JP2017506277A - 帯電防止コーティングされたポリエステルフィルム - Google Patents
帯電防止コーティングされたポリエステルフィルム Download PDFInfo
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- JP2017506277A JP2017506277A JP2016550492A JP2016550492A JP2017506277A JP 2017506277 A JP2017506277 A JP 2017506277A JP 2016550492 A JP2016550492 A JP 2016550492A JP 2016550492 A JP2016550492 A JP 2016550492A JP 2017506277 A JP2017506277 A JP 2017506277A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Abstract
Description
この出願は2014年2月7日に出願された米国仮出願第61/937,154号の利益を請求し、その内容を、全ての目的のためにその全体を参照により本明細書に援用する。
本発明は、少なくともその1面上に帯電防止層を有する自己支持性(self-supporting)ポリエステル基材フィルムを含む帯電防止ポリエステルフィルムであって、その帯電防止層が、
a)下記式(I)
で表される繰り返し単位を含む1以上の帯電防止ポリマー;
b)1以上の非ポリマー性カチオン性帯電防止剤;及び
c)1以上の架橋剤、
を含む、帯電防止ポリエステルフィルムを提供する。
本発明は、ポリエステル基材を、ポリ四級アクリルアミド帯電防止ポリマー、架橋剤、及び非ポリマー性帯電防止剤を含む水性コーティング組成物でコーティングし、次にそのコーティングを乾燥させて基材上に帯電防止層を形成することによって形成される帯電防止ポリエステルフィルムを提供する。本発明によるフィルムは、多くの態様で、一般的な市販されているフィルムよりも優れた帯電防止性能をもたらし、また、その帯電防止特性は、取り扱われること(ハンドリング)による劣化に顕著に抵抗性であり、優れた帯電防止特性とこすり取られることに対する抵抗性を示す。帯電防止組成物でコーティングされた自己支持性ポリエステルフィルム基材を含む上記フィルムを以下で詳細に説明する。
上記コーティング組成物は、下記式(I)で表される繰り返し単位を含む1以上のポリ四級アクリルアミド帯電防止ポリマーを含む。
コーティング組成物は1以上の架橋剤を含む。それらは有機ポリマー架橋剤、例えば、複数のカルボジイミド、イソシアネート、アジリジン、又はオキサゾリン基を有するポリマーであることができる。例には、オキサゾリン官能性アクリルポリマー、例えば、下記式(II)にしたがう繰り返し単位を含む架橋剤が含まれる。
コーティング組成物は、1以上の非ポリマー性カチオン性帯電防止剤、典型的には四級アンモニウム塩、最も典型的には1分子当たり1つの四級アンモニウム基のみ、又は2つのみを有する四級アンモニウム塩を含む。好適な例には、ステアリン酸アミドプロピルジメチル-2-ヒドロキシエチルアンモニウム塩、例えば、硝酸塩又はリン酸二水素塩が含まれる。
1以上の界面活性剤が、典型的には、基材に濡れ性を付与するのに十分な量で含まれる。界面活性剤が存在する場合には、界面活性剤(1又は複数)は合計で、典型的には、乾燥固形分基準で、コーティング組成物の少なくとも0.1質量%、又は少なくとも1質量%、又は少なくとも2質量%を構成する。それら界面活性剤は典型的には最大で10質量%、又は最大で20質量%、又は最大で60質量%を構成する。いくつかの態様では、非イオン性界面活性剤のみが用いられるか、又はカチオン性界面活性剤のみが用いられるか、又はそれらの組み合わせが用いられる。非イオン性界面活性剤の例には、EMULGEN(登録商標)A 60ポリオキシエチレンジスチレン化フェニルエーテル、Kao Specialties Americas, LLC, High Point, NCから入手できる非イオン性界面活性剤、が含まれる。その他の適切な界面活性剤には、Dow Chemical社のTergitol NP-10、Univar Ltd社のCAFLON(登録商標) NP10イソノニルフェニルエトキシレート、及びAir Products社のSURFYNOL(登録商標) 104界面活性剤が含まれる。
ポリエステル基材には、1種以上のグリコール又はジオール(例えば、エチレンもしくはプロピレングリコール、又はブタンジオール)と、1種以上の二塩基酸(diacid)又はそのエステル(典型的にはメチルエステル)との重縮合によって得られる結晶性ポリエステルが含まれる。好適な二塩基酸には、テレフタル酸、ナフタレンジカルボン酸、イソフタル酸、ジフェン酸、及びセバシン酸が含まれる。本発明に有用なポリエステルフィルムの例は、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリプロピレンテレフタレート、及びポリブチレンテレフタレート、又はそれらの混合物を含み、あるいは例には前記のポリエステル類のいずれか1つが存在するコポリエステルフィルムが含まれる。例えば、ポリエチレンテレフタレート/イソフタレート(PETIP)コポリエステルのフィルムを本発明にしたがって用いることができる。別の好適な例は、PET及びPENのコポリエステルから作られたフィルムである。典型的には、PETが用いられる。
