Cap material for ptp and ptp package

Abstract

The present application provides a lid material for PTP, characterized in that it contains a polyethylene-based resin having a weight average molecular weight of 3.5 x 10 4 ~ 5.2 x 10 4 and a crystalline melting heat of 130 J / g or more based on a differential scanning calorimeter (DSC).

Description

Technical Field

[0001] This invention relates to lid materials and PTP packaging bodies for PTP (press-through pack) packaging. Background Technology

[0002] As a packaging method for pharmaceuticals, food, and other products, PTP packaging, which consists of a base material and a lid, is known. PTP packaging is manufactured as follows: a plastic sheet made of polyvinyl chloride (PVC) or polypropylene (PP) resin is vacuum-formed or press-formed to create a base material with a pocket-shaped recess. After the contents are filled into this recess, the lid material is heat-sealed onto the portion outside the recess, i.e., the flange. The contents are then removed by applying force from the outside of the base material toward the lid material, causing the lid material to puncture.

[0003] Previously, lids were made of materials such as aluminum foil and cellophane, which had excellent extrusion properties (easily broken when the contents were extruded). However, in recent years, due to the trend of reducing single-use plastic products and implementing recycling and conversion into renewable resources, recyclable and environmentally friendly PTP packaging has gained attention. This type of packaging uses plastic sheets not only in the bottom material but also in the lid material, thus eliminating the need for sorting when discarded as waste.

[0004] For example, Patent Document 1 discloses a cover material with an extrusion function, which uses a polypropylene resin film and a reinforcing resin layer laminated on the polypropylene resin film as a substrate, and degrades the polypropylene resin film by irradiation with radiation.

[0005] In addition, Patent Documents 2 and 3 disclose a capping material for PTP, which uses a sheet made of a resin composition as a substrate, the resin composition comprising a polyethylene resin or a polypropylene resin and an inorganic substance (talc, etc.) for improving ejection properties.

[0006] Patent document 4 discloses a polyethylene sheet that combines extrusion properties, moisture resistance, and impact resistance by using an ethylene polymer with a specific range of crystallization melting temperature and heat of crystallization, a crystallizing nucleating agent, and a cyclic olefin resin.

[0007] Patent document 5 discloses a sheet for the lid of a blister pack. In order to make it flammable under the same conditions as the base material and to exhibit excellent tensile breaking load, elongation and puncture resistance, a crystalline thermoplastic resin is used as an essential component and is crystallized by heat treatment.

[0008] Patent document 6 discloses a plastic PTP cover film and a PTP packaging body using the cover film. In order to facilitate disposal after use and improve extrusion and print readability, styrene-based resin and inorganic fillers are used.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 7-256842

[0012] Patent Document 2: Japanese Patent Application Publication No. 10-101133

[0013] Patent Document 3: Japanese Patent Application Publication No. 9-11422

[0014] Patent Document 4: Japanese Patent Application Publication No. 2012-172100

[0015] Patent Document 5: Japanese Patent Application Publication No. 2000-7026

[0016] Patent Document 6: Japanese Patent Application Publication No. 2013-234002 Summary of the Invention

[0017] The problem that the invention aims to solve

[0018] However, the cover material described in Patent Document 1 has the following problems: when irradiated with radiation to degrade the polypropylene resin film, the ejection performance deteriorates due to cross-linking of the reinforcing resin layer; and unpleasant odors remain when the polypropylene resin film degrades.

[0019] Furthermore, the cap materials described in Patent Documents 2 to 4 all have room for further improvement in terms of the ability to identify the opening by producing an opening sound when the contents are removed by piercing the cap material.

[0020] In addition to the room for improvement in terms of the aforementioned openability and recognizability, the cap material described in Patent Document 5 also has the problem of being unsuitable for material recycling because it is laminated with different resins such as polystyrene, ethylene-vinyl acetate copolymer saponified and nylon-6.

[0021] The cover material described in Patent Document 6 has the following problems: because it uses styrene-based resin, it is not suitable for recycling, and because it is coated with an emulsion-type heat sealant, it produces an unpleasant odor at high temperatures.

[0022] Therefore, the object of the present invention is to provide a PTP packaging cap material and a PTP packaging body that have excellent ejection and opening recognition and suppress unpleasant odors.

[0023] Methods for solving problems

[0024] In order to solve the above-mentioned problems, the inventors have conducted in-depth research and found that by producing a PTP capping material with a molecular weight of polyethylene resin within a specific range and a specific range of heat of melting of crystallization, the above-mentioned problems can be solved, thus completing the present invention.

[0025] That is, the present invention is as follows. [1]

[0027] A PTP capping material, characterized in that it comprises a weight-average molecular weight of 3.5 × 10⁻⁶. 4 ~5.2×10 4 The heat of fusion for the polyethylene resin based on differential scanning calorimetry (DSC) is above 130 J / g. [2]

[0029] As described in [1], the PTP cover material has an MD orientation degree of -0.035 to 0.035. [3]

[0031] As described in [1], the PTP cover material has an MD orientation degree of -0.025 to 0.025. [4]

[0033] As described in any one of [1] to [3], the maximum load in the fracture zone for every 0.1 mm displacement in the load-displacement curve of the above-mentioned PTP cover material during the puncture test is reduced to 3 to 20 N. [5]

[0035] PTP cover material as described in any of [1] to [4], wherein the thickness is 10 to 100 μm and the water vapor permeability is 10 g / m². 2 For days below, the tensile strength is 10-40 MPa in both MD and TD, and the elongation is below 25% in both MD and TD. [6]

[0037] The PTP cover material as described in any one of [1] to [5] contains 0.1 to 3% by mass of inorganic matter. [7]

[0039] The PTP cover material as described in any one of [1] to [6] comprises: a layer comprising the above-mentioned polyethylene resin; and at least one surface layer comprising polyethylene resin, polypropylene resin or polyolefin elastomer. [8]

[0041] A PTP package, characterized in that it comprises a lid material for PTP according to any one of [1] to [7] and a bottom material having a recess for accommodating the contents.

[0042] Effects of the invention

[0043] According to the present invention, it is possible to provide a lid material for a PTP package and a PTP package that have excellent ejection properties and开封识别性 (it seems there is a mistake here, maybe "开封识别性" should be "开封识别性能" or something else, but keeping it as is for now), and suppress unpleasant odors. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 It is a cross-sectional view showing an embodiment of a PTP package provided with the lid material for PTP of the present invention.

[0045] Figure 2 It is a diagram showing an example of a load-displacement curve obtained when a puncture test is performed on the lid material for PTP of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] Hereinafter, the specific embodiments of the present invention (hereinafter referred to as "the present embodiments") will be described in detail. However, the present invention is not limited to the following description and can be implemented with various modifications within the scope of its gist.

[0047] <Lid material for PTP>

[0048] The lid material for PTP (hereinafter also simply referred to as "lid material") of the present embodiment is characterized in that it contains a polyethylene resin having a weight average molecular weight of 3.5×10 4 ~5.2×10 4 and the heat of fusion of crystallization based on a differential scanning calorimeter (DSC) is 130 J / g or more.

[0049] <Polyethylene resin>

[0050] The polyethylene 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 3.5×10 4 ~5.2×10 4 and can be either an ethylene homopolymer or a copolymer of ethylene and other monomers. For example, it can be: an ethylene homopolymer; ethylene-α-olefin copolymers such as ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer; ethylene-(meth)acrylate copolymers such as ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-ethyl acrylate-methyl methacrylate copolymer; ethylene-vinyl acetate copolymer, etc. Among them, since the lower the density, the more the low-temperature sealing property tends to improve, a low-density ethylene-α-olefin copolymer is preferred.

