JPS6336939B2 - - Google Patents
Info
- Publication number
- JPS6336939B2 JPS6336939B2 JP14873983A JP14873983A JPS6336939B2 JP S6336939 B2 JPS6336939 B2 JP S6336939B2 JP 14873983 A JP14873983 A JP 14873983A JP 14873983 A JP14873983 A JP 14873983A JP S6336939 B2 JPS6336939 B2 JP S6336939B2
- Authority
- JP
- Japan
- Prior art keywords
- resin layer
- thermoformable
- polyethylene resin
- deposited
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002985 plastic film Substances 0.000 claims description 60
- 229920013716 polyethylene resin Polymers 0.000 claims description 59
- 230000004888 barrier function Effects 0.000 claims description 58
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 53
- 229920006026 co-polymeric resin Polymers 0.000 claims description 52
- 239000005022 packaging material Substances 0.000 claims description 38
- 150000002736 metal compounds Chemical class 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 26
- 229920006255 plastic film Polymers 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000009820 dry lamination Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920006284 nylon film Polymers 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 92
- 239000011248 coating agent Substances 0.000 description 32
- 238000001035 drying Methods 0.000 description 14
- 238000007756 gravure coating Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 230000035699 permeability Effects 0.000 description 12
- 238000003856 thermoforming Methods 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920002873 Polyethylenimine Polymers 0.000 description 8
- 238000010030 laminating Methods 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 238000007754 air knife coating Methods 0.000 description 5
- 239000002650 laminated plastic Substances 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 229920001342 Bakelite® Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007666 vacuum forming Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】
本発明はプラスチツクシートを積層してなるバ
リヤー性包装材に関するものである。さらに詳し
くは長期の品質保持が要求される医薬品等の包装
材料としての熱成形用に適したバリヤー性プラス
チツク積層シートに関するものである。
従来、医薬品等のバリヤー性包装材はプラスチ
ツクシートに塩化ビニリデン系共重合樹脂エマル
ジヨンを塗布し、該面上に無機金属化合物の真空
蒸着被膜を設け、しかる後に、これら２枚のプラ
スチツクシートに無機金属化合物の真空蒸着被膜
の面を内側にしてその間に溶融ポリエチレンをＴ
−ダイを用いて押出しラミネーシヨン法で積層又
はポリエチレン樹脂フイルムを介しドライラミネ
ーシヨン法で積層したものがあるが、PTP用包
装材としての性能において充分でなく長期の被包
装物の品質保持にも限界があり、バリヤー性等を
十分に満足できる熱成形用バリヤー性プラスチツ
ク積層シートとはいえない。
これらの欠点を改良すべく鋭意検討を重ねた結
果、従来の塩化ビニリデン系共重合樹脂エマルジ
ヨンをプラスチツクシートに塗布したものに、無
機金属化合物の真空蒸着被膜層を設けた熱成形可
能なプラスチツクフイルムを設けることにより透
明性、熱成形性、PTP用蓋材の硬質アルミニウ
ムの塩化ビニルコート面とのヒートシール性、水
蒸気透過率、酸素透過率を同時に向上させること
ができるという新たな事実を見い出し本発明を完
成するにいたつた。特に熱成形性については無機
金属化合物の真空蒸着被膜層が熱成形可能なプラ
スチツクフイルムに直接蒸着されているため、従
来の物に比べ熱成形の際延展しやすく熱成形品の
形状として絞り比0.3以下であれば熱成形性が特
に好ましく透明性も損われず、水蒸気透過率、酸
素透過率の向上も顕著である。
即ち、本発明は、
(1) 第１の熱成形可能な硬質プラスチツクシー
ト、第１の塩化ビニリデン共重合樹脂層、第１
のポリエチレン樹脂層、第１の熱成形可能なプ
ラスチツクフイルムに無機金属化合物が蒸着さ
れた層、ポリエチレン樹脂層、第２の熱成形可
能なプラスチツクフイルムに無機金属化合物が
蒸着された層、第２のポリエチレン樹脂層、第
２の塩化ビニリデン系共重合樹脂層および第２
の熱成形可能な硬質プラスチツクシートが順次
積層されてなり、かつ前記各塩化ビニリデン系
共重合樹脂層の厚さが1.5〜60μであることを特
徴とするバリヤー性包装材（以下本発明の第１
のバリヤー性包装材と称する）、
(2) 熱成形可能な硬質プラスチツクシート、塩化
ビニリデン系共重合樹脂層、ポリエチレン樹脂
層、前記熱成形可能なプラスチツクフイルムに
無機金属化合物が蒸着された層が順次積層され
てなるバリヤー性包装材（以下本発明の第２の
バリヤー性包装材と称する）及び
(3) ２枚の熱成形可能な硬質プラスチツクシート
の各々の片面に塩化ビニリデン系共重合樹脂エ
マルジヨンを塗布乾燥して塩化ビニリデン系共
重合樹脂層を形成し、該塩化ビニリデン系共重
合樹脂層と無機金属化合物が蒸着された熱成形
可能なプラスチツクフイルムの間に第１のポリ
エチレン樹脂、第２のポリエチレン樹脂のそれ
ぞれで各々を押出しラミネーシヨンして固着せ
しめるか、ポリエチレン樹脂フイルムを介しド
ライラミネーシヨンして固着せしめてそれぞれ
２枚の積層物を得、この２枚の積層物を無機金
属化合物が蒸着された熱成形可能なプラスチツ
クフイルム側をそれぞれ内向させ、その間に溶
融ポリエチレン樹脂を押出しラミネーシヨンし
て一体固着せしめるか、ポリエチレン樹脂フイ
ルムを介し、ドライラミネーシヨンして一体固
着せしめることを特徴とするバリヤー性包装材
の製造法に関する。
なお、本発明の製造法においては、本発明の第
２のバリヤー性包装材を得る場合に、無機金属化
合物蒸着層側を塩化ビニリデン系共重合樹脂層と
内向させてポリエチレン樹脂で一体化させるのが
好ましいが、熱成形可能な硬質プラスチツクフイ
ルム側を塩化ビニリデン系共重合体樹脂層と内向
させてポリエチレン樹脂で一体化させてもよい。
上記本発明の第２のバリヤー性包装材は本発明
の第１のバリヤー性包装材を製造するのに適した
中間原材料の積層シートとして有用であるばかり
か、それ以外のバリヤー性が要求される包装材の
用途にも活用し得る。
次に本発明のバリヤー性包装材を図面によつて
説明する。第１図は本発明のバリヤー性包装材の
好ましい態様を示す概略断面図である。第１図に
おいて１は第１の熱成形可能な硬質プラスチツク
シート、２は第１のアンカーコート層、３は第１
の塩化ビニリデン系共重合樹脂層、４は第２のア
ンカーコート層、５は第１のポリエチレン樹脂
層、６は第３のアンカーコート層、７は第１の無
機金属化合物蒸着層、８は第１の熱成形可能な被
蒸着プラスチツクフイルム、９は第４のアンカー
コート層、１０はポリエチレン樹脂層、１１は第
５のアンカーコート層、１２は第２の熱成形可能
な被蒸着プラスチツクフイルム、１３は第２の無
機金属化合物蒸着層、１４は第６のアンカーコー
ト層、１５は第２のポリエチレン樹脂層、１６は
第７のアンカーコート層、１７は第２の塩化ビニ
リデン系共重合樹脂層、１８は第８のアンカーコ
ート層、１９は第２の熱成形可能な硬質プラスチ
ツクシートである。
第１および第２の熱成形可能な硬質プラスチツ
クシート１，１９としては接触加熱あるいは輻射
加熱による圧空成形や真空成形が容易でかつ成形
後に保形性を有するものが好ましい。かかる観点
から、たとえば硬質塩化ビニル樹脂シート、無延
伸ポリプロピレン樹脂シート、ポリスチレン樹脂
シート、セルローズアセテート樹脂シート、ポリ
カーボネート樹脂シート、無延伸高密度ポリエチ
レン樹脂シートが用いられる。殊に硬質塩化ビニ
