JPWO2018139655A1 - 多孔シートおよび多孔複合体 - Google Patents
多孔シートおよび多孔複合体 Download PDFInfo
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- JPWO2018139655A1 JPWO2018139655A1 JP2018564694A JP2018564694A JPWO2018139655A1 JP WO2018139655 A1 JPWO2018139655 A1 JP WO2018139655A1 JP 2018564694 A JP2018564694 A JP 2018564694A JP 2018564694 A JP2018564694 A JP 2018564694A JP WO2018139655 A1 JPWO2018139655 A1 JP WO2018139655A1
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- porous sheet
- porous
- block copolymer
- sheet
- mass
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Abstract
Description
本発明は、装着直後または静止時・休息時においては、身体に対して良好なフィット性、耐締付け性および爽快性(耐ムレ性)を発揮し、同時に、運動時においては、固定安定性、締付け性および爽快性(耐ムレ性)を発揮することができる多孔シート、ならびに該多孔シートおよび基布を備えてなる多孔複合体に関する。
すなわち、本発明は、以下の好適な態様を提供するものである。
[1]熱可塑性エラストマー組成物(A)からなり、複数のスリットおよび/または孔を有する多孔シートであって、開孔率が5〜80%、異方化率が10%以上、かつ500%伸張で60秒間保持後の伸張応力緩和率が40%以下である、多孔シート。
[2]熱可塑性エラストマー組成物(A)は、(a)少なくとも1種のビニル芳香族化合物から構成される重合体ブロック(X)と少なくとも1種の共役ジエン化合物から構成される重合体ブロック(Y)とからなる、少なくとも1つのブロック共重合体および/または該ブロック共重合体の水素添加物を含む、前記[1]に記載の多孔シート。
[3]ブロック共重合体(a)において、20万以下の重量平均分子量を有する画分の割合が、ブロック共重合体(a)全体を基準として50〜100質量%である、前記[2]に記載の多孔シート。
[4]熱可塑性エラストマー組成物(A)は、ブロック共重合体(a)100質量部に対して10〜400質量部の炭化水素系軟化剤(b)を含む、前記[2]または[3]に記載の多孔シート。
[5]開孔率が5〜50%である、[1]〜[4]のいずれかに記載の多孔シート。
[6]孔のサイズは0.5〜100mm2である、[1]〜[5]のいずれかに記載の多孔シート。
[7]有機または無機添加剤の含有量は熱可塑性エラストマー組成物(A)に対して0〜40質量%である、[1]〜[6]のいずれかに記載の多孔シート。
[8]熱可塑性エラストマー組成物(A)は、ブロック共重合体(a)100質量部に対してオレフィン系樹脂2〜10質量部を含む、[4]〜[7]のいずれかに記載の多孔シート。
[9]メッシュ状である、[1]〜[8]のいずれかに記載の多孔シート。
[10]基布(B)、および該基布(B)上に配置された前記[1]〜[9]のいずれかに記載の多孔シートを備える、多孔複合体。
本発明の一実施態様においては、熱可塑性エラストマー組成物(A)からなり、複数のスリットおよび/または孔を有する多孔シートであって、開孔率が5〜50%、異方化率が10%以上、かつ500%伸張で60秒間保持後の伸張応力緩和率が40%以下である多孔シートが提供される。本発明において、スリットとは、縦横の長さの異なる隙間を意味し、孔とは、後述する各種形状の孔を意味するが、孔はスリットを含む概念であって、スリットは孔を構成する。なお、本発明において、「複数のスリットおよび/または孔」とは、2以上のスリットおよび/または孔を意味する。
異方化率(%)=[(SDmax100%−SDmin100%)/SDmax100%]×100
