JP6144548B2 - 透明導電性積層フィルム、その製造方法及びタッチパネル - Google Patents
透明導電性積層フィルム、その製造方法及びタッチパネル Download PDFInfo
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- JP6144548B2 JP6144548B2 JP2013131774A JP2013131774A JP6144548B2 JP 6144548 B2 JP6144548 B2 JP 6144548B2 JP 2013131774 A JP2013131774 A JP 2013131774A JP 2013131774 A JP2013131774 A JP 2013131774A JP 6144548 B2 JP6144548 B2 JP 6144548B2
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- B32B2457/202—LCD, i.e. liquid crystal displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/144—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers using layers with different mechanical or chemical conditions or properties, e.g. layers with different thermal shrinkage, layers under tension during bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
-
- G—PHYSICS
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- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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Description
前記第1フィルム基材の、前記透明硬化接着剤層とは反対の面に積層された第1透明導電層とを有することを特徴とする透明導電性積層フィルム、に関する。
前記ラジカル重合性化合物(A)は、SP値が29.0(MJ/m3)1/2以上32.0以下(MJ/m3)1/2であり、
前記ラジカル重合性化合物(B)は、SP値が18.0(MJ/m3)1/2以上21.0(MJ/m3)1/2未満であり、
前記ラジカル重合性化合物(C)は、SP値が21.0(MJ/m3)1/2以上23.0(MJ/m3)1/2以下であり、
組成物全量を100重量%としたとき、前記ラジカル重合性化合物(B)を25〜80重量%含有することが好ましい。
第1フィルム基材の一方の面に第1透明導電層が設けられた透明導電性フィルムを準備する工程aと、
前記透明導電性フィルムにおける、前記第1透明導電層を有しない前記第1フィルム基材の他方の面と、第2フィルム基材を、硬化によって、140℃における貯蔵弾性率が1×107Pa以上である透明硬化接着剤層を形成することができる、透明未硬化接着剤層により貼り合わせる工程b、および、
前記透明未硬化接着剤層を硬化させる工程cを有することを特徴とする透明導電性積層フィルムの製造方法、に関する。
本発明において、ラジカル重合性化合物などの溶解度パラメーター(SP値)は、Fedorsの算出法[「ポリマー・エンジニアリング・アンド・サイエンス(Polymer Eng.& Sci.)」,第14巻,第2号(1974),第148〜154ページ参照]すなわち、
ジメチルフェニルスルホニウム、ジメチル(o−フルオロフェニル)スルホニウム、ジメチル(m−クロロフェニル)スルホニウム、ジメチル(p−ブロモフェニル)スルホニウム、ジメチル(p−シアノフェニル)スルホニウム、ジメチル(m−ニトロフェニル)スルホニウム、ジメチル(2,4,6−トリブロモフェニル)スルホニウム、ジメチル(ペンタフルオロフェニル)スルホニウム、ジメチル(p−(トリフルオロメチル)フェニル)スルホニウム、ジメチル(p−ヒドロキシフェニル)スルホニウム、ジメチル(p−メルカプトフェニル)スルホニウム、ジメチル(p−メチルスルフィニルフェニル)スルホニウム、ジメチル(p−メチルスルホニルフェニル)スルホニウム、ジメチル(o−アセチルフェニル)スルホニウム、ジメチル(o−ベンゾイルフェニル)スルホニウム、ジメチル(p−メチルフェニル)スルホニウム、ジメチル(p−イソプロピルフェニル)スルホニウム、ジメチル(p−オクタデシルフェニル)スルホニウム、ジメチル(p−シクロヘキシルフェニル)スルホニウム、ジメチル(p−メトキシフェニル)スルホニウム、ジメチル(o−メトキシカルボニルフェニル)スルホニウム、ジメチル(p−フェニルスルファニルフェニル)スルホニウム、(7−メトキシ−2−オキソ−2H−クロメン−4−イル)ジメチルスルホニウム、(4−メトキシナフタレン−1−イル)ジメチルスルホニウム、ジメチル(p−イソプロポキシカルボニルフェニル)スルホニウム、ジメチル(2−ナフチル)スルホニウム、ジメチル(9−アンスリル)スルホニウム、ジエチルフェニルスルホニウム、メチルエチルフェニルスルホニウム、メチルジフェニルスルホニウム、トリフェニルスルホニウム、ジイソプロピルフェニルスルホニウム、ジフェニル(4−フェニルスルファニル−フェニル)−スルホニウム、4,4’−ビス(ジフェニルスルホニウム)ジフェニルスルフィド、4,4’−ビス[ジ[(4−(2−ヒドロキシ−エトキシ)−フェニル)]スルホニウム]]ジフェニルスルフィド、4,4’−ビス(ジフェニルスルホニウム)ビフェニレン、ジフェニル(o−フルオロフェニル)スルホニウム、ジフェニル(m−クロロフェニル)スルホニウム、ジフェニル(p−ブロモフェニル)スルホニウム、ジフェニル(p−シアノフェニル)スルホニウム、ジフェニル(m−ニトロフェニル)スルホニウム、ジフェニル(2,4,6−トリブロモフェニル)スルホニウム、ジフェニル(ペンタフルオロフェニル)スルホニウム、ジフェニル(p−(トリフルオロメチル)フェニル)スルホニウム、ジフェニル(p−ヒドロキシフェニル)スルホニウム、ジフェニル(p−メルカプトフェニル)スルホニウム、ジフェニル(p−メチルスルフィニルフェニル)スルホニウム、ジフェニル(p−メチルスルホニルフェニル)スルホニウム、ジフェニル(o−アセチルフェニル)スルホニウム、ジフェニル(o−ベンゾイルフェニル)スルホニウム、ジフェニル(p−メチルフェニル)スルホニウム、ジフェニル(p−イソプロピルフェニル)スルホニウム、ジフェニル(p−オクタデシルフェニル)スルホニウム、ジフェニル(p−シクロヘキシルフェニル)スルホニウム、ジフェニル(p−メトキシフェニル)スルホニウム、ジフェニル(o−メトキシカルボニルフェニル)スルホニウム、ジフェニル(p−フェニルスルファニルフェニル)スルホニウム、(7−メトキシ−2−オキソ−2H−クロメン−4−イル)ジフェニルスルホニウム、(4−メトキシナフタレン−1−イル)ジフェニルスルホニウム、ジフェニル(p−イソプロポキシカルボニルフェニル)スルホニウム、ジフェニル(2−ナフチル)スルホニウム、ジフェニル(9−アンスリル)スルホニウム、エチルジフェニルスルホニウム、メチルエチル(o−トリル)スルホニウム、メチルジ(p−トリル)スルホニウム、トリ(p−トリル)スルホニウム、ジイソプロピル(4−フェニルスルファニルフェニル)スルホニウム、ジフェニル(2−チエニル)スルホニウム、ジフェニル(2−フリル)スルホニウム、ジフェニル(9−エチル−9Hカルバゾール−3−イル)スルホニウム等を挙げることができるが、これらに限定されるものではない。
ジメチルフェニルスルホキソニウム、ジメチル(o−フルオロフェニル)スルホキソニウム、ジメチル(m−クロロフェニル)スルホキソニウム、ジメチル(p−ブロモフェニル)スルホキソニウム、ジメチル(p−シアノフェニル)スルホキソニウム、ジメチル(m−ニトロフェニル)スルホキソニウム、ジメチル(2,4,6−トリブロモフェニル)スルホキソニウム、ジメチル(ペンタフルオロフェニル)スルホキソニウム、ジメチル(p−(トリフルオロメチル)フェニル)スルホキソニウム、ジメチル(p−ヒドロキシフェニル)スルホキソニウム、ジメチル(p−メルカプトフェニル)スルホキソニウム、ジメチル(p−メチルスルフィニルフェニル)スルホキソニウム、ジメチル(p−メチルスルホニルフェニル)スルホキソニウム、ジメチル(o−アセチルフェニル)スルホキソニウム、ジメチル(o−ベンゾイルフェニル)スルホキソニウム、ジメチル(p−メチルフェニル)スルホキソニウム、ジメチル(p−イソプロピルフェニル)スルホキソニウム、ジメチル(p−オクタデシルフェニル)スルホキソニウム、ジメチル(p−シクロヘキシルフェニル)スルホキソニウム、ジメチル(p−メトキシフェニル)スルホキソニウム、ジメチル(o−メトキシカルボニルフェニル)スルホキソニウム、ジメチル(p−フェニルスルファニルフェニル)スルホキソニウム、(7−メトキシ−2−オキソ−2H−クロメン−4−イル)ジメチルスルホキソニウム、(4−メトキシナフタレン−1−イル)ジメチルスルホキソニウム、ジメチル(p−イソプロポキシカルボニルフェニル)スルホキソニウム、ジメチル(2−ナフチル)スルホキソニウム、ジメチル(9−アンスリル)スルホキソニウム、ジエチルフェニルスルホキソニウム、メチルエチルフェニルスルホキソニウム、メチルジフェニルスルホキソニウム、トリフェニルスルホキソニウム、ジイソプロピルフェニルスルホキソニウム、ジフェニル(4−フェニルスルファニル−フェニル)−スルホキソニウム、4,4’−ビス(ジフェニルスルホキソニウム)ジフェニルスルフィド、4,4’−ビス[ジ[(4−