chips, wood flour, sawdust, paper waste, sorghum, sugar beet residue, rice straw and other plant-based materials, coniferous materials, hardwood materials, non-tree materials, and waste materials of these materials.

[0042] The aforementioned biomass-derived HDPE is not particularly limited as long as it is obtained using biomass-derived ethylene as a raw material, but specifically, plant-derived HDPE using ethylene synthesized from alcohol obtained by fermenting plants is an example. More specifically, HDPE can be obtained by using conventionally known methods to produce bioethanol by fermenting a sugar solution or starch obtained from the biomass with microorganisms such as yeast, heating this bioethanol in the presence of a catalyst to carry out intramolecular dehydration reactions, etc., and using ethylene and, if necessary, α-olefins (e.g., 1-butene, 1-hexene) as copolymer monomers, and (co)polymerizing them in the presence of a conventional catalyst, similar to the synthesis of HDPE derived from fossil fuels. In addition to biomass-derived α-olefins, the copolymer monomer may also be a fossil fuel-derived comonomer commonly used in the synthesis of conventional high-density polyethylene.

[0043] The aforementioned layer A preferably contains LDPE, as it allows for easy acquisition of a sheet with excellent transparency and pocket moldability.

[0044] The MFR of LDPE, as measured according to ASTM D 1238, is preferably 0.1 to 10 g / 10 min, more preferably 0.5 to 6 g / 10 min, as it allows for easy acquisition of sheets with good pocket moldability.

[0045] LDPE may be a homopolymer of ethylene, or it may be low-density polyethylene obtained by polymerizing ethylene as the main component and α-olefin as a minor component in the presence of a metallocene catalyst or the like. As the α-olefin, one or more types of α-olefins having 3 to 40 carbon atoms, preferably 4 to 35, more preferably 4 to 30, can be used. For example, α-olefins having 3 to 8 carbon atoms and α-olefins having 10 to 26 carbon atoms can be used in combination. When the LDPE is a copolymer, the α-olefin content is preferably 3 to 15 mol% relative to the copolymer.

[0046] LDPE may be biomass-derived LDPE, as it helps to suppress the increase in CO2 in the atmosphere and also contributes to the conservation of petroleum resources. Biomass-derived LDPE can be synthesized using the biomass-derived raw materials listed in the HDPE section above, according to conventionally known methods for synthesizing LDPE.

[0047] The LLDPE may be an ethylene homopolymer, or a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. Furthermore, the copolymer may be a random copolymer or a block copolymer. Examples of α-olefins 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 present individually or in combination of two or more types.

[0048] The MFR measured according to JIS K 7210 (190°C, 2.16 kg load) for LLDPE is preferably 0.1 to 10 g / 10 min, more preferably 0.5 to 7 g / 10 min, due to its superior moldability and other advantages.

[0049] [Propylene resin] Propylene-based resins can be used as the resins for layer A and layer B. In particular, when the sheet is the laminated sheet described above, it is preferable that layer B contains a propylene resin, as it has excellent appearance (surface smoothness) and can be suitably used as a PTP packaging for packaging contents such as pharmaceuticals and food products. While it is preferable that this sheet does not contain an adhesive layer, in the case of the laminated sheet, when a polyethylene-based resin is used as the resin for layer A, it is preferable to use LLDPE together with a propylene-based resin as layer B, since a laminated sheet with excellent interlayer adhesion can be easily obtained without using an adhesive layer.

[0050] The propylene-based resin is not particularly limited and includes propylene homopolymers, copolymers of propylene with at least one selected from ethylene and α-olefins having 4 or more carbon atoms, etc. The copolymer may be a random copolymer or a block copolymer. Examples of α-olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methylpentene-1, 4-methylhexene-1, and 4,4-dimethylpentene-1. The proportion of structural units derived from propylene in the copolymer is preferably 80% by mass or more, more preferably 85% by mass or more.

[0051] The MFR of propylene resins, measured according to JIS K 7210 (230°C, 2.16 kg load), is preferably 0.1 to 10 g / 10 min, more preferably 0.5 to 7 g / 10 min. Using a propylene-based resin with an MFR within the aforementioned range is preferable because it provides superior moldability when manufacturing this sheet.

[0052] <Barium sulfate> The barium sulfate contained in layer A is barium sulfate with an average particle size of 0.05 to 1.5 μm, as measured by laser diffraction and scattering. The barium sulfate contained in layer A may be of one type or two or more types.