[0051] Furthermore, from an environmental perspective, bio-based polyethylene can be used. In addition, polyethylene resins can be used alone or in combination of two or more types.

[0052] The weight-average molecular weight of polyethylene resin is 3.5 × 10⁻⁶. 4 ~5.2×10 4 The preferred value is 3.8×10. 4 ~4.7×10 4 More preferably 4.0×10 4 ~4.5×10 4 Polyethylene resins with a weight-average molecular weight in the above-mentioned range are generally not used in membranes due to their fragility. However, in the PTP capping material of this embodiment, this fragility is utilized to make it a capping material with excellent ejection properties. In addition, by using polyethylene resins with a weight-average molecular weight in the above-mentioned range, it is not necessary to irradiate the resin with radiation as in Patent Document 1, thus avoiding the generation of unpleasant odors caused by resin decomposition during radiation irradiation, the reduction in recyclability caused by cross-linking of the reinforcing resin layer, and the reduction in sealing performance.

[0053] It should be noted that the weight-average molecular weight can be determined using gel permeation chromatography (hereinafter also referred to as "GPC"), specifically by the method described in the examples below.

[0054] When the PTP capping material is set to 100% by mass, the content of the aforementioned polyethylene resin is preferably 60-100% by mass, more preferably 70-95% by mass, and even more preferably 75-90% by mass. When the content of the polyethylene resin is within the above range, it tends to exhibit good ejection properties. Furthermore, especially when the content of the polyethylene resin is 100% by mass, a capping material with excellent recyclability can be produced.

[0055] There are no particular limitations on the manufacturing method of polyethylene resins; known catalysts such as single-active-center catalysts and multi-active-center catalysts can be used for polymerization.

[0056] The PTP cover material in this embodiment can be a laminate having a layer containing the above-mentioned polyethylene resin (hereinafter also referred to as "low molecular weight polyethylene resin layer").

[0057] Other layers laminated on a low molecular weight polyethylene resin layer include, for example: a sealing layer for improving the seal with a PTP substrate; an adjusting layer for adjusting the physical properties of the cover material, such as strength and ejection properties; a reinforcing layer for preventing film breakage during packaging; and a barrier layer for improving gas barrier properties.

[0058] There is no particular limitation on the number of layers, but from the perspective of balancing strength, ejection capability, water vapor barrier, sealing performance, and recyclability, 2 to 5 layers are preferred, and 2 to 3 layers are more preferred.

[0059] When the overall thickness of the PTP capping material is set to 100%, the thickness of the low molecular weight polyethylene resin layer is preferably 60-95%, more preferably 70-95%, and even more preferably 75-90%. When the thickness of the low molecular weight polyethylene resin layer is within the above range, it tends to exhibit good ejection and water vapor barrier properties.

[0060] As one approach, the PTP cover material of this embodiment may include: a layer comprising the above-mentioned polyethylene resin; and at least one surface layer comprising polyethylene resin, polypropylene resin or polyolefin elastomer.

[0061] The surface layer can be either the substrate-side surface layer bonded to the substrate or the outermost surface layer, or both. For example, it can be the outermost surface layer, serving as a reinforcing layer to prevent film breakage during packaging. Furthermore, it is suitable as the substrate-side surface layer because it contains polyethylene-based resins, polypropylene-based resins, or polyolefin-based elastomers, which provide excellent heat-sealing properties. Since these resins can be co-extruded, there is no need to apply emulsion-type heat-sealing agents, and they do not produce unpleasant odors even at high temperatures. Particularly for its excellent low-temperature sealing properties, a layer containing a polyolefin-based elastomer is preferred; from a recyclability perspective, a layer containing a polyethylene-based resin is preferred, so that the entire PTP cap is composed of polyethylene-based resin.

[0062] When the overall thickness of the PTP cover material is 100%, the thickness of the surface layer is preferably 5 to 40%, more preferably 5 to 30%, and even more preferably 10 to 25%. When the thickness of the surface layer is within the above range, good heat-sealing properties can be provided without compromising ejection performance and preventing film rupture.

[0063] As for the types of polyethylene-based resins included in the aforementioned surface layer, examples can be the same as those for low molecular weight polyethylene-based resins. Among these, ethylene-α-olefin copolymers are preferred due to their excellent low-temperature sealing properties. Furthermore, from an environmental perspective, bio-based polyethylene can be used.

[0064] The molecular weight of the polyethylene resin is not particularly limited, but it is preferred to be higher than that of the polyethylene resin contained in the aforementioned low molecular weight polyethylene resin layer. For example, a polyethylene resin with a melt flow rate (MFR, measured according to ASTM D-1238 at 190°C and a load of 2.16 kgf) of 1.5 to 6 g / 10 min can be cited.

[0065] Polyethylene resins can be used alone or in combination of two or more types.

[0066] The polypropylene resin contained in the aforementioned surface layer is not particularly limited; examples include propylene homopolymers, copolymers of propylene with other monomers, and their modified forms. Furthermore, from an environmental perspective, bio-based polypropylene can be used. Among these, propylene-α-olefin copolymers are preferred for their excellent low-temperature sealing properties, while propylene homopolymers are preferred for their excellent heat resistance and water vapor barrier properties.

[0067] Polypropylene resins can be used alone or in combination of two or more.

[0068] Monomers that can copolymerize with propylene include, for example, α-olefins such as ethylene, 1-butene, isobutene, 1-pentene, and 1-hexene. The polymerization form is not particularly limited and can be random copolymers, block copolymers, etc.

[0069] There are no particular limitations on the manufacturing method of polypropylene resins, and known methods such as polymerization of propylene and other monomers in the presence of a catalyst can be used. Specifically, for example, a method can be used to polymerize propylene and other monomers in the presence of a catalyst and an alkyl aluminum compound, at a polymerization temperature of 0 to 100°C and a polymerization pressure of 3 to 100 atmospheres.

[0070] Examples of catalysts mentioned above include titanium trichloride catalysts and titanium halide catalysts supported on supports such as magnesium chloride. To adjust the molecular weight of the polymer, chain transfer agents such as hydrogen can be added.

[0071] In the manufacture of polypropylene resins, in addition to the catalysts mentioned above, electron-donating compounds can be used as a third component, either as internal or external donor components, to improve the isotactic regularity and polymerization activity of polypropylene. There are no particular limitations on the electron-donating compounds; well-known substances can be used, such as ester compounds like ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl toluene; phosphites like triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives like hexamethylphosphoryltriamine; alkoxy ester compounds; aromatic monocarboxylic acid esters; aromatic alkyl alkoxysilanes; aliphatic hydrocarbon alkoxysilanes; various ether compounds; various alcohols; and various phenols.

[0072] The polymerization method described above can be either batch or continuous. Examples of polymerization methods include: solution polymerization in solvents such as butane, pentane, hexane, heptane, and octane; slurry polymerization; bulk polymerization in monomers without solvents; and gas-phase polymerization in gaseous monomers.

[0073] Polypropylene resins can also be modified products obtained by modifying unmodified polypropylene resins with modifiers such as α,β-unsaturated carboxylic acids or their derivatives (including acid anhydrides and esters). Examples of modified polypropylene resins include substances obtained by grafting or adding α,β-unsaturated carboxylic acids or their derivatives onto unmodified polypropylene resins. Specifically, substances obtained by grafting or adding α,β-unsaturated carboxylic acids or their derivatives onto polypropylene resins at a ratio of approximately 0.01 to 10% by mass of the total polypropylene resin can be cited.

[0074] Modified polypropylene resins are obtained, for example, by reacting unmodified polypropylene resin with a modifier in the presence or absence of a free radical initiator, in a molten state, solution state, or slurry state, within a temperature range of 30–350°C.

[0075] When the polypropylene resin is a mixture of unmodified polypropylene and modified polypropylene, there is no particular limitation on the mixing ratio of unmodified polypropylene and modified polypropylene, and it can be any ratio.

[0076] When the PTP capping material is set to 100% by mass, the content of polypropylene resin is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass. When the content of polypropylene resin is within the above range, good heat resistance and heat-sealing properties can be imparted without deteriorating ejection performance, and the film can be prevented from breaking.

[0077] Polyolefin elastomers are low-crystallinity or amorphous olefin polymers with a crystallinity of less than 50%. Examples of monomers (olefins) used in polyolefin elastomers include α-olefins such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, 2-methyl-1-butene, 1-hexene, 1-octene, 1-decene, and 1-dodecene, as well as cyclic olefins such as cyclobutene, cyclopentene, and cyclohexene.

[0078] Among these, polyethylene-based elastomers with low melting points (55–90°C) are preferred due to their excellent low-temperature sealing properties. Additionally, from an environmental perspective, bio-based polyolefin elastomers can be used. Furthermore, one type of polyolefin elastomer can be used alone, or two or more types can be used in combination.

[0079] There are no particular limitations on the manufacturing method of polyolefin elastomers. Polymerization can be carried out using known catalysts such as single-active-center catalysts and multi-active-center catalysts.

[0080] When the PTP cover material is set to 100% by mass, the content of polyolefin elastomer is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass. When the content of polyolefin elastomer is within the above range, good heat-sealing properties can be imparted without compromising ejection performance, and the film rupture can be prevented.

[0081] Alternatively, the PTP cover material of this embodiment may include an adjustment layer between the aforementioned low molecular weight polyethylene resin layer and the surface layer for adjusting the physical properties of the cover material, such as strength and ejection properties.

[0082] When the overall thickness of the PTP cover material is set to 100%, the thickness of the adjustment layer is preferably 10-40%, more preferably 15-35%, and even more preferably 20-30%.

[0083] From a recyclability perspective, the aforementioned conditioning layer preferably uses a polyethylene-based resin.

[0084] As a type of polyethylene resin, other types similar to the polyethylene resins mentioned above can be cited.

[0085] The molecular weight of the polyethylene resin is not particularly limited, but it is preferred to be higher than that of the polyethylene resin contained in the aforementioned low molecular weight polyethylene resin layer. For example, a polyethylene resin with a melt flow rate (MFR, measured according to ASTM D-1238 at 190°C and a load of 2.16 kgf) of 1.5 to 6 g / 10 min can be cited.

[0086] Polyethylene resins can be used alone or in combination of two or more types.

[0087] <Inorganic substances>

[0088] In this embodiment, the PTP cover material may contain inorganic materials to increase the fracture initiation point and improve ejection performance.

[0089] Inorganic substances are not specifically limited, but can include amorphous aluminosilicates, silicon dioxide, alumina, talc, kaolin, mica, wollastonite, clay, calcium carbonate, glass fiber, aluminum sulfate, etc.

[0090] When the PTP capping material is set to 100% by mass, the inorganic content is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass, and even more preferably 0.5 to 1% by mass. When the inorganic content is within the above range, a capping material exhibiting good ejection properties, low impurities, and high recyclability can be produced.

[0091] The PTP cover material of this embodiment may contain additives commonly used in the field of the art, such as metal soaps, colorants, plasticizers, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, antistatic agents, and crystal nucleating agents that assist in the dispersion of the aforementioned inorganic substances.

[0092] In addition, the PTP cover material of this embodiment can be subjected to corona treatment, plasma treatment, ultraviolet treatment, AC (anchor coating) treatment, etc., to improve printing properties.

[0093] In particular, white colorants or printing are preferred for the following reasons. In recent years, the demand for PTP packaging for pharmaceuticals has been increasing: in addition to printing the usual product name and usage instructions, barcodes containing various information such as product codes, expiration dates, manufacturing numbers, and quantities are being printed to prevent medical accidents and ensure traceability. If a cap material mixed with white colorant or a cap material printed in white is used, the white areas (where the cap material is directly visible) contrast with the black areas (where the barcode lines are usually black), making the barcode easier to read.

[0094] When the PTP cover material is 100% by mass, the additive content is preferably 3% by mass or less.

[0095] The thickness of the PTP capping material in this embodiment is preferably 10 to 100 μm, more preferably 30 to 80 μm, and even more preferably 40 to 60 μm. If the thickness is 10 μm or more, it is easy to exhibit tensile strength and water vapor barrier properties that can withstand the processing steps; if it is 100 μm or less, it is easy to exhibit good ejection properties.

[0096] The preferred water vapor transmission rate for PTP cover material is 10 g / m². 2 Less than 1 day, preferably 8g / m 2 Less than 1 day, preferably 5g / m 2 • Less than 1 day. When the water vapor permeability is within the above range, it can inhibit the modification of the contents of medicines and other products due to the action of water vapor, and can be stored for a long time.

[0097] The water vapor transmission rate of PTP cover materials can be adjusted, for example, by adjusting the thickness of the PTP cover material, the type of resin, and the presence or absence of a barrier layer. Increasing the thickness of the PTP cover material or adding a barrier layer tends to reduce the water vapor transmission rate. Examples of such barrier layers include resin layers of ethylene-vinyl alcohol copolymers and cyclic olefins; and inorganic vapor-deposited layers such as aluminum, alumina, and silicon oxide. Furthermore, using a resin with high crystallinity can further reduce the water vapor transmission rate of the PTP cover material.

[0098] It should be noted that the water vapor transmission rate was measured according to JIS K7129 and is a value converted to a thickness of 40 μm. Specifically, it can be obtained by the method described in the examples below.

[0099] The MD tensile strength of the PTP cap material is preferably 10–40 MPa, more preferably 13–35 MPa, and even more preferably 15–30 MPa. When the MD tensile strength is 10 MPa or higher, it can prevent film rupture during processing. In addition, when the MD tensile strength is 40 MPa or lower, a PTP cap material with good ejection properties can be obtained.

[0100] As a method for controlling the MD tensile strength of PTP capping material, one can cite methods such as changing the crystallinity of the resin or stretching it. If the crystallinity is increased or stretching is performed, the MD tensile strength tends to increase.

[0101] The TD tensile strength of the PTP cap material is preferably 10–40 MPa, more preferably 13–35 MPa, and even more preferably 15–30 MPa. When the TD tensile strength is 10 MPa or higher, it can prevent film rupture during processing. In addition, when the TD tensile strength is 40 MPa or lower, a PTP cap material with good ejection properties can be obtained.

[0102] As a method for controlling the TD tensile strength of PTP capping material, one can cite methods such as changing the crystallinity of the resin or stretching it. If the crystallinity is increased or stretching is performed, the TD tensile strength tends to increase.

[0103] It should be noted that the tensile strength of MD and TD can be determined according to JIS K7127, specifically, by the method described in the examples below.

[0104] The MD tensile elongation of the PTP cover material is preferably 25% or less, more preferably 20% or less, and even more preferably 15% or less. When the MD tensile elongation is within the above range, it tends to have good ejection properties in the TD direction (it is easy to break through the cover material with the crack located in the TD direction).