(2−ヒドロキシ−エトキシ)−フェニル)] スルホキソニウム]ジフェニルスルフィド、4,4’−ビス(ジフェニルスルホキソニウム)ビフェニレン、ジフェニル(o−フルオロフェニル)スルホキソニウム、ジフェニル(m−クロロフェニル)スルホキソニウム、ジフェニル(p−ブロモフェニル)スルホキソニウム、ジフェニル(p−シアノフェニル)スルホキソニウム、ジフェニル(m−ニトロフェニル)スルホキソニウム、ジフェニル(2,4,6−トリブロモフェニル)スルホキソニウム、ジフェニル(ペンタフルオロフェニル)スルホキソニウム、ジフェニル(p−(トリフルオロメチル)フェニル)スルホキソニウム、ジフェニル(p−ヒドロキシフェニル)スルホキソニウム、ジフェニル(p−メルカプトフェニル)スルホキソニウム、ジフェニル(p−メチルスルフィニルフェニル)スルホキソニウム、ジフェニル(p−メチルスルホニルフェニル)スルホキソニウム、ジフェニル(o−アセチルフェニル)スルホキソニウム、ジフェニル(o−ベンゾイルフェニル)スルホキソニウム、ジフェニル(p−メチルフェニル)スルホキソニウム、ジフェニル(p−イソプロピルフェニル)スルホキソニウム、ジフェニル(p−オクタデシルフェニル)スルホキソニウム、ジフェニル(p−シクロヘキシルフェニル)スルホキソニウム、ジフェニル(p−メトキシフェニル)スルホキソニウム、ジフェニル(o−メトキシカルボニルフェニル)スルホキソニウム、ジフェニル(p−フェニルスルファニルフェニル)スルホキソニウム、(7−メトキシ−2−オキソ−2H−クロメン−4−イル)ジフェニルスルホキソニウム、(4−メトキシナフタレン−1−イル)ジフェニルスルホキソニウム、ジフェニル(p−イソプロポキシカルボニルフェニル)スルホキソニウム、ジフェニル(2−ナフチル)スルホキソニウム、ジフェニル(9−アンスリル)スルホキソニウム、エチルジフェニルスルホキソニウム、メチルエチル(o−トリル) スルホキソニウム、メチルジ(p−トリル) スルホキソニウム、トリ(p−トリル) スルホキソニウム、ジイソプロピル(4−フェニルスルファニルフェニル) スルホキソニウム、ジフェニル(2−チエニル) スルホキソニウム、ジフェニル(2−フリル) スルホキソニウム、ジフェニル(9−エチル−9Hカルバゾール−3−イル) スルホキソニウム等を挙げることができるが、これらに限定されるものではない。
ホスホニウムカチオンの例:
トリメチルフェニルホスホニウム、トリエチルフェニルホスホニウム、テトラフェニルホスホニウム、トリフェニル(p−フルオロフェニル)ホスホニウム、トリフェニル(o−クロロフェニル)ホスホニウム、トリフェニル(m−ブロモフェニル)ホスホニウム、トリフェニル(p−シアノフェニル)ホスホニウム、トリフェニル(m−ニトロフェニル)ホスホニウム、トリフェニル(p−フェニルスルファニルフェニル)ホスホニウム、(7−メトキシ−2−オキソ−2H−クロメン−4−イル)トリフェニルホスホニウム、トリフェニル(o−ヒドロキシフェニル)ホスホニウム、トリフェニル(o−アセチルフェニル)ホスホニウム、トリフェニル(m−ベンゾイルフェニル)ホスホニウム、トリフェニル(p−メチルフェニル)ホスホニウム、トリフェニル(p−イソプロポキシフェニル)ホスホニウム、トリフェニル(o−メトキシカルボニルフェニル)ホスホニウム、トリフェニル(1−ナフチル)ホスホニウム、トリフェニル(9−アンスリル)ホスホニウム、トリフェニル(2−チエニル) ホスホニウム、トリフェニル(2−フリル) ホスホニウム、トリフェニル(9−エチル−9Hカルバゾール−3−イル) ホスホニウム等を挙げることができるが、これらに限定されるものではない。
ピリジニウムカチオンの例:
N−フェニルピリジニウム、N−(o−クロロフェニル)ピリジニウム、N−(m−クロロフェニル)ピリジニウム、N−(p−シアノフェニル)ピリジニウム、N−(o−ニトロフェニル)ピリジニウム、N−(p−アセチルフェニル)ピリジニウム、N−(p−イソプロピルフェニル)ピリジニウム、N−(p−オクタデシルオキシフェニル)ピリジニウム、N−(p−メトキシカルボニルフェニル)ピリジニウム、N−(9−アンスリル)ピリジニウム、2−クロロ−1−フェニルピリジニウム、2−シアノ−1−フェニルピリジニウム、2−メチル−1−フェニルピリジニウム、2−ビニル−1−フェニルピリジニウム、2−フェニル−1−フェニルピリジニウム、1,2−ジフェニルピリジニウム、2−メトキシ−1−フェニルピリジニウム、2−フェノキシ−1−フェニルピリジニウム、2−アセチル−1−(p−トリル)ピリジニウム、2−メトキシカルボニル−1−(p−トリル)ピリジニウム、3−フルオロ−1−ナフチルピリジニウム、4−メチル−1−(2−フリル)ピリジニウム、N−メチルピリジニウム、N−エチルピリジニウム等を挙げることができるが、これらに限定されるものではない。
キノリニウムカチオンの例:
N−メチルキノリニウム、N−エチルキノリニウム、N−フェニルキノリニウム、N−ナフチルキノリニウム、N−(o−クロロフェニル)キノリニウム、N−(m−クロロフェニル)キノリニウム、N−(p−シアノフェニル)キノリニウム、N−(o−ニトロフェニル)キノリニウム、N−(p−アセチルフェニル)キノリニウム、N−(p−イソプロピルフェニル)キノリニウム、N−(p−オクタデシルオキシフェニル)キノリニウム、N−(p−メトキシカルボニルフェニル)キノリニウム、N−(9−アンスリル)キノリニウム、2−クロロ−1−フェニルキノリニウム、2−シアノ−1−フェニルキノリニウム、2−メチル−1−フェニルキノリニウム、2−ビニル−1−フェニルキノリニウム、2−フェニル−1−フェニルキノリニウム、1,2−ジフェニルキノリニウム、2−メトキシ−1−フェニルキノリニウム、2−フェノキシ−1−フェニルキノリニウム、2−アセチル−1−フェニルキノリニウム、2−メトキシカルボニル−1−フェニルキノリニウム、3−フルオロ−1−フェニルキノリニウム、4−メチル−1−フェニルキノリニウム、2−メトキシ−1−(p−トリル)キノリニウム、2−フェノキシ−1−(2−フリル)キノリニウム、2−アセチル−1−(2−チエニル)キノリニウム、2−メトキシカルボニル−1−メチルキノリニウム、3−フルオロ−1−エチルキノリニウム、4−メチル−1−イソプロピルキノリニウム等を挙げることができるが、これらに限定されるものではない。
イソキノリニウムカチオンの例:
N−フェニルイソキノリニウム、N−メチルイソキノリニウム、N−エチルイソキノリニウム、N−(o−クロロフェニル)イソキノリニウム、N−(m−クロロフェニル)イソキノリニウム、N−(p−シアノフェニル)イソキノリニウム、N−(o−ニトロフェニル)イソキノリニウム、N−(p−アセチルフェニル)イソキノリニウム、N−(p−イソプロピルフェニル)イソキノリニウム、N−(p−オクタデシルオキシフェニル)イソキノリニウム、N−(p−メトキシカルボニルフェニル)イソキノリニウム、N−(9−アンスリル)イソキノリニウム、1,2−ジフェニルイソキノリニウム、N−(2−フリル)イソキノリニウム、N−(2−チエニル)イソキノリニウム、N−ナフチルイソキノリニウム等を挙げることができるが、これらに限定されるものではない。
ベンゾオキサゾリウムカチオンの例:
N−メチルベンゾオキサゾリウム、N−エチルベンゾオキサゾリウム、N−ナフチルベンゾオキサゾリウム、N−フェニルベンゾオキサゾリウム、N−(p−フルオロフェニル)ベンゾオキサゾリウム、N−(p−クロロフェニル)ベンゾオキサゾリウム、N−(p−シアノフェニル)ベンゾオキサゾリウム、N−(o−メトキシカルボニルフェニル)ベンゾオキサゾリウム、N−(2−フリル)ベンゾオキサゾリウム、N−(o−フルオロフェニル)ベンゾオキサゾリウム、N−(p−シアノフェニル)ベンゾオキサゾリウム、N−(m−ニトロフェニル)ベンゾオキサゾリウム、N−(p−イソプロポキシカルボニルフェニル)ベンゾオキサゾリウム、N−(2−チエニル)ベンゾオキサゾリウム、N−(m−カルボキシフェニル)ベンゾオキサゾリウム、2−メルカプト−3−フェニルベンゾオキサゾリウム、2−メチル−3−フェニルベンゾオキサゾリウム、2−メチルチオ−3−(4−フェニルスルファニルフェニル)ベンゾオキサゾリウム、6−ヒドロキシ−3−(p−トリル)ベンゾオキサゾリウム、7−メルカプト−3−フェニルベンゾオキサゾリウム、4,5−ジフルオロ−3−エチルベンゾオキサゾリウム等を挙げることができるが、これらに限定されるものではない。
N−メチルベンゾチアゾリウム、N−エチルベンゾチアゾリウム、N−フェニルベンゾチアゾリウム、N−(1−ナフチル)ベンゾチアゾリウム、N−(p−フルオロフェニル)ベンゾチアゾリウム、N−(p−クロロフェニル)ベンゾチアゾリウム、N−(p−シアノフェニル)ベンゾチアゾリウム、N−(o−メトキシカルボニルフェニル)ベンゾチアゾリウム、N−(p−トリル)ベンゾチアゾリウム、N−(o−フルオロフェニル)ベンゾチアゾリウム、N−(m−ニトロフェニル)ベンゾチアゾリウム、N−(p−イソプロポキシカルボニルフェニル)ベンゾチアゾリウム、N−(2−フリル)ベンゾチアゾリウム、N−(4−メチルチオフェニル)ベンゾチアゾリウム、N−(4−フェニルスルファニルフェニル)ベンゾチアゾリウム、N−(2−ナフチル)ベンゾチアゾリウム、N−(m−カルボキシフェニル)ベンゾチアゾリウム、2−メルカプト−3−フェニルベンゾチアゾリウム、2−メチル−3−フェニルベンゾチアゾリウム、2−メチルチオ−3−フェニルベンゾチアゾリウム、6−ヒドロキシ−3−フェニルベンゾチアゾリウム、7−メルカプト−3−フェニルベンゾチアゾリウム、4,5−ジフルオロ−3−フェニルベンゾチアゾリウム等を挙げることができるが、これらに限定されるものではない。
