JP2004001898A - Press-through package - Google Patents

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JP2004001898A
JP2004001898A JP2003278798A JP2003278798A JP2004001898A JP 2004001898 A JP2004001898 A JP 2004001898A JP 2003278798 A JP2003278798 A JP 2003278798A JP 2003278798 A JP2003278798 A JP 2003278798A JP 2004001898 A JP2004001898 A JP 2004001898A
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sheet
thickness
pocket
packaged
package
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Toshimata Matsui
松井 利又
Tsutomu Hani
羽仁 勉
Teiji Obara
小原 禎二
Yoshio Natsuume
夏梅 伊男
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Zeon Corp
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Nippon Zeon Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a press-through package which is transparent and has no failure such as void, fish eye, curl, twist, waviness and unevenness of thickness, can sufficiently protect an article to be packaged from moisture even under high temperature and high humidity, and exhibits good adhesion of a metal foil at a pocket part, and from which the article to be packaged can easily be taken out. <P>SOLUTION: The press-through package is provided by storing the article to be packaged in a storing pocket of a sheet provided with the storing pocket with a thickness of 50-500 μm by a vacuum forming process, comprising a thermoplastic norbornene resin, especially preferably a hydrogenated dicyclopentadiene ring-opened polymer, and with a thickness of 100-500 μm except the storing pocket, and closing the opening part of the pocket with a metal foil with a thickness of 10-60 μm to package the article to be packaged. <P>COPYRIGHT: (C)2004,JPO

Description

 本発明は、プレス・スルー・パッケージに関し、さらに詳しくは無色透明で、ボイド、フィッシュアイ、カール、ねじれ、波うち、厚さむら等の不良がなく、高温高湿下においても被包装物を十分に防湿でき、ポケット部の金属箔の接着が良好であり、被包装物の取り出しが容易なプレス・スルー・パッケージに関する。 The present invention relates to a press-through package, and more particularly, it is colorless and transparent, has no defects such as voids, fish eyes, curls, twists, wavy waves, uneven thickness, etc. The present invention relates to a press-through package which can be moisture-proof, has good adhesion of a metal foil in a pocket portion, and can easily take out an object to be packaged.

 プレス・スルー・パッケージ(以下、PTPという)の基材である合成樹脂製シートは、ポケット部分から被包装物がよく見えるように透明なものが好ましく、また、被包装物の湿気による変質を防止するため、透湿度の小さいものが好ましく、従来、ポリ塩化ビニル製、またはポリプロピレン製のもの、さらに、特に防湿性が要求されるPTPにおいては、ポリプロピレンとポリビニリデンフルオライドの積層シートが用いられてきた。 The synthetic resin sheet, which is the base material of the press-through package (hereinafter referred to as PTP), is preferably transparent so that the package can be easily seen from the pocket portion, and prevents deterioration of the package due to moisture. Therefore, a material having a small moisture permeability is preferable. Conventionally, a product made of polyvinyl chloride or polypropylene, and in particular, a PTP that requires moisture-proof properties, a laminated sheet of polypropylene and polyvinylidene fluoride has been used. Was.

 しかし、ポリ塩化ビニルでは、湿気により変質しやすい薬剤を包装するには透湿度が十分に小さいとはいえず、使用後も焼却が困難であるという問題があった。一方、ポリプロピレンは真空成形性が良好ではなく、真空成形によりシートにポケット開口部を設ける際に、ポケット部の厚みが不均一になりやすく、また、成形シートがカールしやすく、作業性が悪いという問題があった。また、ポリプロピレンとポリビニリデンフルオライドの積層シートでは、真空成形性、作業性などのほかに焼却処理が困難であるという問題があった。 However, polyvinyl chloride has a problem that the moisture permeability is not small enough to package chemicals that are easily degraded by moisture, and it is difficult to incinerate after use. On the other hand, polypropylene is not good in vacuum formability, and when providing a pocket opening in a sheet by vacuum forming, the thickness of the pocket tends to be uneven, and the molded sheet is easily curled, and workability is poor. There was a problem. In addition, in the case of a laminated sheet of polypropylene and polyvinylidene fluoride, there is a problem that in addition to vacuum formability and workability, incineration is difficult.

 本発明者らは、PTPの基材として熱可塑性ノルボルネン系樹脂製シートを用い、ポケット部等を特定厚さにし、閉塞シートを特定厚さの金属箔とすることにより、透湿度が小さく、焼却処理が容易で、真空成形によりポケット開口部を設ける場合にボイド、フィッシュアイ、カール等の不良がなく、被包装物の取り出しが容易なPTPが得られることを見い出し、本発明を完成するに到った。 The present inventors use a thermoplastic norbornene-based resin sheet as the base material of the PTP, make the pocket portion and the like have a specific thickness, and make the closing sheet a metal foil of a specific thickness, so that the moisture permeability is small and the incineration is small. It has been found that a PTP that is easy to process, has no defects such as voids, fish eyes, and curls when a pocket opening is formed by vacuum forming, and that allows easy removal of a packaged object is obtained. Was.

 かくして本発明によれば、熱可塑性ノルボルネン系樹脂から成る下記厚さを持つシートに設けられた収納ポケットに被包装物を収納した後、該シートのポケット開口部を厚さ10〜60μmの金属箔で閉塞して被包装物を包装したプレス・スルー・パッケージが提供される。
 収納ポケット部の厚さが50〜500μmであり
 収納ポケット部以外の厚さが100〜500μmである。
Thus, according to the present invention, after storing an article to be packaged in a storage pocket provided in a sheet made of a thermoplastic norbornene resin having the following thickness, the pocket opening of the sheet is made of a metal foil having a thickness of 10 to 60 μm. To provide a press-through package in which an object to be packaged is closed.
The thickness of the storage pocket portion is 50 to 500 μm, and the thickness other than the storage pocket portion is 100 to 500 μm.

 本発明のPTPは、無色透明で、ボイド、フィッシュアイ、カール、ねじれ、波うち、厚さむら等の不良がなく、高温高湿下においても被包装物を十分に防湿でき、ポケット部の金属箔の接着が良好であり、被包装物の取り出しが容易である。 The PTP of the present invention is colorless and transparent, free from defects such as voids, fish eyes, curls, twists, wavy waves, and uneven thickness, and can sufficiently protect the packaged object even under high temperature and high humidity. Good adhesion of foil and easy removal of packaged items.

(熱可塑性ノルボルネン系樹脂)
 本発明の熱可塑性ノルボルネン系樹脂は、特開昭51−80400号公報、特開昭60−26024号公報、特開平1−168725号公報、特開平1−190726号公報、特開平3−14882号公報、特開平3−122137号公報、特開平4−63807号公報などで公知の樹脂であり、具体的には、ノルボルネン系単量体の開環重合体、その水素添加物、ノルボルネン系単量体の付加型重合体、ノルボルネン系単量体とオレフィンの付加型重合体などが挙げられる。
(Thermoplastic norbornene resin)
The thermoplastic norbornene resins of the present invention are disclosed in JP-A-51-80400, JP-A-60-26024, JP-A-1-168725, JP-A-1-190726, and JP-A-3-14882. JP-A-3-122137, JP-A-4-63807, and the like. Specific examples thereof include a ring-opened polymer of a norbornene-based monomer, a hydrogenated product thereof, and a norbornene-based monomer. Addition polymers, addition polymers of norbornene monomers and olefins, and the like.