ここで、多孔シートの全ての方向の中で100%の伸度における伸張応力が最大となる方向をDmax方向とし、Dmax方向に対して垂直な方向をDmin方向とする場合、Dmax方向への100%の伸度における多孔シートの伸張応力がSDmax100%であり、Dmin方向への100%の伸度における多孔シートの伸張応力がSDmin100%である。異方化率を測定する際、100%の伸度において伸長応力を測定するのは、100%伸長時においてDmax方向とDmin方向との異方化率が明瞭に発現するためである。具体的には実施例に記載の方法により決定することができる。
伸張応力緩和率(%)=[(SDmax500%・0秒−SDmax500%・60秒)/SDmax500%・0秒]×100
このようにスリットまたは孔のサイズ、とくに長さ、ピッチ、面積を調整することにより、所望の開孔率、異方化率および伸張応力緩和率を得ることができる。
本発明の一実施態様である多孔シートを構成する熱可塑性エラストマー組成物(A)は、熱可塑性エラストマーを含んでなる。熱可塑性エラストマーとしては、例えば、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ニトリル系エラストマー、アミド系エラストマー、ポリブタジエン系エラストマー、アクリル系エラストマー、塩化ビニル系熱可塑性エラストマーなどが挙げられる。中でも、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマーおよびアクリル系エラストマー、ならびにその混合物が好ましい。
本発明の好適な実施態様において、熱可塑性エラストマー組成物(A)は、(a)少なくとも1種のビニル芳香族化合物から構成される重合体ブロック(X)と少なくとも1種の共役ジエン化合物から構成される重合体ブロック(Y)とからなる、少なくとも1つのブロック共重合体および/または該ブロック共重合体の水素添加物を含む。
すなわち、熱可塑性エラストマー組成物に含まれる熱可塑性エラストマーは、(a)少なくとも1種のビニル芳香族化合物から構成される重合体ブロック(X)と少なくとも1種の共役ジエン化合物から構成される重合体ブロック(Y)とからなる、少なくとも1つのブロック共重合体および/または該ブロック共重合体の水素添加物(以下、該ブロック共重合体および/または該ブロック共重合体の水素添加物を総称して「ブロック共重合体(a)」ともいう)である。ブロック共重合体(a)は、該ブロック共重合体は、少なくとも部分的に水素添加されていてもよい。また、ブロック共重合体(a)は、ブロック共重合体とブロック共重合体の水素添加物との混合物であってもよい。
本発明において、熱可塑性エラストマー組成物(A)は、通常、炭化水素系軟化剤(b)、より具体的には炭化水素系ゴム用軟化剤(b)を含む。炭化水素系ゴム用軟化剤(b)(以下、「軟化剤(b)」ともいう)としては、例えばパラフィン系オイル、ナフテン系オイル、アロマ系オイル等のプロセスオイル;流動パラフィン;エチレン、共役ジエン化合物、および/または炭素数4以上のα−オレフィンの単独重合体および共重合体;等が挙げられる。中でも、パラフィン系オイル、ナフテン系オイル等のプロセスオイル、およびポリイソブチレン系樹脂(PIB)が好ましい。これらは1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の一実施態様において、熱可塑性エラストマー組成物(A)は、オレフィン系樹脂(c)を含有してもよい。オレフィン系樹脂(c)としては、強度や成形加工性、耐薬品性、耐熱性、非粘着性の改善の目的から、プロピレン系重合体、エチレン系重合体およびその混合物が好ましい。
熱可塑性エラストマー組成物(A)におけるオレフィン系樹脂(c)の含有量は、ブロック共重合体(a)100質量部に対して0〜20質量部であることが好ましい。熱可塑性エラストマー組成物(A)にオレフィン系樹脂(c)を含有させる場合は、ブロック共重合体(a)100質量部に対して0.1〜20質量部であることが好ましく、より好ましくは1〜15質量部、さらに好ましくは2〜10質量部、さらに最適には3〜8質量部である。
また、熱可塑性エラストマー組成物(A)は、軽量化の観点から、有機または無機添加剤として、中空フィラー、例えば、ガラスバルーン、シリカバルーン等の無機中空フィラー、ポリフッ化ビニリデン、ポリフッ化ビニリデン共重合体等からなる有機中空フィラーを含有してもよい。
有機または無機添加剤として、熱可塑性エラストマー組成物(A)がポリビニル系短繊維、ポリアリレート系短繊維、グラファイト、マイカ、酸化チタン、アルミニウム粉末、および/またはカーボンブラックを含むことが好ましく、この場合、制振性を大きく改善する効果がある。
