JP6626200B2 - 粘着剤組成物、粘着剤層、粘着剤層付光学フィルム、画像表示パネル、及び、液晶表示装置 - Google Patents
粘着剤組成物、粘着剤層、粘着剤層付光学フィルム、画像表示パネル、及び、液晶表示装置 Download PDFInfo
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- WFIYFFUAOQKJJS-UHFFFAOYSA-N tetraoctylphosphanium Chemical compound CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC WFIYFFUAOQKJJS-UHFFFAOYSA-N 0.000 description 1
- SJHQBSVHWPFMTC-UHFFFAOYSA-M tetraoctylphosphanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SJHQBSVHWPFMTC-UHFFFAOYSA-M 0.000 description 1
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- OALBNLALZFTITE-UHFFFAOYSA-M tetrapentylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCC[N+](CCCCC)(CCCCC)CCCCC OALBNLALZFTITE-UHFFFAOYSA-M 0.000 description 1
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- RKYSDIOEHLMYRS-UHFFFAOYSA-N triethoxy(hex-5-enyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCC=C RKYSDIOEHLMYRS-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- IQZRBOPLVCXUST-UHFFFAOYSA-M trifluoromethanesulfonate;trimethyl(oxiran-2-ylmethyl)azanium Chemical compound C[N+](C)(C)CC1CO1.[O-]S(=O)(=O)C(F)(F)F IQZRBOPLVCXUST-UHFFFAOYSA-M 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- NRZWQKGABZFFKE-UHFFFAOYSA-N trimethylsulfonium Chemical compound C[S+](C)C NRZWQKGABZFFKE-UHFFFAOYSA-N 0.000 description 1
- LAGQNGWYNLUQRI-UHFFFAOYSA-N trioctylmethylammonium bis(trifluoromethylsulfonyl)imide Chemical compound FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC LAGQNGWYNLUQRI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 108010033683 von Willebrand factor drug combination factor VIII Proteins 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
本発明の画像表示パネル用粘着剤組成物は、モノマー単位として、カルボキシル基含有モノマー、アミノ基含有モノマー、及び、アミド基含有モノマーからなる群より選択される少なくとも1種のモノマーを全モノマー中、1.5重量%以上含有する(メタ)アクリル系ポリマーを含有することを特徴とする。カルボキシル基、アミノ基、及び、アミド基のような極性官能基を含有するモノマーを、モノマー単位として含有する(メタ)アクリル系ポリマーを使用することにより、帯電防止剤(イオン液体)を粘着剤層中に保持しやすくなり、粘着剤層表面への帯電防止剤の偏析を抑制でき、好ましい態様となる。