本発明による使用のためのコーティング組成物は、揮発性希釈剤(これは溶媒を含みうる)中の溶液の形態である。いくつかの態様では、組成物の全ての成分は揮発性希釈剤に溶かされ、したがって組成物は溶液である。しかし、いくつかの態様では、組成物はいくらかの分散された物質、例えばアクリルエマルションを含んでもよい。ほとんどの場合、希釈剤は水性であり、本明細書で用いる場合に水性とは、希釈剤は少なくとも50質量%水であることを意味する。ほとんどの態様では、水性希釈剤は少なくとも90質量%水であり、多くの場合、それは100質量%水である。そのような溶液は、典型的には、一方向延伸の後のインライン・グラビアロール塗布のためには、約0.5〜15質量%の範囲、さらに典型的には約2〜5質量%の範囲の乾燥固形分を有するが、その他の適用方法に対してはより多いことができる。本明細書で用いる場合、「乾燥固形分」とは、コーティング組成物中に存在する不揮発性物質の量、すなわち、乾燥後にコーティング中に残る物質(その不揮発性物質のいくらかは室温で液体であってもよい)をいう。帯電防止化合物及び界面活性剤の全ては、乾燥固形分を計算する目的のためには不揮発性と考えられる。
EMULGEN(登録商標) A60:ポリオキシエチレンジスチレン化フェニルエーテル、Kao Specialties America, LLC, High Point, NCから入手可能な非イオン性界面活性剤。ここでは20%水溶液として用いる。
ADOGEN(登録商標) 477E:獣脂ジアミンペンタメチルジクロリド(「第四級アンモニウム化合物, N,N,N,N′,N′-ペンタメチル-N′-獣脂アルキルトリメチレンジクロリド」), エタノール中56質量%(測定して)、Evonik Goldschmidt Corporation, Hopewell, VAから入手可能。
CYASTAT(登録商標) SN:ステアリン酸アミドプロピルジメチル-2-ヒドロキシエチルアンモニウム硝酸塩, 50:50のイソプロパノール-水混合物中の50%溶液, Cytec Industries Inc., West Paterson, NJから入手可能。その構造を下に示す。
EPOCROS(商標) WS-300:オキサゾリン官能性の水溶性アクリルコポリマーの10質量%水溶液, 株式会社 日本触媒, 大阪, 日本国から入手可能。
ポリマーA - 下に示す構造を有するカチオン性ホモポリマーの35質量%水溶液。
静電気減衰試験
装置:モンロー静電気分析装置(Monroe Static Analyzer)モデル276A
方法:フルスケール電圧を2000Vに設定した。選択した試験シーケンスは、10秒帯電(charging)、60秒の暗減衰(dark decay)。ピーク電圧、静電気がピーク電圧の2分の1まで減衰するための時間、ピーク電圧の10分の1まで静電気が減衰するための時間、及び静電気が5V未満まで減衰するための時間(完全減衰)を記録した。
装置:デジタル電位計(Keithlay Model 617), 抵抗率アダプター/円形電極(Keithlay Model 6105), 及び作業のためのグローブポートを備えたBlue M Model WP-4800湿度チャンバー。
方法:
電源を100.0Vに設定し、最大2mAで操作した。
約3.5’’(3.5 in = 8.89 cm)×3.5’’(3.5 in = 8.89 cm)の大きさのフィルムサンプルを少なくとも20分間、湿度チャンバー内でコンディショニングした。読み取りは、抵抗率アダプターが閉じられ、係止された後、30秒行った。
計算:
表面抵抗率(log オーム/sq)= log (5340/マイクロアンペア[デジタルディスプレイから]) + アンペア数の指数(指数は、ミリアンペア=3, マイクロアンペア=6, ナノアンペア=9, ピコアンペア=12)
コーティング組成物1及び2を表1に示すように調製し、AB共押出し構造を有するポリエステルフィルムの「A」層の上に、延伸間グラビアコーティング(すなわち、二軸配向の2つの工程間でのコーティング)によってコーティングした。「A」層はシリカ充填された(粗い表面)PET層であり、「B」層は、透明なフィラー添加されていないPETだった。各コーティングを順次希釈し、溶液全体に対する界面活性剤量を同じに保ち、より薄い乾燥厚さをもつコーティングを作成した。希釈されていない及び希釈された組成物から作られたコーティング(それぞれA及びBと記す)の特性が、他の2つの帯電防止コーティング(3及び4、下の例2で調製した)及び5つの市販されている帯電防止コーティングされたPETフィルムについての結果とともに表3に示されている。
コーティング組成物3及び4を表2に示すように調製し、ガラスビーズで粉砕した13Xゼオライト粒子を含む単層PETフィルムの上に、同様に延伸間コーティングをした。ここでも、各コーティングを希釈し、溶液全体に対する界面活性剤の量を同じに保ち、より薄い乾燥厚さをもつコーティングを作成した。コーティングの特性は表3に示されている。
フィルム1: ポリ(3,4-エチレンジオキシチオフェン)
フィルム2: ステアリン酸アミドプロピルジメチル-2-ヒドロキシエチルアンモニウム硝酸塩
フィルム3:リン酸カリウム
フィルム4:不明
フィルム5:トリフルオロメタンスルホン酸リチウム
界面活性剤の量は、コーティングの静電気散逸特性に顕著な影響を及ぼさない。表4は、先の例よりも低い界面活性剤量をもつコーティングであるサンプル5を示す。それを例2に記載したフィルム上にコーティングした。SR値は50%RHにおいて9.6、35%RHにおいて10.4だった。静電気減衰試験における最大の電圧は408Vであり、減衰時間は1/2への減衰までに1.79秒、1/10への減衰までに2.78秒、完全に減衰するまでに4.90秒だった。