このような有機または無機添加剤の含有量は、熱可塑性エラストマー組成物(A)に対して50質量%未満であることが好ましく、より好ましくは0〜40質量%、さらに好ましくは1〜30質量%、よりさらに好ましくは3〜20質量%、特に好ましくは5〜10質量%である。ある実施形態では、熱可塑性エラストマー組成物(A)は有機または無機添加剤を含まない。
本発明の別の実施態様においては、基布(B)、および基布(B)上に配置された上記多孔シートを備える多孔複合体が提供される。多孔複合体において、基布(B)の一方の面に多孔シートが配置されてもよく、基布(B)の両方の面に多孔シートが配置されてもよい。基布(B)の両方の面に多孔シートが配置される場合、2つの多孔シートの開孔率、異方化率および伸張応力緩和率は同一であってもよく、異なっていてもよい。
基布(B)は、特に限定されないが、シート状の繊維質基材である。例えば、天然繊維、人造繊維、合成繊維および/または紙素材等から構成される繊維等からなる織布、不織布、織物および複合布が挙げられる。使用者の快適性の観点から、基布(B)は柔軟性を有することが好ましい。繊維径は特に限定されず、例えば1〜1,000dtexである。
ゲルパーミエーションクロマトグラフィー(GPC)を用い、下記条件下、標準ポリスチレン換算の重量平均分子量Mwを算出した。
GPC;LC Solution (SHIMADZU社製)
検出器:示差屈折率計 RID−10A(SHIMADZU社製)
カラム:TSKgelG4000Hxlを2本直列(TOSOH社製)
ガードカラム:TSKguardcolumnHxl−L(TOSOH社製)
溶媒:テトラヒドロフラン
温度:40℃
流速:1ml/min
濃度:2mg/ml
ブロック共重合体(a)をCDCl3に溶解して、1H−NMR測定を行った(装置:JNM−Lambda 500(日本電子(株)製、測定温度:50℃)。イソプレン由来の構造単位、ブタジエン由来の構造単位、またはイソプレンとブタジエンとの混合物由来の構造単位の全ピーク面積と、イソプレンの構造単位における1,2−結合単位および3,4−結合単位、ブタジエンの構造単位における1,2−結合単位および3,4−結合単位、またはイソプレンとブタジエンの混合物の場合には、それぞれの上記結合単位に対応するピーク面積との比から、ビニル結合含有量(1,2−結合単位と3,4−結合単位の含有量の合計)を算出した。
重合に使用した各モノマー成分の重量から算出した。
多孔シートの全ての方向の中で10%の伸度における多孔シートの伸張応力が最大となる方向をDmax方向とし、Dmax方向に対して垂直な方向をDmin方向とした。10cm×10cmの多孔シートをDmax方向とDmin方向との両方向(縦横方向)にそれぞれ1cm(10%伸張相当)伸張し、複写機(リコー製IPSio0 SP6310 RPCS型)を用い、400%倍率でA4サイズにコピーして多孔シートが印刷されたコピー用紙を得た後、多孔シートの輪郭(外周)以外の部分を除去したコピー用紙の重量(W1[g])を測定した後、コピー用紙の開孔部に相当する部分を全て切り抜き、切り抜いたコピー用紙の重量(W2[g])を測定し、下記の式に従って開孔率(%)を算出した。なお、サンプルは、多孔シートから無作為に10個を切り出して作製し、10回の測定の平均値をそのサンプルの開孔率として採用した。
開孔率(%)=[(W1−W2)/W1]×100
多孔シートの全ての方向の中で100%の伸度における伸張応力が最大となる方向をDmax方向とし、Dmax方向に対して垂直な方向をDmin方向とする場合、Dmax方向への100%の伸度における多孔シートの伸張応力がSDmax100%とし、Dmin方向への100%の伸度における多孔シートの伸張応力がSDmin100%とした。
多孔シートから、7cm(Dmax方向)×2.5cm(Dmin方向)の短冊状サンプル(Dmaxサンプル)および2.5cm(Dmax方向)×7cm(Dmin方向)の短冊状サンプル(Dminサンプル)をそれぞれ無作為に10個ずつ切り出した。次に、島津製オートグラフ(型番:AG−1、500N)を用い、チャック間隔=50mm、引張速度=100mm/分、測定温度=23℃で引張強度測定を行い、100%伸度における伸張応力を測定した。引張方向は、Dmaxサンプルの場合はDmax方向であり、Dminサンプルの場合はDmin方向であった。DmaxサンプルおよびDminサンプルそれぞれの場合において、Dmaxサンプルを用いて算出した100%伸度における伸張応力をSDmax100%、Dminサンプルを用いて算出した100%伸度における伸張応力をSDmin100%とし、異方化率を、以下の式に従って算出し、10回の測定値の平均値をそのサンプルの異方化率として採用した。
