JP2015048394A - 透明導電性フィルム用キャリアフィルム及び積層体 - Google Patents
透明導電性フィルム用キャリアフィルム及び積層体 Download PDFInfo
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- JP2015048394A JP2015048394A JP2013180466A JP2013180466A JP2015048394A JP 2015048394 A JP2015048394 A JP 2015048394A JP 2013180466 A JP2013180466 A JP 2013180466A JP 2013180466 A JP2013180466 A JP 2013180466A JP 2015048394 A JP2015048394 A JP 2015048394A
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- transparent conductive
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Abstract
Description
前記粘着剤層が、
ガラス転移温度が−50℃以下であり、かつ、アルキル(メタ)アクリレート及び水酸基含有モノマーを含むモノマー成分を重合して得られる(メタ)アクリル系ポリマー(A)、
イソシアネート系架橋剤(B)、並びに、
鉄を活性中心とする触媒(C)、を含む粘着剤組成物から形成されたものであることを特徴とする透明導電性フィルム用キャリアフィルム、に関する。
前記透明導電性フィルムの少なくとも片方の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする積層体、に関する。
前記支持体の前記透明導電層と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされているものが挙げられる。
前記機能層の前記支持体と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされているものが挙げられる。
以下、本発明の実施の形態について、図1を用いて詳細に説明する。ただし、本発明は、図1の実施形態に限定されるものではない。
本発明における粘着剤層は、ガラス転移温度が−50℃以下の(メタ)アクリル系ポリマー(A)、イソシアネート系架橋剤(B)、並びに、鉄を活性中心とする触媒(C)、を含む粘着剤組成物から形成されたものである。
(メタ)アクリル系ポリマー(A)は、アルキル(メタ)アクリレート及び水酸基含有モノマーを含むモノマー成分を重合して得られるが、(メタ)アクリル系ポリマー(A)のガラス転移温度(Tg)が−50℃以下になるように調整される。(メタ)アクリル系ポリマー(A)のガラス転移温度は、モノマー成分や組成比を適宜変えることにより、前記範囲内に調整することができる。(メタ)アクリル系ポリマー(A)のガラス転移温度は、ジッピングの発生を抑制する点から、−55℃以下であるのが好ましく、さらには−60℃以下がより好ましく、さらには−65℃以下が好ましい。一方、ガラス転移温度が、低すぎる場合には、凝集力が得られず粘着力が高くなり過ぎたり、糊残りが生じる場合があるため、ガラス転移温度は−100℃以上であるのが好ましい。
イソシアネート系架橋剤(B)としては、イソシアネート基を少なくとも2つ有する化合物を用いることができる。たとえば、一般にウレタン化反応に用いられる公知の脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネートなどが用いられる。
本発明の粘着剤組成物は、鉄を活性中心とする触媒(C)(以下、鉄触媒(C)と称する場合がある)を含む。鉄触媒(C)としては、鉄キレート化合物を好適に用いることができ、たとえば一般式Fe(X)(Y)(Z)として表わすことができる。鉄キレート化合物は(X)(Y)(Z)の組み合わせにより、Fe(X)3、Fe(X)2(Y)、Fe(X)(Y)2、Fe(X)(Y)(Z)のいずれかで表される。鉄キレート化合物Fe(X)(Y)(Z)において(X)(Y)(Z)はそれぞれFeに対する配位子であって、例えば、X、YまたはZがβ−ジケトンの場合、β−ジケトンとして、アセチルアセトン、ヘキサン−2,4−ジオン、ヘプタン−2,4−ジオン、ヘプタン−3,5−ジオン、5−メチル−ヘキサン−2,4−ジオン、オクタン−2,4−ジオン、6−メチルヘプタン−2,4−ジオン、2,6−ジメチルヘプタンー3,5−ジオン、ノナン−2,4−ジオン、ノナン−4,6−ジオン、2,2,6,6−テトラメチルヘプタン−3,5−ジオン、トリデカン−6,8−ジオン、1−フェニル−ブタン−1,3−ジオン、ヘキサフルオロアセチルアセトン、アスコルビン酸等があげられる。