ル樹脂シートはPTP用蓋材である硬質アルミニ
ウムの塩化ビニル樹脂コートの面とのヒートシー
ル性にすぐれているので特に好ましく用いられ
る。熱成形可能な硬質プラスチツクシートの厚さ
は特に制限されないが、通常30〜1000μ程度の厚
さのものが好ましく用いられる。積層シートの全
体の厚みとしては用途上から考えて150〜2000μ
が好ましい。第１の熱成形可能な硬質プラスチツ
クシート１と第２の熱成形可能な硬質プラスチツ
クシート１９とは通常同質材で構成されている
が、異質材であつてもよい。
第１または／および第２の熱成形可能な硬質プ
ラスチツクシートの表面または／および裏面には
所望の印刷を施してもよく、これにより表示効果
および装飾効果がより一層発揮される。
第１および第２の塩化ビニリデン系共重合樹脂
層３，１７としては前記熱成形可能な硬質プラス
チツクシートの熱成形性を害せずに高いバリヤー
性を有するものが好ましい。かかる観点から、共
重合に際して塩化ビニリデンの単量体が80〜95％
（重量％、以下同様）と塩化ビニルの単量体など
が５〜20％の共重合組成を有する塩化ビニリデン
系共重合樹脂のエマルジヨン〔例えばサランラテ
ツクス（旭化成工業(株)商品名）〕が前記第１およ
び第２の熱成形可能な硬質プラスチツクシート
１，１９の片面に直接または第１または第８のア
ンカーコート層２，１８を介して塗布乾燥して形
成される。その成形方法も何ら制限されず、エア
ーナイフコート法、グラビヤコート法、スムージ
ングコート法、ロールコート法などの通常の方法
がいずれも採用されるが、塩化ビニリデン系共重
合樹脂層に充分なバリヤー性を発揮させるために
は、熱成形可能な硬質プラスチツクシートに塩化
ビニリデン系共重合樹脂エマルジヨンを塗布した
後に水分を蒸発させ、塩化ビニリデン系共重合樹
脂の結晶化を進行させるために乾燥させる必要が
あるが、熱収縮等の熱による変形を起さない温度
範囲を選ばなければならない。乾燥温度が低いと
塩化ビニリデン系共重合樹脂エマルジヨンの乾燥
が充分になされず、しかも得られる塩化ビニリデ
ン系共重合樹脂層の結晶化も進行しない。この場
合、バリヤー性も充分に発揮されない上に、熱成
形可能な硬質プラスチツクシートをロール状に捲
きとつた際にブロツキングを生ずる。従つてコー
ターの乾燥温度としては90〜150℃程度とするの
が望ましい。塩化ビニリデン系共重合樹脂層の厚
さは通常1.5〜60μ、好ましくは23〜55μ程度の範
囲から選ばれる。厚さが1.5μ未満の場合はバリヤ
ー性が悪く、また60μより厚くしてもバリヤー性
は向上しにくいから60μより厚いものは経済的に
不利である。
第１および第２の無機金属化合物蒸着層７，１
３は例えば珪素、アルミニウム、チタン、セレ
ン、マグネシウム、バリウム、インジウム、カル
シウム、ジルコニウム、トリウム、タリウム、タ
ンタル、亜鉛等、またはこれらの酸化物、ハロゲ
ン化物、窒化物などの単体または混合物を主体と
する透明な無機金属化合物が前記第１および第２
の熱成形可能な被蒸着プラスチツクフイルム８，
１２に蒸着されるが、熱成形可能な被蒸着プラス
チツクフイルムとしてはポリエステル樹脂、塩化
ビニル樹脂、ポリアミド樹脂（ナイロン）、ポリ
エチレン樹脂、プロプロピレン樹脂等の延伸、ま
たは無延伸フイルムが用いられる。無機金属化合
物が蒸着された熱成形可能な被蒸着プラスチツク
フイルム８，１２は第１および第２のポリエチレ
ン樹脂層５，１５により第１および第２の塩化ビ
ニリデン系共重合樹脂層３，１７と第２のアンカ
ーコート層４、第３のアンカーコート層６、第６
のアンカーコート層１４、第７のアンカーコート
層１６を介して形成される。
無機金属化合物の蒸着層の形成方法は、何ら制
限もなく、真空蒸着法、反応性蒸着法、スパツタ
リング法、反応性スパツタリング法、イオンプレ
ーテイング法、反応性イオンプレーテイング法な
どの通常の方法がいずれも採用される。無機金属
化合物蒸着層の厚さは通常100〜5000Å、好まし
くは300〜800Å程度の範囲から選ばれる。厚さが
100Å未満の場合はバリヤー性が悪く、また5000
Åより厚くしてもバリヤー性は向上しにくいか
ら、5000Åより厚いものは経済的に不利である。
ポリエチレン樹脂層５，１５は前記第１および
第２の塩化ビニリデン系共重合樹脂層３，１７と
無機金属化合物が蒸着された熱成形可能な被蒸着
フイルム８，１２との間にＴ−ダイから280〜330
℃程度の溶融ポリエチレン樹脂を押出し形成する
と同時に両者をラミネーシヨンして一体固着せし
めるものである。ポリエチレン樹脂層の厚さはラ
ミネーシヨンされる熱成形可能な硬質プラスチツ
クシートの厚さにもよるが、通常20〜70μ、好ま
しくは25〜50μ程度の範囲から選ばれるポリエチ
レン樹脂層の厚さが20μ未満の場合は充分なラミ
ネーシヨン強度が得られず、また70μより厚い場
合は溶融したポリエチレン樹脂がＴ−ダイから押
出された後冷却しても完全に冷却されず、ラミネ
ーシヨンされる熱成形可能な硬質プラスチツクシ
ートがポリエチレン樹脂の溶融熱で収縮変形を起
し、製品に波状のしわが発生するので好ましくな
い。ドライラミネーシヨン法でのポリエチレン樹
脂フイルムの厚さはＴ−ダイによる押出しラミネ
ーシヨン法と同様に通常20〜70μ、好ましくは25
〜50μ程度の範囲から選ばれる、ポリエチレン樹
脂フイルムの厚さが20μ未満の場合は衝撃に対す
る緩衝効果が少なく、ドライラミネーシヨン加工
時にポリエチレン樹脂フイルムにしわが発生しや
すいため好ましくない。また70μより厚い場合は
PTP包装においてミシン目によるスリツトが困
難である。ポリエチレン樹脂層１０は第１および
第２の無機金属化合物が蒸着された熱成形可能な
被蒸着プラスチツクフイルム８と１２との間に、
Ｔ−ダイから280〜330℃程度の溶融ポリエチレン
樹脂を押出し形成すると同時に両者をラミネーシ
ヨンして一体固着せしめるものである。ラミネー
シヨンに先立ち無機金属化合物蒸着層または熱成
形可能な被蒸着フイルムの表面をアンカーコート
処理しておいてもよい。ポリエチレン樹脂層の厚
さはラミネーシヨンされる熱成形可能な硬質プラ
スチツクシートの厚さにもよるが、通常20〜
70μ、好ましくは30〜50μ程度の範囲から選ばれ
る。ポリエチレン樹脂層の厚さが20μ未満の場合
は充分なラミネーシヨン強度が得られず、また
70μより厚い場合は溶融したポリエチレン樹脂が
Ｔ−ダイから押出された後冷却しても完全に冷却
されず、ラミネーシヨンされる熱成形可能な硬質
プラスチツクシートがポリエチレン樹脂の溶融熱
で収縮変形を起し、製品に波状のしわが発生する
ので好ましくない。ドライラミネーシヨン法での
ポリエチレン樹脂フイルムの厚さはＴ−ダイによ
る押出ラミネーシヨン法と同様に通常20〜70μ、
好ましくは30〜50μ程度の範囲から選ばれる。ポ
リエチレンフイルムの厚さが20μ未満の場合は衝
撃に対する緩衝効果が少なく、ドライラミネーシ
ヨン加工時にポリエチレン樹脂フイルムにしわが
発生しやすいため好ましくない。また70μより厚
い場合はPTP包装においてミシン目によるスリ
ツトが困難である。
本発明においては厚さが20〜70μのポリエチレ
ン樹脂層５，１０，１５を厚みの厚い熱成形可能
な硬質プラスチツクシートの中間に設けたので衝
撃に対する緩衝作用が働き、かつ厚みの厚い熱成
形可能な硬質プラスチツクシート同志の接着にも
充分な接着強度を発揮するものである。
アンカーコート層２，４，６，９，１１，１
４，１６，１８は熱成形可能な硬質プラスチツク
シートと塩化ビニリデン系共重合樹脂層との間、
塩化ビニリデン系共重合樹脂層とポリエチレン樹
脂層との間、ポリエチレン樹脂層と無機金属化合
物蒸着層との間、熱成形可能な被蒸着プラスチツ
クフイルムとの間、あるいは熱成形可能な被蒸着
プラスチツクフイルムとポリエチレン樹脂層との
間の密着性が悪い場合に設けられる。アンカーコ
ート剤としては例えばアルキルチタネート系、ポ
リイソシアネート系、ポリアルキレンイミン系な
どのものがあげられる。その厚さは通常0.1〜2μ
程度である。またアンカーコート層を設けるかわ
りにコロナ放電処理やプラズマエツチング処理等
が応用されることもあり、アンカーコートとコロ
ナ放電処理やプラズマエツチング処理等が併用さ
れることもある。
第２図は本発明のバリヤー性包装材を用いた包
装体の好ましい態様を示す一部切断斜視図であ
る。第２図においてＡは本発明のバリヤー性包装
材を熱成形して得られる容器、Ｂはシート状塩化
ビニルコート硬質アルミニウムからなる蓋材であ
る。
このようにして得られた熱成形用バリヤー性プ
ラスチツクシートの成形品は、耐水蒸気透過性、
耐気体透過性等のバリヤー性能が、従来のプラス
チツクシートに塩化ビニリデン系共重合樹脂エマ
ルジヨンを塗布し、更に無機金属化合物を蒸着し
たもの、に比べ一段と改良され、又薬品包材とし
てのPTP包装では蓋材として従来より使用して
いる硬質アルミニウムに塩化ビニル樹脂をコート
したシートの塩化ビニル樹脂層と、本発明に係る
熱成形用バリヤー性シートとは容易にヒートシー
ル加工ができ、薬品包材としてのバリヤー性がよ
り具備される。
実施例 １
硬質塩化ビニル樹脂シート（住友ベークライト
株式会社製のスミライトVSS−8142ZUV）の
100μ厚のシートにグラビヤコート法でイソシア
ネート系のアンカーコート剤（日本ポリウレタン
工業株式会社製のコロネートＬ−75）を塗布乾燥
後、塩化ビニリデン共重合樹脂層エマルジヨン
（旭化成工業株式会社製サランラテツクスＬ−
509）をエアーナイフコート法で８回塗布乾燥を
くり返し塩化ビニリデン系共重合樹脂層を厚さ
49μに形成し、ロール状に巻き取つた塩化ビニリ
デン系共重合樹脂層が塗布乾燥された塩化ビニル
樹脂シートを２本作成した。このシートの塩化ビ
ニリデン系共重合樹脂層面にポリエチレンイミン
系のアンカーコート剤（BASF株式会社製ポリミ
ンＰ）をグラビヤコート法で塗布乾燥し、一方、
二軸延伸ナイロン（ユニチカ株式会社製）の厚さ
15μのフイルムにSiOの粉末を10-4Torrの真空下
で500Åの真空蒸着被膜を形成したフイルムの真
空蒸着被膜面にポリエチレンイミン系のアンカー
