WO2022113566A1 - Ｐｔｐ用蓋材およびｐｔｐ包装体 - Google Patents

Ｐｔｐ用蓋材およびｐｔｐ包装体 Download PDF

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Publication number
WO2022113566A1
WO2022113566A1 PCT/JP2021/038438 JP2021038438W WO2022113566A1 WO 2022113566 A1 WO2022113566 A1 WO 2022113566A1 JP 2021038438 W JP2021038438 W JP 2021038438W WO 2022113566 A1 WO2022113566 A1 WO 2022113566A1
Authority
WO
WIPO (PCT)
Prior art keywords
ptp
lid material
polypropylene
layer
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/038438
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
真文 浅野
始基 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp, Asahi Chemical Industry Co Ltd filed Critical Asahi Kasei Corp
Priority to CN202180075573.9A priority Critical patent/CN116457286B/zh
Priority to CA3199705A priority patent/CA3199705A1/en
Priority to US18/253,920 priority patent/US20240002123A1/en
Priority to KR1020237006478A priority patent/KR102852189B1/ko
Priority to EP21897544.9A priority patent/EP4253278A4/en
Priority to JP2022565109A priority patent/JP7416978B2/ja
Publication of WO2022113566A1 publication Critical patent/WO2022113566A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
    • B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
    • B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
    • B65D75/325—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil
    • B65D75/327—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil and forming several compartments
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
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    • B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
    • B65D75/36—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet or blank being recessed and the other formed of relatively stiff flat sheet material, e.g. blister packages, the recess or recesses being preformed
    • B65D75/367—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet or blank being recessed and the other formed of relatively stiff flat sheet material, e.g. blister packages, the recess or recesses being preformed and forming several compartments
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    • B65D77/20—Container closures formed after filling by applying separate lids or covers, i.e. flexible membrane or foil-like covers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Definitions

  • the present invention relates to a lid material for PTP (press-through pack) and a PTP package.
  • a PTP package having a bottom material and a lid material As one of the packaging forms for pharmaceuticals and foods, a PTP package having a bottom material and a lid material is known.
  • a bottom material having a pocket-shaped recess is formed by vacuum molding or pressure molding a plastic sheet made of a polyvinyl chloride resin, a polypropylene resin, or the like, and the recess is filled with the contents.
  • Manufactured by heat-sealing the lid material to the flange portion, which is a portion other than the recess.
  • the stored contents can be taken out by applying a force to the contents from the outside of the bottom material toward the lid material to break through the lid material.
  • Patent Document 1 describes a lid having a press-through function, which uses a polypropylene-based resin film and a reinforcing resin layer laminated on the polypropylene-based resin film as a base material, and deteriorates the polypropylene-based resin film by irradiation with radiation.
  • the material is disclosed.
  • Patent Documents 2 and 3 disclose a lid material for PTP based on a sheet made of a resin composition containing a polypropylene-based resin and an inorganic substance (talc or the like) for improving projectability. ..
  • Patent Document 4 contains a crystalline thermoplastic resin as an essential component and crystallizes by heat treatment in order to have easy incineration property that can be processed under the same conditions as the bottom material and to exhibit excellent tensile cutting load, elongation and easy breakthrough property.
  • a sheet for a lid material of a crystallized blister pack package is disclosed.
  • Patent Document 5 discloses a laminated polypropylene-based film in which a resin having a certain range of heat of crystal melting is laminated on an interlayer portion in order to improve the interlayer adhesive strength in addition to hand-cutting property and mechanical strength.
  • Patent Document 6 in order to facilitate disposal after use and improve press-through property and print readability, a plastic lid material film for PTP using a styrene resin and an inorganic filler and a PTP packaging using the same. The body is disclosed.
  • Japanese Unexamined Patent Publication No. 7-256842 Japanese Unexamined Patent Publication No. 10-101133 Japanese Unexamined Patent Publication No. 9-11422 Japanese Unexamined Patent Publication No. 2000-7026 Japanese Unexamined Patent Publication No. 2000-25173 Japanese Unexamined Patent Publication No. 2013-234002
  • the lid material described in Patent Document 4 has room for improvement in terms of the above-mentioned open recognition, and is laminated with different resins such as polystyrene, ethylene-vinyl acetate copolymer saken, and nylon-6. Therefore, there is a problem that it is not suitable for material recycling. Since the lid material described in Patent Document 5 is laminated with a biaxially oriented polypropylene-based resin, there is a problem that the sticking property and the opening recognition property are deteriorated. Since the lid material described in Patent Document 6 uses a styrene resin, it is not suitable for recycling, and since an emulsion type heat sealant is applied, an unpleasant odor is generated in a high temperature environment. There is a problem of doing.
  • an object of the present invention is to provide a lid material for a PTP package and a PTP package which are excellent in sticking out property and open recognition property and which suppresses an unpleasant odor.
  • the present inventors have solved the above-mentioned problems by using a polypropylene-based resin having a specific range of molecular weight and a lid material for PTP having a specific range of heat of crystal melting. We have found that it can be solved and have completed the present invention.
  • the present invention is as follows.
  • Cover material [2] The PTP lid material according to [1], wherein the MD orientation degree is ⁇ 0.035 to 0.035.
  • the thickness is 10 to 100 ⁇ m
  • the water vapor transmission rate is 10 g / m2 ⁇ day or less
  • the tensile strength is 20 to 50 MPa for both MD and TD
  • the tensile elongation is 15% or less for both MD and TD.
  • the lid material for PTP according to any one of [1] to [4], which contains 0.1 to 3% by mass of an inorganic substance.
  • the lid material for PTP according to any one of [1] to [5], which comprises a layer containing the polypropylene-based resin and at least one surface layer containing a polyethylene-based resin, a polypropylene-based resin, or a polyolefin-based elastomer.
  • a PTP package comprising the PTP lid material according to any one of [1] to [6] and a bottom material having a recess for accommodating the contents.
  • a lid material for a PTP package and a PTP package which are excellent in sticking out property and open recognition property and suppress an unpleasant odor.