本発明の粘着剤組成物は、ケト−エノール互変異性を起こす化合物(D)(以下、ケト−エノール互変異性化合物(D)と称する場合がある)を含むことができる。カルボキシル基を有する(メタ)アクリル系ポリマーを用いると、鉄の触媒(C)の機能を低下させ、架橋反応を速やかに完了させることができない場合がある。ケト−エノール互変異性化合物(D)は、前記(メタ)アクリル系ポリマー(A)を形成するモノマー成分が、カルボキシル基含有モノマーを含む場合に好適である。
アセチルアセトン、ヘキサン−2,4−ジオン、ヘプタン−2,4−ジオン、ヘプタン−3,5−ジオン、5−メチル−ヘキサン−2,4−ジオン、オクタン−2,4−ジオン、6−メチルヘプタン−2,4−ジオン、2,6−ジメチルヘプタンー3,5−ジオン、ノナン−2,4−ジオン、ノナン−4,6−ジオン、2,2,6,6−テトラメチルヘプタン−3,5−ジオン、トリデカン−6,8−ジオン、1−フェニル−ブタン−1,3−ジオン、ヘキサフルオロアセチルアセトン、アスコルビン酸等のβ−ジケトン類;
無水酢酸等の酸無水物;
アセトン、メチルエチルケトン、メチル−n−ブチルケトン、メチルイソブチルケトン、メチル−tert−ブチルケトン、メチルフェニルケトン、シクロヘキサノン等のケトン類;等をあげることが出来る。これらの化合物の中でも、カルボキシル基による触媒機能の失活を防止する効果が高いβ−ジケトン類を用いることが好ましく、その中でもアセチルアセトンがより好ましい。
本発明の透明導電性フィルム用キャリアフィルムを構成する支持体(基材)(図1中の4)として、特に制限されないが、例えば、紙などの紙系支持体;布、不織布、ネットなどの繊維系支持体(その原料としては、特に制限されず、例えば、マニラ麻、レーヨン、ポリエステル、パルプ繊維などを適宜選択することができる);金属箔、金属板などの金属系支持体;プラスチックのフィルムやシートなどのプラスチック系支持体;ゴムシートなどのゴム系支持体;発泡シートなどの発泡体や、これらの積層体(例えば、プラスチック系支持体と他の支持体との積層体や、プラスチックフィルム(又はシート)同士の積層体など)等の適宜な薄葉体を用いることができる。
透明導電性フィルム(薄層基材)1は、図1に示すように、透明導電層1aと支持体1bを有するフィルムを挙げることができる。
また、本発明は、透明導電性フィルム用キャリアフィルムと、前記透明導電性フィルム用キャリアフィルムに積層された透明導電性フィルムを有する積層体であって、
前記透明導電性フィルム用キャリアフィルムが本明細書に記載された透明導電性フィルム用キャリアフィルムであり、
前記透明導電性フィルムは透明導電層及び支持体を有し、
前記支持体の前記透明導電層と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする積層体に関する。
前記透明導電性フィルム用キャリアフィルムが本明細書に記載された透明導電性フィルム用キャリアフィルムであり、
前記透明導電性フィルムは透明導電層及び支持体を有し、さらに前記支持体の前記透明導電層と接触する面とは反対側の表面に機能層を有しており、
前記機能層の前記支持体と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする積層体に関する。
については、前述のものを挙げることができる。
<アクリル系ポリマー(A)の調整>
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つロフラスコに、2−エチルヘキシルアクリレート(2EHA)100重量部、4−ヒドロキシブチルアクリレート(HBA)10重量部、重合開始剤として2,2’−アゾビスイソブチロニトリル0.2重量部、酢酸エチル205重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を63℃付近に保って約4時間重合反応を行い、アクリル系ポリマー(A1)溶液(約35重量%)を調製した。前記アクリル系ポリマー(A1)の重量平均分子量は60万であり、Tgは−67℃であった。
上記アクリル系ポリマー(A1)溶液(約35重量%)を酢酸エチルで29重量%に希釈し、この溶液のアクリル系ポリマー100重量部(固形分)に対して、トリメチロールプロパン/トリレンジイソシアネート3量体付加物(日本ポリウレタン工業社製,商品名「コロネートL」)4重量部、鉄触媒としてトリス(アセチルアセトナート)鉄(日本化学産業社製,商品名「ナーセム第二鉄」)0.01重量部、ケト−エノール互変異性を起こす化合物としてアセチルアセトン0.69重量部を加えて、25℃付近に保って約1分間混合撹拌を行い、アクリル系粘着剤組成物(1)を調製した。