ジフリルヨードニウム、ジチエニルヨードニウム、ビス(4,5−ジメチル−2−フリル)ヨードニウム、ビス(5−クロロ−2−チエニル)ヨードニウム、ビス(5−シアノ−2−フリル)ヨードニウム、ビス(5−ニトロ−2−チエニル)ヨードニウム、ビス(5−アセチル−2−フリル)ヨードニウム、ビス(5−カルボキシ−2−チエニル)ヨードニウム、ビス(5−メトキシカルボニル−2−フリル)ヨードニウム、ビス(5−フェニル−2−フリル)ヨードニウム、ビス(5−(p−メトキシフェニル)−2−チエニル)ヨードニウム、ビス(5−ビニル−2−フリル)ヨードニウム、ビス(5−エチニル−2−チエニル)ヨードニウム、ビス(5−シクロヘキシル−2−フリル)ヨードニウム、ビス(5−ヒドロキシ−2−チエニル)ヨードニウム、ビス(5−フェノキシ−2−フリル)ヨードニウム、ビス(5−メルカプト−2−チエニル)ヨードニウム、ビス(5−ブチルチオ−2−チエニル)ヨードニウム、ビス(5−フェニルチオ−2−チエニル)ヨードニウム等を挙げることができるが、これらに限定されるものではない。
ジフェニルヨードニウム、ビス(p−トリル)ヨードニウム、ビス(p−オクチルフェニル)ヨードニウム、ビス(p−オクタデシルフェニル)ヨードニウム、ビス(p−オクチルオキシフェニル)ヨードニウム、ビス(p−オクタデシルオキシフェニル)ヨードニウム、フェニル(p−オクタデシルオキシフェニル)ヨードニウム、4−イソプロピル−4’−メチルジフェニルヨードニウム、(4−イソブチルフェニル)−p−トリルヨードニウム、ビス(1−ナフチル)ヨードニウム、ビス(4−フェニルスルファニルフェニル)ヨードニウム、フェニル(6−ベンゾイル−9−エチル−9H−カルバゾール−3−イル)ヨードニウム、(7−メトキシ−2−オキソ−2H−クロメン−3−イル)−4’−イソプロピルフェニルヨードニウム等を挙げることができるが、これらに限定されるものではない。
分子内に1個以上のエポキシ基を有する化合物又は分子内に2個以上のエポキシ基を有する高分子(エポキシ樹脂)を用いる場合は、エポキシ基との反応性を有する官能基を分子内に二つ以上有する化合物を併用してもよい。ここでエポキシ基との反応性を有する官能基とは、例えば、カルボキシル基、フェノール性水酸基、メルカプト基、1級又は2級の芳香族アミノ基等が挙げられる。これらの官能基は、3次元硬化性を考慮して、一分子中に2つ以上有することが特に好ましい。
分子内にアルコキシル基を有する化合物としては、分子内に1個以上のアルコキシル基を有するものであれば特に制限なく、公知のものを使用できる。このような化合物としては、メラミン化合物、アミノ樹脂、シランカップリング剤などが代表として挙げられる。なお、接着剤層のガラス転移温度Tgを計算する際には、アルコキシル基を有する化合物及び高分子(H)を計算には入れないこととする。
活性エネルギー線として、紫外線(ガリウム封入メタルハライドランプ) 照射装置:Fusion UV Systems,Inc社製Light HAMMER10 バルブ:Vバルブ ピーク照度:1600mW/cm2、積算照射量1000/mJ/cm2(波長380〜440nm)を使用した。なお、紫外線の照度は、Solatell社製Sola−Checkシステムを使用して測定した。
フィルム基材、接着剤層の膜厚は、膜厚計(Peacock社製のデジタルダイアルゲージDG‐205)を用いて測定した。なお、直接厚みを計測することが困難な層の場合は、各層を設けた基材の総厚みを測定し、基材の厚みを差し引くことで各層の膜厚を算出した。
表2に記載の配合表に従い、各成分を混合して50℃で1時間撹拌し、活性エネルギー線硬化型接着剤組成物を得た。表中の数値は組成物全量を100重量%としたときの重量%を示す。使用した各成分は以下のとおりである。
(2)ラジカル重合性化合物(B):ARONIX M−220(トリプロピレングリコールジアクリレート)、SP値19.0、東亞合成社製;
ラジカル重合性化合物(B):ライトアクリレートDCP−A(ジメチロール−トリシクロデカンジアクリレート)、SP値20.3、共栄社化学社製;
(3)ラジカル重合性化合物(C):ACMO(アクリロイルモルホリン)、SP値22.9、興人社製;
ラジカル重合性化合物(C):IB‐XA(イソボニルアクリレート)、SP値22.4、共栄社化学社製;
(4)(メタ)アクリルモノマーを重合してなるアクリル系オリゴマー(D):ARUFON UP−1190、東亞合成社製;
(5)ラジカル重合性化合物(E):2HEA(2−ヒドロキシエチルアクリレート)、SP値25.5、三菱レイヨン社製;
(6)光重合開始剤:KAYACURE DETX−S(ジエチルチオキサントン),日本化薬社製、IRGACURE907(2−メチル−1−(4−メチルチオフェニル)−2−モルフォリノプロパン−1−オン),BASF社製。
(7)活性メチレン基を有するラジカル重合性化合物(F)
AAEM(2−アセトアセトキシエチルメタクリレート)、SP値 20.23(MJ/M3)1/2、ホモポリマーのTg 9℃、日本合成化学社製
(8)水素引き抜き作用のあるラジカル重合開始剤(G)
KAYACURE DETX−S(DETX−S)(ジエチルチオキサントン)、日本化薬社製