  • FIG. 1 is a cross-sectional view showing an embodiment of a PTP package provided with a PTP lid material according to the present invention.
  • FIG. 2 is a graph showing an example of a load-displacement curve obtained when a puncture test is performed on a PTP lid material according to the present invention.
  • the present embodiment will be described in detail, but the present invention is not limited to the following description and varies within the scope of the gist thereof. It can be transformed and implemented.
  • the PTP lid material (hereinafter, also simply referred to as “cover material”) of the present embodiment contains a polypropylene-based resin having a weight average molecular weight of 2.0 ⁇ 10 5 to 3.5 ⁇ 105, and is differential scanning. It is characterized in that the amount of heat of crystal melting by a calorimeter (DSC) is 70 J / g or more.
  • the polypropylene-based resin contained in the lid material for PTP of the present embodiment is not particularly limited as long as the weight average molecular weight is 2.0 ⁇ 10 5 to 3.5 ⁇ 105 , and for example, a propylene homopolymer. Examples thereof include copolymers of propylene and other monomers, and modified products thereof. Further, from the viewpoint of environmental friendliness, biopolypropylene may be used. Of these, propylene homopolymers are preferable from the viewpoints of heat resistance, water vapor barrier property, and tensile elongation.
  • the polypropylene-based resin may be used alone or in combination of two or more.
  • Examples of the monomer copolymerizable with propylene include ⁇ -olefins such as ethylene, 1-butene, isobutylene, 1-pentene, and 1-hexene.
  • the polymerization form is not particularly limited, and may be a random copolymer, a block copolymer, or the like.
  • the method for producing the polypropylene-based resin is not particularly limited, and a known method such as a method for polymerizing propylene or other monomers in the presence of a catalyst can be used. Specific examples thereof include a method of polymerizing propylene and other monomers in the presence of a catalyst and an alkylaluminum compound at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of 3 to 100 atm.
  • the catalyst include a titanium trichloride catalyst, a titanium halide catalyst supported on a carrier such as magnesium chloride, and the like.
  • a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.
  • an electron-donating compound can be used as an internal donor component or an external donor component as a third component in order to enhance the isotacticity and polymerization activity of polypropylene.
  • the electron donating compound is not particularly limited, and known compounds can be used.
  • ester compounds such as ⁇ -caprolactone, methyl methacrylate, ethyl benzoate, methyl tolulate and the like; triphenyl phosphite, phosphite phosphite, etc. can be used.
  • Subphosphate esters such as tributyl; Phosphoric acid derivatives such as hexamethylphosphoric triamide; alkoxy ester compounds; Aromatic monocarboxylic acid esters; Aromatic alkylalkoxysilanes; aliphatic hydrocarbon alkoxysilanes; Various ether compounds; Various alcoholskind: Various phenols and the like can be mentioned.
  • the polymerization method in the above method may be either a batch method or a continuous method.
  • Examples of the polymerization method include solution polymerization under a solvent such as butane, pentane, hexane, heptane, and octane, slurry polymerization, massive polymerization in a monomer under no solvent, and gas phase polymerization in a gaseous monomer. ..
  • the polypropylene-based resin may be an unmodified polypropylene-based resin modified with a modifying agent such as ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof (including acid anhydride and ester).
  • a modifying agent such as ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof (including acid anhydride and ester).
  • the modified polypropylene-based resin include those obtained by grafting or adding an unmodified polypropylene-based resin with ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof. Specific examples thereof include those in which ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof is grafted or added to the polypropylene resin at a ratio of about 0.01 to 10% by mass of the total polypropylene resin. ..
  • the modified polypropylene-based resin reacts the unmodified polypropylene-based resin with the modifying agent in the range of 30 to 350 ° C., for example, in the presence or absence of a radical generator, in a molten state, in a solution state, or in a slurry state. Obtained by letting.
  • the mixing ratio of the unmodified polypropylene and the modified polypropylene is not particularly limited and may be any ratio.
  • the weight average molecular weight of the polypropylene-based resin is 2.0 ⁇ 10 5 to 3.5 ⁇ 105, preferably 2.2 ⁇ 10 5 to 3.2 ⁇ 10 5 , and more preferably 2.3 ⁇ 10 5 . It is ⁇ 3.0 ⁇ 105 .
  • a polypropylene resin having a weight average molecular weight in the above range is not usually used for a film because of its fragility, but the PTP lid material of the present embodiment takes advantage of this fragility and has excellent projectability. ..
  • the weight average molecular weight can be measured by gel permeation chromatography (hereinafter, also referred to as “GPC”), and specifically, can be measured by the method described in Examples described later. ..
  • the content of the polypropylene-based resin is preferably 60 to 100% by mass, more preferably 70 to 95% by mass, still more preferably 75 to 90% by mass, with the PTP lid material as 100% by mass. be.
  • the content of the polypropylene-based resin is in the above range, good projectivity tends to be easily exhibited. Further, in particular, when the content of the polypropylene-based resin is 100% by mass, the lid material has excellent recyclability.
  • the lid material for PTP of the present embodiment may be a laminate having a layer containing the above-mentioned polypropylene-based resin (hereinafter, also referred to as “low molecular weight polypropylene-based resin layer”).
  • Other layers laminated on the low molecular weight polypropylene resin layer include, for example, a sealing layer for improving the sealing property with the bottom material for PTP, and an adjusting layer for adjusting the physical properties of the lid material such as strength and protrusion. Examples thereof include a reinforcing layer for preventing film breakage during packaging, a barrier layer for improving gas barrier properties, and the like.
  • the number of layers is not particularly limited, but is preferably 2 to 5 layers, more preferably 2 to 3 layers, from the viewpoint of the balance between strength, protrusion property, water vapor barrier property, sealing property, and recyclability. ..
  • the thickness of the low molecular weight polypropylene-based resin layer is preferably 60 to 95%, more preferably 70 to 95%, still more preferably 75 to 90%, with the total thickness of the PTP lid material being 100%. be.
  • the thickness of the low molecular weight polypropylene-based resin layer is in the above range, it tends to easily exhibit good protrusion property and water vapor barrier property.
