JP7115977B2 - バリアフィルムまたはシートおよびそのフィルムまたはシートを含むラミネート包装材料およびそれから作られた包装容器 - Google Patents
バリアフィルムまたはシートおよびそのフィルムまたはシートを含むラミネート包装材料およびそれから作られた包装容器 Download PDFInfo
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- JP7115977B2 JP7115977B2 JP2018516768A JP2018516768A JP7115977B2 JP 7115977 B2 JP7115977 B2 JP 7115977B2 JP 2018516768 A JP2018516768 A JP 2018516768A JP 2018516768 A JP2018516768 A JP 2018516768A JP 7115977 B2 JP7115977 B2 JP 7115977B2
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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- Laminated Bodies (AREA)
- Packages (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
1/OTR=SUMi(1/OTRi)
に従う単純なラミネート理論によって説明することはできないが、このようにして各ラミネート層によるOTRの個々の寄与を超えて全体のバリアを改善する。DLC被覆とポリオレフィン表面との間の優れた接着性は、2つの材料間の特に良好は統合界面をもたらし、それによって改善された酸素バリア特性をもたらすと考えられている。
12μmの厚膜の二軸配向ポリエチレンテレフタレート(三菱製のBOPET Hostaphan RNK12)は、真空条件下でプラズマ強化化学気相堆積(PECVD)により、ロール・ツー・ロールプラズマ反応器において、堆積被覆される。プラズマは、40kHzの周波数で供給される電力に容量結合され、および回転ドラムの周面、結合されたフィルム-ウェブ移送手段および電極から少し離れて置かれた不平衡マグネトロン電極によって磁気的に閉じ込められている。フィルムはまず、3標準リットル/分(slm)の流量のアルゴンガスおよび5kWの前処理電力で前処理された。続いて、フィルムは、24kWの総被覆電力、12slmの総アセチレン流量および約0.03mbarのプロセスガス圧力で、純粋なアセチレンガスから形成されたプラズマからの非晶質の水素化ダイヤモンドライク被覆DLCを堆積させることによって被覆された。ポリマーフィルム基材は、ドラム型ウェブ-移送手段内の冷却手段によって、10℃以下の一定温度で冷却された。DLC被覆は約23nmの厚さで適用された。
厚さ12μmの二軸配向ポリエチレンテレフタレート(三菱製のBOPET Hostaphan RNK12およびRNK12-2DEF)からのフィルムは、ロール・ツー・ロールプラズマ反応器において、真空条件下のプラズマ強化化学気相堆積(PECVD)によって種々の被覆で堆積被覆された。ダイヤモンドライク非晶質水素化炭素コーティング(DLC)が、本発明に従って、いくつかのフィルム試料上に被覆され、一方他のPECVDバリア被覆が他の試料上に被覆された。比較例の対象である他のPECVDバリア被覆は、xが1.5から2.2で変化するSiOx、(y+z)/xが1から1.5であるSiOxCy被覆およびSiOxCyNz被覆であった。これらの他のケイ素含有バリア被覆は、オルガノシラン前駆体ガス化合物から形成された。本発明によるフィルム試料は、純粋なアセチレンガスから形成されたプラズマからの非晶質水素化ダイヤモンドライクコーティングDLCを堆積させることによって被覆された。
上記の実施例で使用したものと同様のBOPETフィルムは、表2で説明するように、片面および両面に、同様の薄いDLC被覆で被覆された。OTRは、上記の実施例と同様の方法で、23℃および50%のRHでcc/m2/day/atmで測定された。DLC被覆フィルムは次いで、15g/m2のLDPEの結合層による外側LDPE層を有する板紙を含む包装材料構造にラミネートされ、およびフィルムの反対側に25g/m2のLDPEおよびmLLDPEの混合の内側層でさらに被覆されている。OTRは、前に説明したような同じ方法によりラミネート包装材料上で測定された。