[0053] The average particle size is 0.05 to 1.5 μm, preferably 0.06 to 0.9 μm, and more preferably 0.1 to 0.6 μm, because it allows for easy acquisition of sheets with excellent dispersibility and pocket-forming properties of barium sulfate, low haze value, and excellent contrast enhancement. If the average particle size falls below 0.05 μm, the dispersibility of barium sulfate is poor, and if it exceeds 1.5 μm, the surface irregularities of the resulting film become larger, and the gloss decreases.

[0054] In this invention, the average particle size of barium sulfate is the particle size (D50) at which the cumulative total from the smallest particles in the particle size distribution curve, measured using a laser diffraction-scattering particle size analyzer, is 50%. As the laser diffraction / scattering particle size analyzer, for example, the "MT3200II" laser diffraction / scattering particle size analyzer manufactured by Nikkiso Co., Ltd. can be used.

[0055] Examples of the barium sulfate mentioned above include crushed natural minerals (e.g., barite) and precipitated barium sulfate. The barium sulfate may contain impurities such as iron, manganese, strontium, calcium, and sulfides, as long as it does not impair the effects of the present invention, but it is preferable that it does not contain such impurities or has a low impurity content.

[0056] The barium sulfate may be surface-treated by known surface treatments such as fatty acid treatment or SiO2-Al2O3 treatment, or it may be an untreated product. While surface-treated materials may be preferable when considering miscibility with resins, for example, when using polyvinyl chloride-based resins, the resulting sheets may become discolored (burned), so it is preferable to use untreated materials.

[0057] The amount of barium sulfate in this sheet is such that the barium sulfate content per unit area falls within the aforementioned range. The concentration of barium sulfate in layer A is preferably 7 to 35% by mass, more preferably 16 to 30% by mass, and even more preferably 16 to 26% by mass, from the viewpoint that it is possible to easily obtain a sheet with excellent dispersibility of barium sulfate, a low haze value, and excellent contrast enhancement.

[0058] <Other ingredients> This sheet may, if necessary, contain other components besides resin and barium sulfate, to the extent that they do not impair the effects of the present invention.

[0059] Other components mentioned above include, for example, dispersants, stabilizers such as heat stabilizers and light stabilizers, ultraviolet absorbers, softeners, plasticizers, lubricants, processing aids, reinforcing agents, pigments, ultraviolet scattering agents, antistatic agents, and antioxidants. Each of these other components may be used individually or in combination of two or more.

[0060] [Dispersant] The aforementioned dispersant can be any dispersant that has been used in conventional PTP packaging sheets, and is not particularly limited, but examples include surfactants such as anionic, nonionic, cationic, and amphoteric surfactants.

[0061] [Stabilizer] The stabilizer can be any stabilizer that has been used in conventional PTP packaging sheets, and is not particularly limited. Examples include metal compounds such as lithium, sodium, potassium, magnesium, calcium, aluminum, barium, zinc, and tin; β-diketone compounds such as dibenzoylmethane; organic phosphite esters; polyhydric alcohols; phenolic compounds; epoxy compounds; and organic phosphite compounds. Metal compounds such as calcium, barium, and zinc, and β-diketone compounds are preferred because they provide a sheet with excellent safety and stability.

[0062] [UV absorber] As for the UV absorber, any UV absorber that has been used in conventional PTP packaging sheets can be used, and there are no particular limitations, but examples include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, salicylate-based UV absorbers, triazine-based UV absorbers, benzoate-based UV absorbers, and cyanoacrylate-based UV absorbers.

[0063] [Fabric softener] As the softener, any softener that has been used in conventional PTP packaging sheets can be used and is not particularly limited. However, in terms of improving the impact resistance of the resulting sheet, impact-improving resins such as butyl acrylate-methyl (meth)acrylate copolymer, butyl acrylate-styrene-methyl (meth)acrylate copolymer, ethylene-vinyl acetate copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, epoxy-modified ethylene-propylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-ethylene-butylene copolymer, and styrene-ethylene-propylene copolymer are preferred.

[0064] [Plasticizer] The aforementioned plasticizer can be any plasticizer that has been used in conventional PTP packaging sheets, and is not particularly limited. Examples include phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP); and adipate ester plasticizers such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA). Examples of plasticizers include epoxidized ester plasticizers such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, and octyl epoxy stearate; trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM); and phosphate ester plasticizers such as trimethyl phosphate (TMP) and triethyl phosphate (TEP). Among these, epoxidized ester plasticizers are preferred in terms of sheet moldability and processability.