  • the lid material for PTP of the present embodiment may include a layer containing the above-mentioned polypropylene-based resin and at least one surface layer containing a polyethylene-based resin, a polypropylene-based resin, or a polyolefin-based elastomer.
  • the surface layer may be either one or both of the surface layer on the bottom material side and the outer surface layer (outermost layer) adhered to the bottom material.
  • an outer surface layer may be used as a reinforcing layer for preventing the film from breaking during packaging.
  • the heat-sealing property is excellent, and since these resins can be co-extruded, it is not necessary to apply an emulsion-type heat-sealing agent, and the environment is high. However, since no unpleasant odor is generated, it is suitable as a surface layer on the bottom material side to be adhered to the bottom material.
  • a layer containing a polyolefin-based elastomer is preferable because it is particularly excellent in low-temperature sealing property, and from the viewpoint of recyclability, a polypropylene-based resin is used so that the entire lid material for PTP is composed of a polypropylene-based resin. It is preferably a layer containing.
  • the thickness of the surface layer is preferably 5 to 40%, more preferably 5 to 30%, still more preferably 10 to 25%, with the thickness of the entire PTP lid material as 100%. When the thickness of the surface layer is within the above range, good heat-sealing properties can be imparted and film breakage can be prevented without deteriorating the projecting property.
  • the polyethylene-based resin contained in the surface layer is not particularly limited and may be either an ethylene homopolymer or a copolymer of ethylene and another monomer.
  • an ethylene homopolymer an ethylene-propylene copolymer.
  • Ethylene-butene copolymer ethylene- ⁇ -olefin copolymer such as ethylene-octene copolymer; ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-ethyl acrylate-methyl methacrylate copolymer
  • examples thereof include ethylene- (meth) acrylic acid ester copolymers and the like; ethylene-vinyl acetate copolymers and the like.
  • a low-density ethylene- ⁇ -olefin copolymer is preferable because the lower the density, the better the low-temperature sealing property tends to be.
  • biopolyethylene may be used.
  • the polyethylene-based resin may be used alone or in combination of two or more.
  • the method for producing the polyethylene-based resin is not particularly limited, and polymerization can be carried out using a known catalyst such as a single-site catalyst or a multi-site catalyst.
  • the content of the polyethylene-based resin is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass, with the PTP lid material as 100% by mass. ..
  • the content of the polyethylene-based resin is within the above range, good heat-sealing properties can be imparted and film breakage can be prevented without deteriorating the projecting property.
  • Examples of the polypropylene-based resin contained in the surface layer include the same types as the above-mentioned low molecular weight polypropylene-based resin. Above all, a low-density propylene- ⁇ -olefin copolymer is preferable from the viewpoint of excellent low-temperature sealing property.
  • the molecular weight of the polypropylene-based resin is not particularly limited, but is preferably higher than that of the polypropylene-based resin contained in the above-mentioned low molecular weight polypropylene-based resin layer.
  • the melt flow rate (measured at 230 ° C. and a load of 2.16 kgf according to ASTM D-1238, MFR) is 3 to 15 g / 10 minutes.
  • the polypropylene-based resin may be used alone or in combination of two or more.
  • the polyolefin-based elastomer is a low-crystalline to amorphous olefin-based polymer having a crystallinity of 50% or less, and examples of the monomer (olefin) of the polyolefin-based elastomer include ethylene, propylene, 1-butene, and isobutylene. , 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, 2-methyl-1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, etc.
  • Cyclic olefins such as ⁇ -olefin, cyclobutene, cyclopentene, and cyclohexene can be mentioned.
  • polypropylene-based elastomers having a low melting point 55 to 90 ° C.
  • a biopolyolefin-based elastomer may be used.
  • the polyolefin-based elastomer may be used alone or in combination of two or more.
  • the method for producing the polyolefin-based elastomer is not particularly limited, and polymerization can be carried out using a known catalyst such as a single-site catalyst or a multi-site catalyst.
  • the content of the polyolefin-based elastomer is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass, with the PTP lid material as 100% by mass. ..
  • the content of the polyolefin-based elastomer is within the above range, good heat-sealing properties can be imparted and film breakage can be prevented without deteriorating the projecting property.
  • the PTP lid material of the present embodiment has an adjusting layer for adjusting the physical properties of the lid material such as strength and protrusion between the above-mentioned low molecular weight polypropylene resin layer and the surface layer. It may be included.
  • the thickness of the adjusting layer is preferably 10 to 40%, more preferably 15 to 35%, still more preferably 20 to 30%, with the thickness of the entire PTP lid material as 100%.
  • polypropylene resin for the adjusting layer.
  • the type of polypropylene-based resin include those similar to the above-mentioned low molecular weight polypropylene-based resin.
  • the molecular weight of the polypropylene-based resin is not particularly limited, but is preferably higher than that of the polypropylene-based resin contained in the above-mentioned low molecular weight polypropylene-based resin layer.
  • the melt flow rate (measured at 230 ° C. and a load of 2.16 kgf according to ASTM D-1238, MFR) is 3 to 15 g / 10 minutes.
  • the polypropylene-based resin may be used alone or in combination of two or more.
  • the lid material for PTP of the present embodiment may contain an inorganic substance in order to increase the starting point of fracture and improve the projectability.
  • the inorganic substance is not particularly limited, and examples thereof include amorphous alumina silicate, silica, alumina, talc, kaolin, mica, wallastnite, clay, calcium carbonate, glass fiber, and aluminum sulfate.
  • the content of the inorganic substance is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass, still more preferably 0.5 to 1 by mass, assuming that the lid material for PTP is 100% by mass. It is mass%.
  • the lid material exhibits good projecting property, has few impurities, and is highly recyclable.
  • the lid material for PTP of the present embodiment is an additive usually used in the art, for example, a metal soap, a colorant, a plasticizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, which assists in the dispersion of the above-mentioned inorganic substances. It may contain a lubricant, an antistatic agent, a crystal nucleating agent and the like. Further, the PTP lid material of the present embodiment may be subjected to treatments such as corona treatment, plasma treatment, ultraviolet treatment, and AC (anchor coating) treatment for the purpose of improving printing characteristics. In particular, white colorants and printing are preferable for the following reasons.