上記アクリル系粘着剤組成物(1)を、ポリエチレンテレフタレート(PET)基材(厚さ125μm、支持体)の片面に塗布し、150℃で90秒間加熱して、厚さ20μmの粘着剤層を形成した。次いで、前記粘着剤層の表面に、片面にシリコーン処理を施したPET剥離ライナー(厚さ25μm)のシリコーン処理面を貼り合せ、50℃で2日間保存して、透明導電性フィルム用キャリアフィルムを作製した。なお、使用時には、前記剥離ライナーは除去して使用した。
表1及び表2に示すように、アクリル系ポリマーを構成するモノマー成分や、粘着剤組成物を構成する架橋剤、触媒、ケト−エノール互変異性化合物の種類または配合量を変更した以外は、実施例1と同様の方法にて、透明導電性フィルム用キャリアフィルムを作製した。
作製したポリマーの重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグ
ラフィー)により測定した。
カラム:
サンプルカラム;東ソー社製、TSKguardcolumn Super HZ−H
(1本)+TSKgel Super HZM−H(2本)
リファレンスカラム;東ソー社製、TSKgel Super H−RC(1本)
流量:0.6ml/min
注入量:10μl
カラム温度:40℃
溶離液:THF
注入試料濃度:0.2重量%
検出器:示差屈折計
なお、重量平均分子量はポリスチレン換算により算出した。
ガラス転移温度(Tg)(℃)は、各モノマーによるホモポリマーのガラス転移温度Tgn(℃)として下記の文献値を用い、下記の式により求めた。
(式中、Tg(℃)は共重合体のガラス転移温度、Wn(−)は各モノマーの重量分率、Tgn(℃)は各モノマーによるホモポリマーのガラス転移温度、nは各モノマーの種類を表す。)
2−エチルヘキシルアクリレート(2EHA):−70℃
イソノニルアクリレート(i−NA):−58℃
ブチルアクリレート(BA):−55℃
エチルアクリレート(EA):−20℃
4−ヒドロキシブチルアクリレート(HBA):−32℃
2−ヒドロキシエチルアクリレート(HEA):−15℃
2−ヒドロキシエチルメタリレート(HEMA):55℃
アクリル酸:106℃
なお、文献値として「アクリル樹脂の合成・設計と新用途開発」(中央経営開発センター出版部発行)を参照した。
HCフィルム((株)きもと製、KBフィルムG01、PETフィルム上にハードコート層を有するフィルム)の「HC面:ハードコート面」に、透明導電性フィルム用キャリアフィルムの粘着剤層の「粘着面」を貼り合せた(貼り合わせ機にて圧着:0.25MPa、圧着速度2.0m/min)。次いで、140℃で90分間加熱し、その後30分以上、常温(25℃)で放置した後、前記透明導電性フィルム用キャリアフィルムを、前記HCフィルムから剥離した。
前記HCフィルムのHC面を、蛍光灯下で目視し、前記AR面に凹凸が存在するか否かを、下記の基準で確認した。
HC面に凹凸がまったく確認されなかった場合:◎
HC面に凹凸がほとんど確認されなかった場合:○
HC面に凹凸がはっきりと確認された場合:×
被着体として、SUS板(SUS430BA)に固定された幅50mm、長さ100mmのHCフィルム((株)きもと製、KBフィルムG01、PETフィルム上にハードコート層を有するフィルム)の「HC面:ハードコート面」に、透明導電性フィルム用キャリアフィルムの粘着剤層の「粘着面」を貼り合せた(貼り合わせ機にて圧着:0.25MPa、圧着速度2.0m/min)。次いで、140℃で90分間加熱し、その後30分以上、常温(25℃)で放置した後、同環境下で万能引張試験機を用いて、剥離速度0.3m/min、剥離角度180°の条件でHCフィルムから透明導電性フィルム用キャリアフィルムを80mm剥離し、このときの剥離力(N/50mm)を測定した。
上記剥離力の後半60mm分の測定データを用いて、下記の式によりジッピングの有無を判断した。
ΔF/F(Ave)<15%:ジッピングが発生しない(○)
ΔF/F(Ave)>15%:ジッピングが発生する(×)
F(Ave):平均剥離力
F(Max):最大剥離力
F(Min):最小剥離力
ΔF:F(Max)−F(Min)
被着体として、SUS板(SUS430BA)に固定された幅50mm、長さ100mmの透明導電性フィルム(日東電工(株)製、エレクリスタV150M-OFAD2,PETフィルムの片面に透明導電層を有し、他の片面に機能層を有するフィルム)の「機能層面」に、透明導電性フィルム用キャリアフィルムの粘着剤層の「粘着面」を貼り合せた(貼り合わせ機にて圧着:0.25MPa、圧着速度2.0m/min)。次いで、140℃で90分間加熱し、その後30分以上、常温(25℃)で放置した後、同環境下で万能引張試験機を用いて、剥離速度0.3m/min(低速剥離)、及び、10m/min(高速剥離)、剥離角度180°の条件で透明導電性フィルムから透明導電性フィルム用キャリアフィルムを剥離し、このときの剥離力(N/50mm)を測定した。