[0065] [Lubricant] The lubricant can be any lubricant that has been used in conventional PTP packaging sheets, and is not particularly limited. Examples include dimethylpolysiloxane, fatty acid alcohol esters, and low molecular weight polyethylene. Fatty acid alcohol esters are preferred from the viewpoint of sheet processability and other factors. The fatty acid alcohol ester is preferably a 1-3 valent ester compound of glycerin and a fatty acid. Examples include stearate glyceride lubricants such as stearate monoglyceride, stearate diglyceride, and stearate triglyceride, as well as oleate glyceride lubricants and palmitate glyceride lubricants.

[0066] [Processing aid] The processing aids mentioned above can be those that have been used in conventional PTP packaging sheets, and are not particularly limited. However, acrylic processing aids such as methyl methacrylate-ethyl acrylate copolymers and high molecular weight polymethyl methacrylates are preferred.

[0067] [Enhancing agent] The reinforcing agent can be any reinforcing agent that has been used in conventional PTP packaging sheets, and is not particularly limited. For example, methyl methacrylate-butadiene-styrene copolymer (MBS) and acrylic resin reinforcing agents are preferred.

[0068] [Pigments] The aforementioned pigments can be those conventionally used in PTP packaging sheets and are not particularly limited, but examples include coloring pigments such as azo pigments, quinacridone, isoindoline, anthraquinone, imidazolon, cobalt, phthalocyanine, carbon, titanium dioxide, iron oxide, mica, and other pearl pigments, as well as extender pigments such as talc, calcium carbonate, silica, alumina, carbon black, zinc oxide, zeolite, hydrotalcite, glass fiber, paper powder, and wood powder.

[0069] <How to manufacture this sheet> The sheet, particularly layer A and the single-layer sheet, can be manufactured by, for example, forming a resin composition containing the resin, barium sulfate, and optionally the other components into a sheet using known methods such as the single-layer T-die method or the calendering method of melt molding.

[0070] The laminated sheet and the multilayer sheet can be manufactured by a method similar to that used for manufacturing conventionally known laminates. For example, the laminated sheet and the multilayer sheet may be manufactured by superimposing sheets forming layer B onto both sides of layer A and then heat-sealing them, or by bonding the sheets forming each layer via an adhesive layer or the like. In order to improve the interlayer adhesion of the resulting laminated sheet or the multilayer sheet, the surface of any of the layers forming the laminated sheet or the multilayer sheet may be pre-treated by methods such as corona treatment, low-temperature plasma treatment, ion bombardment treatment, chemical treatment, or solvent treatment.

[0071] In addition, the laminated sheet and the multilayer sheet can be manufactured by using the raw materials for forming the respective layers, and if necessary, by using a premixed material of the raw materials for forming the respective layers, through common multilayer sheet forming methods such as co-extrusion methods like the multilayer T-die method and the multilayer inflation method, extrusion coating, dry lamination, heat lamination, and casting methods such as the wet casting method and the dry casting method.

[0072] The temperature during co-extrusion can be appropriately selected according to the raw materials used, but it is preferably 160 to 300°C, more preferably 180 to 250°C. For example, the temperature for extruding layer A and the temperature for extruding layer B may be different.

[0073] <PTP package> This sheet is usually used by manufacturing a PTP package using this sheet. The method for manufacturing a PTP package using this sheet is not particularly limited. For example, pockets are formed in this sheet by a known forming method, contents such as pharmaceuticals and foods are accommodated in each pocket, and the PTP package can be manufactured by adhering this sheet and a sealing material (lid material) so as to seal the accommodated contents.

[0074] Here, specific methods for forming pockets in this sheet include the following methods. · Heat-pressure air forming method: A method of sandwiching this sheet between a lower mold having holes through which high-temperature and high-pressure air is supplied and an upper mold having a pocket-shaped recess, and supplying air while heating and softening to form a pocket. · Preheater flat plate type air forming method: A method of heating and softening this sheet, then sandwiching it between a lower mold having holes through which high-pressure air is supplied and an upper mold having a pocket-shaped recess, and supplying air to form a pocket. · Drum type vacuum forming method: A method of partially heating and softening this sheet with a heated drum having a pocket-shaped recess, and then performing vacuum suction on the recess to form a pocket. • Pin forming method: This method involves heating and softening the sheet, then pressing it into place using a pocket-shaped mold with raised and recessed areas. • Preheater plug-assisted pressure forming method: This method involves heating and softening the sheet, then sandwiching it between a lower mold having holes for supplying high-pressure air and an upper mold having a pocket-shaped recess, and supplying air to form a pocket. During forming, a convex-shaped plug is raised and lowered to assist in the forming process.