図1aにおいて、本発明のバリアフィルム10aの第1の実施形態の断面図が示されている。ポリマーフィルム基材11は、酸素バリア特性を改善するために(OTR値を低減するために)、プラズマ強化化学気相堆積(PECVD)被覆により、耐久性非晶質DLC被覆12で被覆された、PETまたはPAまたはポリオレフィン、好ましくはBOPETのフィルム基材である。気相堆積された被覆12は、褐色の透明な被覆色へ均一に堆積された炭素被覆(C:H)である。耐久性DLC被覆の厚さは、好ましくは5から50nm、より好ましくは5から30μmである。
分析条件:
・ 一次イオンBi+ 25keV、I~1.86pA
・ 分析面積 70×70μm2、256×256ピクセル
・ 負の二次イオンが分析される
・ 電荷補償(<20eV)
スパッタリング条件:
・ 一次イオンCs+ 500eV、40nA
・ スパッタリング面積:250×250μm2
分析/スパッタリングサイクル:
・ 0から300umaまでの2分析スキャン(タイム・オブ・フライト最大=50μs)
・ スパッタリング:1.638秒
スパッタリングと分析の間の休止:0.5秒。
10a、10b 耐久性バリアフィルム
11 ポリマーフィルム基材
12 バリア被覆
13 接着促進プライマー被覆
20a、20b ラミネート包装材料
21 バルク層
22 ヒートシール可能な層
23 ヒートシール可能な層
24 ポリマーフィルム基板
25 バリア材料
26 中間結合層
27 接着促進プライマー被覆
28 耐久性バリアフィルム
31 バルク層
33 耐久性バリアフィルム
35 押出ステーション
36 ローラーニップ
37-1 ラミネーションニップ
37-2 押出フィードブロック
37-3 最内のヒートシール可能な層
38-1 ラミネーションニップ
38-2 押出フィードブロック
39 終了した包装ラミネート
44 フィルム基材
45 マグネトロン電極
46 フィルム搬送ドラム
50 プラズマ
50a 包装容器
50b 包装容器
50c 折り畳み形成された破風の上部容器
50d ボトル状容器
51a 長手方向シール
52a 横方向シール
52b 横方向シール
53 開口デバイス
54 チューブ状スリーブ
55 頂部
61 チューブ
62 ウェブの長手方向縁部
63 オーバーラップ継手
64 液体食品
65 横方向のシール
66 容器
Claims (16)
- 12μm以下の厚さを有しているPETのポリマーフィルム基材(11)およびプラズマ強化化学気相堆積(PECVD)により、10から35nmの厚さで、前記ポリマーフィルム基材上に気相堆積被覆された耐久性ダイヤモンドライクカーボン(DLC)バリア被覆(12)を含み、包装材料および包装材料から製作された容器においてガスバリア特性および水蒸気バリア特性を提供する、液体食品用のラミネート包装材料に使用するためのバリアフィルム(10a;10b;10c)であって、前記被覆は、前記ポリマーフィルム基材との界面から被覆の表面に向かって前記被覆の深さの至るところで、酸素イオン濃度を最小値まで減少させる勾配およびそれに続く増加を示す単層の勾配ダイヤモンドライクカーボン被覆(DLC)であり、バリア被覆の表面(B)から、バリア被覆とポリマーフィルムとの間の界面(A)までを測定し、動的タイム・オブ・フライト二次イオン質量分析法(ToF-SiMS)の表面分析によって強度対厚さの図表で示され、TEM顕微鏡の厚さ測定に較正されるときに、減少勾配は、被覆厚さナノメートルあたり9×104から1.1×105カウントの傾きを有しており、最小値は被覆の深さの40から60%に位置しており、一方、炭素および水素イオン基の濃度は、被覆の深さの至るところで実質的に一定のレベルにとどまっており、前記ポリマーフィルム基材(C)の表面から測定するときに、10から15nmに位置する水素イオンおよび3価の炭素イオンの局所的および一時的な濃度減少(A)があり、前記耐久性DLCバリア被覆(12)は、sp2およびsp3混成結合の総含有量に基づいて、60から70%のsp2混成結合の含有量を有しており、前記バリアフィルムは、23℃および50%のRHでMocon 2/60により測定したときに、3.0cc/day/m2/atmの上側規格限界(USL)以下の酸素透過率OTR、38℃および90%のRHでMocon PermatranまたはLyssy装置によって測定したときに、1.0g/day/m2以下の水蒸気透過率WVTR、および2%以上の欠陥開始ひずみCOSを有している、バリアフィルム。
- 酸素イオン濃度の減少勾配は、被覆厚さナノメートルあたり10 5 カウントの傾きを有している、請求項1に記載のバリアフィルム。
- 最小値は、前記バリア被覆の表面(B)から、前記バリア被覆と前記ポリマーフィルム基材(11)との間の界面(A)までを測定したときに、被覆の深さの45から55%に位置している、請求項1に記載のバリアフィルム。
- 前記ポリマーフィルム基材(11)は、配向PETフィルムである、請求項1から3のいずれか一項に記載のバリアフィルム。