 ノルボルネン系単量体も、上記公報や特開平2−227424号公報、特開平2−276842号公報などで公知の単量体であって、例えば、ノルボルネン、そのアルキル、アルキリデン、芳香族置換誘導体およびこれら置換または非置換のオレフィンのハロゲン、水酸基、エステル基、アルコキシ基、シアノ基、アミド基、イミド基、シリル基等の極性基置換体、例えば、2−ノルボルネン、5−メチル−2−ノルボルネン、5,5−ジメチル−2−ノルボルネン、5−エチル−2−ノルボルネン、5−ブチル−2−ノルボルネン、5−エチリデン−2−ノルボルネン、5−メトキシカルボニル−2−ノルボルネン、5−シアノ−2−ノルボルネン、5−メチル−5−メトキシカルボニル−2−ノルボルネン、5−フェニル−2−ノルボルネン、5−フェニル−5−メチル−2−ノルボルネン、5−ヘキシル−2−ノルボルネン、5−オクチル−2−ノルボルネン、5−オクタデシル2−ノルボルネン等; ノルボルネンに一つ以上のシクロペンタジエンが付加した単量体、その上記と同様の誘導体や置換体、例えば、1,4:5,8−ジメタノ−1,2,3,4,4a,5,8,8a−2,3−シクロペンタジエノオクタヒドロナフタレン、6−メチル−1,4:5,8−ジメタノ−1,4,4a,5,6,7,8,8a−オクタヒドロナフタレン、1,4:5,10:6,9−トリメタノ−1,2,3,4,4a,5,5a,6,9,9a,10,10a−ドデカヒドロ−2,3−シクロペンタジエノアントラセン等; シクロペンタジエンの多量体である多環構造の単量体、その上記と同様の誘導体や置換体、例えば、ジシクロペンタジエン(以下、DCPという)、2,3−ジヒドロジシクロペンタジエン等; シクロペンタジエンとテトラヒドロインデン等との付加物、その上記と同様の誘導体や置換体、例えば、1,4−メタノ−1,4,4a,4b,5,8,8a,9a−オクタヒドロフルオレン、5,8−メタノ−1,2,3,4,4a,5,8,8a−オクタヒドロ−2,3−シクロペンタジエノナフタレン等; 等が挙げられる。 Norbornene-based monomers are also monomers known in the above publications, JP-A-2-227424, JP-A-2-276842 and the like, and include, for example, norbornene, its alkyl, alkylidene, aromatic-substituted derivatives and Polar groups such as halogen, hydroxyl, ester, alkoxy, cyano, amide, imide, and silyl of these substituted or unsubstituted olefins, for example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene , 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbo Nene, 5-phenyl-5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene and the like; a unit obtained by adding one or more cyclopentadiene to norbornene , Its derivatives and substituents as described above, for example, 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienoocta Hydronaphthalene, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano -1,2,3,4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene; etc .; a monocyclic compound having a polycyclic structure which is a multimer of cyclopentadiene Mers, Derivatives and substituents similar to the above, for example, dicyclopentadiene (hereinafter, referred to as DCP), 2,3-dihydrodicyclopentadiene and the like; adducts of cyclopentadiene with tetrahydroindene, etc .; Substitutes, for example, 1,4-methano-1,4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a, 5,8 , 8a-octahydro-2,3-cyclopentadienonaphthalene and the like.

 なお、本発明においてはノルボルネン系単量体を重合させる場合には、本発明の効果を実質的に妨げない範囲において重合可能な他のシクロオレフィン類等を併用して、共重合体とすることができる。開環重合の場合の共重合可能なシクロオレフィンの具体例としては、例えば、シクロペンテン、シクロオクテンなどのごとき反応性の二重結合を1個以上有する化合物が例示される。 In the present invention, when a norbornene-based monomer is polymerized, other copolymerizable cycloolefins or the like may be used in combination within a range that does not substantially hinder the effects of the present invention to form a copolymer. Can be. Specific examples of the copolymerizable cycloolefin in the case of ring-opening polymerization include, for example, compounds having at least one reactive double bond such as cyclopentene and cyclooctene.

 ノルボルネン系単量体の重合は公知の方法でよく、一般には、重合触媒としてTiCl4、WCl6、MoCl5、VCl5、NiCl2、PdCl2などの遷移金属化合物と、Al、Li、Na、Mgなどの典型金属のアルキル化合物などを組み合わせて重合する。また、必要に応じて、公知の方法、例えば、Ni、Pdなどを触媒として、水素添加することにより、熱可塑性ノルボルネン系樹脂水素添加物とすることができる。 The polymerization of the norbornene-based monomer may be performed by a known method. Generally, a transition metal compound such as TiCl 4 , WCl 6 , MoCl 5 , VCl 5 , NiCl 2 , or PdCl 2 is used as a polymerization catalyst, and Al, Li, Na, Polymerization is performed by combining an alkyl compound of a typical metal such as Mg. Further, if necessary, a hydrogenated thermoplastic norbornene resin can be obtained by hydrogenation using a known method, for example, using Ni, Pd or the like as a catalyst.

 なお、従来公知の重合方法では、重合体中に重合触媒由来の遷移金属が残留する。PTPの被包装物が医薬や食品である場合、樹脂に残留する遷移金属が溶出するのは好ましくなく、樹脂中に実質的に残留しないことが好ましい。そのためには、細孔容積0.5cm3/g以上、好ましくは0.7cm3/g以上、好ましくは比表面積250m2/g以上のアルミナなどの吸着剤に、ニッケルなどの水素添加触媒金属を担持させた不均一系触媒を用いて重合体を水素添加したり、このような吸着剤で樹脂溶液を処理して金属原子を吸着させたり、樹脂溶液を酸性水と純水で繰り返し洗浄したりするなどにより、重合触媒由来の遷移原子を1ppm以下にする。 In addition, in the conventionally well-known polymerization method, the transition metal derived from the polymerization catalyst remains in the polymer. When the PTP package is a medicine or food, it is not preferable that the transition metal remaining in the resin elutes, and it is preferable that the transition metal does not substantially remain in the resin. To that end, pore volume 0.5 cm 3 / g or more, preferably 0.7 cm 3 / g or more, preferably in the adsorbent such as a specific surface area of 250 meters 2 / g or more alumina, a hydrogenation catalyst metal such as nickel Hydrogenation of the polymer using a supported heterogeneous catalyst, treatment of the resin solution with such an adsorbent to adsorb metal atoms, washing of the resin solution repeatedly with acidic water and pure water, etc. For example, the transition atom derived from the polymerization catalyst is reduced to 1 ppm or less.