本発明の画像表示パネル用粘着剤組成物は、イオン液体を含有することを特徴とする。前記イオン液体を帯電防止成分(導電剤、帯電防止剤)として用いることで、粘着特性を損なうことなく、帯電防止効果の高い粘着剤層が得られる。イオン液体を用いることで優れた帯電防止特性が得られる理由の詳細は明らかでないが、イオン液体は、通常の固体のアルカリ金属塩やイオン性固体と比べ、低融点(融点40℃以下)であるため、分子運動が容易であり、優れた帯電防止能が得られるものと考えられる。特に、融点が40℃以下(好ましくは25℃以下)のイオン液体は、湿熱環境下や長期保管で粘着剤中での析出が起こりにくく、優れた外観と安定した帯電防止性が得られる。
本発明の画像表示パネル用粘着剤組成物には、酸化防止剤を含有することも可能である。酸化防止剤を含有することにより、得られる粘着剤層の酸化劣化に伴う(メタ)アクリル系ポリマーの主鎖切断を抑制でき、加熱・加湿環境下でも、低収縮性を維持でき、好ましい態様となる。特に、酸化防止剤を含まず、架橋剤を含む場合と比較しても、加熱・加湿環境下での発泡や剥がれに起因する耐久性にも優れ、有用である。
本発明の画像表示パネル用粘着剤層は、前記画像表示パネル用粘着剤組成物により形成されることが好ましい。前記粘着剤組成物により、前記粘着剤層を形成するにあたっては、架橋剤全体の使用量を調整することとともに、架橋処理温度や架橋処理時間の影響を十分考慮することが好ましい。
前記光学フィルムとしては、液晶表示装置等の画像表示装置の形成に用いられるものが使用され、その種類は特に制限されない。例えば、光学フィルムとしては偏光フィルムが挙げられる。偏光フィルムは偏光子の片面または両面に透明保護フィルムを有するものが一般に用いられる。
アンカー層としては、各種の帯電防止剤組成物から形成することができ、アンカー層を形成する帯電防止剤としては、導電性ポリマーが用いることができる。
表面処理層としては、偏光フィルムの前記アンカー層を設けない側に設けることができる。表面処理層は、偏光フィルムに用いられる透明保護フィルムに設けることができるほか、別途、透明保護フィルムとは別体のものとして設けることもできる。前記表面処理層としては、ハードコート層、防眩処理層、反射防止層、スティッキング防止層などを設けることができる。
本発明の粘着剤層付光学フィルムには、前記の各層の他に、光学フィルム(偏光フィルム)のアンカー層を設ける側の表面に、易接着層を設けたり、コロナ処理、プラズマ処理等の各種易接着処理を施したりすることができる。
一般的に、インセル用液晶セルには、液晶セル上に導電層を有するタイプ(セミインセル型)と導電層を有さないタイプ(フルインセル型)が存在する。セミインセル型は、センサー用兼帯電防止用のパターニングされた導電層(例えば、ITO層)を有するが、フルインセル型は、液晶セル上に導電層がない代わりに、偏光板側(粘着剤層など)に導電層を有することで、帯電防止性に寄与している。本発明は、フルインセル型であり、導電層を有することなく(介することなく)、前記粘着剤層付光学フィルムを有する画像表示パネル(特に、インセル型液晶パネル)であることが好ましい態様である。但し、セミインセル型でも導電層上にオーバーコート層等を有し、帯電防止性の劣るパネルに対しては、好適に用いることができる。
本発明の液晶表示装置は、前記画像表示パネルを有することが好ましい。前記画像表示パネル(特に、インセル型液晶パネル)を用いたタッチセンシング機能を内蔵した液晶表示装置は、照明システムにバックライトあるいは反射板を用いたもの等の液晶表示装置を形成する部材を適宜に用いることができる。特に、本発明の画像表示パネル用粘着剤組成物を用いるため、帯電防止剤(導電剤)による外観不良や耐久性の問題がなく、帯電防止性に優れたものとなる有用である。
(メタ)アクリル系ポリマーの重量平均分子量(Mw)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。
・分析装置:東ソー社製、HLC−8120GPC
・カラム:東ソー社製、G7000HXL+GMHXL+GMHXL
・カラムサイズ:各7.8mmφ×30cm 計90cm
・カラム温度:40℃
・流量:0.8mL/min
・注入量:100μL
・溶離液:テトラヒドロフラン
・検出器:示差屈折計(RI)
・標準試料:ポリスチレン
(偏光フィルムの作製)
厚さ30μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸した。その後、65℃のホウ酸エステル水溶液中で、トータルの延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、厚さ12μmの偏光子を得た。当該偏光子の片面に、けん化処理した厚さ25μmのトリアセチルセルロース(TAC)フィルムを、もう一方の面に、コロナ処理した厚さ13μmのシクロオレフィンポリマー(COP)フィルムを、それぞれ紫外線硬化型アクリル系接着剤により貼り合せて偏光フィルムを作製した。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート80.3部、フェノキシエチルアクリレート16部、N−ビニル−2−ピロリドン(NVP)3部、アクリル酸0.3部、4−ヒドロキシブチルアクリレート0.4部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物(固形分)100部に対して、重合開始剤として2,2’−アゾビスイソブチロニトリル0.1部を酢酸エチル100部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を55℃付近に保って8時間重合反応を行って、重量平均分子量(Mw)150万のアクリル系ポリマーの溶液を調製した。