異方化率(%)=[(SDmax100%−SDmin100%)/SDmax100%]×100
多孔シートの全ての方向の中で500%の伸度における多孔シートの伸張応力が最大となる方向をDmax方向とし、Dmax方向に対して垂直な方向をDmin方向とした。
多孔シートから、7cm(Dmax方向)×2.5cm(Dmin方向)の短冊状サンプル(Dmaxサンプル)を無作為に10個切り出し、サンプルを作製した。
次に、島津製オートグラフ(型番:AG−1、500N)を用い、チャック間隔=50mm、引張速度=500mm/分、測定温度=23℃で引張強度測定を行った。Dmax方向に伸度500%で伸張した直後の伸張応力(SDmax500%・0秒)および伸度500%で60秒間保持した時の伸張応力(SDmax500%・60秒)を測定した。各サンプルを用いてこの測定を行い、伸張応力緩和率(%)を、以下の式に従って算出し、その平均値をそのサンプルの伸張応力緩和率として採用した。
伸張応力緩和率(%)=[(SDmax500%・0秒−SDmax500%・60秒)/SDmax500%・0秒]×100
樹脂組成物(A)からなるペレットを製造する際の成形加工性を評価した。評価基準に関しては、押出機からの溶融状態の樹脂組成物(A)のダイス吐出が不安定な場合、または、樹脂組成物(A)からなるペレットを溶融し、製膜して得られるシートの表面の厚さムラおよび/または流れムラなどの外観不良が発生した場合は、「不良」とし、それ以外の場合は「良好」と判断した。
各実施例および比較例における樹脂組成物(A)を調製するために、以下の成分を用いた。
特許第2703335号公報または特開2003−128870号公報に準じ、乾燥され、窒素で置換された耐圧反応器において、溶媒としてシクロヘキサン、開始剤としてn−ブチルリチウム、共触媒としてテトラヒドロフラン(THF)を用い、スチレンモノマー、イソプレンモノマー、スチレンモノマーの順に添加し重合することにより、A−B−Aの構造を有するブロック共重合体を得た。その後、得られたブロック共重合体を、シクロヘキサン中において、触媒としてPd−Cを用いて水素圧20kg/cm2で水素添加反応を行った。共触媒の添加量ならびにモノマーの添加比率および添加速度を適宜変更することにより、以下のブロック共重合体(a−1)〜(a−4)をそれぞれ製造した。
種類:スチレンーイソプレン・ブタジエンースチレン型トリブロック共重合体、重量平均分子量Mw:270,000、ビニル結合含有量:8モル%、スチレン含有量:30モル%
・ブロック共重合体(a−2)
種類:スチレンーイソプレン・ブタジエンースチレン型トリブロック共重合体、重量平均分子量Mw:170,000、ビニル結合含有量:8モル%、スチレン含有量:32モル%
・ブロック共重合体(a−3)
種類:スチレンーイソプレン・ブタジエンースチレン型トリブロック共重合体、重量平均分子量Mw:90,000、ビニル結合含有量:8モル%、スチレン含有量:30モル%
・ブロック共重合体(a−4)
種類:スチレンーイソプレンースチレン型トリブロック共重合体、重量平均分子量Mw:270,000、ビニル結合含有量:73モル%、スチレン含有量:20モル%
・成分(b−1)
ダイアナプロセスオイルPW−380(商品名)、出光石油化学株式会社製、パラフィン系オイル、動粘度(40℃):381.6mm2/s、環分析パラフィン:73%、環分析ナフテン:27%、重量平均分子量:1304
・成分(c−1)
ポリプロピレン、プライムポリプロ J108M(商品名)、株式会社プライムポリマー製、MFR(230℃、2.16kg荷重):45g/10分
二軸押出機(口径46mm、L/D=46)を用いて、下記の表1に記載の各構成成分を、表1に示す配合に従って、190℃で溶融混練することにより、ペレット状の樹脂組成物(A)を製造した。
表1に記載の各構成成分および配合比率を適用したこと以外は、実施例1と同様にして、多孔複合体(2)および(3)をそれぞれ得た。各部分における開孔率、異方化率、および伸張応力緩和率の測定結果を表1に示す。
開孔処理を行わなかった以外は、実施例1と同様にして、多孔複合体(1)’を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表1に示す。