  • the thickness of the PTP lid material of the present embodiment is preferably 10 to 100 ⁇ m, more preferably 30 to 80 ⁇ m, and further preferably 40 to 60 ⁇ m.
  • the thickness is 10 ⁇ m or more, the tensile strength and the water vapor barrier property that can withstand the processing step are easily exhibited, and when the thickness is 100 ⁇ m or less, good protrusion property is easily exhibited.
  • the water vapor transmission rate of the PTP lid material of the present embodiment is preferably 10 g / m 2 ⁇ day or less, more preferably 8 g / m 2 ⁇ day or less, and further preferably 5 g / m 2 ⁇ day or less. Is. When the water vapor transmission rate is within the above range, it is possible to prevent the contents of pharmaceutical products and the like from being denatured by water vapor, and long-term storage is possible.
  • the water vapor transmission rate of the PTP lid material can be adjusted by, for example, the thickness of the PTP lid material, the selection of the type of resin, the presence or absence of the barrier layer, and the like.
  • the water vapor transmission rate tends to decrease.
  • the barrier layer include a resin layer such as an ethylene-vinyl alcohol copolymer and a cyclic olefin, and an inorganic vapor deposition layer such as aluminum, aluminum oxide and silicon oxide.
  • a resin having a high degree of crystallinity the water vapor transmission rate of the PTP lid material can be lowered.
  • the water vapor transmission rate is a value measured in accordance with JIS K7129 and converted into a thickness of 40 ⁇ m, and can be specifically obtained by the method described in Examples described later.
  • the MD tensile strength of the PTP lid material of the present embodiment is preferably 20 to 50 MPa, more preferably 20 to 45 MPa, and even more preferably 25 to 35 MPa.
  • the MD tensile strength is 20 MPa or more, it is possible to prevent the film from breaking in the processing process. Further, when the MD tensile strength is 50 MPa or less, a PTP lid material having good protrusionability can be obtained.
  • Examples of the method for controlling the MD tensile strength of the PTP lid material include a method of changing the crystallinity of the resin and stretching, and the MD tensile strength tends to increase when the crystallinity is increased or stretched. It is in.
  • the TD tensile strength of the PTP lid material of the present embodiment is preferably 20 to 50 MPa, more preferably 20 to 45 MPa, and even more preferably 25 to 35 MPa.
  • the TD tensile strength is 20 MPa or more, it is possible to prevent the film from breaking in the processing process. Further, when the TD tensile strength is 50 MPa or less, a PTP lid material having good protrusionability can be obtained.
  • Examples of the method for controlling the TD tensile strength of the PTP lid material include a method of changing the crystallinity of the resin and stretching, and when the crystallinity is increased or stretched, the MD tensile strength tends to increase. It is in.
  • the tensile strengths of MD and TD can be measured in accordance with JIS K7127, and specifically, can be measured by the method described in Examples described later.
  • the MD tensile elongation of the PTP lid material of the present embodiment is preferably 15% or less, more preferably 11% or less, still more preferably 9% or less.
  • the protrusion property in the TD direction tends to be good (the lid material tends to be easily pierced in a state where the crack enters the TD direction).
  • the method for controlling the MD tensile elongation of the PTP lid material include a method of adjusting the crystallinity, MD orientation degree, fracture starting point, vulnerability, breaking strength, etc. of the PTP lid material.
  • the fragility is increased by increasing the ratio of the fragile layer such as the resin layer, and the breaking strength is decreased by softening the fragile layer.
  • the TD tensile elongation of the PTP lid material of the present embodiment is preferably 15% or less, more preferably 11% or less, still more preferably 9% or less.
  • the protrusion property in the MD direction tends to be good (the lid material is likely to be pierced in a state where the crack enters the MD direction).
  • Examples of the method for controlling the TD tensile elongation of the PTP lid material include a method of adjusting the crystallinity, the TD orientation degree, the fracture starting point, the brittleness, the fracture strength and the like of the PTP lid material.
  • TD tensile elongation
  • increase the crystallinity of the lid material for PTP decrease the degree of orientation of TD, increase the starting point of fracture by adding an inorganic substance, etc., and the above-mentioned low molecular weight polypropylene system.
  • the fragility is increased by increasing the ratio of the fragile layer such as the resin layer, and the breaking strength is decreased by softening the fragile layer.
  • the tensile elongation of MD and TD can be measured according to JIS K7127, and specifically, can be measured by the method described in Examples described later.
  • the MD tensile elastic modulus of the PTP lid material of the present embodiment is preferably 300 to 1500 MPa, more preferably 400 to 1400 MPa, and further preferably 600 to 1200 MPa.
  • the MD tensile elastic modulus is 300 MPa or more, the film is suppressed from stretching when printing on the PTP lid material, and printing misalignment can be prevented.
  • the MD tensile elastic modulus is 1500 MPa or less, it is possible to suppress the PTP lid material from becoming hard and prevent cracking during processing.
  • Examples of the method for controlling the MD tensile elastic modulus of the PTP lid material include a method of adjusting the crystallization degree and the MD orientation degree of the PTP lid material. When the crystallization degree and the MD orientation degree are lowered, the MD tension is used. The elastic modulus tends to decrease.
  • the TD tensile elastic modulus of the PTP lid material of the present embodiment is preferably 1500 MPa or less, more preferably 1400 MPa or less, and further preferably 1200 MPa or less.
  • the method for controlling the TD tensile elastic modulus of the PTP lid material include a method of adjusting the crystallization degree and the MD orientation degree of the PTP lid material. When the crystallization degree and the MD orientation degree are lowered, the TD tension The elastic modulus tends to decrease.
  • the tensile elastic modulus of MD and TD can be measured according to JIS K7127, and specifically, can be measured by the method described in Examples described later.
  • the amount of heat of crystal melting measured by the differential scanning calorimetry (DSC) of the lid material for PTP of the present embodiment is 70 J / g or more, preferably 75 to 200 J / g, and more preferably 80 to 200 J / g. be.