下記に示す範囲により剥離力を評価した。
0.2N以上〜1.0N未満/50mm:さらに好ましい範囲(◎)
1.0N以上〜3.0N未満/50mm:好ましい範囲(○)
3.0N以上/50mm:好ましくない範囲(×)
C/L:イソシアネート系架橋剤(トリメチロールプロパン/トリレンジイソシアネート3量体付加物,日本ポリウレタン工業社製,商品名「コロネートL」);
C/HX:イソシアネート系架橋剤(ヘキサメチレンジイソシアネートのイソシアヌレート体,日本ポリウレタン工業社製,商品名「コロネートHX」);
MR−400:イソシアネート系架橋剤(ポリメリックMDI(ポリメチレンポリフェニルポリイソシアネート),日本ポリウレタン工業社製,商品名「ミリオネートMR−400」);
タケネート500:イソシアネート系架橋剤(1,3−ビスイソシアネートメチルベンゼン,三井化学社製,商品名「タケネート500」);
T/C:エポキシ系架橋剤(三菱ガス化学社製,TETRAD−C);を示す。
触媒は、
鉄触媒:トリス(アセチルアセトナート)鉄(日本化学産業社製,商品名「ナーセム第二鉄」);
スズ触媒:ジオクチルスズジラウレート(東京ファインケミカル社製、商品名「エンビライザー OL−1」)、を示す。
ケト−エノール互変異性を起こす化合物は、アセチルアセトンを示す。
1b 支持体(基材)
1 透明導電性フィルム
2 機能層
3 粘着剤層
4 支持体(基材)
10 機能層付き透明導電性フィルム
20 機能層付き透明導電性フィルム用キャリアフィルム
A 支持体と接触する面と反対側の粘着面
Claims (13)
- 支持体の少なくとも片面に粘着剤層を有する透明導電性フィルム用キャリアフィルムであって、
前記粘着剤層が、
ガラス転移温度が−50℃以下であり、かつ、アルキル(メタ)アクリレート及び水酸基含有モノマーを含むモノマー成分を重合して得られる(メタ)アクリル系ポリマー(A)、
イソシアネート系架橋剤(B)、並びに、
鉄を活性中心とする触媒(C)、を含む粘着剤組成物から形成されたものであることを特徴とする透明導電性フィルム用キャリアフィルム。 - 前記(メタ)アクリル系ポリマー(A)を形成するモノマー成分が、モノマー成分全量に対して、アルキル(メタ)アクリレートを65重量%以上、水酸基含有モノマーを1〜25重量%含むことを特徴とする請求項1記載の透明導電性フィルム用キャリアフィルム。
- 前記イソシアネート系架橋剤(B)の配合量が、前記(メタ)アクリル系ポリマー(A)100重量部に対し、1〜30重量部であることを特徴とする請求項1または2記載の透明導電性フィルム用キャリアフィルム。
- 前記鉄を活性中心とする触媒(C)が、鉄キレート化合物であることを特徴とする請求項1〜3のいずれかに記載の透明導電性フィルム用キャリアフィルム。
- 前記鉄を活性中心とする触媒(C)の配合量が、前記(メタ)アクリル系ポリマー(A)100重量部に対し、を0.002〜0.5重量部であることを特徴とする請求項1〜4のいずれかに記載の透明導電性フィルム用キャリアフィルム。
- 前記(メタ)アクリル系ポリマー(A)を形成するモノマー成分が、カルボキシル基含有モノマーを含むことを特徴とする請求項1〜5のいずれかに記載の透明導電性フィルム用キャリアフィルム。
- モノマー成分全量に対して、カルボキシル基含有モノマーを0.005〜5重量%含むことを特徴とする請求項6記載の透明導電性フィルム用キャリアフィルム。
- 前記粘着剤組成物が、ケト−エノール互変異性を起こす化合物(D)を含むことを特徴とする請求項1〜7のいずれかに記載の透明導電性フィルム用キャリアフィルム。
- 前記ケト−エノール互変異性を起こす化合物(D)が、β−ジケトンであることを特徴とする請求項8記載の透明導電性フィルム用キャリアフィルム。
- 前記鉄を活性中心とする触媒(C)に対する前記ケト−エノール互変異性を起こす化合物(D)の重量比(D/C)が3〜70であることを特徴とする請求項9記載の透明導電性フィルム用キャリアフィルム。
- 請求項1〜10のいずれかに記載の透明導電性フィルム用キャリアフィルムと、前記透明導電性フィルム用キャリアフィルムに積層された透明導電性フィルムを有する積層体であって、
前記透明導電性フィルムの少なくとも片方の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする積層体。 - 前記透明導電性フィルムは透明導電層及び支持体を有し、