コート剤（BASF株式会社製ポリミンＰ）をグラ
ビヤコート法で塗布乾燥したフイルムを２本作成
した。
塩化ビニリデン系共重合樹脂層面と真空蒸着被
膜面との間に押出機Ｔ−ダイからポリエチレン樹
脂（旭化成工業株式会社製サンテツクLD）を厚
み30μで押出して２本のロールを２種のアンカー
コート剤を介して積層して本発明の第２のバリヤ
ー性包装材を２本得た。次いでこの２本の二軸延
伸ナイロンフイルム面にアンカーコート剤として
ポリエチレンイミン（BASF株式会社製ポリミン
Ｐ）をグラビヤコート法で塗布乾燥し、押出機Ｔ
−ダイからポリエチレン樹脂（旭化成工業株式会
社製サンテツクLD）を厚み35μで押出して２本の
ロールの二軸延伸ナイロン面同志をアンカーコー
ト剤を介して積層し全体の厚みが約430μになる
本発明の第１のバリヤー性包装材（バリヤー性プ
ラスチツク積層シート）を得、真空成形法により
絞り比0.25の容器を得た。容器の中に水蒸気透過
率を測定するために乾燥用シリカゲルを入れ塩化
ビニル樹脂コート硬質アルミニウムからなる蓋材
の塩化ビニル樹脂コート面と容器とをヒートシー
ラーにより密封しバリヤー性包装体（PTP包装
体）を得た。バリヤー性、熱成形性、外観等は表
１の通りであつた。
実施例 ２
硬質塩化ビニル樹脂シート（住友ベークライト
株式会社製のスミライトVSS−8142ZUV）の
100μ厚のシートにグラビヤコート法でイソシア
ネート系のアンカーコート剤（日本ポリウレタン
工業株式会社製のコロネートＬ−75）を塗布乾燥
後、塩化ビニリデン系共重合樹脂エマルジヨン
（旭化成工業株式会社製サランラテツクスＬ−
400）をエアーナイフコート法で６回塗布乾燥を
くり返し塩化ビニリデン系共重合樹脂層を50μに
形成し、ロール状に巻き取つた塩化ビニリデン系
共重合樹脂エマルジヨンの塗布乾燥された塩化ビ
ニル樹脂シートを２本作成した。このシートの塩
化ビニリデン系共重合樹脂層面にポリエチレンイ
ミン系のアンカーコート剤（BASF株式会社製ポ
リミンＰ）をグラビヤコート法で塗布乾燥し、一
方、二軸延伸ポリエステル樹脂フイルム（東洋紡
績株式会社製）の厚み12μのフイルムにAl2O3の
粉末を10-4Torrの真空下で700Åの真空蒸着被膜
を形成したフイルムの真空蒸着被膜面にポリエチ
レンイミン系のアンカーコート剤（BASF株式会
社製ポリミンＰ）をグラビヤコート法で塗布乾燥
したフイルムを２本作成した。
塩化ビニリデン系共重合樹脂層面と真空蒸着被
膜面との間に押出機Ｔ−ダイからポリエチレン樹
脂（旭化成工業株式会社製サンテツクLD）を厚
み30μで押出して２本のロールを２種のアンカー
コート剤を介して積層して本発明の第２のバリヤ
ー性包装材を２本得た。次いでこの２本の二軸延
伸ポリエステル樹脂フイルム面にアンカーコート
剤としてポリエチレンイミン（BASF株式会社製
ポリミンＰ）をグラビヤコート法で塗布乾燥し、
押出機Ｔ−ダイからポリエチレン樹脂を厚み50μ
で押出して２本のロールの二軸延伸ナイロン面同
志をアンカーコート剤を介して積層し全体の厚み
が約440μになる本発明の第１のバリヤー性包装
材（熱成形用バリヤー性プラスチツク積層シー
ト）を得、真空成形法により絞り比0.3の容器を
得た。容器の中に水蒸気透過率を測定するため乾
燥用シリカゲルを入れ塩化ビニル樹脂コート硬質
アルミニウムからなる蓋材の塩化ビニル樹脂コー
ト面と容器とをヒートシーラーにより密封し
PTPの包装体を得た。バリヤー性、熱成形性、
外観等は表１の通りである。
比較例 １
硬質塩化ビニル樹脂シート（住友ベークライト
株式会社製のスミライトVSS−8142ZUV）の
100μ厚のシートにグラビヤコート法でイソシア
ネート系のアンカーコート剤（日本ポリウレタン
工業株式会社製のコロネートＬ−75）を塗布乾燥
後、塩化ビニリデン系共重合樹脂エマルジヨン
（旭化成工業株式会社製サランラテツクスＬ−
400）をエアーナイフコート法で６回塗り重ねし
て塩化ビニリデン系共重合樹脂層を厚さ49μに形
成し、ロール状に巻きとつた塩化ビニリデン系共
重合樹脂層が塗布された塩化ビニル樹脂シートを
２本作成したこのシートの塩化ビニリデン共重合
樹脂層面にポリウレタン系アンカーコート剤（東
洋モートン株式会社製AD−527）をグラビヤコ
ート法で塗布乾燥後、Al2O3の粉末を10-4Torrの
真空下で300Åの真空蒸着被膜を連続蒸着した、
２本の真空蒸着被膜面にアンカーコート剤として
ポリエチレンイミン（BASF株式会社製ポリミン
Ｐ）をグラビヤコート法で塗布乾燥し、押出機Ｔ
−ダイからポリエチレンを厚み35μで押出して２
本のロールの真空蒸着被膜面同志をアンカーコー
ト剤を介して積層し全体の厚みが約337μになる
バリヤー性包装材（熱成形用バリヤー性プラスチ
ツク積層シート）を得、次いでこれを真空成形法
により絞り比0.3の容器を得た。容器の中に水蒸
気透過率を測定するため乾燥用シリカゲルを入
れ、塩化ビニル樹脂コート硬質アルミニウムから
なる蓋材の塩化ビニル樹脂コート面と容器とをヒ
ートシーラーにより密封しPTPの包装体を得た。
バリヤー性、熱成形性、外観等は表１の通りであ
る。
比較例 ２
硬質塩化ビニル樹脂シート（住友ベークライト
株式会社製のスミライトVSS−8142ZUV）の
100μ厚のシートにグラビヤコート法でイソシア
ネート系のアンカーコート剤（日本ポリウレタン
工業株式会社製のコロネートＬ−75）を塗布乾燥
後、塩化ビニリデン系共重合樹脂エマルジヨン
（旭化成工業株式会社製サランラテツクスＬ−
400）をエアーナイフコート法で３回塗り重ねし
て塩化ビニリデン系共重合樹脂層を18μに形成
し、ロール状に巻き取つた塩化ビニリデン系共重
合樹脂エマルジヨンの塗布された塩化ビニル樹脂
シートを２本作成した。この塩化ビニリデン系共
重合樹脂層面にポリウレタン系アンカーコート剤
（東洋モートン株式会社製AD−527）をグラビヤ
コート法で塗布乾燥後Al2O3の粉末を10-4Torrの
真空下で700Åの真空蒸着被膜を連続蒸着した。
２本の真空蒸着被膜面にアンカーコート剤として
ポリエチレンイミン（BASF株式会社製ポリミン
Ｐ）をグラビヤコート法で塗布乾燥し、押出機Ｔ
−ダイからポリエチレン樹脂（旭化成工業株式会
社製サンテツクLD）を厚み60μで押出して２本の
ロールの真空蒸着被膜面同志をアンカーコート剤
を介して積層し、全体の厚みが約300μになるバ
リヤー性包装材（熱成形用バリヤー性プラスチツ
ク積層シート）を得、これを真空成形法により絞
り比0.3の容器を得た。容器の中に水蒸気透過率
を測定するため乾燥用シリカゲルを入れ塩化ビニ
ル樹脂コート硬質アルミニウムからなる蓋材の塩
化ビニル樹脂コート面と容器とをヒートシーラー
により密封しPTPの包装体を得た。バリヤー性、
熱成形性、外観等は表１の通りである。
表１中に記した熱成形性については布施真空株
式会社製（型式TM−4PW）熱成形機で成形し、
プラスチツクシートの熱成形後の成形品の破れ、
熱成形金型での型再現性等を観察し、成形品に破
れの発生したものは×印、破れの発生がないもの
を〇印で判定した。
外観については熱成形後の成形品につき目視判
定により細かい亀裂の発生により白化現象の生じ
たものは×印、生じなかつたものを〇印で表わし
た。
水蒸気透過率はJIS−Ｚ−0208に準じて測定し
１ｇ／m2・24hr以上を×印、１ｇ／m2・24hr未満
を〇印で表わした。
酸素透過率は23℃における同圧法で測定し、１
c.c.／m2・24hr・atm以上を×印、１c.c.／m2・
24hr・atm未満を〇印で表わした。
これらの特性のうち全てが〇印のものが総合的
に満足できるもので一特性でも×印があれば本発
明の目的に合致しない。従つて実施例１、実施例
２は本発明に係る透明性のあるウルトラハイバリ
ヤーPTP用包装材として目的を十分かなえるも
のである。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a barrier packaging material made of laminated plastic sheets. More specifically, the present invention relates to a barrier plastic laminate sheet suitable for thermoforming as a packaging material for pharmaceutical products that require long-term quality maintenance. Conventionally, barrier packaging materials for pharmaceuticals and the like have been produced by applying a vinylidene chloride copolymer resin emulsion to a plastic sheet, and then providing a vacuum-deposited film of an inorganic metal compound on the surface, and then coating these two plastic sheets with an inorganic metal. Place the molten polyethylene in between with the surface of the vacuum-deposited compound film facing inside.