[0075] The shape, size, depth, number, and arrangement of the pockets should be appropriately selected depending on the shape and purpose of the contents.

[0076] The sealing material (lid material) is preferably one having a heat-sealable resin layer, as it can seal the contents by heat sealing (heat bonding). The heat-sealable resin layer is not particularly limited as long as it is a layer that fuses with the main sheet containing the contents during heat sealing, but examples include a layer containing one or more of the following: LDPE, medium-density polyethylene (MDPE), HDPE, 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), ionomer (IO), etc.

[0077] Furthermore, the sealing material (lid material) preferably has a metal vapor-deposited film layer such as an aluminum layer or a metal foil layer, as this provides good gas barrier properties. [Examples]

[0078] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0079] [Example 1] A PTP packaging sheet with a thickness of 180 μm was produced by calendering a mixture of polyvinyl chloride (TVS-118 [manufactured by Taisei Chemical Co., Ltd.]) and untreated barium sulfate (average particle size: 0.3 μm) so that the barium sulfate concentration was 16% by mass.

[0080] [Example 2] A PTP packaging sheet with a thickness of 200 μm was produced by calendering the mixture obtained in the same manner as in Example 1, except that the concentration of barium sulfate was changed to 20% by mass.

[0081] [Example 3] A PTP packaging sheet with a thickness of 200 μm was produced by calendering the mixture obtained in the same manner as in Example 1, except that the concentration of barium sulfate was changed to 24% by mass.

[0082] [Example 4] A PTP packaging sheet with a thickness of 250 μm was produced by calendering the mixture obtained in the same manner as in Example 1, except that the concentration of barium sulfate was changed to 30% by mass.

[0083] [Example 5] A PTP packaging sheet with a thickness of 139 μm was produced by calendering a mixture of polyvinyl chloride (TVS-118 [manufactured by Taisei Chemical Co., Ltd.]) and barium sulfate (average particle size: 0.6 μm) so that the barium sulfate concentration was 20% by mass.

[0084] [Example 6] A PTP packaging sheet was prepared in the same manner as in Example 5, except that the thickness was changed to 248 μm.

[0085] [Example 7] A PTP packaging sheet was fabricated as follows, consisting of a laminate in which the first, second, and third layers were stacked in that order.

[0086] As the material for forming the first and third layers, PP (homopolypropylene, MFR (compliant with JIS K 7210, 230°C, 2.16 kg load): 3.0 g / 10 min) was melt-kneaded at 200-230°C using a φ65 mm single-screw extruder. Furthermore, as the second layer forming material, PP (homopolypropylene, MFR (compliant with JIS K 7210, 230℃, 2.16kg load): 3.0g / 10min) and barium sulfate (average particle size: 0.6μm) were compounded to a barium sulfate concentration of 20% by mass, and then melt-kneaded at 200℃ using a φ65mm twin-screw extruder.

[0087] PTP packaging sheets were produced by co-extruding the materials for the first to third layers from a two-type, three-layer multi-manifold nozzle at a die temperature of 205-215°C, while adjusting the discharge rate so that the thickness of the first and third layers was 30 μm and the thickness of the second layer was 130 μm. The resulting sheets were then cooled using a cast roll.

[0088] [Example 8] A PTP packaging sheet was prepared in the same manner as in Example 7, except that the thickness of the second layer was changed to 240 μm.

[0089] [Example 9] A PTP packaging sheet was fabricated as follows, consisting of a laminate in which the first, second, and third layers were stacked in that order.

[0090] As the material for forming the first and third layers, 6 parts by mass of PP1 (homopolypropylene, MFR (compliant with JIS K 7210, 230°C, 2.16 kg load): 3.0 g / 10 min), 30 parts by mass of PP2 (homopolypropylene, MFR (compliant with JIS K 7210, 230°C, 2.16 kg load): 7.0 g / 10 min), and 10 parts by mass of LLDPE (linear low-density polyethylene, MFR (compliant with JIS K 7210, 190°C, 2.16 kg load): 1.2 g / 10 min) were dry blended, and then melt-kneaded at 215°C using a φ65 mm single-screw extruder. Furthermore, as the second layer forming material, HDPE (biomass high-density polyethylene, density (ASTM D 792): 0.952 g / cm³) is used. 3 MFR (compliant with JIS K 7210, 190℃, 2.16kg load): 2.0g / 10min, biomass content (ASTM D 6866): 96% and barium sulfate (average particle size: 0.6μm) were compounded so that the barium sulfate concentration was 20% by mass (in this process, 0.2 parts by mass of dispersant was used for every 1 part by mass of barium sulfate), and then melt-kneaded at 200℃ using a φ65mm twin-screw extruder.