上記で得られたアクリル系ポリマーの溶液の固形分100部に対して、表1に示す使用量で、導電剤(帯電防止剤)として、イオン液体であるMPP−TFSI(三菱マテリアル電子化成社製のメチルプロピルピロリジニウムビス(トリフルオロメタンスルホニル)イミド)10部を配合し、さらにイソシアネート架橋剤(D160N:三井化学社製のタケネートD−160N、トリメチロールプロパンヘキサメチレンジイソシアネート)0.1部、ベンゾイルパーオキサイド(BPO:日本油脂社製のナイパーBMT)0.3部およびシランカップリング剤(信越化学工業社製:X−41−1810)0.1部を配合して、アクリル系粘着剤組成物溶液を調製した。
次いで、上記アクリル系粘着剤組成物溶液を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(セパレータフィルム:三菱化学ポリエステルフィルム(株)製、MRF38)の片面に、乾燥後の粘着剤層の厚さが20μmになるように塗布し、155℃で1分間乾燥を行い、セパレータフィルムの表面に粘着剤層を形成した。当該粘着剤層は、上記偏光フィルムに転写し、粘着剤層付偏光フィルムを作製した。
実施例1と同様にして、表1に示す配合内容に基づき粘着剤層を作製し、これを用いて粘着剤層付偏光フィルムを作製した。なお、表1中の配合量は全て固形分もしくは有効成分100%の場合を示す。
得られた粘着剤層付偏光フィルムからセパレータフィルムを剥がした後、粘着剤層表面の表面抵抗値を測定した。測定は、三菱化学アナリテック社製MCP−HT450を用いて行った。測定結果は、表2中に記載した。
粘着剤層付偏光フィルムを70mm×120mmにカットし、セパレータフィルムを剥がした後、インセル型液晶セルの視認側に貼り合わせた。
次に、貼り合せた偏光フィルムの短辺側側面部に10mm幅の銀ペーストを偏光フィルム、粘着剤層の各側面部を覆うように塗布し、外部からのアース電極と接続した。
なお、アンカー層を有する場合は、前記銀ペーストを偏光フィルム、アンカー層、粘着剤層の各側面部を覆うように塗布した。
前記液晶表示パネルをバックライト装置上にセットし、視認側の偏光フィルム面に静電気放電銃(Electrostatic discharge Gun)を印加電圧9kVにて発射して、電気により白ヌケした部分が消失するまでの時間を測定した。
なお、白ヌケが消失するまでの時間は短ければ短いほどよく、本構成とサイズでの評価において、実用レベルは3s以下であり、2s以下が好ましく、1s以下がより好ましく、0.1s以下が更に好ましい。
得られた粘着剤層付偏光フィルムを室温(23℃65%Rh)で、1週間放置した後、粘着剤層の外観を目視および光学顕微鏡にて、導電剤成分由来の析出物の有無を確認した。
(評価基準)
○:析出物が無く、外観良好である場合。
析出×:導電剤成分由来の析出物が確認される場合。
得られた粘着剤層付偏光フィルムを60℃95%Rhの雰囲気下で、120時間投入し、室温に取り出して、10分後にヘイズを測定した。
(評価基準)
◎:ヘイズ5以下、良好
○:ヘイズ5〜10、実用上問題のないレベル
×:ヘイズ10以上、実用上問題のあるレベル
粘着剤層付偏光フィルムを15インチサイズに切断したものをサンプルとした。当該サンプルを、厚さ0.7mmの無アルカリガラス(コーニング社製、EG−XG)にラミネーターを用いて貼着した。
次いで、50℃、0.5MPaで15分間オートクレーブ処理して、上記サンプルを完全に無アルカリルガラスに密着させた。かかる処理の施されたサンプルに、60℃95%RHの雰囲気下で500時間処理を施した後、偏光フィルムと無アルカリガラスの間の外観を下記基準で目視にて評価した。
(評価基準)
○:発泡、剥がれ等の外観上の変化なし。
△:端部に剥がれ、または発泡があるが、特別な用途でなければ、実用上問題なし。
×:端部に著しい剥がれあり、実用上問題あり。