前記支持体の前記透明導電層と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする請求項11記載の積層体。 - 前記透明導電性フィルムは透明導電層及び支持体を有し、さらに前記支持体の前記透明導電層と接触する面とは反対側の表面に機能層を有しており、
前記機能層の前記支持体と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする請求項11記載の積層体。
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- 2014-08-15 TW TW103128169A patent/TWI631203B/zh active
- 2014-08-18 KR KR1020140106804A patent/KR102249902B1/ko active IP Right Grant
- 2014-08-20 US US14/464,218 patent/US20150064460A1/en not_active Abandoned
- 2014-09-01 CN CN201410440713.XA patent/CN104419342B/zh active Active
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JP2016506439A (ja) * | 2013-11-15 | 2016-03-03 | エルジー・ケム・リミテッド | 粘着剤組成物 |
WO2016175232A1 (ja) * | 2015-04-30 | 2016-11-03 | 日東電工株式会社 | 透明導電性フィルム用キャリアフィルム及び積層体 |
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JP2017043710A (ja) * | 2015-08-27 | 2017-03-02 | 日東電工株式会社 | 粘着剤組成物、粘着剤層、透明導電性フィルム用キャリアフィルム、及び積層体 |
CN109715755A (zh) * | 2016-08-19 | 2019-05-03 | 狮王特殊化学株式会社 | 粘合剂组合物和粘合片材 |
JPWO2018034353A1 (ja) * | 2016-08-19 | 2019-07-11 | ライオン・スペシャリティ・ケミカルズ株式会社 | 粘着剤組成物および粘着シート |
WO2018034353A1 (ja) * | 2016-08-19 | 2018-02-22 | ライオン・スペシャリティ・ケミカルズ株式会社 | 粘着剤組成物および粘着シート |
JP2020500240A (ja) * | 2016-11-04 | 2020-01-09 | エルジー・ケム・リミテッド | 粘着フィルムの製造方法 |
US11091672B2 (en) | 2016-11-04 | 2021-08-17 | Lg Chem, Ltd. | Method for manufacturing pressure-sensitive adhesive film |
JP2020158691A (ja) * | 2019-03-27 | 2020-10-01 | 東洋インキScホールディングス株式会社 | 粘着剤および粘着シート |
JP2021095483A (ja) * | 2019-12-17 | 2021-06-24 | 東洋インキScホールディングス株式会社 | 粘着剤および粘着シート |
JP7338444B2 (ja) | 2019-12-17 | 2023-09-05 | 東洋インキScホールディングス株式会社 | 粘着剤および粘着シート |
Also Published As
Publication number | Publication date |
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JP6126500B2 (ja) | 2017-05-10 |
CN104419342A (zh) | 2015-03-18 |
KR20150026841A (ko) | 2015-03-11 |
TW201518465A (zh) | 2015-05-16 |
KR102249902B1 (ko) | 2021-05-11 |
CN104419342B (zh) | 2019-09-10 |
TWI631203B (zh) | 2018-08-01 |
US20150064460A1 (en) | 2015-03-05 |
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