微小菱形のサイズを9±1mm(Dmax方向)×3.2±0.2mm(Dmin方向)、Dmax方向における孔間隔を12±1mm、Dmin方向における孔間隔を4.5±1mm、1つの孔の面積は14.4±1mm2とすることにより開孔率、異方化率および伸張応力緩和率を変更したこと以外は、実施例2と同様にして、多孔複合体(2)’を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表1に示す。なお、伸張応力緩和率は、測定開始より破れが発生したため測定できなかった。
微小菱形のサイズを9±1mm(Dmax方向)×1.6±0.2mm(Dmin方向)、Dmax方向における孔間隔を40±1mm、Dmin方向における孔間隔を30±1mm、1つの孔の面積は7.2±1mm2とすることにより開孔率、異方化率、および伸張応力緩和率を変更したこと以外は、実施例3と同様にして、多孔複合体(3)’を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表1に示す。
その後、選手10名に15分間の練習試合を行わせた。その試合中(運動時)のインナートレーナーパンツの固定安定性、締付け性および爽快性(耐ムレ性)の官能評価を選手10名により行った。10名の選手の評価の平均値を、装着性の評価として採用した。その結果を表2に示す。なお、比較例2においては、シートを成形できず、成形加工性が不良となったため、装着性に関する評価を行うことができなかった。
ランク1:良好
ランク2:比較的良好
ランク3:普通、少し違和感あり
ランク4:違和感あり
ランク5:違和感あり、使用したくない。
二軸押出機(口径46mm、L/D=46)を用いて、下記の表3に記載の各構成成分を、表3に示す配合に従って、190℃で溶融混練することにより、ペレット状の樹脂組成物(A)を製造した。
表3に記載の各構成成分および配合比率を適用したこと、および図2に記載の微小菱形の孔の作製に代えて、図3(図中の黒色部分はスリットまたは孔を示す)に示すスリットを作製したこと以外は、実施例4と同様にして、多孔複合体(5)を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表3に示す。
表3に記載の各構成成分および配合比率を適用したこと以外は、実施例4と同様にして、多孔複合体(6)〜(11)を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表3に示す。
表3に記載の各構成成分および配合比率を適用したこと、および図2に記載の微小菱形の孔の作製に代えて、図4(図中の黒色部分はスリットまたは孔を示す)に示す複数の長方形(長さ10mm、幅5mmのスリット)を作製したこと以外は、実施例4と同様にして、多孔複合体(12)を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表3に示す。
表3に記載の各構成成分および配合比率を適用したこと、および図2に記載の微小菱形の孔の作製に代えて、図5(図中の黒色部分はスリットまたは孔を示す)に示す複数の円形で縦の間隔と横の間隔が異なるメッシュ状多孔シート{径7mmの円形、縦方向の円と円の間隔(円端部と円端部の長さ)7mm、横方向の円と円の間隔4mm}を作製したこと以外は、実施例4と同様にして、多孔複合体(13)を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表3に示す。
表3に記載の各構成成分および配合比率を適用したこと、および孔を作製しなかったこと以外は、実施例4と同様にして、多孔複合体(4)’を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表3に示す。
表3に記載の各構成成分および配合比率を適用したこと以外は、実施例4と同様にして、多孔複合体(5)’〜(10)’を得た。開孔率、異方化率、および伸張応力緩和率の測定結果を表3に示す。なお、比較例7において、伸張応力緩和率の測定開始より破れが発生し、また、比較例8においては、成形不可につき測定できなかった。
その後、選手10名に15分間の練習試合を行わせた。その試合中(運動時)のスポーツブラの固定安定性、締付け性および爽快性(耐ムレ性)の官能評価を選手10名により行った。10名の選手の評価の平均値を、装着性の評価として採用した。その結果を表4に示す。