(9)光重合開始剤(一般式(2)で表される化合物))
IRGACURE907(IRG907)(2−メチル−1−(4−メチルチオフェニル)−2−モルフォリノプロパン−1−オン)、BASF社製
(10)光酸発生剤(H)
CPI−100P(トリアリールスルホニウムヘキサフルオロホスフェートを主成分とする有効成分50%のプロピレンカーボネート溶液)、サンアプロ社製
(11)アルコキシ基、エポキシ基いずれかを含む化合物(I)
デナコールEX−611(ソルビトールポリグリシジルエーテル)、ナガセケムテックス社製
ニカレジンS−260(メチロール化メラミン)、 日本カーバイト工業社製
KBM−5103(3−アクリロキシプロピルトリメトキシシラン)、信越化学工業社製
(12)アミノ基を有するシランカップリング剤(J)
KBM−603(γ−(2−アミノエチル)アミノプロピルトリメトキシシラン)、信越化学工業社製
KBM−602(γ−(2−アミノエチル)アミノプロピルメチルジメトキシシラン)、信越化学工業社製
KBE−9103 3−トリエトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン、信越化学工業社製
(第1透明導電層の形成)
厚さは25μmのポリエンレンテレフタレートフィルム(第1フィルム基材)の片面に、酸化インジウム97重量%、酸化スズ3重量%のインジウムスズ酸化物の焼結体ターゲットを備えたスパッタ装置を用いて、厚さは22nmのインジウムスズ酸化物(ITO)層を形成した。
た。
次に、ポリエチレンテレフタレートフィルム(第1フィルム基材)の、インジウムスズ酸化物層の反対側の面に、MCDコーター(富士機械社製,セル形状:ハニカム,グラビアロール線数:300本/inch,回転速度150%/対ライン速)を用いて、表2に示す配合で調製した活性エネルギー線硬化型接着剤組成物を塗布して、厚み1μmの透明未硬化接着剤層を形成した。次いで、当該未硬化接着剤層に、厚さ100μmのポリエチレンテレフタレートフィルム(第2フィルム基材)を貼り合わせた。その後、第2フィルム基材の側から、照射装置:Fusion UV Systems,Inc社製Light HAMMER10 バルブ:Vバルブ ピーク照度:1600mW/cm2、積算照射量1000/mJ/cm2(波長380〜440nm)を照射して、前記接着剤層を硬化させて、透明導電性積層フィルムを得た。
実施例1において、第1フィルム基材、第2フィルム基材の厚み、活性エネルギー線硬化型接着剤組成物の配合割合、接着剤層の厚みを表2,3に示すように変えたこと以外は実施例1と同様にして、透明導電性積層フィルムを作製した。なお、実施例9では、第2フィルム基材についても、第1フィルム基材と同様にして、厚さ22nmの第2透明導電層を形成したものを用いた。透明導電性積層フィルムの作製にあたっては、第2フィルム基材は、第2透明導電層を形成した反対側を、未硬化接着剤層に貼り合わせた。
実施例及び比較例で得られた透明導電性積層フィルムについて、下記評価を行なった。結果を表2,3に示す。表2,3には、フィルム基材、接着剤層の厚みを併せて示す。
貯蔵弾性率は、TAインスツルメンツ製動的粘弾性測定装置RSAIIIを用い以下の測定条件で測定した。
サンプルサイズ:幅10mm、長さ30mm、
クランプ距離20mm、
測定モード:引っ張り、周波数:1Hz、昇温速度:5℃/分
動的粘弾性の測定を行い、貯蔵弾性率の140℃での測定値とした。
透明導電性積層フィルムにおける第1フィルム基材の延伸方向と平行に200mm、直行方向に20mmの大きさに切り出した。次いで、切り出した透明導電性フィルムの第1フィルム基材と第2フィルム基材の間にカッターナイフで切り込みを入れた。
テンシロンにより、第1フィルムと第2フィルムとを剥離速度300mm/minでT字剥離し、その剥離強度を測定した。また、剥離後の剥離面の赤外吸収スペクトルをATR法によって測定し、剥離界面を下記の基準に基づき評価した。
A:フィルムの凝集破壊
B:フィルム/接着剤層間の界面剥離
上記基準において、Aは、接着力がフィルムの凝集力以上であるため、接着力が非常に優れることを意味する。一方、Bは、フィルム/接着剤層の界面の接着力が不足している(接着力が劣る)ことを意味する。これらを勘案して、Aの場合の接着力を○、A・B(「フィルムの凝集破壊」と「フィルム/接着剤層間の界面剥離」とが同時に発生)である場合の接着力を△、Bのみの場合の接着力を×とする。
透明導電性積層フィルムを140℃で90分間加熱処理して、透明導電層(インジウムスズ酸化物層)を結晶化させた。その後、透明導電体層を50℃の10%塩酸水溶液に10分間浸漬して透明導電体層を除去した際の透明導電性積層フィルム端部のハガレ、浮きを目視で評価した。
○;ハガレ、浮きなし
△:1mm未満のハガレ、浮きが発生
×:1mm以上のハガレ、浮きが発生