[0105] Methods for controlling the MD tensile elongation of PTP capping materials include adjusting the crystallinity, MD orientation, fracture initiation point, fragility, and tensile strength of the PTP capping material. To reduce the MD tensile elongation, methods include increasing the crystallinity of the PTP capping material, decreasing the MD orientation, increasing the fracture initiation point by adding inorganic substances, increasing the fragility by increasing the proportion of fragility layers such as the aforementioned low molecular weight polyethylene resin layer, and reducing tensile strength by making the fragility layers softer.

[0106] The TD tensile elongation of the PTP cover material in this embodiment is preferably 25% or less, more preferably 20% or less, and even more preferably 15% or less. When the TD tensile elongation is within the above range, it tends to have good ejection properties in the MD direction (it is easy to break through the cover material with the crack located in the MD direction).

[0107] Methods for controlling the tensile elongation at break (TD) of PTP capping materials include adjusting the crystallinity, TD orientation, fracture initiation point, fragility, and tensile strength of the PTP capping material. To reduce the TD tensile elongation, methods include increasing the crystallinity of the PTP capping material, decreasing the TD orientation, increasing the fracture initiation point by adding inorganic substances, increasing the proportion of fragility layers such as low molecular weight polyethylene resin layers to increase fragility, and reducing tensile strength by making the fragility layers softer.

[0108] It should be noted that the tensile elongation of MD and TD can be determined according to JIS K7127, specifically, by the method described in the examples below.

[0109] The tensile modulus of elasticity (MD) of the PTP cover material in this embodiment is preferably 300–1000 MPa, more preferably 350–900 MPa, and even more preferably 400–800 MPa. When the MD tensile modulus of elasticity is 300 MPa or higher, film elongation can be suppressed and printing misalignment can be prevented during printing on the PTP cover material. Furthermore, when the MD tensile modulus of elasticity is 1000 MPa or lower, hardening of the PTP cover material can be suppressed, preventing cracking during processing.

[0110] As a method to control the MD tensile modulus of elasticity of PTP cover material, one example is to adjust the crystallinity and MD orientation of the PTP cover material. If the crystallinity and MD orientation decrease, the MD tensile modulus of elasticity tends to decrease.

[0111] In this embodiment, the TD tensile modulus of the PTP cover material is preferably 1000 MPa or less, more preferably 900 MPa or less, and even more preferably 800 MPa or less. When the TD tensile modulus is 1000 MPa or less, it is possible to suppress the hardening of the PTP cover material and prevent cracking during processing.

[0112] As a method for controlling the TD tensile modulus of elasticity of PTP cover material, one example is to adjust the crystallinity and MD orientation of the PTP cover material. If the crystallinity and MD orientation decrease, the TD tensile modulus of elasticity tends to decrease.

[0113] It should be noted that the tensile modulus of elasticity of MD and TD can be determined according to JIS K7127, specifically, by the method described in the examples below.

[0114] The heat of fusion for crystallization of the PTP capping material in this embodiment, as measured by differential scanning calorimetry (DSC), is 130 J / g or more, preferably 145 to 290 J / g, and more preferably 160 to 290 J / g. When the heat of fusion is within the above range, the MD and TD tensile elongation and puncture elongation are suitable, and it tends to exhibit good ejection properties.

[0115] Methods for controlling the heat of fusion during crystallization of PTP capping materials include adjusting the cooling of the capping material during manufacturing, post-manufacturing annealing, and the addition of crystallization nucleating agents. For example, the heat of fusion during crystallization can be increased by slow cooling during the manufacturing of PTP capping materials using the direct blowing method, annealing after manufacturing, and adding crystallization nucleating agents.

[0116] It should be noted that the determination of the heat of fusion of crystallization based on differential scanning calorimetry (DSC) can be specifically performed using the method described in the examples below.

[0117] In this embodiment, the relative value of the crystallization amount of the PTP capping material, as measured by a Fourier transform infrared spectrophotometer (FT-IR), is preferably 0.8 or more, more preferably 0.82 or more, and even more preferably 0.84 or more. When the relative value of the crystallization amount is within the above range, the MD and TD tensile elongation and puncture elongation are suitable, exhibiting good ejection properties.

[0118] Methods for controlling the relative value of the amount of crystallization in PTP capping materials include adjusting the cooling of the capping material during manufacturing, post-manufacturing annealing, and the addition of crystallizing nucleating agents. For example, the relative value of the amount of crystallization can be increased by: slow cooling of the capping material using airing during direct blowing manufacturing, annealing after manufacturing, and adding crystallizing nucleating agents.

[0119] It should be noted that the determination of the relative value of crystallization based on FT-IR can be performed specifically by the method described in the examples below, or by using a Raman spectrophotometer.

[0120] The MD orientation degree of the PTP capping material in this embodiment is preferably -0.035 to 0.035, more preferably -0.025 to 0.025, and even more preferably -0.02 to 0.02. When the MD orientation degree is within the above range, the MD tensile elongation and TD tensile elongation are easily within a suitable range, the balance between MD and TD tensile elongation is excellent, and good ejection performance is exhibited.

[0121] Methods for controlling the MD orientation degree of PTP cover material include adjusting the cooling of the cover material, the TD stretch ratio (BUR), or the timing during the manufacturing of PTP cover material. For example, the MD orientation degree can be reduced by: slowing down the cooling of the cover material using ventilation during the manufacturing of PTP cover material by the direct blow molding method; increasing the TD stretch ratio (BUR); or manufacturing by successive secondary stretching.

[0122] It should be noted that the MD orientation degree can be measured using FT-IR, specifically, it can be measured using the method described in the examples below.

[0123] Furthermore, the MD orientation degree represents the orientation in the MD direction relative to the TD direction. Therefore, the orientation in the MD direction relative to the thickness direction and the orientation in the TD direction relative to the thickness direction of the PTP cover material can be measured separately, and calculations can be performed based on the measured results. In the case where the PTP cover material has a multi-layer structure, the thickest layer is more likely to affect the properties of the PTP cover material. Therefore, it is sufficient to measure the orientation degree of the thickest layer (any one of the two thickest layers).

[0124] In addition, MD orientation can also be measured using a Raman spectrophotometer in the same way as when using FT-IR.

[0125] In the load-displacement curve of the puncture test for PTP caps, the maximum load reduction per 0.1 mm displacement in the fracture region is preferably 3 to 20 N, more preferably 4 to 18 N, and even more preferably 5 to 15 N. For PTP caps with a maximum load reduction of more than 20 N per 0.1 mm displacement, they exhibit characteristics of being difficult to break when removing tablets or other contents from the PTP packaging, and tend to lack ejection capability. In addition, the maximum load reduction per 0.1 mm displacement is one of the factors that has the greatest impact on opening identification. If the maximum load reduction per 0.1 mm displacement is less than 3 N, it indicates that the PTP cap is brittle, and almost no sound is produced when removing tablets or other contents, tending to have poor opening identification.

[0126] Figure 2 An example of a load-displacement curve obtained when a puncture test is performed on the PTP cover material of this embodiment is shown. Figure 2 With PTP cover material, the maximum load per 0.1 mm displacement is reduced to 8 N.

[0127] As a method to control the maximum load reduction per 0.1 mm displacement of the PTP cover material, for example, adjusting the weight-average molecular weight of the polypropylene resin, the thickness of the PTP cover material, and the reinforcing layer can be used. Increasing the weight-average molecular weight of the polypropylene resin or the thickness of the PTP cover material, or adding a reinforcing layer, can increase the maximum load reduction per 0.1 mm displacement.

[0128] It should be noted that the maximum load reduction for every 0.1 mm displacement in the fracture region of the load-displacement curve can be specifically determined by the method described in the embodiments below.