-There are products that are laminated by extrusion lamination using a die or dry lamination using polyethylene resin film, but these do not have sufficient performance as PTP packaging materials and are not suitable for maintaining the quality of the packaged items over a long period of time. Due to its limitations, it cannot be said to be a barrier plastic laminate sheet for thermoforming that fully satisfies barrier properties and the like. As a result of extensive research to improve these shortcomings, we developed a thermoformable plastic film in which a conventional vinylidene chloride copolymer resin emulsion is coated on a plastic sheet, and a vacuum-deposited coating layer of an inorganic metal compound is applied. The present invention has been made based on the discovery of a new fact that by providing this, transparency, thermoformability, heat sealability with the vinyl chloride coated surface of hard aluminum of PTP lid material, water vapor permeability, and oxygen permeability can be simultaneously improved. I have come to complete it. In particular, regarding thermoformability, the vacuum-deposited coating layer of an inorganic metal compound is directly deposited on a thermoformable plastic film, so it is easier to spread during thermoforming compared to conventional products, and the shape of the thermoformed product has a drawing ratio of 0.3. If it is below, thermoformability is particularly favorable, transparency is not impaired, and water vapor permeability and oxygen permeability are significantly improved. That is, the present invention provides: (1) a first thermoformable hard plastic sheet, a first vinylidene chloride copolymer resin layer, a first
a polyethylene resin layer, a layer in which an inorganic metal compound is deposited on a first thermoformable plastic film; a polyethylene resin layer, a layer in which an inorganic metal compound is deposited on a second thermoformable plastic film; A polyethylene resin layer, a second vinylidene chloride copolymer resin layer, and a second
A barrier packaging material (hereinafter referred to as the first aspect of the present invention) characterized in that thermoformable rigid plastic sheets of
(2) A thermoformable hard plastic sheet, a vinylidene chloride copolymer resin layer, a polyethylene resin layer, and a layer in which an inorganic metal compound is deposited on the thermoformable plastic film are sequentially formed. A layered barrier packaging material (hereinafter referred to as the second barrier packaging material of the present invention) and (3) a vinylidene chloride copolymer resin emulsion on one side of each of two thermoformable hard plastic sheets. A vinylidene chloride copolymer resin layer is formed by coating and drying, and a first polyethylene resin and a second polyethylene resin are placed between the vinylidene chloride copolymer resin layer and a thermoformable plastic film on which an inorganic metal compound is vapor-deposited. The two laminates are obtained by extrusion lamination and fixation with each resin, or by dry lamination and fixation through a polyethylene resin film, and these two laminates are coated with an inorganic metal compound by vapor deposition. The barrier property is characterized by having the thermoformable plastic film sides facing inward, and extruding molten polyethylene resin between them and laminating them together to fix them together, or by dry laminating them through a polyethylene resin film to fix them together. Concerning the manufacturing method of packaging materials. In addition, in the manufacturing method of the present invention, when obtaining the second barrier packaging material of the present invention, the inorganic metal compound vapor-deposited layer side is made to face inward with the vinylidene chloride-based copolymer resin layer and integrated with the polyethylene resin. However, the thermoformable hard plastic film side may face inward with the vinylidene chloride copolymer resin layer and may be integrated with the polyethylene resin. The second barrier packaging material of the present invention is not only useful as a laminated sheet of intermediate raw materials suitable for manufacturing the first barrier packaging material of the present invention, but also requires other barrier properties. It can also be used as a packaging material. Next, the barrier packaging material of the present invention will be explained with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the barrier packaging material of the present invention. In FIG. 1, 1 is a first thermoformable hard plastic sheet, 2 is a first anchor coat layer, and 3 is a first thermoformable hard plastic sheet.