透明導電性積層フィルムを140℃で90分間加熱処理して、透明導電層(インジウムスズ酸化物層)を結晶化させた。その後、第1透明導電層(第1フィルム基材側)の表面に所望のパターンフォトレジストを形成した。次いで、第1透明導電体層を50℃の10%塩酸水溶液に10分間浸漬して不要な第1透明導電体層を除去した。次いで、140℃で30分間乾燥させて、ストライプ状の透明電極パターンを形成した(エッチング工程)。得られた透明導電性積層フィルムにおける透明電極パターンのある部分とない部分のうねり(高低差:μm)を評価した。うねりは(高低差:μm)は光学式プロファイロメーター(Veeco Instruments社製のOptical Profilometer NT3000)を用いて測定した。
10cm×10cmの大きさに切り出し、四隅に印をつけた透明導電性積層フィルムを、140℃で90分間加熱処理して透明導電層(インジウムスズ酸化物層)を結晶化させた。その後、透明導電層(第1透明導電層,但し実施例9では両側の第1および第2透明導電層)の全面をポリイミドテープで覆ったサンプル1とポリイミドテープで全く覆わないサンプル2を作成した。
次に、サンプル1とサンプル2を10%塩酸に浸漬した。サンプル2からは透明導電層を除去した(これが、積層フィルムA´に対応)。サンプル1では、浸漬後に、ポリイミドテープを剥離した(これが、透明導電性積層フィルムAに対応)。その時のサンプル1とサンプル2の正確な大きさを測定した(処理前)。次いで、サンプル1とサンプル2を、140℃で30分間乾燥させてから、再度、サンプル1とサンプル2の大きさを測定した(処理後)。
収縮率は、前記処理前と処理後の大きさから、下記式により求めた。
収縮率(%)={(処理前の大きさ−処理後の大きさ)/(処理前の大きさ)}×100
収縮率差は、サンプル1の収縮率−サンプル2の収縮率、である。
各サンプル1、2の大きさの測定は画像測定機クイックビジョン(ミツトヨ社製)を用いて測定した。
12 第2フィルム基材
13 第3フィルム基材
21 第1透明導電層
22 第2透明導電層
3 透明硬化接着剤層
A 透明導電性積層フィルム
A´ 積層フィルム
Claims (30)
- 透明な第1フィルム基材と透明な第2フィルム基材を有する複数の透明なフィルム基材が、140℃における貯蔵弾性率が1×107Pa以上である透明硬化接着剤層を介して積層されている積層フィルムと、
前記第1フィルム基材の、前記透明硬化接着剤層とは反対の面に積層された第1透明導電層とを有することを特徴とする透明導電性積層フィルム。 - 前記透明導電性積層フィルムと、前記積層フィルムとは、140℃で30分間加熱処理した際の収縮率の差が0.3%以下であることを特徴とする請求項1記載の透明導電性積層フィルム。
- 前記透明硬化接着剤層が、硬化性成分としてのラジカル重合性化合物(A)、(B)および(C)を含有する活性エネルギー線硬化型接着剤組成物から形成されていて、
前記ラジカル重合性化合物(A)は、SP値が29.0(MJ/m3)1/2以上32.0以下(MJ/m3)1/2であり、
前記ラジカル重合性化合物(B)は、SP値が18.0(MJ/m3)1/2以上21.0(MJ/m3)1/2未満であり、
前記ラジカル重合性化合物(C)は、SP値が21.0(MJ/m3)1/2以上23.0(MJ/m3)1/2以下であり、
組成物全量を100重量%としたとき、前記ラジカル重合性化合物(B)を25〜80重量%含有することを特徴とする請求項1または2記載の透明導電性積層フィルム。 - 前記活性エネルギー線硬化型接着剤組成物は、さらに、(メタ)アクリルモノマーを重合してなるアクリル系オリゴマー(D)を含有することを特徴とする請求項3記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物は、組成物全量を100重量%としたとき、(メタ)アクリルモノマーを重合してなるアクリル系オリゴマー(D)を20重量%以下の範囲で含有することを特徴とする請求項4記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物は、組成物全量を100重量%としたとき、前記ラジカル重合性化合物(A)を3〜40重量%、前記ラジカル重合性化合物(C)を5〜55重量%含有することを特徴とする請求項3〜5のいずれかに記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物は、前記ラジカル重合性化合物の全量を100重量部としたとき、前記ラジカル重合性化合物(A)、(B)および(C)を合計で85重量部以上含有し、さらにSP値が23.0(MJ/m3)1/2を超えて29.0(MJ/m3)1/2未満であるラジカル重合性化合物(E)を15重量部以下の範囲で含有することを特徴とする請求項3〜6のいずれかに記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物が、活性メチレン基を有するラジカル重合性化合物(F)と、水素引き抜き作用のあるラジカル重合開始剤(G)とを含有する請求項3〜7のいずれかに記載の透明導電性積層フィルム。