[0129] The puncture strength of the PTP cap material in this embodiment is preferably 4 to 15 N, more preferably 5 to 13 N, and even more preferably 6 to 11 N. When the puncture strength is 4 N or more, it is possible to prevent the PTP cap material from being damaged by external forces during the transport of the PTP package. In addition, when the puncture strength is 15 N or less, a PTP cap material with excellent ejection properties can be obtained.

[0130] As a method for controlling the puncture strength of PTP capping material, one can cite methods such as adjusting the weight-average molecular weight of polyethylene resin, the thickness of PTP capping material, and the reinforcing layer. If the weight-average molecular weight of polyethylene resin or the thickness of PTP capping material is increased, or a reinforcing layer is provided, there is a tendency for the puncture strength to increase.

[0131] It should be noted that the puncture strength is a value converted to a thickness of 40 μm. Specifically, it can be calculated using the method described in the examples below.

[0132] The puncture elongation of the PTP cap material in this embodiment is preferably 1 to 4 mm, more preferably 1.2 to 3 mm, and even more preferably 1.5 to 2.5 mm. A puncture elongation of 1 mm or more can prevent damage to the PTP cap material due to external forces during the transport of the PTP package. Furthermore, puncture elongation, like tensile elongation and ejection strength, is one of the factors that has the greatest impact on ejection performance; a puncture elongation of 4 mm or less results in a PTP cap material with excellent ejection performance.

[0133] Methods for controlling the puncture elongation of PTP capping materials include adjusting the weight-average molecular weight of polyethylene resin, the layer ratio of PTP capping material, crystallinity, and MD and TD orientation. If the weight-average molecular weight of polyethylene resin is reduced, the proportion of low molecular weight polyethylene resin is increased, crystallinity is increased, or MD and TD orientation is reduced, the puncture elongation tends to decrease.

[0134] It should be noted that the puncture elongation rate can be specifically measured by the method described in the following examples.

[0135] <Method for manufacturing a lid material for PTP>

[0136] The method for manufacturing the lid material for PTP is not particularly limited. As an example, the direct blow-up method can be cited. In this method, the above-mentioned constituent materials are extruded into a tubular shape using a known melt extruder equipped with an annular die, and then air is directly blown in for stretching. When the lid material for PTP is a laminate composed of two or more layers, the co-extrusion direct blow-up method is preferably used.

[0137] The following is an explanation of the outline of the method for manufacturing a lid material for PTP as a laminate by the co-extrusion direct blow-up method.

[0138] The resin or resin composition as the constituent material of each layer is melted above the melting temperature of the resin, and each layer is simultaneously extruded using an extruder corresponding to the number of layers. The resin or resin composition of each extruded layer is sent to the annular die through a feed pipe, and a tubular film in which each layer is laminated is formed by the annular die. Then, a gas (air, nitrogen, etc.) is blown into the film to form a bubble, and the film is stretched in the MD and TD directions, thereby manufacturing the lid material for PTP.

[0139] The MD draw ratio (DDR) of the film is preferably 8 to 23 times, more preferably 10 to 20 times. When the MD draw ratio is 8 times or more, the pulsation of the bubble is suppressed, and the stretching tends to become stable. In addition, when the MD draw ratio is 23 times or less, a lid material with an appropriate MD orientation degree, an excellent balance between the MD and TD orientation degrees, and good ejection properties can be obtained.

[0140] In addition, the TD draw ratio (BUR) of the film is preferably 1.3 to 4 times, more preferably 1.5 to 2.5 times. When the TD draw ratio is 1.3 times or more, a lid material with an appropriate MD orientation degree, an excellent balance between the MD and TD orientation degrees, and good ejection properties can be obtained. In addition, when the TD draw ratio is 4 times or less, the pulsation of the bubble is suppressed, and the stretching tends to become stable.

[0141] It should be noted that the MD draw ratio can be adjusted by the speed of the pinch rolls, and the TD draw ratio can be adjusted by the volume of air blown into the film.

[0142] The stretching temperature of the film is preferably 70 to 130 °C, more preferably 80 to 120 °C. When the stretching temperature is 70 °C or higher, the crystallinity of the lid material is likely to be in an appropriate range, and a lid material with excellent balance between MD and TD orientation degrees and good ejection properties can be obtained. In addition, when the stretching temperature is 130 °C or lower, the stretching tends to be stable.

[0143] It should be noted that the stretching temperature is the temperature actually measured by a non-contact thermometer on the film surface at a part 32 cm vertically away from the discharge surface of the annular die toward the downstream side of the manufacturing process, and can be adjusted by the wind speed of the ventilation for cooling the molten resin, the discharge amount of the molten resin, DDR, etc.

[0144] <PTP package>

[0145] The PTP package of the present embodiment is characterized in that it includes the PTP lid material of the present embodiment and a bottom material having a recess for accommodating the contents.

[0146] Figure 1 It 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 that adheres to the lid material 2, and the contents 6 are filled in the recess 4.

[0147] <Bottom material>

[0148] As the bottom material constituting the PTP package of the present embodiment, for example, a sheet containing a known synthetic resin such as a polyvinyl chloride-based resin, a polyvinylidene chloride-based resin, a polyolefin-based resin (such as a polyethylene-based resin, a polypropylene-based resin, an ethylene-vinyl alcohol copolymer resin, a cyclic olefin resin, etc.), polychlorotrifluoroethylene, or a polyester can be cited, and a sheet composed of these synthetic resins is preferred. Among them, from the aspect of recyclability, a sheet containing a polyethylene-based resin, a polypropylene-based resin, or a cyclic olefin resin is preferred, and most preferably contains a polypropylene-based resin like the PTP lid material.

[0149] From the aspect of the breadth of the molding condition range for vacuum or pressure molding of the pocket-shaped recess of the bottom material, the bottom material preferably has a heat distortion temperature of 50 to 160 °C, more preferably 80 to 120 °C according to JIS K7191.

[0150] Regarding the shape of the bottom material, as long as it has a recess for accommodating the contents, there is no particular limitation. The shapes of the bottom surface part and the opening part of the recess can be rectangular (square, rectangle, triangle, etc.) or circular (circle, ellipse, etc.), and the corners of the rectangle can also have a curvature.

[0151] The size of the base material is not particularly limited and can be appropriately determined according to the size, number, etc. of the contents. For example, the depth of the recess can be 1 to 15 mm, preferably 2 to 10 mm. In addition, particularly when the shapes of the opening portion and the bottom surface portion of the recess are circular, the diameter of the opening portion can be, for example, 5 to 150 mm, preferably 10 to 100 mm, and the diameter of the bottom surface portion can be 5 to 20% smaller than the diameter of the opening portion, respectively.

[0152] In addition, the portion other than the recess, that is, the flange portion, is not particularly limited and can be provided in a manner that extends in a direction orthogonal to the depth direction of the recess.

[0153] As the average width of the flange portion, for example, it can be 2 to 100 mm, preferably 4 to 50 mm.

[0154] The thickness of the base material 1 is not particularly limited and can be, for example, 100 to 500 μm, preferably 150 to 300 μm.

[0155] <Method for manufacturing a PTP package>

[0156] The PTP package of the present embodiment can be manufactured by overlapping the surface (flange portion) of the base material and the surface of the lid material and performing heat sealing.

[0157] Regarding the heat sealing temperature, for example, 80 to 120 °C can be cited. From the aspects of not easily generating burn marks on the contents and the heat resistance of the PTP lid material, it is preferably 90 to 110 °C. In addition, the heat sealing time can be cited, for example, 0.05 to 3 seconds. From the aspects of not easily generating burn marks on the contents and obtaining sufficient sealing strength, it is preferably 0.2 to 1 second. In addition, the heat sealing pressure can be cited, for example, 0.2 to 0.6 MPa. From the aspects of not easily generating burn marks on the contents and obtaining sufficient sealing strength, it is preferably 0.3 to 0.5 MPa.