アクリル及びその他のエマルションをコーティングに組み込み、乾燥コーティング厚さを増大させて、帯電防止性能を保つことができる。表5は2つのコーティング配合物を示しており、これらを、マイヤーバー(Mayer bar)を使用して、充填剤が添加されていないPET上に延伸間に、1330Åの計算した乾燥コーティング厚さに適用した。帯電防止性能は非常に良好であり、表6にみられるとおりである。
Claims (13)
- 少なくともその1面上に帯電防止層を有する自己支持性ポリエステル基材フィルムを含む帯電防止ポリエステルフィルムであって、
前記帯電防止層が、
a)下記式(I)
で表される繰り返し単位を含む1以上の帯電防止ポリマー;
b)1以上の非ポリマー性カチオン性帯電防止剤;及び
c)1以上の架橋剤、
を含む、帯電防止ポリエステルフィルム。 - 前記帯電防止層が1以上の非イオン性及び/又はカチオン性界面活性剤をさらに含む、請求項1に記載のフィルム。
- 前記1以上の架橋剤が複数のオキサゾリン基を有するポリマーを含む、請求項1又は2に記載のフィルム。
- 前記帯電防止層がエマルションポリマーを含まない、請求項1〜4のいずれか一項に記載のフィルム。
- 前記帯電防止層が、ポリマー架橋剤以外の非帯電防止ポリマーを含まない、請求項1〜5のいずれか一項に記載のフィルム。
- 前記1以上の非ポリマー性カチオン性帯電防止剤が、ステアリン酸アミドプロピルジメチル-2-ヒドロキシエチルアンモニウム リン酸二水素塩を含む、請求項1〜6のいずれか一項に記載のフィルム。
- 前記1以上の非ポリマー性カチオン性帯電防止剤が、ステアリン酸アミドプロピルジメチル-2-ヒドロキシエチルアンモニウム 硝酸塩を含む、請求項1〜6のいずれか一項に記載のフィルム。
- 前記1以上の非ポリマー性カチオン性帯電防止剤が、獣脂ジアミンペンタメチルジクロリドを含む、請求項1〜6のいずれか一項に記載のフィルム。
- R1及びR2がそれぞれHであり、R3が(CH2)3であり、nがゼロであり、R4及びR5がそれぞれCH3であり、mが1である、請求項1〜9のいずれか一項に記載のフィルム。
- Y−がCH3SO3 −である、請求項1〜10のいずれか一項に記載のフィルム。
- R7及びR8がそれぞれHである、請求項4〜11のいずれか一項に記載のフィルム。
- 前記帯電防止層がスリップ粒子をさらに含む、請求項1〜12のいずれか一項に記載のフィルム。
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2015
- 2015-02-04 EP EP15704911.5A patent/EP3102629A1/en not_active Withdrawn
- 2015-02-04 JP JP2016550492A patent/JP2017506277A/ja active Pending
- 2015-02-04 WO PCT/US2015/014411 patent/WO2015120018A1/en active Application Filing
- 2015-02-04 KR KR1020167024532A patent/KR20160118332A/ko not_active Application Discontinuation
- 2015-02-04 US US15/111,221 patent/US10301483B2/en not_active Expired - Fee Related
- 2015-02-04 CN CN201580007630.4A patent/CN106170507A/zh active Pending
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JPH08504384A (ja) * | 1992-12-09 | 1996-05-14 | ヘキスト・アクチェンゲゼルシャフト | 帯電防止コーティングが被覆されている二軸延伸penbbフィルム |
JPH10330518A (ja) * | 1997-06-03 | 1998-12-15 | Teijin Ltd | 帯電防止性ポリエステルフィルム |
WO2004085524A1 (ja) * | 2003-03-25 | 2004-10-07 | Teijin Dupont Films Japan Limited | 帯電防止性積層ポリエステルフィルム |
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JP2019034532A (ja) * | 2017-01-17 | 2019-03-07 | 東レ株式会社 | 積層フィルムおよびその製造方法 |
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US20160333196A1 (en) | 2016-11-17 |
CN106170507A (zh) | 2016-11-30 |
EP3102629A1 (en) | 2016-12-14 |
WO2015120018A1 (en) | 2015-08-13 |
US10301483B2 (en) | 2019-05-28 |
KR20160118332A (ko) | 2016-10-11 |
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