- 前記活性メチレン基がアセトアセチル基である請求項8に記載の透明導電性積層フィルム。
- 前記活性メチレン基を有するラジカル重合性化合物(F)が、アセトアセトキシアルキル(メタ)アクリレートである請求項8または9に記載の透明導電性積層フィルム。
- 前記ラジカル重合開始剤(G)が、チオキサントン系ラジカル重合開始剤である請求項8〜10のいずれかに記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物全量を100重量%としたとき、前記活性メチレン基を有するラジカル重合性化合物(F)を1〜50重量%、およびラジカル重合開始剤(G)を0.1〜10重量%含有する請求項8〜11のいずれかに記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物が、光酸発生剤(H)を含有することを特徴とする請求項3〜12のいずれかに記載の透明導電性積層フィルム。
- 光酸発生剤(H)として、PF6 −、SbF6 −およびAsF6 −からなる群より選択される少なくとも1種をカウンターアニオンとして有する光酸発生剤を含有する請求項13に記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物中に光酸発生剤(H)とアルコキシ基、エポキシ基いずれかを含む化合物(I)を併用することを特徴とする請求項3〜14のいずれかに記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物が、アミノ基を有するシランカップリング剤(J)を含有する請求項3〜15のいずれかに記載の透明導電性積層フィルム。
- 前記活性エネルギー線硬化型接着剤組成物全量を100重量%としたとき、アミノ基を有するシランカップリング剤(J)を0.01〜20重量%含有する請求項16の透明導電性積層フィルム。
- 前記第1フィルム基材の厚さが、15μm〜75μmであることを特徴とする請求項1〜17のいずれかに記載の透明導電性積層フィルム。
- 前記透明硬化接着剤層の厚さが0.01μm以上10μm以下であることを特徴とする請求項1〜18のいずれかに記載の透明導電性積層フィルム。
- 前記積層フィルムの第1透明導電層とは反対側の面に第2透明導電層を有することを特徴とする請求項1〜19のいずれかに記載の透明導電性積層フィルム。
- 前記フィルム基材を形成する材料は、ポリエステル樹脂、環状ポリオレフィン樹脂、またはポリカーボネート樹脂のいずれかであることを特徴とする請求項1〜20のいずれかに記載の透明導電性積層フィルム。
- 前記透明導電層を形成する材料は、インジウムスズ酸化物またはインジウム亜鉛酸化物のいずれかであることを特徴とする請求項1〜21いずれかに記載の透明導電性積層フィルム。
- 前記透明導電層が結晶化していることを特徴とする請求項1〜22のいずれかに記載の透明導電性積層フィルム。
- 前記透明導電層がパターニングされていることを特徴とする請求項1〜23のいずれかに記載の透明導電性積層フィルム。
- 請求項1〜24のいずれかに記載の透明導電性積層フィルムを少なくとも1つ備えていることを特徴とするタッチパネル。
- 請求項1〜24のいずれかに記載の透明導電性積層フィルムの製造方法であって、
第1フィルム基材の一方の面に第1透明導電層が設けられた透明導電性フィルムを準備する工程aと、
前記透明導電性フィルムにおける、前記第1透明導電層を有しない前記第1フィルム基材の他方の面と、第2フィルム基材を、硬化によって、140℃における貯蔵弾性率が1×107Pa以上である透明硬化接着剤層を形成することができる、透明未硬化接着剤層により貼り合わせる工程b、および、
前記透明未硬化接着剤層を硬化させる工程cを有することを特徴とする透明導電性積層フィルムの製造方法。 - 工程cの後に、さらに、前記透明導電層を加熱処理して結晶化する工程dを有することを特徴とする請求項26記載の透明導電性積層フィルムの製造方法。
- 工程cの後に、さらに、前記透明導電層をパターニングする工程eを有することを特徴とする請求項26または27記載の透明導電性積層フィルムの製造方法。
- 前記工程cは、活性エネルギー線を前記透明未硬化接着剤層に照射することにより、前記透明未硬化接着剤層を硬化させる工程であり、
前記活性エネルギー線は、波長範囲380〜450nmの可視光線を含むものである請求項26〜28のいずれかに記載の透明導電性積層フィルムの製造方法。 - 前記活性エネルギー線は、波長範囲380〜440nmの積算照度と波長範囲250〜370nmの積算照度との比が100:0〜100:50である請求項29に記載の透明導電性積層フィルムの製造方法。
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