[0158] As the molding machine used in the molding of the PTP package in the present embodiment, for example, a roll-type sealing molding machine that sandwiches the lid material and the base material between a heat sealing roll and a sealing lower roll; a flat-plate sealing molding machine that has a heating mold with flat plates on the upper and lower sides and sandwiches the lid material and the base material between the molds, etc. Among them, it is preferable to use a flat-plate sealing molding machine that can easily obtain sufficient sealing strength.

[0159] Examples

[0160] Specific examples and comparative examples are given below to illustrate the present embodiment, but the present embodiment is not limited to these.

[0161] The raw materials used in the examples and comparative examples are as described below.

[0162] Polyethylene (PE) resin

[0163] • PE1: Polyethylene (manufactured by Asahi Kasei Corporation, Suntec HD J300, weight average molecular weight: 4.0 × 10⁻⁶) 4 )

[0164] PE2: Polyethylene (manufactured by Asahi Kasei Corporation, Suntec HD J311, weight average molecular weight: 4.9×10⁻⁶) 4 )

[0165] PE3: Polyethylene (manufactured by Asahi Kasei Corporation, Suntec HD J320, weight average molecular weight: 5.5×10⁻⁶) 4 )

[0166] PE4: Polyethylene (manufactured by Ube Maruzen Polyethylene Co., Ltd., Umerit 0520F, weight average molecular weight: 6.0×10⁻⁶) 4 )

[0167] PE5: Polyethylene (manufactured by Asahi Kasei Corporation, Suntec HD B161, weight average molecular weight: 1.4 × 10⁻⁶) 5 )

[0168] <Polypropylene (PP) resin>

[0169] •PP1: Polypropylene (manufactured by Sun Allomer Co., Ltd., PLB00A)

[0170] •PP2: Polypropylene (manufactured by Sun Allomer Co., Ltd., PL500A)

[0171] <Polyolefin elastomers (TPO)>

[0172] • Ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals, Ltd., TAFMER A4085S)

[0173] <Ethylene-vinyl acetate copolymer saponification (EVOH)>

[0174] • Ethylene-vinyl acetate copolymer saponification (manufactured by Mitsubishi Chemical Corporation, Soarnol DC3203)

[0175] <Adhesive Resin>

[0176] • Acid-modified polyolefin composition (manufactured by Mitsui Chemicals, Inc., Admer NF587)

[0177] <Polystyrene resin (PS)>

[0178] • Polystyrene (manufactured by PS Japan Co., Ltd., PSJ-Polystyrene G9305)

[0179] Cyclic Olefin Resins (COC)

[0180] • Cyclic olefin copolymer (manufactured by Poly Plastics Co., Ltd., TOPAS 8007F-600)

[0181] <Crystallization nucleating agent>

[0182] • Crystallizing nucleating agent masterbatch for polyethylene (manufactured by Riken Vitamin Co., Ltd., Rikemaster CN-002)

[0183] <Inorganic substances>

[0184] • Amorphous aluminum silicate (manufactured by Mizusawa Chemical Industry Co., Ltd., Silton JC-30)

[0185] <Substrate>

[0186] • PP / PE: A multilayer sheet with a thickness of 300μm, produced by co-extrusion direct blow molding, consisting of polypropylene (manufactured by Sun Allomer Co., Ltd., PL500A), polypropylene (manufactured by Sun Allomer Co., Ltd., PC540R), and polyethylene (manufactured by Ube Maruzen Polyethylene Co., Ltd., Umerit 0520F). It is molded into a substrate having a recess with a depth of 4mm, an opening diameter of 10mm (circular), and a bottom surface diameter of 8mm (circular). It also has a flange with an average width of 10mm extending in a direction orthogonal to the depth direction. The openings are arranged in mutually orthogonal longitudinal and transverse rows, with a center-to-center distance of 20mm in both the longitudinal and transverse directions.

[0187] • PVC: Polyvinyl chloride single-layer sheet (SUMITOMO BAKELITE Co., Ltd., SUMILITE VSS-F110 (thickness 250μm)). Molded in the same manner as the polypropylene single-layer sheet described above.

[0188] The measurement and evaluation methods used in the examples and comparative examples are described below.

[0189] (1) Weight-average molecular weight

[0190] For the polyethylene resins used in the examples and comparative examples for PTP capping materials, the weight-average molecular weight (Mw) was determined according to the following steps.

[0191] First, o-dichlorobenzene was added to the sample to a concentration of 1.3 mg / mL, and the mixture was stirred at 150 °C for 1 hour to dissolve it. The weight-average molecular weight was then determined using a GPC (Waters 150-C ALC / GPC).

[0192] In addition, the molecular weight (Mw) of commercially available standard polystyrene was multiplied by a factor of 0.43 to obtain the equivalent molecular weight of polyethylene. A calibration straight line was then constructed based on the data graph of dissolution time versus the equivalent molecular weight of polyethylene. The weight-average molecular weight was calculated based on the GPC test results and the above calibration curve. It should be noted that the column used in the test was obtained by connecting one AT-807S column manufactured by Showa Denko Corporation and two TSK-gel GMH-H6 columns manufactured by Tosoh Corporation, and the column temperature was set to 140°C.

[0193] (2) Water vapor transmission rate

[0194] For the PTP cover material obtained in the examples and comparative examples, the water vapor transmission rate was measured using a water vapor transmission rate measuring device (MOCON, PERMATRAN-W Model 398). The measurement was conducted according to JIS K7129 at 38°C and 90% RH (g / m³). 2 (·day), converted to a thickness of 40μm.

[0195] (3) Tensile strength, tensile elongation, and tensile modulus

[0196] For the PTP cover material obtained in the examples and comparative examples, the tensile strength, elongation and modulus of elasticity of MD and TD were measured according to JIS K7127.

[0197] Strip-shaped test pieces (150 mm in length × 10 mm in width) were cut from PTP cover material. The ends of these test pieces were mounted on a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph) with a clamping distance of 50 mm. The machine was moved at a clamping speed of 200 mm / min, and the maximum load and maximum elongation required for fracture were measured, which were recorded as tensile strength (MPa) and tensile elongation (%), respectively. The load at 2% elongation was recorded as the tensile modulus of elasticity (MPa). The values ​​measured on 10 test pieces were averaged to obtain the tensile strength, tensile elongation, and tensile modulus of elasticity for the PTP cover material.

[0198] (4) Heat of crystallization and melting

[0199] Samples (5–10 mg) of the PTP capping material obtained in the Examples and Comparative Examples were cut and measured using a differential scanning calorimeter (DSC) (Hitachi High-Tech Science, DSC7000X) under a nitrogen atmosphere with indium as the heat standard. As a heating procedure, the sample was heated from 0°C to 200°C at a rate of 10°C / min. For the endothermic peak caused by melting in the obtained heat flow curve, the straight line extrapolated from the high-temperature side was used as the baseline to determine the heat of fusion (J / g). It should be noted that if there are two or more endothermic peaks caused by melting, the sum of the heats of fusion of each peak is taken as the heat of fusion of fusion of the PTP capping material.

[0200] (5) Relative value of crystallization amount

[0201] For the PTP capping materials obtained in the examples and comparative examples, the relative values ​​of crystallinity were determined using a Fourier transform infrared spectrophotometer (manufactured by Nippon Spectrophotometer Co., Ltd., FT / IR4100). The calculation of the relative values ​​of crystallinity used 720 cm⁻¹ of polyethylene resin. -1 (Peaks from crystalline and amorphous materials) and 730 cm⁻¹ -1 The absorbance (in the following text, absorbance refers to the height of the peak) of the crystallization peak is obtained by the following formula.