 不均一系触媒の製造方法は公知の方法に従えばよく、特公昭50−15474号公報、特公昭49−32187号公報、特公昭49−11312号公報、特公昭51−48479号公報などで公知の方法に従い、乾燥や焼成の条件によって、担体の吸着能を制御すればよい。例えば、ニッケルを活性アルミナに担持した不均一系触媒の場合、濃度10〜20%の硫酸ニッケルまたは硝酸ニッケル水溶液に水酸化アルミニウム粉末を10〜20%の濃度で懸濁し、水酸化ナトリウムで加水分解することにより、水酸化アルミニウムの表面に水酸化ニッケルを担持させる。この粉末を濾過により回収し、押し出しにより固め、350〜450℃で焼成し、水素と100〜200℃で接触させて表面を還元し、さらに酸素の存在下で80〜120℃に熱することにより金属表面を酸化し、酸化被膜を形成することにより、活性アルミナに担持したニッケル触媒が得られる。なお、ニッケルの表面が酸化ニッケルで覆われているが、水素添加反応の系中では還元により、酸化ニッケルがニッケルとなり、触媒として機能する。 The method for producing the heterogeneous catalyst may be in accordance with a known method, and is known in JP-B-50-15474, JP-B-49-32187, JP-B-49-111212, JP-B-51-48479, and the like. According to the method described above, the adsorption capacity of the carrier may be controlled by the conditions of drying and baking. For example, in the case of a heterogeneous catalyst in which nickel is supported on activated alumina, aluminum hydroxide powder is suspended in an aqueous solution of nickel sulfate or nickel nitrate at a concentration of 10 to 20% at a concentration of 10 to 20%, and hydrolyzed with sodium hydroxide. Thereby, nickel hydroxide is supported on the surface of the aluminum hydroxide. The powder is collected by filtration, solidified by extrusion, calcined at 350-450 ° C., contacted with hydrogen at 100-200 ° C. to reduce the surface, and further heated to 80-120 ° C. in the presence of oxygen. By oxidizing the metal surface to form an oxide film, a nickel catalyst supported on activated alumina can be obtained. Although the surface of nickel is covered with nickel oxide, nickel oxide becomes nickel by reduction in a hydrogenation reaction system and functions as a catalyst.

 押し出しの条件、焼成の温度や圧力等により、活性アルミナの微細な構造が変化するので、細孔容積0.5cm3/g以上、好ましくは0.7cm3/g以上、また好ましくは比表面積250m2/g以上になるように条件を選択する。さらに、高温で水素添加する場合は、酸化被膜が厚いほど耐熱性を持つので、酸化の温度、時間、酸素濃度などを調節して、好ましい条件を選択すればよい。こうして得られた焼成物を粉砕して不均一系触媒を得ることができる。 Extrusion conditions, the temperature and pressure, etc. of the firing, since the fine structure of the activated alumina is changed, the pore volume of 0.5 cm 3 / g or more, preferably 0.7 cm 3 / g or more, and preferably a specific surface area 250m Select the condition so that it is 2 / g or more. Furthermore, when hydrogenation is performed at a high temperature, the thicker the oxide film, the higher the heat resistance. Therefore, the preferable conditions may be selected by adjusting the oxidation temperature, time, oxygen concentration, and the like. The thus obtained calcined product can be pulverized to obtain a heterogeneous catalyst.

 一般的な重合触媒の遷移金属化合物として、塩化遷移金属を使用した場合、通常、塩素原子も2ppm以上残留する。塩素原子も遷移金属原子と同様に医療用器材中に残留しないようにすることが好ましく、除去することが好ましい。除去する方法は、遷移金属原子と同様の処理で除去でき、残留量を1ppm以下にすることができる。 (4) When a transition metal chloride is used as a transition metal compound of a general polymerization catalyst, 2 ppm or more of chlorine atoms usually remain. It is preferable that the chlorine atom does not remain in the medical device like the transition metal atom, and it is preferable that the chlorine atom is removed. The removal method can be performed by the same treatment as that for the transition metal atoms, and the residual amount can be reduced to 1 ppm or less.

 本発明で使用する熱可塑性ノルボルネン系樹脂の数平均分子量は、トルエン溶媒によるGPC(ゲル・パーミエーション・クロマトグラフィ)法で測定したポリスチレン換算値で、10,000〜200,000、好ましくは15,000〜100,000、より好ましくは20,000〜50,000である。また、熱可塑性ノルボルネン系樹脂が分子構造中に不飽和結合を有している場合は、水素添加することにより、熱可塑性飽和ノルボルネン系樹脂とすることができる。水素添加する場合、水素添加率は耐熱劣化性、耐光劣化性などの観点から、90%以上、好ましくは95%以上、より好ましくは、99%以上である。 The number average molecular weight of the thermoplastic norbornene resin used in the present invention is 10,000 to 200,000, preferably 15,000, in terms of polystyrene measured by GPC (gel permeation chromatography) using a toluene solvent. 100100,000, more preferably 20,0002050,000. Further, when the thermoplastic norbornene-based resin has an unsaturated bond in the molecular structure, it can be converted into a thermoplastic saturated norbornene-based resin by hydrogenation. In the case of hydrogenation, the hydrogenation rate is 90% or more, preferably 95% or more, more preferably 99% or more, from the viewpoint of heat deterioration resistance and light deterioration resistance.

 熱可塑性ノルボルネン系樹脂の中でも、耐熱劣化性、耐光劣化性などに優れた熱可塑性飽和ノルボルネン系樹脂が好ましく、成形性に優れたノルボルネン系開環重合体水素添加物がより好ましく、防湿性に優れたDCP系開環重合体水素添加物がさらに好ましい。DCP系開環重合体水素添加物は、DCP、そのアルキル、アルキリデン、芳香族置換誘導体およびこれらのハロゲン、水酸基、エステル基、アルコキシ基、シアノ基、アミド基、イミド基、シリル基等の極性基置換体等のDCP系単量体に由来する開環繰り返し構造単位を50重量%以上、好ましくは60重量%以上含有している重合体を水素添加したものである。DCP系単量体に由来する開環繰り返し構造単位が多いほど防湿性に優れる。さらに、防湿性の観点から、DCP系開環重合体水素添加物の中でも、極性基を含有しないものが特に好ましく、極性基を有しないDCP系単量体開環ホモポリマー水素添加物、または極性基を有しないDCP系単量体とノルボルネン、1,4:5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレンあるいはこれらのアルキル、アルキリデン、芳香族置換誘導体の開環コポリマー水素添加物が最も好ましい。 Among the thermoplastic norbornene-based resins, a thermoplastic saturated norbornene-based resin having excellent heat deterioration resistance and light deterioration resistance is preferable, and a norbornene-based ring-opening polymer hydrogenated product having excellent moldability is more preferable, and has excellent moisture resistance. Further, a hydrogenated DCP-based ring-opening polymer is more preferable. DCP ring-opening polymer hydrogenated products include DCP, its alkyl, alkylidene, aromatic-substituted derivatives and their polar groups such as halogen, hydroxyl, ester, alkoxy, cyano, amide, imide, and silyl groups. It is obtained by hydrogenating a polymer containing 50% by weight or more, preferably 60% by weight or more of a ring-opening repeating structural unit derived from a DCP-based monomer such as a substituted product. The greater the number of ring-opening repeating structural units derived from the DCP monomer, the better the moisture resistance. Further, from the viewpoint of moisture resistance, among the hydrogenated DCP-based ring-opening polymers, those containing no polar group are particularly preferable, and the DCP-based monomer-opened homopolymer hydrogenated product having no polar group, or Group-free DCP monomer and norbornene, 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or their alkyl, alkylidene, aromatic Most preferred are ring-opened copolymer hydrogenated substituted derivatives.

