JP2016120642A - 3次元形状を有する物品を加熱延伸により被覆することが可能なフィルム及び加飾フィルム - Google Patents
3次元形状を有する物品を加熱延伸により被覆することが可能なフィルム及び加飾フィルム Download PDFInfo
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- JP2016120642A JP2016120642A JP2014261370A JP2014261370A JP2016120642A JP 2016120642 A JP2016120642 A JP 2016120642A JP 2014261370 A JP2014261370 A JP 2014261370A JP 2014261370 A JP2014261370 A JP 2014261370A JP 2016120642 A JP2016120642 A JP 2016120642A
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- Prior art keywords
- polyurethane
- layer
- film
- heat
- article
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Abstract
【解決手段】本開示の一実施態様により提供される、3次元形状を有する物品を加熱延伸により被覆することが可能なフィルムは、最表面に配置される最外層と、ポリエステル系ポリウレタン及びポリカーボネート系ポリウレタンからなる群より選択される熱可塑性ポリウレタンを含み、加熱延伸時に物品に加熱接着されるポリウレタン加熱接着層と含み、ポリウレタン加熱接着層の破断強度が135℃で1MPa以上であり、150℃、周波数1.0Hzにおける貯蔵弾性率が5×103Pa〜5×105Paであり、損失係数tanδが0.1以上である。
【選択図】図1
Description
53.0部の3−メチル−1,5−ペンタンジオール、及び47.0部のエチレンカーボネートに、触媒として酢酸鉛三水和物0.00072部を加えたのち、160℃で16時間反応させ、数平均分子量1000のポリカーボネートジオールを調製した。64.0部の上記ポリカーボネートジオール、8.0部の1,4−ブタンジオール、28.0部の1,6−ヘキサメチレンジイソシアネート、0.01部のジブチルスズジラウレートを混合し、180℃で3時間反応させた後、加圧成形機にて厚さ100μmのフィルムを作製した。得られたポリウレタンのGPC法により測定した分子量は、数平均分子量28,000、重量平均分子量89,000であった。
21.6部のアジピン酸、及び29.6部の1,4−ブタンジオールに、触媒として40ppmのチタニウムテトラブチレートを加えたのち、240℃でエステル化反応を行い、数平均分子量500のポリエステルポリオールを調製した。56.0部の上記ポリエステルポリオール、15.0部のクラレポリオールPMHC−1050、2.0部の1,6−ヘキサンジオール、27.0部の1,6−ヘキサメチレンジイソシアネート、0.01部のジブチルスズジラウレートを混合し、180℃で3時間反応させた後、加圧成形機にて厚さ50μm及び100μmのフィルムを作製した。得られたポリウレタンのGPC法により測定した分子量は、数平均分子量46,000、重量平均分子量120,000であった。
63.0部のポリライト(商標)OD−X−240、6.0部の1,4−ブタンジオール、31.0部の4,4’−ジフェニルメタンジイソシアネート、0.01部のジブチルスズジラウレートを混合し、180℃で3時間反応させた後、加圧成形機にて厚さ200μmのフィルムを作製した。得られたポリウレタンのGPC法により測定した分子量は、数平均分子量50,000、重量平均分子量100,000であった。
49.0部のアジピン酸、14.5部のイソフタル酸、及び36.5部の1,4−ブタンジオールに、触媒として40ppmのチタニウムテトラブチレートを加えたのち、240℃でエステル化反応を行い、数平均分子量1200のポリエステルポリオールを調製した。63.0部の上記ポリエステルポリオール、5.0部の1,4−ブタンジオール、32.0部のジシクロヘキシルメタン−4,4’−ジイソシアネート、0.01部のジブチルスズジラウレートを混合し、180℃で3時間反応させた後、加圧成形機にて厚さ150μmのフィルムを作製した。得られたポリウレタンのGPC法により測定した分子量は、数平均分子量51,000、重量平均分子量120,000であった。
72.0部のポリテトラメチレンエーテルグリコールPTMG 650、28.0部の4,4’−ジフェニルメタンジイソシアネート、及び0.01部のジブチルスズジラウレートを混合し、180℃で3時間反応させた後、加圧成形機にて厚さ200μmのフィルムを作製した。得られたポリウレタンのGPC法により測定した分子量は、数平均分子量31,000、重量平均分子量65,000であった。
57.0部のポリライト(商標)OD−X−240、7.5部の1,4−ブタンジオール、35.5部の4,4’−ジフェニルメタンジイソシアネート、0.01部のジブチルスズジラウレートを混合し、180℃で3時間反応させた後、加圧成形機にて厚さ150μmのフィルムを作製した。得られたポリウレタンのGPC法により測定した分子量は、数平均分子量47,000、重量平均分子量96,000であった。