[0202] The relative value of crystallization amount = absorbance (730cm) -1 ) / Absorbance (720cm) -1 )

[0203] It should be noted that the cumulative number of measurements was 32, and the decomposition energy was 2 cm⁻¹. -1 The average value obtained from measuring 5 test pieces is taken as the crystallinity.

[0204] (6) MD Orientation

[0205] For the PTP capping materials obtained in the examples and comparative examples, the MD orientation degree was measured using a Fourier transform infrared spectrophotometer (manufactured by Nippon Spectrophotometer Co., Ltd., FT / IR4100). For the PTP capping materials, measurements were performed using grating polarization elements at 0° (MD) and 90° (TD), using 720 cm⁻¹ of each polyethylene resin. -1 The absorbance is used to calculate the MD orientation degree using the following formula.

[0206] Dichroism ratio (R) = Absorbance (TD) / Absorbance (MD)

[0207] MD Orientation Degree = (R-1) / (R+2)

[0208] It should be noted that the cumulative number of measurements was 32, and the decomposition energy was 2 cm⁻¹.-1 The average value obtained from measuring 5 test pieces is taken as the MD orientation degree.

[0209] (7) Puncture strength and puncture elongation

[0210] For the PTP capping material obtained in the examples and comparative examples, the puncture strength and puncture elongation were determined according to the following steps.

[0211] The PTP capping material was fixed in place on a 10mm diameter frame. A 4mm diameter needle with a flat tip was mounted on a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph) and pressed into the fixed PTP capping material to perform a puncture test. The test was conducted at 23°C and 50% RH, with the needle moving at a speed of 50mm / min. The maximum load applied to the needle at the point of breakage was taken as the puncture strength (N), converted to a thickness of 40μm. The depth of the needle tip at the point of breakage (the displacement from the point of contact between the needle and the fixed PTP capping material until the point of breakage) was taken as the puncture elongation (mm). The average values ​​obtained from the measurements of 5 test pieces were taken as the puncture strength and puncture elongation of the PTP capping material.

[0212] (8) The maximum load at fracture during the puncture test was reduced.

[0213] For the PTP capping material obtained in the examples and comparative examples, the load reduction at fracture during the puncture test was measured according to the following steps.

[0214] The PTP capping material was fixed in place on a 10mm diameter frame. A 4mm diameter needle with a flat tip was mounted on a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph) and pressed into the fixed PTP capping material to perform a puncture test. Measurements were taken at 23°C and 50% RH, with the needle moving at a speed of 50mm / min. The maximum load reduction per 0.1mm displacement was determined in the fracture zone of the obtained load-displacement curve (the load reduction associated with failure). The average values ​​measured on five test pieces were taken as the maximum load reduction per 0.1mm displacement for the PTP capping material.

[0215] (9) Sealing strength

[0216] For the PTP cover material obtained in the examples and comparative examples, the sealing strength was measured in the following order.

[0217] First, the PTP cover and substrate were heat-sealed using a heat-sealing tester (manufactured by TESTER SANGYO). The sealing temperature was set at 110°C, the sealing time at 2 seconds, and the sealing pressure at 0.25 MPa. Then, strip-shaped test pieces were cut (40 mm long for both the PTP cover and substrate (total 80 mm) × 15 mm wide). The ends of these test pieces were installed between the jaws of a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph) with a 30 mm gap between the jaws, arranged with the sealing portion positioned between them. A 180° peel test was performed by moving the test pieces at a speed of 200 mm / min between the jaws. The maximum load until the seal was completely peeled off was taken as the sealing strength (N / 15 mm). The average value obtained from measuring 10 test pieces was taken as the sealing strength of the PTP cover.

[0218] (10) Extrusion

[0219] The puncture elongation of the PTP cap material obtained in the examples and comparative examples, and whether interlayer peeling occurred when the cap material of the PTP package was punctured, were summarized, and the ejection performance was evaluated according to the following evaluation criteria.

[0220] [Evaluation Criteria]

[0221] ◎(Excellent): The puncture elongation is less than 2.6 mm, and no interlayer peeling or partial breakage occurs when the cap material of the PTP packaging is punctured.

[0222] ○ (Good): The puncture elongation is greater than 2.6 mm and less than 3.2 mm, and no interlayer peeling or partial breakage occurs when the cap material of the PTP packaging is punctured.

[0223] × (Defective): The puncture elongation is 3.2 mm or more, and interlayer peeling or partial breakage occurs when the capping material of the PTP packaging is punctured.

[0224] (11) Kaifeng identification

[0225] For the PTP packaging obtained in the examples and comparative examples, the opening sound when the lid is pierced and the contents are removed was measured using a common noise meter (manufactured by Rion Co., Ltd., NA-29), and the opening recognition was evaluated according to the following evaluation criteria. When measuring the opening sound, the distance between the front end of the microphone and the pierced lid was set to 30 mm, and the average value of 10 measurements was used.

[0226] [Evaluation Criteria]

[0227] ◎(Excellent): Above 80dB

[0228] ○ (Good): Above 60dB, below 80dB

[0229] × (Defective): Less than 60dB, or cannot penetrate the cover material.

[0230] (12) Membrane odor

[0231] For the PTP capping materials obtained in the examples and comparative examples, the presence or absence of membrane odor was determined using dynamic headspace GC / MS (DHS manufactured by Gestel, GC-7890MSD-5977B manufactured by Agilent). Regarding sample preparation, 2 g of PTP capping material was added to a 20 mL glass vial and heated at 50°C for 30 minutes. During this time, 1950 mL of nitrogen gas was used to adsorb the odor components contained in the PTP capping material onto activated carbon adsorbent materials (Carbopack B / Carbopack X manufactured by Agilent). After heating, a thermal desorption device (TDU2 manufactured by Gestel) located at the GC / MS inlet was used to desorb the gas adsorbed by the activated carbon adsorbent materials at 300°C in the TDU section. During this period, the gas was reconcentrated at -40°C in the CIS section and then heated to 300°C for GC / MS analysis. The unpleasant odor components of the PTP cover material included acetic acid, butyric acid, and acetylacetone. The membrane odor was evaluated based on the detection levels of butyric acid and acetic acid, as described below.

[0232] [Evaluation Criteria]

[0233] ○ (Excellent): Butyric acid detection amount is less than 0.01 ppm and acetic acid detection amount is less than 0.1 ppm.

[0234] × (Poor): Butyric acid content is above 0.01 ppm, or acetic acid content is above 0.1 ppm.

[0235] [Example 1]

[0236] A two-layer PTP capping material is manufactured using a co-extrusion direct blow molding method, which laminates a polyethylene resin (PE) layer (first layer) and a polyolefin elastomer (TPO) layer (second layer).

[0237] Specifically, the resin granules used as raw materials for each layer are melted above the resin's melting temperature, and each layer is simultaneously extruded using two or more extruders. The extruded resin layers are fed into an annular die through a feed pipe, and a tubular laminated film is formed by layering the layers using the annular die. It should be noted that the thickness ratio is adjusted to PE layer:TPO layer = 80:20.

[0238] Next, the laminated film is stretched by blowing air into it, thereby obtaining a PTP cover material with a thickness of 40 μm. It should be noted that the stretching ratio is set to MD30 times and TD2 times, and the stretching temperature is set to 78°C.