vinylidene chloride copolymer resin layer, 4 is the second anchor coat layer, 5 is the first polyethylene resin layer, 6 is the third anchor coat layer, 7 is the first inorganic metal compound vapor deposited layer, 8 is the third 1 a thermoformable deposited plastic film, 9 a fourth anchor coat layer, 10 a polyethylene resin layer, 11 a fifth anchor coat layer, 12 a second thermoformable deposited plastic film, 13 is the second inorganic metal compound vapor deposited layer, 14 is the sixth anchor coat layer, 15 is the second polyethylene resin layer, 16 is the seventh anchor coat layer, 17 is the second vinylidene chloride copolymer resin layer, 18 is an eighth anchor coat layer, and 19 is a second thermoformable hard plastic sheet. The first and second thermoformable hard plastic sheets 1, 19 are preferably those that can be easily pressure-formed or vacuum-formed by contact heating or radiation heating, and that have shape retention properties after molding. From this point of view, for example, hard vinyl chloride resin sheets, unstretched polypropylene resin sheets, polystyrene resin sheets, cellulose acetate resin sheets, polycarbonate resin sheets, and unstretched high-density polyethylene resin sheets are used. In particular, a hard vinyl chloride resin sheet is particularly preferably used because it has excellent heat sealability with the vinyl chloride resin-coated surface of hard aluminum, which is the lid material for PTP. The thickness of the thermoformable hard plastic sheet is not particularly limited, but a thickness of about 30 to 1000 microns is usually preferably used. The overall thickness of the laminated sheet is 150 to 2000μ considering the usage.
is preferred. The first thermoformable rigid plastic sheet 1 and the second thermoformable rigid plastic sheet 19 are usually constructed of the same material, but they may be of different materials. The front and/or back sides of the first and/or second thermoformable rigid plastic sheets may be provided with desired printing, thereby providing even greater display and decorative effects. The first and second vinylidene chloride copolymer resin layers 3 and 17 are preferably those having high barrier properties without impairing the thermoformability of the thermoformable hard plastic sheet. From this point of view, during copolymerization, vinylidene chloride monomer accounts for 80 to 95%.
An emulsion of a vinylidene chloride copolymer resin having a copolymerization composition of 5% to 20% (by weight, the same applies hereinafter) and a vinyl chloride monomer (for example, Saran Latex (trade name of Asahi Kasei Industries, Ltd.)) It is formed by coating and drying on one side of the first and second thermoformable hard plastic sheets 1, 19 directly or via the first or eighth anchor coat layer 2, 18. The molding method is not limited in any way, and conventional methods such as air knife coating, gravure coating, smoothing coating, and roll coating can be used, but the vinylidene chloride copolymer resin layer has sufficient barrier properties. In order to achieve this, it is necessary to evaporate the water after coating a thermoformable hard plastic sheet with a vinylidene chloride copolymer resin emulsion, and then dry it to promote crystallization of the vinylidene chloride copolymer resin. However, a temperature range must be selected that does not cause thermal deformation such as thermal contraction. If the drying temperature is low, the vinylidene chloride copolymer resin emulsion will not be sufficiently dried, and the resulting vinylidene chloride copolymer resin layer will not crystallize. In this case, not only the barrier properties are not sufficiently exhibited, but also blocking occurs when the thermoformable hard plastic sheet is rolled up into a roll. Therefore, the drying temperature of the coater is preferably about 90 to 150°C. The thickness of the vinylidene chloride copolymer resin layer is usually selected from a range of 1.5 to 60μ, preferably about 23 to 55μ. If the thickness is less than 1.5μ, the barrier properties are poor, and even if it is thicker than 60μ, it is difficult to improve the barrier properties, so anything thicker than 60μ is economically disadvantageous. First and second inorganic metal compound vapor deposited layers 7, 1
3 is mainly composed of, for example, silicon, aluminum, titanium, selenium, magnesium, barium, indium, calcium, zirconium, thorium, thallium, tantalum, zinc, etc., or their oxides, halides, nitrides, etc. alone or in mixtures. A transparent inorganic metal compound is included in the first and second
thermoformable deposited plastic film 8,
12, stretched or unstretched films of polyester resin, vinyl chloride resin, polyamide resin (nylon), polyethylene resin, propylene resin, etc. are used as thermoformable plastic films to be deposited. The thermoformable plastic films 8 and 12 on which an inorganic metal compound has been vapor-deposited are bonded to the first and second vinylidene chloride copolymer resin layers 3 and 17 by the first and second polyethylene resin layers 5 and 15. 2 anchor coat layer 4, third anchor coat layer 6, sixth
The anchor coat layer 14 and the seventh anchor coat layer 16 are interposed therebetween. There are no restrictions on the method for forming the vapor deposited layer of the inorganic metal compound, and conventional methods such as vacuum vapor deposition, reactive vapor deposition, sputtering, reactive sputtering, ion plating, and reactive ion plating may be used. Both will be adopted. The thickness of the inorganic metal compound vapor-deposited layer is usually selected from a range of 100 to 5000 Å, preferably about 300 to 800 Å. Thickness
If it is less than 100Å, the barrier properties are poor, and if it is less than 5000Å,
Even if the thickness is thicker than 5000 Å, it is difficult to improve the barrier properties, so a layer thicker than 5000 Å is economically disadvantageous. The polyethylene resin layers 5, 15 are formed from a T-die between the first and second vinylidene chloride copolymer resin layers 3, 17 and the thermoformable films 8, 12 on which the inorganic metal compound is vapor-deposited. 280~330
This involves extruding molten polyethylene resin at a temperature of approximately 0.9°C, and simultaneously laminating the two and fixing them together. The thickness of the polyethylene resin layer depends on the thickness of the thermoformable hard plastic sheet to be laminated, but is usually 20 to 70μ, preferably 25 to 50μ.The thickness of the polyethylene resin layer is 20μ. If it is less than 70μ, sufficient lamination strength cannot be obtained, and if it is thicker than 70μ, even if the molten polyethylene resin is extruded from the T-die and cooled, it will not be completely cooled, making it possible to thermoform lamination. This is undesirable because the hard plastic sheet shrinks and deforms due to the heat of melting the polyethylene resin, resulting in wavy wrinkles in the product. The thickness of the polyethylene resin film in the dry lamination method is usually 20 to 70μ, preferably 25μ, as in the extrusion lamination method using a T-die.