85.0部のポリテトラメチレンエーテルグリコールPTMG 1500、15.0部のジシクロヘキシルメタン−4,4’−ジイソシアネート、0.01部のジブチルスズジラウレートを混合し、180℃で3時間反応させた後、加圧成形機にて厚さ150μmのフィルムを作製した。得られたポリウレタンのGPC法により測定した分子量は、数平均分子量48,000、重量平均分子量140,000であった。
ポリウレタンフィルムの分子量は、以下の条件でゲル浸透クロマトグラフィ(GPC)法により決定する。
装置:Agilent 1200 series LC system
PLゲル ガードカラム(50mm×7.5mm、内径10μm)
PLゲル MIXED−B×2(300mm×7.5mm、内径10μm)
溶媒:テトラヒドロフラン(THF)又はN−メチルピロリドン(NMP)
流量:1.0mL/分
検出器:RI
カラム温度:40℃(THF)、60℃(NMP)
濃度:0.1%
サンプル量:100μL
標準:ポリスチレン(THF)、ポリメチルメタクリレート(NMP)
ポリウレタンフィルムの引張強度及び伸びは、以下の条件を用いてJIS K 7311(1995)に準拠して決定する。
(1)試験温度25℃
試料:JIS K 7311(1995)に記載のダンベル試験片、幅5.0mm、ゲージ長20.0mm
引張速度:300mm/分
(2)試験温度135℃
試料:JIS K 7311(1995)に記載のダンベル試験片、幅10.0mm、ゲージ長20.0mm
引張速度:300mm/分
(1)50%伸び時引張強度(T50)
T50(MPa)=F50/A
F50(N):50%伸び時の測定値、A:断面積(m2)
(2)破断強度(TB)
TB(MPa)=FB/A
FB(N):破断時の測定値、A:断面積(m2)
(3)伸びE
E(%)=[(L1−L0)/L0]×100
L1:破断時のゲージ長(mm)、L0:初期ゲージ長さ(mm)(=20.0mm)
粘弾性特性は、動的粘弾性測定装置ARES(ティー・エイ・インスツルメント・ジャパン株式会社製、日本国東京都品川区)を使用して測定する。フィルムを直径7.9mmに打ち抜いて試料を作製し、所定温度にて周波数1.0Hzのせん断モードで測定し、せん断貯蔵弾性率G’及び損失係数tanδ(=せん断損失弾性率G”/せん断貯蔵弾性率G’)を得る。
初期密着性評価は、JIS K5400:1990(廃版)の碁盤目テープ試験に準拠して行う。具体的には、TOMを用いて、成形温度135℃で面積伸び率が100%となるように加熱延伸フィルムをPC/ABS板(CK43黒色、テクノポリマー株式会社製、日本国東京都港区)に接着した後、カッターを使用して1mm間隔でフィルム上に碁盤目状にスリットを入れて、100個の区画を形成する。碁盤目状にスリットが入ったフィルム上にセロテープ(登録商標)(ニチバン株式会社製CT405AP−18、日本国東京都文京区)を十分に圧着し、90度方向に引っ張る。フィルム上に残存する碁盤目状の区画の数をカウントして密着性評価の値とする。残存する区画が100個(100/100)を最良とし、90個以上(90/100以上)を良好とする。
TOMを用いて、成形温度135℃で面積伸び率が100%となるように加熱延伸フィルムをPC/ABS板(CK43黒色、テクノポリマー株式会社製、日本国東京都港区)に接着する。TOMにより成形した後、以下のヒートサイクルにかけて外観を観察する。
(1)25℃から105℃に1時間で加熱し、105℃で6時間保持する。
(2)−30℃に2時間で冷却し、−30℃で2時間保持する。
(3)50℃/95%RHに2時間で加熱及び加湿し、50℃/95%RHで6時間保持する。
(4)−30℃(乾燥)に2時間で冷却し、−30℃で2時間保持する。
(5)25℃に1時間で加熱する。
(6)(1)〜(5)を5回繰り返す。
TOMを用いて、成形温度135℃で面積伸び率が100%となるように加熱延伸フィルムをPC/ABS板(CK43黒色、テクノポリマー株式会社製、日本国東京都港区)に接着する。得られた積層体を25mm幅×50mm長さでカットし試験片を作製する。テンシロン(登録商標)万能試験機RTC−1325A(ロードセル50N、UR−50N−D)(株式会社オリエンテック製、日本国東京都豊島区)を用い、クリップ間距離を約50mm、引張速度を300mm/分として温度23℃で試験片を180度方向に引っ張って加熱延伸フィルムをPC/ABS板から剥がしたときの測定値の平均を接着力とする。
アクリル樹脂最外層、接合層、金属蒸着膜、及びポリウレタン加熱接着層をこの順で含むフィルムを作製した。
メチルメタクリレート(MMA)/2−ヒドロキシエチルメタクリレート(HEMA)=97質量%/3質量%のアクリル共重合体を、一般的な溶液重合により調製して、固形分35質量%の酢酸エチル/酢酸ブチル溶液の形態で得た。この溶液にイソシアヌレート架橋剤デュラネート(商標)TPA−100を、共重合体に対して固形分で2.7質量%となる量で添加した。得られた溶液を厚さ75μmのポリエステルフィルムに塗布し、100℃で10分乾燥し、その後150℃で10分乾燥した。このようにして、厚さ50μmのアクリル樹脂最外層をポリエステルフィルム上に得た。