[0239] The tablets are filled into the recesses of the PP / PE substrate, and the PP / PE substrate (PE layer side) and the cap material (TPO layer side) are bonded together by heat sealing using an Eshin Pack Sealer (manufactured by Eshin Pack Industries, semi-automatic OS) to obtain the PTP package.

[0240] Assume the heat sealing conditions are: temperature 110℃, pressure 0.4MPa, and time 1 second.

[0241] Table 1 shows the measurement and evaluation results of each physical property.

[0242] [Examples 2-5, Comparative Examples 1-3]

[0243] In Examples 2-5 and Comparative Examples 1-3, the raw materials and mixing amounts were changed as shown in Table 1. Otherwise, the PTP cap material was prepared in the same manner as in Example 1 to obtain the PTP packaging body.

[0244] It should be noted that in the first layer of Example 5, amorphous aluminosilicate was mixed in polyethylene resin (PE2) before extrusion.

[0245] The detailed conditions and the results of the determination and evaluation of each property are shown in Table 1.

[0246] [Example 6]

[0247] In Example 6, the raw materials and mixing amounts were changed as shown in Table 1, and a PTP capping material was prepared in the same manner as in Example 1, consisting of a polypropylene resin (PP) layer (first layer), a polyethylene resin (PE) layer (second layer), and a polyolefin elastomer (TPO) layer (third layer) laminated sequentially. The PP / PE substrate (PE layer side) was bonded to the capping material (TPO layer side) in the same manner as in Example 1 to obtain a PTP packaging body.

[0248] The detailed conditions and the results of the determination and evaluation of each property are shown in Table 1.

[0249] [Example 7]

[0250] In Example 7, the raw materials and mixing amounts were changed as shown in Table 1. A two-layer film, consisting of a first layer and a second layer, was fabricated in the same manner as in Example 1. Then, the surface of the first layer was corona-treated to form a 10nm inorganic aluminum vapor-deposited layer (third layer) based on vacuum evaporation, thereby producing a PTP cap. The PP / PE substrate (PE layer side) and the cap (TPO layer side) were bonded together in the same manner as in Example 1 to obtain the PTP packaging body.

[0251] The detailed conditions and the results of the determination and evaluation of each property are shown in Table 1.

[0252] [Comparative Example 4]

[0253] In Comparative Example 4, the raw materials and mixing amounts were changed as shown in Table 1. A two-layer film, consisting of a first layer and a second layer, was fabricated in the same manner as in Example 1. Then, the film was irradiated with electron beams at an accelerating voltage of 250 kV and a radiation dose of 60 kGy, as per Patent Document 1, to produce a PTP cover material. The PP / PE substrate (PE layer side) and the cover material (PE layer side) were bonded together in the same manner as in Example 1 to obtain a PTP packaging body.

[0254] The detailed conditions and the results of the determination and evaluation of each property are shown in Table 1.

[0255] [Comparative Example 5]

[0256] Referring to Patent Document 4, polyethylene resin (PE5), cyclic olefin copolymer, and polyethylene nucleating agent masterbatch were dry-mixed at a mass ratio of 67.5:30:2.5, and a 40 μm thick PTP cap material was produced using a direct blow molding method. Subsequently, the PP / PE substrate (PE layer side) was bonded to the cap material (PE layer side) in the same manner as in Example 1 to obtain the PTP packaging body.

[0257] The detailed conditions and the results of the determination and evaluation of each property are shown in Table 1.

[0258] [Comparative Example 6]

[0259] Referring to Patent Document 5, a three-layer laminated film was fabricated using a co-extrusion direct blow molding method, consisting of an ethylene-vinyl acetate copolymer saponified (EVOH) layer (first layer), an acid-modified polyolefin composition layer (second layer), and a polystyrene resin (PS) layer (third layer). The thickness of each layer was adjusted to a ratio of EVOH layer: acid-modified polyolefin composition layer: PS layer = 20:10:70, resulting in a total thickness of 40 μm.

[0260] Next, an ethylene vinyl acetate (EVA) emulsion heat sealant was applied to the PS layer surface of the obtained laminated film at a dry film thickness of 9 μm to produce a PTP cap. Subsequently, the PVC substrate was bonded to the cap (heat sealant side) in the same manner as in Example 1 to obtain the PTP package.

[0261] The detailed conditions and the results of the determination and evaluation of each property are shown in Table 1.

[0262]

[0263] Industrial applicability

[0264] The PTP packaging cap material of the present invention can be appropriately used in the packaging of pharmaceuticals such as tablets and capsules, or food products such as candy and chocolate.

[0265] Explanation of symbols

[0266] 1PTP packaging

[0267] 2PTP cover material

[0268] 3 Substrate

[0269] 4 recesses

[0270] 5 flange portion

[0271] 6 contents

Claims

1. A cover material for PTP, characterized in that, It contains a weight-average molecular weight of 3.5 × 10⁻⁶. 4 ~5.2×10 4 The heat of fusion for the polyethylene resin, based on differential scanning calorimetry (DSC), is 130–290 J / g.

2. The PTP cover material as described in claim 1, wherein, The MD orientation degree is -0.035 to 0.

035.

3. The PTP cover material as described in claim 1, wherein, The MD orientation degree is -0.025 to 0.

025.

4. The PTP cover material as described in any one of claims 1 to 3, wherein, In the load-displacement curve of the puncture test of the PTP cover material, the maximum load in the fracture region decreases to 3N to 20N per 0.1mm displacement.

5. The PTP cover material as described in any one of claims 1 to 3, wherein, Thickness ranges from 10 μm to 100 μm, with a water vapor permeability of 10 g / m. 2 • For less than 10 days, the tensile strength is between 10 MPa and 40 MPa in both MD and TD, and the elongation is less than 25% in both MD and TD.

6. The PTP cover material according to any one of claims 1 to 3, comprising 0.1% to 3% by mass of inorganic matter.

7. The PTP cover material according to any one of claims 1 to 3, comprising: a layer comprising the polyethylene resin; and at least one surface layer comprising a polyethylene resin, a polypropylene resin, or a polyolefin elastomer.

8. The PTP cover material as described in any one of claims 1 to 3, wherein, The weight-average molecular weight of the polyethylene resin is 3.8 × 10⁻⁶. 4 ~5.2×10 4 .

9. The cover material for PTP as described in claim 4, wherein, The maximum load per 0.1 mm displacement is reduced to 4 N to 18 N.

10. The cover material for PTP as described in claim 5, wherein, The thickness is 30μm to 80μm.

11. The cover material for PTP as described in claim 5, wherein, Water vapor transmission rate is 8 g / m 2 Below the heavens.

12. The PTP cover material as described in claim 5, wherein, The tensile strength is 13MPa to 35MPa in both MD and TD.

13. The cover material for PTP as described in claim 5, wherein, The elongation at both MD and TD is below 20%.

14. The cover material for PTP as described in claim 7, wherein, When the overall thickness of the PTP cover material is set to 100%, the thickness of the polyethylene resin layer is greater than 62.5% and less than 95%.

15. The PTP cover material as described in any one of claims 1 to 3, wherein, The relative value of the amount of crystallization, as determined by Fourier transform infrared spectrophotometer, is above 0.

8.

16. The PTP cover material as described in any one of claims 1 to 3, wherein, The puncture intensity is 4N to 15N.

17. The PTP cover material according to any one of claims 1 to 3, wherein, The puncture elongation rate is 1mm to 4mm.

18. The PTP cover material as described in any one of claims 1 to 3, wherein, The heat of fusion for crystallization based on differential scanning calorimetry (DSC) is above 141 J / g.

19. A PTP packaging body, characterized in that, It comprises a cover material for PTP as described in any one of claims 1 to 18, and a base material having a recess for receiving contents.

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