If the thickness of the polyethylene resin film is less than 20 μm, which is selected from the range of about 50 μm, it is not preferable because the cushioning effect against impact is low and wrinkles are likely to occur in the polyethylene resin film during dry lamination processing. Also, if it is thicker than 70μ
It is difficult to slit the perforations in PTP packaging. A polyethylene resin layer 10 is formed between thermoformable deposited plastic films 8 and 12 having first and second inorganic metal compounds deposited thereon.
Molten polyethylene resin at about 280 to 330°C is extruded from a T-die, and at the same time, both are laminated and fixed together. Prior to lamination, the surface of the inorganic metal compound vapor-deposited layer or the thermoformable film to be vapor-deposited may be subjected to an anchor coating treatment. The thickness of the polyethylene resin layer depends on the thickness of the thermoformable rigid plastic sheet to be laminated, but is usually between 20 and 20 mm.
It is selected from the range of about 70μ, preferably from about 30 to 50μ. If the thickness of the polyethylene resin layer is less than 20μ, sufficient lamination strength cannot be obtained, and
If it is thicker than 70μ, the molten polyethylene resin will not be completely cooled even after being extruded from the T-die and the thermoformable hard plastic sheet to be laminated will shrink and deform due to the melting heat of the polyethylene resin. However, this is not preferable because it causes wavy wrinkles in the product. The thickness of the polyethylene resin film in the dry lamination method is usually 20 to 70μ, similar to the extrusion lamination method using a T-die.
It is preferably selected from a range of about 30 to 50μ. If the thickness of the polyethylene film is less than 20 μm, it is not preferable because it has little impact cushioning effect and wrinkles are likely to occur in the polyethylene resin film during dry lamination processing. Also, if the thickness is more than 70μ, it is difficult to slit the perforations in PTP packaging. In the present invention, the polyethylene resin layers 5, 10, and 15 with a thickness of 20 to 70 μm are provided between the thick thermoformable hard plastic sheets, so that they act as shock absorbers and are also thick thermoformable. It exhibits sufficient adhesive strength for adhering hard plastic sheets together. Anchor coat layer 2, 4, 6, 9, 11, 1
4, 16, and 18 are between the thermoformable hard plastic sheet and the vinylidene chloride copolymer resin layer;
Between a vinylidene chloride copolymer resin layer and a polyethylene resin layer, between a polyethylene resin layer and an inorganic metal compound vapor-deposited layer, between a thermoformable plastic film to be vaporized, or between a thermoformable plastic film to be vaporized. This is provided when the adhesion between the polyethylene resin layer and the polyethylene resin layer is poor. Examples of anchor coating agents include those based on alkyl titanates, polyisocyanates, and polyalkyleneimines. Its thickness is usually 0.1~2μ
That's about it. Furthermore, instead of providing an anchor coat layer, corona discharge treatment, plasma etching treatment, etc. may be applied, and the anchor coat and corona discharge treatment, plasma etching treatment, etc. may be used together. FIG. 2 is a partially cutaway perspective view showing a preferred embodiment of a package using the barrier packaging material of the present invention. In FIG. 2, A is a container obtained by thermoforming the barrier packaging material of the present invention, and B is a lid material made of sheet-like vinyl chloride coated hard aluminum. The molded thermoformable barrier plastic sheet thus obtained has water vapor permeability,
Barrier performance such as gas permeability is much improved compared to conventional plastic sheets coated with vinylidene chloride copolymer resin emulsion and then vapor-deposited with inorganic metal compounds. The vinyl chloride resin layer of a sheet made of hard aluminum coated with vinyl chloride resin, which has been conventionally used as a lid material, and the barrier sheet for thermoforming according to the present invention can be easily heat-sealed and can be used as a drug packaging material. It has better barrier properties. Example 1 Hard vinyl chloride resin sheet (Sumilite VSS-8142ZUV manufactured by Sumitomo Bakelite Co., Ltd.)
An isocyanate-based anchor coating agent (Coronate L-75, manufactured by Nippon Polyurethane Industries, Ltd.) was coated on a 100 μ thick sheet using the gravure coating method, and after drying, a vinylidene chloride copolymer resin layer emulsion (Saran Latex L, manufactured by Asahi Kasei Industries, Ltd.) was applied. −
509) was applied 8 times using the air knife coating method and dried repeatedly to form a thick layer of vinylidene chloride copolymer resin.
Two vinyl chloride resin sheets were prepared, each coated with a vinylidene chloride copolymer resin layer formed to a thickness of 49 μm and wound into a roll and dried. A polyethyleneimine anchor coating agent (Polymin P manufactured by BASF Corporation) was coated on the surface of the vinylidene chloride copolymer resin layer of this sheet using a gravure coating method and dried.
Thickness of biaxially stretched nylon (manufactured by Unitika Co., Ltd.)
A 500 Å vacuum-deposited film was formed on a 15μ film with SiO powder under a vacuum of 10 -4 Torr. A polyethyleneimine anchor coating agent (Polymin P manufactured by BASF Corporation) was gravure-coated on the vacuum-deposited film surface of the film. Two coated and dried films were prepared. Polyethylene resin (Santech LD manufactured by Asahi Kasei Corporation) was extruded from an extruder T-die to a thickness of 30μ between the vinylidene chloride copolymer resin layer surface and the vacuum-deposited coating surface, and two rolls were coated with two types of anchor coating agents. Two pieces of the second barrier packaging material of the present invention were obtained by laminating the two pieces of the second barrier packaging material of the present invention. Next, polyethyleneimine (Polymin P manufactured by BASF Corporation) was coated as an anchor coating agent on the surfaces of these two biaxially stretched nylon films using a gravure coating method and dried.
- The present invention by extruding polyethylene resin (Santetsu LD manufactured by Asahi Kasei Corporation) from a die to a thickness of 35 μm and laminating the biaxially stretched nylon surfaces of two rolls together via an anchor coating agent, resulting in a total thickness of approximately 430 μm. A first barrier packaging material (barrier plastic laminate sheet) was obtained, and a container with a drawing ratio of 0.25 was obtained by vacuum forming. In order to measure the water vapor permeability, drying silica gel was placed inside the container, and the vinyl chloride resin-coated surface of the lid made of vinyl chloride resin-coated hard aluminum was sealed with a heat sealer to form a barrier packaging (PTP packaging). ) was obtained. The barrier properties, thermoformability, appearance, etc. were as shown in Table 1. Example 2 Hard vinyl chloride resin sheet (Sumilite VSS-8142ZUV manufactured by Sumitomo Bakelite Co., Ltd.)
An isocyanate-based anchor coating agent (Coronate L-75 manufactured by Nippon Polyurethane Industries, Ltd.) was coated on a 100 μ thick sheet using the gravure coating method, and after drying, vinylidene chloride-based copolymer resin emulsion (Saran Latex L manufactured by Asahi Kasei Industries, Ltd.) was applied. −
400) was applied and dried 6 times using the air knife coating method to form a vinylidene chloride copolymer resin layer with a thickness of 50μ, and the vinyl chloride resin sheet coated with the vinylidene chloride copolymer resin emulsion and dried was wound into a roll. I created two. A polyethyleneimine anchor coating agent (Polymin P manufactured by BASF Corporation) was applied to the surface of the vinylidene chloride copolymer resin layer of this sheet by gravure coating and dried, while a biaxially stretched polyester resin film (manufactured by Toyobo Co., Ltd.) was coated and dried. A 700 Å vacuum-deposited film of Al 2 O 3 powder was formed on a 12μ-thick film under a vacuum of 10 -4 Torr.A polyethyleneimine-based anchor coating agent (Polymin P manufactured by BASF Corporation) was applied to the vacuum-deposited film surface of the film. ) was coated and dried using a gravure coating method to prepare two films. Polyethylene resin (Santech LD manufactured by Asahi Kasei Corporation) was extruded from an extruder T-die to a thickness of 30μ between the vinylidene chloride copolymer resin layer surface and the vacuum-deposited coating surface, and two rolls were coated with two types of anchor coating agents. Two pieces of the second barrier packaging material of the present invention were obtained by laminating the two pieces of the second barrier packaging material of the present invention. Next, polyethyleneimine (Polymin P manufactured by BASF Corporation) was applied as an anchor coating agent to the surfaces of these two biaxially stretched polyester resin films using a gravure coating method and dried.