  • the amount of heat for melting the crystal is in the above range, the MD and TD tensile elongations and the piercing elongations are suitable, and tend to show good ejection properties.
  • Examples of the method for controlling the amount of heat of crystal melting of the PTP lid material include a method of adjusting cooling of the lid material during production of the PTP lid material, annealing after production, addition of a crystal nucleating agent, and the like.
  • DSC differential scanning calorimeter
  • the crystallinity measured by the Fourier transform infrared spectrophotometer (FT-IR) of the lid material for PTP of the present embodiment is preferably 46% or more, more preferably 47% or more, still more preferably. It is over 48%.
  • the method for controlling the crystallinity of the PTP lid material include a method of adjusting the cooling of the lid material at the time of producing the PTP lid material, annealing after production, addition of a crystal nucleating agent, and the like.
  • the lid material for PTP is manufactured by the direct inflation method
  • the cooling of the lid material by airing is gradually cooled
  • the lid material is annealed after the manufacture, and a crystal nucleating agent is added to crystallize.
  • the degree of crystallinity can be increased.
  • the crystallinity by FT-IR can be specifically measured by the method described in Examples described later, and can be similarly measured by using a Raman spectrophotometer.
  • the MD orientation of the PTP lid material of the present embodiment is preferably ⁇ 0.035 to 0.035, more preferably ⁇ 0.03 to 0.03, and even more preferably ⁇ 0.02 to 0.02 to 0.02 to 0.03. It is 0.02.
  • the MD orientation degree is in the above range, the MD tensile elongation and the TD tensile elongation are likely to be in the preferable range, the balance between the MD and TD tensile elongations is excellent, and good protrusionability is exhibited.
  • Examples of the method for controlling the MD orientation of the PTP lid material include a method of adjusting the cooling of the lid material, the TD stretching ratio (BUR), the timing, and the like when manufacturing the PTP lid material.
  • the degree of MD orientation can be reduced.
  • the degree of MD orientation can be measured using FT-IR, and specifically, it can be measured by the method described in Examples described later. Further, since the degree of MD orientation indicates the orientation toward MD with respect to TD, it may be calculated from the results of measuring the orientation toward MD with respect to the thickness direction and the orientation toward TD with respect to the thickness direction of the PTP lid material. ..
  • the thickest layer tends to affect the characteristics of the PTP lid material, so that the thickest layer (if there are a plurality of thickest layers, the thickest layer). Either) may be measured. Further, the MD orientation degree can be measured by using a Raman spectrophotometer as in the case of using FT-IR.
  • the maximum load decrease per 0.1 mm displacement in the fracture region is preferably 3 to 20 N, more preferably 4 to 18 N, still more preferably 5. It is ⁇ 15N.
  • the PTP lid material having a maximum load reduction of more than 20 N per 0.1 mm displacement shows that the contents such as tablets are not easily torn when the contents such as tablets are taken out from the PTP package, and the sticking property tends to be poor.
  • the maximum load decrease per 0.1 mm displacement is one of the factors most affecting the open recognition, and when the maximum load decrease per 0.1 mm displacement is less than 3N, the lid material for PTP is brittle.
  • FIG. 2 shows an example of a load-displacement curve obtained when a puncture test is performed on the PTP lid material of the present embodiment.
  • the maximum load reduction per displacement of 0.1 mm is 8N.
  • the method for controlling the maximum load reduction per 0.1 mm displacement of the PTP lid material include a method of adjusting the weight average molecular weight of the polypropylene-based resin, the thickness of the PTP-based lid material, and the reinforcing layer.
  • the maximum load reduction per 0.1 mm of displacement can be increased.
  • the maximum load decrease per 0.1 mm of displacement in the fracture region of the load-displacement curve can be measured by the method described in Examples described later.
  • the puncture strength of the PTP lid material of the present embodiment is preferably 6 to 15N, more preferably 7 to 13N, and even more preferably 8 to 10N.
  • the piercing strength is 6 N or more, it is possible to prevent the PTP lid material from being torn by an external force during transportation of the PTP package. Further, when the piercing strength is 15 N or less, a PTP lid material having excellent protrusionability can be obtained.
  • Examples of the method for controlling the puncture strength of the PTP lid material include a method of adjusting the weight average molecular weight of the polypropylene resin, the thickness of the PTP lid material, and the reinforcing layer, and the weight average molecular weight of the polypropylene resin and the PTP lid. Increasing the thickness of the material or providing a reinforcing layer tends to increase the puncture strength.
  • the puncture strength is a value converted into a thickness of 40 ⁇ m, and can be specifically obtained by the method described in Examples described later.
  • the piercing elongation of the PTP lid material of the present embodiment is preferably 1 to 4 mm, more preferably 1.2 to 3 mm, still more preferably 1.5 to 2.5 mm.
  • the piercing elongation is 1 mm or more, it is possible to prevent the PTP lid material from being torn by an external force during transportation of the PTP package.
  • the piercing elongation is one of the factors having the greatest influence on the protruding property as well as the tensile elongation and the protruding strength, and when the piercing elongation is 4 mm or less, the PTP lid material having excellent protruding property is obtained. Can be obtained.
  • Examples of the method for controlling the piercing elongation of the PTP lid material include a method of adjusting the weight average molecular weight of the polypropylene resin, the layer ratio of the PTP lid material, the degree of crystallization, the degree of MD and TD orientation, and the like.
  • the weight average molecular weight of the polypropylene resin is reduced, the proportion of the low molecular weight polypropylene resin is increased, the degree of crystallization is increased, or the degree of MD and TD orientation is decreased, the puncture elongation tends to decrease. be.
  • the puncture elongation can be measured by the method described in Examples described later.
  • the method for producing the lid material for PTP is not particularly limited, but as an example, direct inflation in which the constituent material is extruded into a tube shape using a known melt extruder equipped with an annular die and then directly blown with air for stretching. The law is mentioned.
  • the lid material for PTP is a laminated body composed of a plurality of layers
  • the coextrusion direct inflation method is preferable.