ランク1:良好
ランク2:比較的良好
ランク3:普通、少し違和感あり
ランク4:違和感あり
ランク5:違和感あり、使用したくない。
Claims (10)
- 熱可塑性エラストマー組成物(A)からなり、複数のスリットおよび/または孔を有する多孔シートであって、開孔率が5〜80%、異方化率が10%以上、かつ500%伸張で60秒間保持後の伸張応力緩和率が40%以下である、多孔シート。
- 熱可塑性エラストマー組成物(A)は、(a)少なくとも1種のビニル芳香族化合物から構成される重合体ブロック(X)と少なくとも1種の共役ジエン化合物から構成される重合体ブロック(Y)とからなる、少なくとも1つのブロック共重合体および/または該ブロック共重合体の水素添加物を含む、請求項1に記載の多孔シート。
- ブロック共重合体(a)において、20万以下の重量平均分子量を有する画分の割合が、ブロック共重合体(a)全体を基準として50〜100質量%である、請求項2に記載の多孔シート。
- 熱可塑性エラストマー組成物(A)は、ブロック共重合体(a)100質量部に対して10〜400質量部の炭化水素系軟化剤(b)を含む、請求項2または3に記載の多孔シート。
- 開孔率が5〜50%である、請求項1〜4のいずれかに記載の多孔シート。
- 孔のサイズは0.5〜100mm2である、請求項1〜5のいずれかに記載の多孔シート。
- 有機または無機添加剤の含有量は熱可塑性エラストマー組成物(A)に対して0〜40質量%である、請求項1〜6のいずれかに記載の多孔シート。
- 熱可塑性エラストマー組成物(A)は、ブロック共重合体(a)100質量部に対してオレフィン系樹脂2〜10質量部を含む、請求項4〜7のいずれかに記載の多孔シート。
- メッシュ状である、請求項1〜8のいずれかに記載の多孔シート。
- 基布(B)、および該基布(B)上に配置された請求項1〜9のいずれかに記載の多孔シートを備える、多孔複合体。
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PCT/JP2018/002792 WO2018139655A1 (ja) | 2017-01-30 | 2018-01-29 | 多孔シートおよび多孔複合体 |
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JP7058110B2 (ja) * | 2017-11-21 | 2022-04-21 | スリーエム イノベイティブ プロパティズ カンパニー | 伸縮材、伸縮材の製造方法、伸縮性部材、及び衣料製品 |
KR20210106429A (ko) * | 2018-12-27 | 2021-08-30 | 주식회사 쿠라레 | 관통공을 포함하는 구조체를 갖는 적층체 |
CN113227288B (zh) * | 2018-12-27 | 2022-08-02 | 株式会社可乐丽 | 具有包含贯通孔的结构体的层叠体 |
JP7557728B2 (ja) | 2019-06-27 | 2024-09-30 | パナソニックIpマネジメント株式会社 | 伸縮性回路基板、及び伸縮性回路実装品 |
US11696606B2 (en) | 2019-12-06 | 2023-07-11 | Under Armour, Inc. | Athletic bra |
USD952289S1 (en) * | 2020-02-07 | 2022-05-24 | Under Armour, Inc. | Brassiere |
CA3181312A1 (en) * | 2020-06-09 | 2021-12-16 | Ethel BERMEJO | 3d embossed film |
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EP3575351A1 (en) | 2019-12-04 |
EP3575351A4 (en) | 2020-08-26 |
CA3052024A1 (en) | 2018-08-02 |
CN110325573A (zh) | 2019-10-11 |
WO2018139655A1 (ja) | 2018-08-02 |
US11345788B2 (en) | 2022-05-31 |
US20190390024A1 (en) | 2019-12-26 |
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