Thickness 50μ of polyethylene resin from extruder T-die
The first barrier packaging material of the present invention (barrier plastic laminated sheet for thermoforming) is made by extruding the biaxially stretched nylon surfaces of two rolls and laminating them together via an anchor coating agent to obtain a total thickness of approximately 440μ. ), and a container with a drawing ratio of 0.3 was obtained by vacuum forming. In order to measure the water vapor permeability, drying silica gel was placed inside the container and the container was sealed with the vinyl chloride resin-coated surface of the lid made of vinyl chloride resin-coated hard aluminum using a heat sealer.
A PTP package was obtained. barrier properties, thermoformability,
The appearance etc. are as shown in Table 1. Comparative Example 1 Hard vinyl chloride resin sheet (Sumilite VSS-8142ZUV manufactured by Sumitomo Bakelite Co., Ltd.)
An isocyanate-based anchor coating agent (Coronate L-75 manufactured by Nippon Polyurethane Industries, Ltd.) was coated on a 100 μ thick sheet using the gravure coating method, and after drying, vinylidene chloride-based copolymer resin emulsion (Saran Latex L manufactured by Asahi Kasei Industries, Ltd.) was applied. −
A vinyl chloride resin sheet coated with a vinylidene chloride copolymer resin layer that is coated with 400) six times using an air knife coating method to form a vinylidene chloride copolymer resin layer with a thickness of 49 μm and wound into a roll. A polyurethane anchor coating agent (AD-527 manufactured by Toyo Morton Co., Ltd.) was applied to the vinylidene chloride copolymer resin layer surface of two sheets using the gravure coating method. After drying, Al 2 O 3 powder was applied at 10 -4 Torr. A 300Å vacuum-deposited film was continuously deposited under a vacuum of
Polyethyleneimine (Polymin P manufactured by BASF Corporation) was applied as an anchor coating agent to the surfaces of the two vacuum-deposited coatings using a gravure coating method, dried, and extruded using an extruder T.
- Extrude polyethylene from the die to a thickness of 35 μm.
A barrier packaging material (barrier plastic laminated sheet for thermoforming) with a total thickness of approximately 337 μm is obtained by laminating the vacuum-deposited coating surfaces of book rolls together via an anchor coating agent, which is then vacuum-formed. A container with a drawing ratio of 0.3 was obtained. Silica gel for drying was placed in a container to measure the water vapor permeability, and the vinyl chloride resin coated surface of the lid material made of vinyl chloride resin coated hard aluminum and the container were sealed with a heat sealer to obtain a PTP package.
The barrier properties, thermoformability, appearance, etc. are shown in Table 1. Comparative Example 2 Hard vinyl chloride resin sheet (Sumilite VSS-8142ZUV manufactured by Sumitomo Bakelite Co., Ltd.)
An isocyanate-based anchor coating agent (Coronate L-75 manufactured by Nippon Polyurethane Industries, Ltd.) was coated on a 100 μ thick sheet using the gravure coating method, and after drying, vinylidene chloride-based copolymer resin emulsion (Saran Latex L manufactured by Asahi Kasei Industries, Ltd.) was applied. −
400) was coated three times using the air knife coating method to form a vinylidene chloride copolymer resin layer with a thickness of 18μ, and the vinyl chloride resin sheet coated with the vinylidene chloride copolymer resin emulsion was wound into a roll. I created this book. A polyurethane anchor coating agent (AD-527 manufactured by Toyo Morton Co., Ltd.) was applied to the surface of this vinylidene chloride copolymer resin layer using a gravure coating method. After drying, Al 2 O 3 powder was applied under a vacuum of 10 -4 Torr to 700 Å. Vapor deposition films were continuously deposited.
Polyethyleneimine (Polymin P manufactured by BASF Corporation) was applied as an anchor coating agent to the surfaces of the two vacuum-deposited coatings using a gravure coating method, dried, and extruded using an extruder T.
- Extrude polyethylene resin (Santetsu LD manufactured by Asahi Kasei Corporation) from a die to a thickness of 60 μm and laminate the vacuum-deposited coating surfaces of two rolls together via an anchor coating agent, resulting in a total thickness of approximately 300 μm. Barrier properties A packaging material (thermoformable barrier plastic laminate sheet) was obtained, and a container with a drawing ratio of 0.3 was obtained by vacuum forming the material. In order to measure the water vapor permeability, drying silica gel was placed in a container, and the vinyl chloride resin coated surface of the lid made of vinyl chloride resin coated hard aluminum and the container were sealed with a heat sealer to obtain a PTP package. barrier properties,
Thermoformability, appearance, etc. are shown in Table 1. Regarding the thermoformability listed in Table 1, molding was performed using a thermoforming machine manufactured by Fuse Vacuum Co., Ltd. (model TM-4PW).
Breakage of the molded product after thermoforming the plastic sheet,
The mold reproducibility, etc. in the thermoforming mold was observed, and molded products with cracks were marked with an x mark, and those with no cracks were marked with an ○ mark. Regarding the external appearance, visually judged molded products after thermoforming were marked with an "X" if a whitening phenomenon occurred due to the generation of fine cracks, and "○" marked if the phenomenon did not occur. The water vapor permeability was measured according to JIS-Z-0208, and 1 g/m 2 ·24 hr or more was indicated by an x mark, and less than 1 g/m 2 -24 hr was indicated by an ○ mark. Oxygen permeability was measured using the isobaric method at 23°C.
cc/m 2・24hr・atm or more is crossed, 1c.c./m 2・
Less than 24 hours/ATM is indicated by a circle. If all of these characteristics are marked with an O mark, the product is comprehensively satisfied, and if even one property is marked with an X mark, the object of the present invention is not met. Therefore, Examples 1 and 2 sufficiently fulfill the purpose as transparent packaging materials for ultra-high barrier PTP according to the present invention. 【table】
第１図は本発明のバリヤー性包装材の好ましい
態様を示す概略断面図である。第２図は本発明の
バリヤー性包装材を用いた包装体の好ましい態様
を示す一部切断斜視図である。
１……第１の熱成形可能な硬質プラスチツクシ
ート、２……第１のアンカーコート層、３……第
１の塩化ビニリデン系共重合樹脂層、４……第２
のアンカーコート層、５……第１のポリエチレン
樹脂層、６……第３のアンカーコート層、７……
第１の無機金属化合物蒸着層、８……第１の熱成
形可能な被蒸着プラスチツクフイルム、９……第
４のアンカーコート層、１０……ポリエチレン樹
脂層、１１……第５のアンカーコート層、１２…
…第２の熱成形可能な被蒸着プラスチツクフイル
ム、１３……第２の無機金属化合物蒸着層、１４
……第６のアンカーコート層、１５……第２のポ
リエチレン樹脂層、１６……第７のアンカーコー
ト層、１７……第２の塩化ビニリデン系共重合樹
脂層、１８……第８のアンカーコート層、１９…
…第２の熱成形可能な硬質プラスチツクシート、
Ａ……容器、Ｂ……蓋材。
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the barrier packaging material of the present invention. FIG. 2 is a partially cutaway perspective view showing a preferred embodiment of a package using the barrier packaging material of the present invention. DESCRIPTION OF SYMBOLS 1... First thermoformable hard plastic sheet, 2... First anchor coat layer, 3... First vinylidene chloride copolymer resin layer, 4... Second
Anchor coat layer, 5... first polyethylene resin layer, 6... third anchor coat layer, 7...