  • a method for manufacturing the PTP lid material, which is a laminated body, by the coextrusion direct inflation method will be described in outline.
  • the resin or resin composition that is the constituent material of each layer is melted at a temperature higher than the melting temperature of the resin, and each layer is extruded at the same time using the number of extruders corresponding to the number of layers.
  • the extruded resin or resin composition of each layer is sent to an annular die through a feed pipe to prepare a tubular film in which each layer is laminated via the annular die. Subsequently, air (air, nitrogen, etc.) is blown into the film to form bubbles, and the film is stretched in the MD and TD directions to manufacture a lid material for PTP.
  • the MD stretch ratio (DDR) of the film is preferably 8 to 23 times, more preferably 10 to 20 times.
  • the MD stretching ratio is 8 times or more, the pulsation of the bubble is suppressed and the stretching tends to be stabilized.
  • the MD draw ratio is 23 times or less, a lid material having a suitable MD orientation degree, an excellent balance between the MD and TD orientation degrees, and a good protrusion property can be obtained.
  • the TD stretch ratio (BUR) of the film is preferably 1.3 to 4 times, more preferably 1.5 to 2.5 times. When the TD stretching ratio is 1.3 times or more, the MD orientation degree is suitable, the balance between the MD and TD orientation degree is excellent, and a lid material showing good protrusion property can be obtained.
  • the MD draw ratio can be adjusted by the speed of the pinch roller, and the TD draw ratio can be adjusted by the volume of air blown into the film.
  • the stretching temperature of the film is preferably 70 to 160 ° C, more preferably 80 to 120 ° C.
  • the stretching temperature is the temperature measured by a non-contact thermometer on the film surface at a portion vertically 32 cm away from the ejection surface of the annular die on the downstream side of the manufacturing process, and is the wind speed of the air ring for cooling the molten resin. It can be adjusted by the discharge amount of the molten resin, DDR and the like.
  • FIG. 1 is a cross-sectional view showing an example of a PTP package provided with the PTP lid material of the present embodiment.
  • the PTP package 1 includes a PTP lid material 2 and a bottom material 3.
  • the bottom material 3 has a pocket-shaped recess 4 and a flange portion 5 bonded to the lid material 2, and the recess 4 is filled with the contents 6.
  • Examples of the bottom material constituting the PTP package of the present embodiment include a polyvinyl chloride resin, a polyvinylidene chloride resin, and a polyolefin resin (for example, a polyethylene resin, a polypropylene resin, and an ethylene-vinyl alcohol copolymer resin). , Cyclic olefin resin, etc.), polychlorotrifluoroethylene, polyester and other well-known synthetic resins, and preferred are sheet materials made of these synthetic resins.
  • a polyethylene resin a polypropylene resin, and a cyclic olefin resin
  • a polypropylene resin as in the case of the lid material for PTP.
  • the bottom material preferably has a heat distortion temperature of 50 to 160 ° C., preferably 80 to 120 ° C., in accordance with JIS K7191 from the viewpoint of a wide range of molding conditions for vacuum or pneumatic molding the pocket-shaped recesses of the bottom material. Is more preferable.
  • the shape of the bottom material is not particularly limited as long as it has a recess for accommodating the contents, and the shape of the bottom surface portion and the opening portion of the recess is rectangular (square, rectangle, triangle, etc.) or circular (circle, ellipse, etc.). ), And the rectangle may have rounded corners.
  • the size of the bottom material is not particularly limited and may be appropriately determined according to the size and number of the contents.
  • the depth of the recess may be 1 to 15 mm, preferably 2 to 10 mm. ..
  • the diameter of the opening portion may be, for example, 5 to 150 mm, preferably 10 to 100 mm, respectively, and the diameter of the bottom surface portion is set. Each may be 5 to 20% smaller than the diameter of the opening.
  • the flange portion which is a portion other than the concave portion is not particularly limited, but may be provided so as to extend in a direction orthogonal to the depth direction of the concave portion.
  • the average width of the flange portion may be, for example, 2 to 100 mm, preferably 4 to 50 mm.
  • the thickness of the bottom material 1 is not particularly limited, and may be, for example, 100 to 500 ⁇ m, preferably 150 to 300 ⁇ m.
  • the PTP package of the present embodiment can be manufactured by superimposing the surface of the bottom material (flange portion) and the surface of the lid material and heat-sealing them.
  • the heat seal temperature is, for example, 100 to 160 ° C., and is preferably 100 to 140 ° C. from the viewpoint of making it difficult for the contents to be burnt.
  • the heat sealing time is, for example, 0.05 to 3 seconds, and is preferably 0.2 to 1 second from the viewpoint that the contents are less likely to be burnt and a sufficient sealing strength can be obtained.
  • the heat-sealing pressure is, for example, 0.2 to 0.6 MPa, and is preferably 0.3 to 0.5 MPa from the viewpoint of preventing burn marks on the contents and obtaining sufficient sealing strength.
  • a roll seal molding machine in which a lid material and a bottom material are sandwiched between a heat seal roll and a roll under the seal to perform heat sealing, and heating of flat plates up and down.
  • a flat seal molding machine having a mold and sandwiching a lid material and a bottom material with a mold for molding. Above all, it is preferable to use a flat seal molding machine that can easily obtain sufficient seal strength.
  • TPO Polyolefin-based elastomer
  • Toughmer XM7070 Polyolefin-based elastomer
  • Adhesive resin > -Acid-modified polyolefin composition (manufactured by Mitsui Chemicals, Inc., Admar NF587)
  • ⁇ Bottom material> -PP Polypropylene single-layer sheet (Sumilite NS-3450 (thickness 300 ⁇ m) manufactured by Sumitomo Bakelite Co., Ltd.). It was formed into a bottom material having a depth: 4 mm, an opening portion: a circle having a diameter of 10 mm, and a bottom portion: a circular recess having a diameter of 8 mm, and having a flange portion having an average width of 10 mm extending in a direction orthogonal to the depth direction.
  • the opening portions were arranged in columns and rows orthogonal to each other, and the distance between the centers of the opening portions was 20 mm in the vertical direction and 20 mm in the horizontal direction.