 また、防湿性及び真空成形性の点から、ガラス転移温度(以下、Tgという)は50〜160℃、好ましくは60〜140℃、より好ましくは70〜110℃である。Tgが低すぎると透湿度が高くなり、Tgが高すぎると真空成形温度が高くなるため真空成形が困難になり、また、成形シートがカールしたり、波打ち状になりやすい。 {Circle around (5)} In terms of moisture resistance and vacuum moldability, the glass transition temperature (hereinafter, referred to as Tg) is 50 to 160 ° C, preferably 60 to 140 ° C, and more preferably 70 to 110 ° C. If the Tg is too low, the moisture permeability becomes high, and if the Tg is too high, the vacuum forming temperature becomes high, so that vacuum forming becomes difficult, and the formed sheet tends to be curled or wavy.

 本発明で用いる熱可塑性ノルボルネン系樹脂には、所望により、フェノール系やリン系等の老化防止剤; フェノール系等の熱劣化防止剤; ベンゾフェノン系等の紫外線吸収剤; アミン系等の帯電防止剤; 脂肪族アルコールのエステル、多価アルコールの部分エステル部分及び部分エーテル等の滑剤; 等の各種添加剤を添加してもよい。本発明の目的を損なわない範囲で、他の樹脂、ゴム質重合体などを混合して用いることもできる。また、本発明で用いる熱可塑性ノルボルネン系樹脂製のシートは、一般に、被包装物が外部から見ることができるように透明性が高いほど好ましいが、被包装物が可視光により劣化するものである場合は、被包装物を保護するため、遮光剤として色素、染料、顔料等を添加して、可視光、特に600nm以下の光線を遮光することが好ましい。 The thermoplastic norbornene-based resin used in the present invention may optionally include a phenol-based or phosphorus-based antioxidant; a phenol-based thermal degradation inhibitor; a benzophenone-based ultraviolet absorber; an amine-based antistatic agent. Lubricants such as esters of aliphatic alcohols, partial ester portions of polyhydric alcohols and partial ethers, and the like. As long as the object of the present invention is not impaired, other resins, rubbery polymers and the like can be mixed and used. Further, the thermoplastic norbornene-based resin sheet used in the present invention is generally preferable to have higher transparency so that the packaged object can be seen from the outside, but the packaged object is deteriorated by visible light. In this case, it is preferable to add a dye, a dye, a pigment, or the like as a light-shielding agent to shield visible light, particularly light having a wavelength of 600 nm or less, in order to protect the packaged object.

(熱可塑性ノルボルネン系樹脂製シート)
 本発明で用いるポケットを有する熱可塑性ノルボルネン系樹脂製シートを成形する方法は特に限定されない。射出成形、溶融押し出し、熱プレス、溶剤キャスト、インフレーションなど、熱可塑性樹脂の一般の成形方法を単独、または組み合わせて用いることができる。例えば、溶剤キャスト、溶融押し出し、インフレーション等の方法により、ポケットのないシートを成形した後、真空成形法、圧空成形法等によりポケットを成形する。
(Sheet made of thermoplastic norbornene resin)
The method for forming the thermoplastic norbornene-based resin sheet having pockets used in the present invention is not particularly limited. General molding methods for thermoplastic resins, such as injection molding, melt extrusion, hot pressing, solvent casting, and inflation, can be used alone or in combination. For example, after a sheet having no pocket is formed by a method such as solvent casting, melt extrusion, or inflation, the pocket is formed by a vacuum forming method, a pressure forming method, or the like.

 このポケットのないシートの透湿度は、40℃、90RH%の環境下で測定した場合、シート厚300μmに換算して、一般に、熱可塑性ノルボルネン系樹脂で1.0g/m2・24時間以下、DCP系開環重合体水素添加物で0.6g/m2・24時間以下であり、DCP系開環重合体水素添加物の中でも、極性基を有しないDCP系単量体開環ホモポリマー水素添加物、または極性基を有しないDCP系単量体とノルボルネン、1,4:5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレンあるいはこれらのアルキル、アルキリデン、芳香族置換誘導体の開環コポリマー水素添加物では0.4g/m2・24時間以下のものも得られる。このDCP系開環重合体水素添加物としては、好ましくは極性基を有しないDCP系単量体由来の開環繰り返し構造単位を50重量%以上、より好ましくは65重量%以上、さらに好ましくは80重量%以上、特に好ましくは90重量%以上含有する開環重合体を水素添加率70%以上、好ましくは90%以上、より好ましくは95%以上、特に好ましくは99%以上に水素添加したものである。DCP系単量体由来の開環繰り返し構造単位を多く含有するほど防湿性に優れ、透湿度が低い。 The moisture permeability of the sheet without the pocket, when measured in an environment of 40 ° C. and 90 RH%, is converted to a sheet thickness of 300 μm, and is generally 1.0 g / m 2 · 24 hours or less for a thermoplastic norbornene resin. The hydrogenated DCP-based ring-opening polymer is 0.6 g / m 2 · 24 hours or less, and among the hydrogenated DCP-based ring-opening polymers, among the DCP-based monomer-opened homopolymer hydrogens having no polar group, Additives or DCP monomers having no polar group and norbornene, 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or alkyls thereof , Alkylidene and a hydrogenated ring-opened copolymer of an aromatic-substituted derivative can be obtained in an amount of 0.4 g / m 2 · 24 hours or less. The hydrogenated DCP-based ring-opening polymer preferably contains at least 50% by weight, more preferably at least 65% by weight, even more preferably at least 80% by weight of a ring-opening repeating structural unit derived from a DCP-based monomer having no polar group. By weight of a ring-opening polymer containing at least 70% by weight, particularly preferably at least 90% by weight, to a hydrogenation rate of at least 70%, preferably at least 90%, more preferably at least 95%, particularly preferably at least 99%. is there. The more the ring-opening repeating structural units derived from the DCP-based monomer are contained, the better the moisture resistance and the lower the moisture permeability.

 ポケットのないシートを成形した後に真空成形法などによりポケットを成形する場合、シートを延伸することが好ましい。同じ樹脂で成形された同じ厚さのシートであれば、延伸しないシートに比べて、延伸したシートは透湿度が低い。延伸は一軸延伸が好ましい。二軸延伸は作業工程が複雑になり、また、透湿度の低下は一軸延伸したシートと大きく変わることがない。それに対し、一軸延伸は、公知の方法でよく、例えば、押し出し成形やインフレーション成形等の場合は引き取りロールで押し出し方向に連続的に延伸しながら巻き取ればよい等、簡単な工程で行うことがで、生産性に優れており、また透湿度の改善効果も大きい。 場合 When forming a pocket by a vacuum forming method after forming a sheet without a pocket, it is preferable to stretch the sheet. As long as the sheets are formed of the same resin and have the same thickness, the stretched sheet has a lower moisture permeability than the unstretched sheet. The stretching is preferably uniaxial stretching. Biaxial stretching complicates the working process, and the reduction in moisture permeability does not differ significantly from a uniaxially stretched sheet. On the other hand, the uniaxial stretching may be a known method.For example, in the case of extrusion molding or inflation molding, it may be performed in a simple process, such as winding while continuously stretching in the extrusion direction with a take-up roll. It is excellent in productivity and has a great effect of improving moisture permeability.