[0091] PTP packaging sheets were produced by co-extruding the materials for the first to third layers from a 2-type, 3-layer multi-manifold type die at a die temperature of 210°C, while adjusting the discharge rate so that the thickness of the first and third layers was 25 μm and the thickness of the second layer was 87 μm. The resulting sheets were then cooled using a cast roll.

[0092] [Example 10] A PTP packaging sheet was prepared in the same manner as in Example 9, except that the thickness of the second layer was changed to 160 μm.

[0093] [Example 11] A PTP packaging sheet with a thickness of 180 μm was produced by calendering a mixture of polyvinyl chloride (TVS-118 [manufactured by Taisei Chemical Co., Ltd.]) and barium sulfate (average particle size: 0.1 μm) so that the barium sulfate concentration was 20.45% by mass.

[0094] [Example 12] A PTP packaging sheet with a thickness of 180 μm was produced by calendering a mixture of polyvinyl chloride (TVS-118 [manufactured by Taisei Chemical Co., Ltd.]) and barium sulfate (average particle size: 0.06 μm) so that the barium sulfate concentration was 20.45% by mass.

[0095] [Example 13] A PTP packaging sheet with a thickness of 540 μm was produced by calendering a mixture of polyvinyl chloride (TVS-118 [manufactured by Taisei Chemical Co., Ltd.]) and barium sulfate (average particle size: 0.1 μm) so that the barium sulfate concentration was 10% by mass.

[0096] [Comparative Example 1] A PTP packaging sheet was prepared in the same manner as in Example 1, except that the thickness was changed to 160 μm.

[0097] [Comparative Example 2] A PTP packaging sheet was prepared in the same manner as in Example 7, except that the thickness of the second layer was changed to 117 μm.

[0098] [Comparative Example 3] A PTP packaging sheet with a thickness of 180 μm was produced by calendering a mixture of polyvinyl chloride (TVS-118 [manufactured by Taisei Chemical Co., Ltd.]) and barium sulfate (average particle size: 3.0 μm) so that the barium sulfate concentration was 20.45% by mass. However, the resulting sheet had a rough surface and lacked gloss, making it unsuitable for use as a PTP packaging sheet.

[0099] [Comparative Example 4] A PTP packaging sheet with a thickness of 180 μm was produced by calendering a mixture of polyvinyl chloride (TVS-118 [manufactured by Taisei Chemical Co., Ltd.]) and barium sulfate (average particle size: 0.03 μm) so that the barium sulfate concentration was 20.45% by mass.

[0100] <Barium sulfate content per unit area> The density of the PTP packaging sheets prepared in the examples and comparative examples was measured. The barium sulfate content per unit area (g / m²) of a surface perpendicular to the thickness direction of the PTP packaging sheet is calculated from the product of the measured density of the PTP packaging sheet, the thickness of the barium sulfate-containing layer (the second layer in Examples 7-10 and Comparative Example 2), and the concentration of barium sulfate in the barium sulfate-containing layer. 2) was calculated. The results are shown in Table 1.

[0101] <Radiopacity> Using the PTP packaging sheets prepared in the examples and comparative examples, an X-ray photograph was taken using an X-ray imaging apparatus (manufactured by Shimadzu Corporation, microfocus X-ray transmission apparatus SMX-1000) at an X-ray tube voltage of 90 kV and an X-ray tube current of 110 μA, and the radiopacity was visually evaluated based on the following criteria. The results are shown in Table 1. In addition, the X-ray contrast photographs of the PTP packaging sheets prepared in Examples 4 to 6, Example 10, and Comparative Example 2 are shown in FIGS. 1 to 5, respectively.

[0102] (Evaluation criteria) ◎: The photographed image has a density equal to or higher than that of the photograph of the PTP packaging sheet prepared in Example 6 (content of barium sulfate per unit area: 76.2 g / m 2 ), and the outline is clearly shown. ○: The photographed image clearly shows the outline, and the density of the photographed image is equal to or higher than that of the photograph of the PTP packaging sheet prepared in Example 5 (content of barium sulfate per unit area: 42.7 g / m 2 ), but is thinner than the photograph of the PTP packaging sheet obtained in Example 6. ×: The density of the photographed image is thinner than that of the photograph of the PTP packaging sheet prepared in Example 5, or the outline of the photographed image is blurred.