  • -PP / PE Polypropylene (manufactured by SunAllomer Ltd., PL500A), polypropylene (manufactured by SunAllomer Ltd., PC540R), polyethylene (manufactured by Ube-Maruzen Polyethylene Co., Ltd., Ube-Maruzen Polyethylene Co., Ltd., Umerit 0520F) by the coextrusion direct inflation method.
  • a laminated multilayer sheet having a thickness of 300 ⁇ m was produced. The polyethylene side of the multilayer sheet was used as a heat-sealing surface, and molding was performed in the same manner as the polypropylene single-layer sheet described above.
  • -PVC Polyvinyl chloride single layer sheet (Sumilite VSS-F110 (thickness 250 ⁇ m) manufactured by Sumitomo Bakelite Co., Ltd.). It was molded in the same manner as the polypropylene single layer sheet described above.
  • Weight average molecular weight With respect to the polypropylene-based resin used as the lid material for PTP in Examples and Comparative Examples, the weight average molecular weight was measured by the following procedure. First, 1,2,4-trichlorobenzene was added to the sample so that the concentration became 1 mg / mL, and the sample was allowed to stand at 160 ° C. for 30 minutes and then shaken at 160 ° C. for 1 hour to dissolve. The solution was filtered through a 0.5 ⁇ m PTFE filter, and the polystyrene-equivalent weight average molecular weight was measured with GPC (PL-GPC220, manufactured by Agilent). The column used for the measurement was a combination of two TSK-gelGMH HR -H (20) HT (7.8 mm ⁇ 30 cm) manufactured by Tosoh Corporation, and the column temperature was 160 ° C.
  • the movement was performed at a moving speed of 200 mm / min between the chucks, and at that time, the maximum load and the maximum elongation required for breaking were measured and used as the tensile strength (MPa) and the tensile elongation (%), respectively. Further, the load at the time of 2% elongation was defined as the tensile elastic modulus (MPa). The values measured for 10 test pieces were averaged and used as the tensile strength, tensile elongation, and tensile elastic modulus of the PTP lid material.
  • Crystallinity The crystallinity (%) of the PTP lids obtained in Examples and Comparative Examples was measured using a Fourier transform infrared spectrophotometer (FT / IR4100, manufactured by JASCO Corporation). did. To calculate the crystallinity, the absorbance of polypropylene resin 973 cm -1 (peak derived from crystals and amorphous) and 998 cm -1 (peak derived from crystals) (hereinafter, the absorbance indicates the height of the peak). was calculated by the following formula.
  • Crystallinity 0.56 x Absorbance (998 cm -1 ) / Absorbance (973 cm -1 ) x 100 The number of integrations during measurement was 16 times, the resolution was 4 cm -1 , and the average value of the values measured for 5 test pieces was taken as the crystallinity.
  • MD orientation of the PTP lid materials obtained in Examples and Comparative Examples was measured using a Fourier transform infrared spectrophotometer (FT / IR4100, manufactured by JASCO Corporation).
  • the degree of MD orientation was determined by the following formula using the absorbance of 973 cm -1 of each polypropylene resin measured at 0 ° (MD) and 90 ° (TD) of the grid splitter for the PTP lid material. rice field.
  • the number of integrations during measurement was 16 times, the resolution was 4 cm -1 , and the average value of the values measured for 5 test pieces was taken as the MD orientation degree.
  • Puncture strength and piercing elongation were measured by the following procedure.
  • the lid material for PTP was fixed in a state of being stretched on a frame having a diameter of 10 mm.
  • a puncture test was performed by attaching a needle with a diameter of 4 mm and a flat tip to a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph) and pushing it into a fixed PTP lid material.
  • the measurement was performed in an environment of a temperature of 23 ° C. and a humidity of 50% RH, and the moving speed of the needle was 50 mm / min.
  • the maximum load applied to the needle at the time of tearing was defined as the puncture strength (N) and converted into a thickness of 40 ⁇ m. Further, the depth of the position of the tip of the needle at the time of occurrence of tear (displacement from the contact of the needle with the fixed PTP lid material to the position at the time of occurrence of tear) was defined as the puncture elongation (mm). The values measured for the five test pieces were averaged and used as the puncture strength and puncture elongation of the PTP lid material.
  • the load reduction at break in the piercing test was measured by the following procedure.
  • the lid material for PTP was fixed in a state of being stretched on a frame having a diameter of 10 mm.
  • a puncture test was performed by attaching a needle with a diameter of 4 mm and a flat tip to a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph) and pushing it into a fixed PTP lid material.
  • the measurement was performed in an environment of a temperature of 23 ° C. and a humidity of 50% RH, and the moving speed of the needle was 50 mm / min.
  • this test piece was attached so that a seal portion was placed between the chucks of a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph) and the distance between the chucks was 30 mm. The movement was performed at a moving speed of 200 mm / min between the chucks, a 180 ° peeling test was carried out, and the maximum load until the sealed portion was completely peeled was defined as the sealing strength (N / 15 mm). The values measured for 10 test pieces were averaged and used as the sealing strength of the PTP lid material.
  • Opening recognition For the PTP packages obtained in Examples and Comparative Examples, the opening sound when the contents were taken out by breaking through the lid material was recorded using a normal sound level meter (NA-29, manufactured by Rion Co., Ltd.). The opening recognition was evaluated according to the following evaluation criteria. At the time of opening sound measurement, the distance between the tip of the microphone and the lid material to break through was set to 30 mm, and the average value of 10 measurements was adopted. [Evaluation criteria] ⁇ (excellent): 80 dB or more ⁇ (good): 60 dB or more, less than 80 dB ⁇ (defective): less than 60 dB, or it is impossible to break through the lid material
  • the gas adsorbed on the activated carbon-based adsorbent was desorbed at 300 ° C. in the TDU section using a heat desorption device (TDU2 manufactured by Gestel) installed in the GC / MS injection port. During that time, the gas was reconcentrated at ⁇ 40 ° C. in the CIS section and heated again to 300 ° C. for GC / MS measurement.