 延伸は、Tg〜Tg+100℃、好ましくはTg+10℃〜Tg+80℃で行い、延伸倍率は110〜500%、好ましくは120〜400%、より好ましくは130〜250%にする。延伸加工時の温度が低すぎると、延伸中にシートが破断しやすく、加工性に劣り、また、破断しない場合も延伸後のシートの強度が低下することがある。延伸加工温度が高すぎると、作業性が低下する。延伸倍率が小さすぎると、透湿度の低下が小さく、多きすぎると延伸後のシートの強度が低下し、またピンホールを生じやすいという問題がある。 Stretching is performed at Tg to Tg + 100 ° C., preferably Tg + 10 ° C. to Tg + 80 ° C., and the stretching ratio is 110 to 500%, preferably 120 to 400%, more preferably 130 to 250%. If the temperature at the time of stretching is too low, the sheet tends to break during stretching, resulting in poor workability, and when not breaking, the strength of the sheet after stretching may decrease. If the stretching temperature is too high, the workability decreases. If the stretching ratio is too small, the reduction in moisture permeability is small, and if it is too large, the strength of the sheet after stretching is reduced, and pinholes are liable to occur.

 例えば、DCP系開環重合体水素添加物、特に極性基を有しないDCP系単量体開環ホモポリマー水素添加物、または極性基を有しないDCP系単量体とノルボルネン、1,4:5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレンあるいはこれらのアルキル、アルキリデン、芳香族置換誘導体の開環コポリマー水素添加物では0.25g/m2・24時間以下のものも得ることができる。 For example, a hydrogenated product of a DCP-based ring-opening polymer, particularly a hydrogenated product of a ring-opened homopolymer of a DCP-based monomer having no polar group, or a DCP-based monomer having no polar group and norbornene, 1,4: 5 , 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or their hydrogenated ring-opening copolymers of alkyl, alkylidene and aromatic substituted derivatives are 0.25 g / m 2. 24 hours or less can also be obtained.

 収納ポケットを設けたシートはポケット部以外は厚さ100〜500μm、好ましくは150〜400μm、より好ましくは200〜350μm、ポケット部は厚さ50〜500μm、好ましくは70〜350μm、より好ましくは100〜300μm、特に好ましくは150〜250μmのものであり、開口部、収納ポケットは、被包装物の形状、大きさに応じた形状、大きさを有している。シートの厚さが厚すぎると強靱になりすぎるため被包装物が取り出しにくいという問題が生じ、薄過ぎると強度が不足して破損しやすく、また、防湿性が低下するという問題がある。このシートにはさらに他の樹脂層を積層していてもよい。また、このシートは、ポケット部分から被包装物がよく見えるように一般には、波長400〜800nmの光線透過率が好ましくは70%以上、より好ましくは80%以上、特に好ましくは90%以上である。 The sheet provided with the storage pocket has a thickness of 100 to 500 μm, preferably 150 to 400 μm, more preferably 200 to 350 μm, and the pocket portion has a thickness of 50 to 500 μm, preferably 70 to 350 μm, more preferably 100 to 500 μm except for the pocket portion. The opening and the storage pocket have a shape and a size corresponding to the shape and size of the article to be packaged. If the thickness of the sheet is too large, there is a problem that it is difficult to take out the packaged object because the sheet becomes too strong. If the thickness is too small, there is a problem that the strength is insufficient and the package is easily broken, and the moisture resistance is reduced. This sheet may be further laminated with another resin layer. In addition, this sheet generally has a light transmittance of preferably at least 70%, more preferably at least 80%, particularly preferably at least 90%, so that the packaged object can be easily seen from the pocket portion. .

(被包装物)
 本発明のPTPで包装される被包装物は特に限定されない。代表的な被包装物として医薬の錠剤、カプセルなどが挙げられる。
(Package)
The items to be packaged with the PTP of the present invention are not particularly limited. Representative tablets include pharmaceutical tablets, capsules and the like.

(ポケット閉塞用シート)
 本発明で用いるポケット閉塞用シートは、防湿性を有し、通常は包装を維持するのに十分な強度を有し、ポケット部を押すとそのポケットを閉塞していた部分が容易に破れて被包装物が取り出せるものであれば、特に限定されないが、一般には、金属箔の両面に樹脂層を積層したシートが用いられる。
(Pocket closure sheet)
The pocket closing sheet used in the present invention has moisture proof properties and usually has sufficient strength to maintain the packaging. When the pocket portion is pushed, the portion that closed the pocket is easily torn and covered. There is no particular limitation as long as the package can be taken out, but in general, a sheet in which resin layers are laminated on both surfaces of a metal foil is used.

 金属箔は厚さ好ましくは10〜60μm、より好ましくは15〜50μm、特に好ましくは20〜40μmのものであり、防湿性と被包装物の取りだしやすさという観点からアルミ箔が好ましい。金属箔の厚さが厚すぎると取りだしにくく、薄すぎると破損しやすく、防湿性も低下する。 (4) The metal foil has a thickness of preferably 10 to 60 μm, more preferably 15 to 50 μm, and particularly preferably 20 to 40 μm, and an aluminum foil is preferable from the viewpoints of moisture resistance and easy removal of the packaged object. If the thickness of the metal foil is too large, it is difficult to remove the metal foil.

 金属箔の両面に積層する樹脂は特に限定されないが、被包装物が食品や医薬品等の場合、有害物質が許容限度以上溶出しない樹脂にする。金属箔の強度が不十分な場合には、補強できる樹脂が好ましく、金属箔の防湿性が不十分な場合には、防湿性の高い樹脂が好ましい。 樹脂 The resin to be laminated on both sides of the metal foil is not particularly limited, but when the object to be packaged is a food or a pharmaceutical, the resin should be such that harmful substances do not elute beyond an allowable limit. When the strength of the metal foil is insufficient, a resin that can be reinforced is preferable, and when the moisture resistance of the metal foil is insufficient, a resin having high moisture resistance is preferable.

(接着方法)
 シートに金属箔でポケット開口部を閉塞して被包装物を包装する際の、ポケットを有するシートと閉塞用シートの接着方法は、特に限定されない。接着剤を用いて、ヒートシール、超音波シール、ドライラミネート、ウェットラミネート等をする方法、熱圧着する方法などがある。ポケットを有するシートまたは閉塞用シートに接着剤層を形成しておき、被包装物をポケットに収納した後、ヒートシールする方法が一般的である。また、ポケットを有するシートに接着前にコロナ放電処理やプラズマ処理等の前処理を行ってもよい。
(Adhesion method)
The method of bonding the sheet having the pocket and the sheet for closing when the object is packaged by closing the pocket opening with the metal foil is not particularly limited. There are a method of performing heat sealing, ultrasonic sealing, dry lamination, wet lamination, etc., and a method of thermocompression bonding using an adhesive. A general method is to form an adhesive layer on a sheet having a pocket or a sheet for closing, and to heat-seal after storing an article to be packaged in a pocket. Further, a pretreatment such as a corona discharge treatment or a plasma treatment may be performed on the sheet having pockets before bonding.