- 前記ポリマーフィルム基材(11)は、8から12μm、好ましくは12μmの厚さを有している、請求項1から4のいずれか一項に記載のバリアフィルム。
- 前記ポリマーフィルム基材(11)は、前記単層の勾配耐久性DLCバリア被覆(12)で被覆された面の反対側の他の面に接着促進プライマー被覆(13)を有している、請求項1から5のいずれか一項に記載のバリアフィルム。
- 前記接着促進プライマー被覆(13)は、第2のDLC被覆である、請求項1から6のいずれか一項に記載のバリアフィルム。
- 前記耐久性DLCバリア被覆(12)は、20から30nmの厚さで適用される、請求項1から7のいずれか一項に記載のバリアフィルム。
- 前記接着促進プライマー被覆(13)は、第2のDLC被覆であり、2から5nmの厚さで適用される、請求項1から7のいずれか一項に記載のバリアフィルム。
- 請求項1から9のいずれか一項に記載のバリアフィルム(10a、10b、10c)を含むラミネート包装材料(20a、20b)であって、第1の最外の液密でヒートシール可能なポリオレフィン層(22)および第2の最内の液密でヒートシール可能なポリオレフィン層(23)をさらに含む、ラミネート包装材料。
- 請求項1から9のいずれか一項に記載のバリアフィルム(10a、10b、10c)を含むラミネート包装材料(20a、20b)であって、紙または板紙または他のセルロース系材料のバルク層(21)、第1の最外の液密でヒートシール可能なポリオレフィン層(22)、第2の最内の液密でヒートシール可能なポリオレフィン層(23)、および紙または板紙のバルク層(21)の内側で、前記バルク層と前記最内の層との間に配置された、前記バリアフィルム(10a;10b;10c;28)をさらに含む、ラミネート包装材料。
- 前記バリアフィルム(10a;10b;10c;28)は、前記バリアフィルム(10a;10b;10c;28)の前記耐久性DLCバリア被覆(12;25;25a)の表面を前記バルク層(21)に結合させる中間熱可塑性ポリマー結合層(26)によって、前記バルク層(21)に結合される、請求項11に記載のラミネート包装材料。
- 前記バリアフィルムの前記ポリマーフィルム基材(24)は、前記単層の勾配耐久性DLCバリア被覆(25、25a)で被覆された面の反対側の他の面上に接着促進プライマー被覆(27、25b)を有しており、前記バリアフィルムは、前記接着促進プライマー被覆(27)によって前記第2の最内の液密でヒートシール可能なポリオレフィン層(23)に結合される、請求項10から12のいずれか一項に記載のラミネート包装材料。
- 前記ラミネート包装材料の前記バリアフィルムは、二重バリアフィルムであり、これは中間熱可塑性結合層によってさらに同一のまたは類似の第2のバリアフィルム(10a;10b;10c)にラミネートされて、および結合されている第1のバリアフィルム(10a;10b;10c)を含む、請求項10から13のいずれか一項に記載のラミネート包装材料。
- 第1のバリアフィルム(10a;10b;10c)は、中間熱可塑性結合層によって、さらに同一のまたは類似の第2のバリアフィルム(10a;10b;10c)にラミネートされて、および結合されており、前記ラミネート包装材料は、前記第1のバリアフィルムの反対側で、ラミネートされていない側の第1の最外の液密でヒートシール可能なポリマー層(12)および前記第2のバリアフィルムの反対側で、ラミネートされていない側の第2の最内の液密でヒートシール可能なポリマー層(13)をさらに含む、請求項10に記載のラミネート包装材料。
- 請求項10から15のいずれか一項に記載のラミネート包装材料を含む包装容器。
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PCT/EP2016/075695 WO2017072122A1 (en) | 2015-10-29 | 2016-10-25 | Barrier film or sheet and laminated packaging material comprising the film or sheet and packaging container made therefrom |
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JP2018516768A Active JP7115977B2 (ja) | 2015-10-29 | 2016-10-25 | バリアフィルムまたはシートおよびそのフィルムまたはシートを含むラミネート包装材料およびそれから作られた包装容器 |
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