  • the unpleasant odor components of the lid material for PTP include acetic acid, butanoic acid, acetylacetone and the like, and the film odor was evaluated as follows based on the detected amounts of butanoic acid and acetic acid.
  • Example 1 Using the coextrusion direct inflation method, a two-layer PTP lid material in which a polypropylene resin (PP) layer (first layer) and a polyolefin-based elastomer (TPO) layer (second layer) were laminated was produced. Specifically, the pellets of the resin, which is the raw material of each layer, were melted at a temperature equal to or higher than the melting temperature of the resin, and each layer was extruded at the same time using a plurality of extruders. The extruded resin of each layer was sent to an annular die through a feed pipe, and a tubular laminated film in which each layer was laminated was produced through the annular die.
  • PP polypropylene resin
  • TPO polyolefin-based elastomer
  • the stretching ratio was MD30 times and TD2 times, and the stretching temperature was 61 ° C.
  • a tablet is filled in the recess of the PP bottom material, and the PP bottom material and the lid material (TPO layer side) are adhered by heat sealing using an Acein pack sealer (manufactured by Acein pack industry, semi-automatic OS) to form a PTP package.
  • Got The conditions for heat sealing were a temperature of 140 ° C., a pressure of 0.4 MPa, and a time of 1 second. Table 1 shows the measurement / evaluation results of each physical property.
  • Example 2 to 5 and Comparative Examples 1 to 3 PTP lids were prepared in the same manner as in Example 1 except that the raw materials, blending amounts, etc. were changed as shown in Table 1, and PTP packages were obtained. rice field.
  • amorphous aluminosilicate was mixed with polypropylene resin (PP2) before extrusion.
  • Table 1 shows the detailed conditions and the measurement / evaluation results of each physical property.
  • Example 6 In Example 6, as shown in Table 1, the raw materials, the blending amount, and the like were changed to prepare a two-layer film in which the first layer and the second layer were laminated in the same manner as in Example 1, and then the first layer was prepared.
  • a lid material for PTP was produced by corona treating the side surface and providing an inorganic vapor deposition layer (third layer) of aluminum by a vacuum vapor deposition method at 10 nm.
  • the PP bottom material and the lid material (TPO layer side) were adhered in the same manner as in Example 1 to obtain a PTP package.
  • Table 1 shows the detailed conditions and the measurement / evaluation results of each physical property.
  • Comparative Example 4 In Comparative Example 4, as shown in Table 1, the raw materials, the blending amount, and the like were changed to prepare a two-layer film in which the first layer and the second layer were laminated in the same manner as in Example 1, and then Patent Document 1 A lid material for PTP was produced by irradiating an electron beam having an acceleration voltage of 250 kV and an irradiation dose of 60 kGy with reference to. The PP / PE bottom material (PE layer side) and the lid material (PE layer side) were adhered in the same manner as in Example 1 to obtain a PTP package. Table 1 shows the detailed conditions and the measurement / evaluation results of each physical property.
  • EVA ethylene vinyl acetate
  • the PP bottom material and the lid material (TPO layer side) were adhered in the same manner as in Example 1 to obtain a PTP package.
  • Table 1 shows the detailed conditions and the measurement / evaluation results of each physical property.
  • the lid material for a PTP package of the present invention can be suitably used for packaging pharmaceutical products such as tablets and capsules and food products such as candy and chocolate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Packages (AREA)
PCT/JP2021/038438 2020-11-24 2021-10-18 Ｐｔｐ用蓋材およびｐｔｐ包装体 Ceased WO2022113566A1 (ja)

Priority Applications (6)

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CN202180075573.9A CN116457286B (zh) 2020-11-24 2021-10-18 Ptp用盖材和ptp包装体
CA3199705A CA3199705A1 (en) 2020-11-24 2021-10-18 Lid material for ptp and ptp body
US18/253,920 US20240002123A1 (en) 2020-11-24 2021-10-18 Lid material for ptp and ptp body
KR1020237006478A KR102852189B1 (ko) 2020-11-24 2021-10-18 Ptp 용 덮개재 및 ptp 포장체
EP21897544.9A EP4253278A4 (en) 2020-11-24 2021-10-18 COVERING MATERIAL FOR PTP AND PTP PACKAGE
JP2022565109A JP7416978B2 (ja) 2020-11-24 2021-10-18 Ｐｔｐ用蓋材およびｐｔｐ包装体

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JPH0911422A (ja) 1995-07-04 1997-01-14 Idemitsu Petrochem Co Ltd ブリスター蓋材用フィルム
JP3173767B2 (ja) 1996-09-30 2001-06-04 住友ベークライト株式会社 Ｐｔｐ用蓋材シート
JP2000007026A (ja) 1998-06-19 2000-01-11 Gunze Ltd ブリスタ−パック包装体の蓋材用シート
JP2000025173A (ja) 1998-07-08 2000-01-25 Toray Ind Inc 積層ポリプロピレン系フイルム
KR20020063300A (ko) * 2000-01-21 2002-08-01 미쓰이 가가쿠 가부시키가이샤 올레핀계 블록 공중합체, 그 제조방법 및 그 용도
EP1911803A4 (en) * 2005-08-02 2009-07-15 Mitsui Chemicals Inc POLYPROPLYENE-RESIN COMPOSITION, FOIL, STRIPED SLIP, MULTILAYER BODY, AND SCRAPPED SLIP
JP5515856B2 (ja) * 2010-02-26 2014-06-11 三菱化学株式会社 積層体およびそれを使用した包装材料
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JPH11105217A (ja) * 1997-10-06 1999-04-20 Tohcello Co Ltd プレススルーパックカバー用積層フィルム
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CA3199705A1 (en) 2022-06-02
EP4253278A1 (en) 2023-10-04
JPWO2022113566A1 (https=) 2022-06-02
KR20230042733A (ko) 2023-03-29
CN116457286B (zh) 2025-09-26
EP4253278A4 (en) 2024-05-22
KR102852189B1 (ko) 2025-08-28
US20240002123A1 (en) 2024-01-04
CN116457286A (zh) 2023-07-18

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