 接着剤としては、合成ゴム系ホットメルト接着剤、スチレン・エチレン・ブチレン・スチレン・ブロック共重合体、スチレン・イソプレン・スチレン・ブロック共重合体、スチレン・イソプレン・スチレン・ブロック共重合体水素添加物等の特殊合成ゴム系ホットメルト接着剤、ポリプロピレン系無水マレイン酸グラフト樹脂、ポリエチレン系無水マレイン酸グラフト樹脂、塩素化ポリオレフィン等のオレフィン末端変成物、エチレン・アクリル酸共重合体、エチレン・メタクリル酸共重合体、エチレン・メチルアクリレート・無水マレイン酸共重合体等のオレフィン共重合体等の接着性樹脂; アクリル系、合成ゴム系、ウレタン系等の溶液型接着剤; アクリル系、合成ゴム系、ウレタン系等のエマルジョン型接着剤; 等が使用できる。 Adhesives include synthetic rubber-based hot melt adhesives, styrene / ethylene / butylene / styrene / block copolymers, styrene / isoprene / styrene / block copolymers, and hydrogenated styrene / isoprene / styrene / block copolymers Special synthetic rubber-based hot melt adhesives, polypropylene-based maleic anhydride graft resin, polyethylene-based maleic anhydride graft resin, modified olefins such as chlorinated polyolefin, ethylene / acrylic acid copolymer, ethylene / methacrylic acid Adhesive resins such as polymers, olefin copolymers such as ethylene / methyl acrylate / maleic anhydride copolymers; Solution-based adhesives such as acrylic, synthetic rubber, and urethane; acrylic, synthetic rubber, and urethane Emulsion type adhesive such as a system;

 温度変化の幅の大きい環境下で使用する場合、樹脂と金属箔の膨張収縮の大きさの違いによりPTPがカールしないように、可撓性を有する接着剤を用いたり、特開平3−14403号公報に記載されたように、ポケット開口部の周辺のみを接着するなどの方法が好ましい。 When used in an environment having a large range of temperature change, a flexible adhesive is used so that the PTP does not curl due to the difference in expansion and contraction between the resin and the metal foil. As described in the publication, a method of bonding only the periphery of the pocket opening is preferable.

 以下に参考例、実施例、比較例を挙げて、本発明を具体的に説明する。
 参考例1
 DCP開環重合体水素添加物(数平均分子量26,000、ガラス転移温度93℃、水素添加率99.7%以上、遷移金属は検出されなかった)をスクリュー径65mmの押し出し機を用い、樹脂温度200℃で、400mm幅のTダイより押し出し、85℃のロールで引き取り厚さ300μmのシートを作製した。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。このシートの透湿度をJIS Z 0208の条件Bの方法で測定した結果、温度40℃、相対湿度90%RHの環境下で、0.26g/m2・24時間であった。
Hereinafter, the present invention will be specifically described with reference to Reference Examples, Examples, and Comparative Examples.
Reference Example 1
A DCP ring-opening polymer hydrogenated product (number average molecular weight 26,000, glass transition temperature 93 ° C., hydrogenation rate 99.7% or more, no transition metal was detected) was extruded with a resin extruder having a screw diameter of 65 mm. The sheet was extruded at a temperature of 200 ° C. from a T-die having a width of 400 mm and taken up by a roll at 85 ° C. to produce a sheet having a thickness of 300 μm.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability of this sheet was measured by the method under condition B of JIS Z 0208, and as a result, it was 0.26 g / m 2 · 24 hours under the environment of a temperature of 40 ° C. and a relative humidity of 90% RH.

 参考例2
 DCP由来の開環繰り返し構造単位70重量%と6−メチル−1,4:5,8−ジメタノ−1,4,4a,5,6,7,8,8a−オクタヒドロナフタレン由来の開環繰り返し構造単位30重量%から成る開環共重合体の水素添加物(数平均分子量28,000、ガラス転移温度109℃、水素添加率99.7%以上、遷移金属は検出されなかった)をスクリュー径65mmの押し出し機を用い、樹脂温度215℃で、400mm幅のTダイより押し出し、95℃のロールで引き取り、厚さ300μmのシートを作製した。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。参考例1と同様に測定した透湿度は0.32g/m2・24時間であった。
Reference Example 2
70% by weight of DCP-derived ring-opening repeating structural unit and 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene-derived ring-opening repeating unit The screw diameter of the hydrogenated product of the ring-opening copolymer composed of 30% by weight of the structural unit (number average molecular weight: 28,000, glass transition temperature: 109 ° C., hydrogenation rate: 99.7% or more, and no transition metal was detected) Using a 65 mm extruder, the resin was extruded from a T-die having a width of 400 mm at a resin temperature of 215 ° C. and taken up by a roll at 95 ° C. to produce a sheet having a thickness of 300 μm.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability measured in the same manner as in Reference Example 1 was 0.32 g / m 2 · 24 hours.

 参考例3
 6−メチル−1,4:5,8−ジメタノ−1,4,4a,5,6,7,8,8a−オクタヒドロナフタレンの開環共重合体水素添加物(数平均分子量34,000、ガラス転移温度160℃、水素添加率99.7%以上、遷移金属は検出されなかった)をスクリュー径65mmの押し出し機を用い、樹脂温度260℃で、400mm幅のTダイより押し出し、150℃のロールで引き取り厚さ300μmのシートを作製した。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。参考例1と同様に測定した透湿度は0.76g/m2・24時間であった。
Reference Example 3
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene ring-opening copolymer hydrogenated product (number average molecular weight 34,000, A glass transition temperature of 160 ° C., a hydrogenation rate of 99.7% or more, and no transition metal was detected) was extruded from a 400 mm wide T-die at a resin temperature of 260 ° C. using an extruder having a screw diameter of 65 mm. A sheet having a thickness of 300 μm was prepared with a roll.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability measured in the same manner as in Reference Example 1 was 0.76 g / m 2 · 24 hours.

 参考例4
 DCP由来の開環繰り返し構造単位90重量%と6−メチル−1,4,5,8−ジメタノ−1,4,4a,5,6,7,8,8a−オクタヒドロキシナフタレン由来の開環繰り返し構造単位10重量%から成る開環重合体の水素添加物(数平均分子量約35,000、ガラス転移温度105℃、水素添加率99.7%以上、遷移金属は検出されなかった)をスクリュー径65mmの押し出し機を用い、樹脂温度200℃で、400mm幅のTダイより押し出し、90℃のロールで引き取り厚さ300μmのシートを作製した。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。参考例1と同様に測定した透湿度は0.32g/m2・24時間であった。
Reference example 4
90% by weight of DCP-derived ring-opening repeating structural unit and 6-methyl-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydroxynaphthalene-derived ring-opening repeating unit A hydrogenated product of a ring-opening polymer composed of 10% by weight of structural units (number-average molecular weight: about 35,000, glass transition temperature: 105 ° C, hydrogenation rate: 99.7% or more, and no transition metal was detected) Using a 65 mm extruder, the sheet was extruded from a T-die having a width of 400 mm at a resin temperature of 200 ° C. and rolled at 90 ° C. to produce a sheet having a thickness of 300 μm.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability measured in the same manner as in Reference Example 1 was 0.32 g / m 2 · 24 hours.