スズをポリウレタン加熱接着層上に蒸着した。ポリウレタン加熱接着層は予め厚さ50μmのポリエステルフィルムに積層して、蒸着処理中このフィルムに担持させた。蒸着条件は以下のとおりである。
装置:真空蒸着装置EX−400(株式会社アルバック製、日本国神奈川県茅ヶ崎市)
ターゲット金属蒸発のエネルギー源:電子線
スズ蒸着膜の厚さ:430オングストローム
スズ蒸着膜の成膜速度:5オングストローム/秒
100質量部のポリエステルポリオールSEIKABOND(商標)E−295NT及び2.9質量部のイソシアネート硬化剤C−55を混合して、上記のとおり調製したアクリル樹脂最外層の上に塗布し、100℃のオーブンで3分間加熱し、アクリル樹脂最外層の上に厚さ15μmの接合層を形成した。
加熱転写可能な意匠転写層を含む加熱延伸加飾フィルムを以下の手順で作製した。
装置:真空蒸着装置EX−400(株式会社アルバック製、日本国神奈川県茅ヶ崎市)
ターゲット金属蒸発のエネルギー源:電子線
スズ蒸着膜の成膜速度:5オングストローム/秒
10 加熱延伸フィルム
11 最外層
12 ポリウレタン加熱接着層
13 意匠層
14 金属光輝層
130 意匠転写層
131 第1表面層
132 第2表面層
20 物品
21 物品裏面
30 真空加熱圧着装置
31 第1真空室
32 第2真空室
33 台座
34 仕切り板
35 昇降台
Claims (8)
- 3次元形状を有する物品を加熱延伸により被覆することが可能なフィルムであって、
前記フィルムは、
最表面に配置される最外層と、
ポリエステル系ポリウレタン及びポリカーボネート系ポリウレタンからなる群より選択される熱可塑性ポリウレタンを含み、前記加熱延伸時に前記物品に加熱接着されるポリウレタン加熱接着層と
を含み、
前記ポリウレタン加熱接着層の破断強度が135℃で1MPa以上であり、150℃、周波数1.0Hzにおける貯蔵弾性率が5×103Pa〜5×105Paであり、損失係数tanδが0.1以上である、フィルム。 - 周波数1.0Hzで測定した前記ポリウレタン加熱接着層の−20℃の貯蔵弾性率と110℃の貯蔵弾性率の比(−20℃の貯蔵弾性率/110℃の貯蔵弾性率)が100以下である、請求項1に記載のフィルム。
- 前記熱可塑性ポリウレタンがポリカーボネート系ポリウレタンであり、前記最外層と前記ポリウレタン加熱接着層との間に前記ポリウレタン加熱接着層上に配置された金属光輝層をさらに含む、請求項1又は2のいずれかに記載のフィルム。
- ポリイソシアネートが前記熱可塑性ポリウレタン全体に対して20質量%〜40質量%の量で前記熱可塑性ポリウレタンに組み込まれている、請求項1〜3のいずれか一項に記載のフィルム。
- 前記ポリウレタン加熱接着層が着色されている、請求項1〜4のいずれか一項に記載のフィルム。
- 3次元形状を有する物品を加熱延伸により被覆することが可能な加飾フィルムであって、
前記フィルムは、
最表面に配置される最外層と、
ポリエステル系ポリウレタン及びポリカーボネート系ポリウレタンからなる群より選択される熱可塑性ポリウレタンを含み、前記加熱延伸時に前記物品に加熱接着されるポリウレタン加熱接着層と、
前記最外層と前記ポリウレタン加熱接着層の間に配置される意匠層と
を含み、
前記ポリウレタン加熱接着層の破断強度が135℃で1MPa以上であり、150℃、周波数1.0Hzにおける貯蔵弾性率が5×103Pa〜5×105Paであり、損失係数tanδが0.1以上である、加飾フィルム。 - 前記意匠層として加熱転写可能な意匠転写層を含む、請求項6に記載の加飾フィルム。
- 請求項1〜5のいずれか一項に記載のフィルム又は請求項6若しくは7のいずれかに記載の加飾フィルムを物品に被覆し一体化させた物品。
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Also Published As
Publication number | Publication date |
---|---|
MX2017008233A (es) | 2017-10-06 |
BR112017013828A2 (pt) | 2018-01-16 |
EP3237199A1 (en) | 2017-11-01 |
CN107107580A (zh) | 2017-08-29 |
EP3237199B1 (en) | 2019-01-30 |
JP6574088B2 (ja) | 2019-09-11 |
CA2971723A1 (en) | 2016-06-30 |
CN107107580B (zh) | 2019-04-16 |
WO2016106207A1 (en) | 2016-06-30 |
KR101887324B1 (ko) | 2018-08-09 |
US20170348953A1 (en) | 2017-12-07 |
KR20170091749A (ko) | 2017-08-09 |
US10046545B2 (en) | 2018-08-14 |
PL3237199T3 (pl) | 2019-06-28 |
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