[0103] For the PTP packaging sheets with radiopacity of ◎ and ○, even in radiography using a chest / abdomen X-ray water phantom, the presence of the PTP packaging sheet could be confirmed visually without problems. Therefore, it can be judged that this sheet can also be radiopaque in the body.

[0104] <Dispersion> The PTP packaging sheets prepared in the examples and comparative examples were visually observed, and the dispersion of barium sulfate was evaluated based on the following evaluation criteria. The results are shown in Table 1.

[0105] (Evaluation criteria) ○: There is no aggregation and it is uniformly dispersed. ×: Aggregation occurs or there is a bias in the barium sulfate in the sheet.

[0106] <Transparency (Haze value)> The haze values of the PTP packaging sheets prepared in the examples and comparative examples were measured based on JIS K 7136. The results are shown in Table 1.

[0107]

Table 1

[0108] <PTP package formability> The PTP package formability of the PTP packaging sheets prepared in Examples 1, 7, and 9 was confirmed by the following method. In a PTP molding machine (manufactured by CKD Co., Ltd., FBP-M2), the PTP packaging sheets prepared in Examples 1, 7, and 9 were heated at 120 °C using a pinpoint heating plate, and then molded using a φ11.0 × H4.0 tablet mold (diameter 11 mmφ, depth 4.0 mm) and a plug assist mechanism, and the mold following property of the PTP packaging sheet to the mold (tablet mold) was evaluated. The mold following property was evaluated visually for the appearance unevenness of the pocket top, corner, and side portions. Furthermore, the obtained PTP packaging sheet having a pocket portion was sealed with an aluminum foil, and after making a slit in the obtained PTP package, it was punched out to a width of 50 mm, a length of 108 mm, and a corner R of 5 mm. The appearance of the die marks, which is the adhesion portion between the aluminum foil and the PTP packaging sheet, and the breakage of the aluminum foil of the obtained PTP package were evaluated visually.

[0109] The PTP packaging sheets prepared in Examples 1, 7, and 9 were excellent in the mold following property to the mold (tablet mold), and there were no problems with the appearance of the die marks and no breakage of the aluminum foil, and they were excellent in the formability of the PTP package.

[0110] <Safety to the human body> The impact on the human body and safety of the amount of barium sulfate used in toys were evaluated based on the international standard for toy safety (ISO 8124-3:2010). ISO 8124-3:2010 is an elution test that determines whether heavy metals such as barium in toys for children under 6 years old are present at levels that could affect health through contact or accidental ingestion. The test involves elution using hydrochloric acid at a concentration simulating gastric juice (simulating accidental ingestion), and the resulting eluate is measured by ICP mass spectrometry. In the case of barium, the elution limit is set at 1,000 mg / kg.

[0111] The PTP packaging sheet prepared in Example 2 was evaluated according to the international standard (ISO 8124-3:2010), and the barium elution amount was 134 mg / kg. This result indicates that the barium elution amount of the sheet obtained in Example 2 fully conforms to the international standard. Furthermore, it is considered that the barium elution amount of the sheet obtained in Example 4 also fully conforms to the international standard. Therefore, all of the sheets obtained in the above embodiments fully conform to international standards and can be said to be highly safe for the human body.

Claims

1. A PTP packaging sheet for containing contents, and a PTP packaging sheet that allows the contents to be visible throughout the entire sheet, The PTP packaging sheet is a single-layer sheet consisting only of layer A, which contains resin and barium sulfate with an average particle size of 0.1 to 0.6 μm as measured by laser diffraction and scattering. The barium sulfate content per unit area of ​​the surface perpendicular to the thickness direction of the PTP packaging sheet is 40 to 130 g / m². PTP packaging sheets.

2. The PTP packaging sheet according to claim 1, wherein the concentration of barium sulfate in layer A is 7 to 35% by mass.

3. A PTP packaging sheet according to claim 1 or 2, wherein the thickness is 50 to 600 μm.

4. The PTP packaging sheet according to any one of claims 1 to 3, wherein the resin is at least one selected from vinyl chloride resin, ethylene resin, and propylene resin.

5. A PTP packaging sheet according to any one of claims 1 to 4, wherein the haze value is 80% or less.

6. The PTP packaging sheet according to any one of claims 1 to 5, wherein the PTP packaging sheet is a sheet that can be visualized even when present in the body.

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