 参考例5
 厚さを450μmにする以外は参考例1と同様にして、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良がなく、外観が良好なシートを得た。このシートをクレップテンターを用いて、130℃の環境下で1.5倍に一軸延伸加工し、厚さ300μmのシートを得た。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。参考例1と同様に測定した透湿度は0.19g/m2・24時間であった。
Reference example 5
A sheet was obtained in the same manner as in Reference Example 1 except that the thickness was changed to 450 μm. The sheet was colorless and transparent, had no defects such as voids and fish eyes, and no external defects such as curl, twist, and wavy. This sheet was uniaxially stretched 1.5 times in an environment of 130 ° C. using a crepe tenter to obtain a sheet having a thickness of 300 μm.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability measured in the same manner as in Reference Example 1 was 0.19 g / m 2 · 24 hours.

 参考例6
 厚さを450μmにする以外は参考例2と同様にして、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良がなく、外観が良好なシートを得た。このシートをクレップテンターを用いて、140℃の環境下で1.5倍に一軸延伸加工し、厚さ300μmのシートを得た。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。参考例1と同様に測定した透湿度は0.23g/m2・24時間であった。
Reference Example 6
A sheet was obtained in the same manner as in Reference Example 2, except that the thickness was changed to 450 μm, and was colorless and transparent, free from defects such as voids and fish eyes, and from external defects such as curl, twist, and wavy, and having a good appearance. This sheet was uniaxially stretched 1.5 times in an environment of 140 ° C. using a crepe tenter to obtain a sheet having a thickness of 300 μm.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability measured in the same manner as in Reference Example 1 was 0.23 g / m 2 · 24 hours.

 参考例7
 厚さを430μmにする以外は参考例3と同様にして、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良がなく、外観が良好なシートを得た。このシートをクレップテンターを用いて、220℃の環境下で1.5倍に一軸延伸加工し、厚さ300μmのシートを得た。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。参考例1と同様に測定した透湿度は0.60g/m2・24時間であった。
Reference Example 7
A sheet having good appearance was obtained in the same manner as in Reference Example 3 except that the thickness was changed to 430 μm, and was colorless and transparent, free of defects such as voids and fish eyes, and without external defects such as curl, twist, and wavy. This sheet was uniaxially stretched 1.5 times in an environment of 220 ° C. using a crepe tenter to obtain a sheet having a thickness of 300 μm.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability measured in the same manner as in Reference Example 1 was 0.60 g / m 2 · 24 hours.

 参考例8
 厚さを445μmにする以外は参考例4と同様にして、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良がなく、外観が良好なシートを得た。このシートをクレップテンターを用いて、130℃の環境下で1.5倍に一軸延伸加工し、厚さ300μmのシートを得た。
 得られたシートは無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。参考例1と同様に測定した透湿度は0.22g/m2・24時間であった。
Reference Example 8
A sheet was obtained in the same manner as in Reference Example 4, except that the thickness was changed to 445 μm, and was colorless and transparent, free from defects such as voids and fish eyes, and from external defects such as curl, twist, and wavy, and having a good appearance. This sheet was uniaxially stretched 1.5 times in an environment of 130 ° C. using a crepe tenter to obtain a sheet having a thickness of 300 μm.
The obtained sheet was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The moisture permeability measured in the same manner as in Reference Example 1 was 0.22 g / m 2 · 24 hours.

 実施例1
 口部直径14mm、底部直径12mm、深さ5mmのポケットが3mm間隔で縦6個横2個配列された下型と下型のポケットとかみ合う底部直径12mm、頂部直径10mm、高さ4mmの凸部が5mm間隔で縦6個横2個配列された上型からなる真空金型内に下型と上型を開いた状態で参考例1で得たシートを固定し、140℃で1分間余熱し、下型と上型を閉じると同時にポケット部を減圧して、ポケットを有するシートを作製した。
 このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは190μm、ポケット部側面の厚さは120μmであった。
Example 1
A convex part with a bottom diameter of 12 mm, a top diameter of 10 mm, and a height of 4 mm that engages with a lower mold and a lower mold pocket in which 6 pockets each having a mouth diameter of 14 mm, a bottom diameter of 12 mm, and a depth of 5 mm are arranged at intervals of 3 mm in a length of 6 rows and 2 rows. The sheet obtained in Reference Example 1 was fixed with the lower mold and the upper mold open in a vacuum mold consisting of an upper mold having 6 pieces arranged vertically and 2 pieces arranged horizontally at an interval of 5 mm, and preheated at 140 ° C. for 1 minute. Then, the lower mold and the upper mold were closed, and at the same time, the pressure of the pocket portion was reduced to produce a sheet having pockets.
This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the pocket bottom was 190 μm, and the thickness of the pocket side was 120 μm.

 このシートの閉塞用シートとの接着面にポリプロピレン系無水マレイン酸グラフト樹脂接着剤(三菱油化株式会社製、モディック M410F)を塗布し、乾燥して厚さ約10μmの接着剤層を形成した。各ポケット部に各々シリカゲル0.25gを充填した後、厚さ22μmアルミ箔の閉塞用シートを接合し、接着面を100℃に加熱して圧着してPTPを作製した。ポケットを有するシートと閉塞用シートの接着は良好であった。
 このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、10.4mgであった。
A polypropylene-based maleic anhydride graft resin adhesive (Modick M410F, manufactured by Mitsubishi Yuka Co., Ltd.) was applied to the adhesive surface of the sheet with the closing sheet, and dried to form an adhesive layer having a thickness of about 10 μm. After filling each pocket with 0.25 g of silica gel, a 22 μm-thick aluminum foil closing sheet was joined, and the adhesive surface was heated to 100 ° C. and pressed to produce PTP. The adhesion between the sheet having pockets and the sheet for closing was good.
After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 10.4 mg.

 実施例2
 参考例1で得たシートの代わりに参考例2で得たシートを用い、金型の余熱温度を150℃にする以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは110μm、ポケット部側面の厚さは165μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、14.3mgであった。
Example 2
A sheet having pockets was prepared in the same manner as in Example 1 except that the sheet obtained in Reference Example 2 was used instead of the sheet obtained in Reference Example 1, and the residual heat temperature of the mold was set to 150 ° C. This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the pocket bottom was 110 μm, and the thickness of the pocket side was 165 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After keeping this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 14.3 mg.

 実施例3
 参考例1で得たシートの代わりに参考例3で得たシートを用い、金型の余熱温度を200℃にする以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは180μm、ポケット部側面の厚さは125μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、29.8mgであった。
Example 3
A sheet having pockets was prepared in the same manner as in Example 1 except that the sheet obtained in Reference Example 3 was used instead of the sheet obtained in Reference Example 1, and the preheating temperature of the mold was set to 200 ° C. This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the pocket bottom was 180 μm, and the thickness of the pocket side was 125 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 29.8 mg.