First inorganic metal compound vapor deposited layer, 8...First thermoformable plastic film to be vapor deposited, 9...Fourth anchor coat layer, 10...Polyethylene resin layer, 11...Fifth anchor coat layer , 12...
...Second thermoformable plastic film to be deposited, 13...Second inorganic metal compound deposited layer, 14
...Sixth anchor coat layer, 15...Second polyethylene resin layer, 16...Seventh anchor coat layer, 17...Second vinylidene chloride copolymer resin layer, 18...Eighth anchor Coat layer, 19...
...a second thermoformable rigid plastic sheet,
A... Container, B... Lid material.
Claims (1)
ト、第１の塩化ビニリデン系共重合樹脂層、第１
のポリエチレン樹脂層、第１の熱成形可能なプラ
スチツクフイルムに無機金属化合物が蒸着された
層、ポリエチレン樹脂層、第２の熱成形可能なプ
ラスチツクフイルムに無機金属化合物が蒸着され
た層、第２のポリエチレン樹脂層、第２の塩化ビ
ニリデン系共重合樹脂層および第２の熱成形可能
な硬質プラスチツクシートが順次積層されてな
り、かつ、前記各塩化ビニリデン系共重合樹脂層
の厚さが1.5〜60μであることを特徴とするバリヤ
ー性包装材。 ２ バリヤー性包装材の総厚が、150〜2000μで
ある特許請求の範囲第１項記載のバリヤー性包装
材。 ３ 熱成形可能な硬質プラスチツクシートが、厚
さ30〜1000μの硬質塩化ビニル樹脂シートである
特許請求の範囲第１項または第２項記載のバリヤ
ー性包装材。 ４ 無機金属化合物蒸着層が、厚さ100〜5000Å
の硅素酸化物蒸着層である特許請求の範囲第１項
または第２項記載のバリヤー性包装材。 ５ 無機金属化合物が蒸着された熱成形可能なプ
ラスチツクフイルムが厚さ８〜50μのナイロンフ
イルムである特許請求の範囲第１項または第２項
記載のバリヤー性包装材。 ６ 第１のポリエチレン樹脂層、ポリエチレン樹
脂層、第２のポリエチレン樹脂層の厚さが、各々
20〜70μである特許請求の範囲第１項または第２
項記載のバリヤー性包装材。 ７ 熱成形可能な硬質プラスチツクシート、塩化
ビニリデン系共重合樹脂層、ポリエチレン樹脂
層、前記熱成形可能なプラスチツクフイルムに無
機金属化合物が蒸着された層が順次積層されてな
るバリヤー性包装材。 ８ ２枚の熱成形可能な硬質プラスチツクシート
の各々の片面に塩化ビニリデン系共重合樹脂エマ
ルジヨンを塗布乾燥して塩化ビニリデン系共重合
樹脂層を形成し、該塩化ビニリデン系共重合樹脂
層と無機金属化合物が蒸着された熱成形可能なプ
ラスチツクフイルムの間に第１のポリエチレン樹
脂、第２のポリエチレン樹脂のそれぞれで各々を
押出しラミネーシヨンして固着せしめるか、ポリ
エチレン樹脂フイルムを介しドライラミネーシヨ
ンして固着せしめてそれぞれ２枚の積層物を得、
この２枚の積層物を無機金属化合物が蒸着された
熱成形可能なプラスチツクフイルム側をそれぞれ
内向させ、その間に溶融ポリエチレン樹脂を押出
しラミネーシヨンして一体固着せしめるか、ポリ
エチレン樹脂フイルムを介し、ドライラミネーシ
ヨンして一体固着せしめることを特徴とするバリ
ヤー性包装材の製造法。[Scope of Claims] 1. A first thermoformable hard plastic sheet, a first vinylidene chloride copolymer resin layer, a first
a polyethylene resin layer, a layer in which an inorganic metal compound is deposited on a first thermoformable plastic film; a polyethylene resin layer, a layer in which an inorganic metal compound is deposited on a second thermoformable plastic film; A polyethylene resin layer, a second vinylidene chloride copolymer resin layer, and a second thermoformable hard plastic sheet are sequentially laminated, and each vinylidene chloride copolymer resin layer has a thickness of 1.5 to 60 μm. A barrier packaging material characterized by: 2. The barrier packaging material according to claim 1, wherein the barrier packaging material has a total thickness of 150 to 2000μ. 3. The barrier packaging material according to claim 1 or 2, wherein the thermoformable hard plastic sheet is a hard vinyl chloride resin sheet having a thickness of 30 to 1000 μm. 4 The inorganic metal compound vapor deposited layer has a thickness of 100 to 5000 Å
The barrier packaging material according to claim 1 or 2, which is a silicon oxide vapor-deposited layer. 5. The barrier packaging material according to claim 1 or 2, wherein the thermoformable plastic film on which the inorganic metal compound is vapor-deposited is a nylon film with a thickness of 8 to 50 μm. 6 The thickness of the first polyethylene resin layer, the polyethylene resin layer, and the second polyethylene resin layer are each
Claim 1 or 2 which is 20 to 70μ
Barrier packaging material as described in section. 7. A barrier packaging material comprising a thermoformable hard plastic sheet, a vinylidene chloride copolymer resin layer, a polyethylene resin layer, and a layer in which an inorganic metal compound is vapor-deposited on the thermoformable plastic film. 8. A vinylidene chloride copolymer resin emulsion is coated on one side of each of two thermoformable hard plastic sheets and dried to form a vinylidene chloride copolymer resin layer, and the vinylidene chloride copolymer resin layer and the inorganic metal are coated and dried. The first polyethylene resin and the second polyethylene resin are extruded and laminated between thermoformable plastic films on which the compound has been vapor-deposited, or are fixed by dry lamination through a polyethylene resin film. Obtain at least two laminates each,
These two laminates are made with the thermoformable plastic film side on which an inorganic metal compound is vapor-deposited facing inward, and molten polyethylene resin is extruded between them and laminated to bond them together, or dry lamination is performed via a polyethylene resin film. A method for manufacturing a barrier packaging material, which is characterized by adhesively bonding the barrier packaging material together.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14873983A JPS6040245A (en) | 1983-08-16 | 1983-08-16 | Barrier property packaging material, manufacture thereof andbarrier property package |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14873983A JPS6040245A (en) | 1983-08-16 | 1983-08-16 | Barrier property packaging material, manufacture thereof andbarrier property package |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6040245A JPS6040245A (en) | 1985-03-02 |
| JPS6336939B2 true JPS6336939B2 (en) | 1988-07-22 |
Family
ID=15459532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14873983A Granted JPS6040245A (en) | 1983-08-16 | 1983-08-16 | Barrier property packaging material, manufacture thereof andbarrier property package |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6040245A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002166486A (en) * | 2000-11-30 | 2002-06-11 | Dainippon Printing Co Ltd | Barrier film |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0825245B2 (en) * | 1989-04-17 | 1996-03-13 | 凸版印刷株式会社 | Gas barrier packaging bag |
| JP4581267B2 (en) * | 2000-03-17 | 2010-11-17 | 王子製紙株式会社 | Adhesive sheet using metal vapor deposition film |
| JP5509534B2 (en) * | 2008-04-07 | 2014-06-04 | 大日本印刷株式会社 | Laminated tube barrel forming laminated sheet and laminated tube |
-
1983
- 1983-08-16 JP JP14873983A patent/JPS6040245A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002166486A (en) * | 2000-11-30 | 2002-06-11 | Dainippon Printing Co Ltd | Barrier film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6040245A (en) | 1985-03-02 |
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