 実施例4
 参考例1で得たシートの代わりに参考例4で得たシートを用いる以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは170μm、ポケット部側面の厚さは120μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、12.7mgであった。
Example 4
A sheet having pockets was produced in the same manner as in Example 1 except that the sheet obtained in Reference Example 4 was used instead of the sheet obtained in Reference Example 1. This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the pocket bottom was 170 μm, and the thickness of the pocket side was 120 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 12.7 mg.

 実施例5
 参考例1で得たシートの代わりに参考例5で得たシートを用いる以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは180μm、ポケット部側面の厚さは130μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、7.9mgであった。
Example 5
A sheet having pockets was produced in the same manner as in Example 1 except that the sheet obtained in Reference Example 5 was used instead of the sheet obtained in Reference Example 1. This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the bottom of the pocket was 180 μm, and the thickness of the side of the pocket was 130 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 7.9 mg.

 実施例6
 参考例1で得たシートの代わりに参考例6で得たシートを用いる以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは160μm、ポケット部側面の厚さは120μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、10.6mgであった。
Example 6
A sheet having pockets was produced in the same manner as in Example 1 except that the sheet obtained in Reference Example 6 was used instead of the sheet obtained in Reference Example 1. This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the pocket bottom was 160 μm, and the thickness of the pocket side was 120 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 10.6 mg.

 実施例7
 参考例1で得たシートの代わりに参考例7で得たシートを用いる以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは170μm、ポケット部側面の厚さは125μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、23.7mgであった。
Example 7
A sheet having pockets was produced in the same manner as in Example 1 except that the sheet obtained in Reference Example 7 was used instead of the sheet obtained in Reference Example 1. This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the pocket bottom was 170 μm, and the thickness of the pocket side was 125 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 23.7 mg.

 実施例8
 参考例1で得たシートの代わりに参考例8で得たシートを用いる以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うち、厚さムラなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは170μm、ポケット部側面の厚さは120μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、9.3mgであった。
Example 8
A sheet having pockets was produced in the same manner as in Example 1 except that the sheet obtained in Reference Example 8 was used instead of the sheet obtained in Reference Example 1. This sheet transferred the shape of the mold well, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, wavy, and uneven thickness, and had a good appearance. The thickness of the pocket bottom was 170 μm, and the thickness of the pocket side was 120 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 9.3 mg.

 比較例1
 参考例1で得たシートの代わりに厚さ300μmのポリ塩化ビニルシートを用い、金型の余熱温度を125℃にする以外は実施例1と同様にポケットを有するシートを作製した。このシートは、金型形状をよく転写し、無色透明で、ボイドやフィッシュアイなどの欠陥、カール、ねじれ、波うちなどの外形不良はなく、外観は良好であった。また、ポケット底部の厚さは160μm、ポケット部側面の厚さは135μmであった。
 このシートを用い、実施例1と同様にPTPを作製したが、ポケットを有するシートと閉塞用シートの接着は良好であった。このPTPを40℃、90RH%の環境下に5日間保持した後、重量増加量を測定したところ、137.2mgであった。
Comparative Example 1
A sheet having pockets was produced in the same manner as in Example 1 except that a polyvinyl chloride sheet having a thickness of 300 μm was used instead of the sheet obtained in Reference Example 1, and the residual heat temperature of the mold was set to 125 ° C. This sheet had a good transfer of the mold shape, was colorless and transparent, had no defects such as voids and fish eyes, no external defects such as curl, twist, and wavy, and had a good appearance. The thickness of the bottom of the pocket was 160 μm, and the thickness of the side of the pocket was 135 μm.
Using this sheet, a PTP was produced in the same manner as in Example 1, but the adhesion between the sheet having pockets and the closing sheet was good. After maintaining this PTP in an environment of 40 ° C. and 90 RH% for 5 days, the weight increase was measured and found to be 137.2 mg.

Claims (5)

熱可塑性ノルボルネン系樹脂から成る下記厚さを持つシートに設けられた収納ポケットに被包装物を収納した後、該シートのポケット開口部を厚さ10〜60μmの金属箔で閉塞して被包装物を包装したプレス・スルー・パッケージ。
 収納ポケット部の厚さが50〜500μmであり
 収納ポケット部以外の厚さが100〜500μmである。
After storing an article to be packaged in a storage pocket provided in a sheet made of a thermoplastic norbornene-based resin and having the following thickness, the pocket opening of the sheet is closed with a metal foil having a thickness of 10 to 60 μm, and the article to be packaged is closed. Press-through package.
The thickness of the storage pocket portion is 50 to 500 μm, and the thickness other than the storage pocket portion is 100 to 500 μm.
熱可塑性ノルボルネン系樹脂が、シート厚300μm、40℃、90RH%の条件下で測定した場合に1.0g/m・24時間以下の透湿度を有するものである請求項1記載のプレス・スルー・パッケージ。 The thermoplastic norbornene-based resin, sheet thickness 300 [mu] m, 40 ° C., a press-through according to claim 1, wherein those having a moisture permeability of less 1.0 g / m 2 · 24 hours when measured under the conditions of 90 RH% ·package. 金属箔がアルミ箔である請求項1記載のプレス・スルー・パッケージ。 The press-through package according to claim 1, wherein the metal foil is an aluminum foil. 金属箔がその両面に樹脂層を積層されたものである請求項1記載のプレス・スルー・パッケージ。 2. The press-through package according to claim 1, wherein the metal foil has a resin layer laminated on both surfaces thereof. 熱可塑性ノルボルネン系樹脂から成るシートが、一軸延伸したシートに収納ポケットを設けたものである請求項1、2、3または4記載のプレス・スルー・パッケージ。 5. The press-through package according to claim 1, wherein the sheet made of a thermoplastic norbornene resin is provided with a storage pocket in a uniaxially stretched sheet.
JP2003278798A 1993-01-29 2003-07-24 Press-through package Pending JP2004001898A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52110769A (en) * 1976-03-15 1977-09-17 Takeda Chemical Industries Ltd Method of molding blister packaging plastic shell
JPS59167252A (en) * 1983-03-15 1984-09-20 東レ株式会社 Composite film for molding
JPS6045353A (en) * 1983-08-19 1985-03-11 マルホ自動機株式会社 Film molding apparatus for ptp
JPH0218027A (en) * 1988-07-06 1990-01-22 Iwaguro Seisakusho:Kk Manufacturing method of packaging container
JPH04272937A (en) * 1991-02-28 1992-09-29 Toray Ind Inc Composite polymer sheet
JPH04137836U (en) * 1991-06-13 1992-12-22 株式会社細川洋行 Sheet for PTP packaging

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52110769A (en) * 1976-03-15 1977-09-17 Takeda Chemical Industries Ltd Method of molding blister packaging plastic shell
JPS59167252A (en) * 1983-03-15 1984-09-20 東レ株式会社 Composite film for molding
JPS6045353A (en) * 1983-08-19 1985-03-11 マルホ自動機株式会社 Film molding apparatus for ptp
JPH0218027A (en) * 1988-07-06 1990-01-22 Iwaguro Seisakusho:Kk Manufacturing method of packaging container
JPH04272937A (en) * 1991-02-28 1992-09-29 Toray Ind Inc Composite polymer sheet
JPH04137836U (en) * 1991-06-13 1992-12-22 株式会社細川洋行 Sheet for PTP packaging

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