サンプルを、幅25mm×長さ100mmに裁断し、厚さ0.7mmの無アルカリガラス板(コーニング社製、EG−XG)に、ラミネーターを用いて貼り付け、次いで50℃、5atmで15分間オートクレーブ処理して完全に密着させた。その後、サンプルを引張り試験機(オートグラフSHIMAZU AG-1 10KN)にて、剥離角度90°、剥離速度300mm/minで引き剥がす際の接着力(N/25mm)を測定した。測定は、1回/0.5sの間隔でサンプリングし、その平均値を測定値とした。
BA:ブチルアクリレート
PEA:フェノキシエチルアクリレート
NVP:N−ビニル−ピロリドン
AA:アクリル酸
HBA:4−ヒドロキシブチルアクリレート
D160N:トリメチロールプロパンのヘキサメチレンジイソシアネートのアダクト体(三井化学社製、タケネートD160N)、イソシアネート系架橋剤
CL:トリメチロールプロパンのトリレンジイソシアネートのアダクト体(日本ポリウレタン工業社製、コロネートL)、イソシアネート系架橋剤
BPO:ベンゾイルパーオキサイド(日本油脂社製、ナイパーBMT)、過酸化物系架橋剤
MPP−TFSI:メチルプロピルピロリジニウムビス(トリフルオロメタンスルホニル)イミド(三菱マテリアル社製)、イオン液体
EMI−TFSI:1−エチル−3−メチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド(第一工業製薬社製)、イオン液体
MOPy−FSI:1-オクチル-4-メチルピリジニウムビス(フルオロスルホニル)イミド(第一工業製薬社製)、イオン液体
EMI−FSI:1−エチル−3−メチルイミダゾリウムビス(フルオロスルホニル)イミド(第一工業製薬社製)、イオン液体
Li−TFSI:ビス(トリフルオロメタンスルホニル)イミドリチウム(東京化成工業社製)、アルカリ金属塩
EMP−TFSI:1−エチル−1−メチルピロリジニウムビス(トリフルオロメタンスルホニル)イミド(三菱マテリアル社製)、イオン性固体
X−41−1810:チオール基含有オリゴマー型シランカップリング剤(信越化学工業社製)
A100:アセトアセチル基含有シランカップリング剤(綜研化学社製、A−100)
KBM403:エポキシ基含有シランカップリング剤(信越化学工業社製)
Irganox1010:酸化防止剤(BASF社製)
2 光学フィルム(偏光フィルム)
3 アンカー層
4 粘着剤層
5 画像表示パネル(インセル型液晶パネル)
6 導通構造(導電性ペースト)
10 粘着剤層付偏光フィルム
20 画像表示パネル(インセル型液晶パネル)
Claims (9)
- モノマー単位として、アミド基含有モノマーを含み、
前記アミド基含有モノマーが、N−ビニル基含有ラクタム系モノマーであり、
前記アミド基含有モノマーを全モノマー中、1.5重量%以上含有する(メタ)アクリル系ポリマー、及び、イオン液体を含有し、
前記イオン液体が、ビス(フルオロスルホニル)イミドアニオンから構成されることを特徴とする画像表示パネル用粘着剤組成物。 - 前記(メタ)アクリル系ポリマーが、モノマー単位として、カルボキシル基含有モノマー、及び/又は、アミノ基含有モノマーを含有することを特徴とする請求項1に記載の画像表示パネル用粘着剤組成物。
- 前記イオン液体が、有機カチオンから構成されることを特徴とする請求項1又は2に記載の画像表示パネル用粘着剤組成物。
- 前記(メタ)アクリル系ポリマー100重量部に対して、前記イオン液体を1.5〜20重量部含有することを特徴とする請求項1〜3のいずれかに記載の画像表示パネル用粘着剤組成物。
- 架橋剤を含有し、
前記架橋剤が、イソシアネート系架橋剤及び過酸化物系架橋剤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画像表示パネル用粘着剤組成物。 - 請求項1〜5のいずれかに記載の画像表示パネル用粘着剤組成物により形成されることを特徴とする画像表示パネル用粘着剤層。
- 光学フィルムの少なくとも片側に、請求項6に記載の画像表示パネル用粘着剤層が形成されていることを特徴とする粘着剤層付光学フィルム。
- 請求項7に記載の粘着剤層付光学フィルムが、前記粘着剤層と接する画像表示パネルの表面に、導電層を介することなく貼付されていることを特徴とする画像表示パネル。
- 請求項8に記載の画像表示パネルを有することを特徴とする液晶表示装置。
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KR101721397B1 (ko) | 2015-04-10 | 2017-03-29 | 닛폰고세이가가쿠고교 가부시키가이샤 | 점착제 조성물, 및 이를 포함하는 점착제 및 편광판용 점착제 |
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JPWO2018008712A1 (ja) | 2019-04-25 |
JP6820397B2 (ja) | 2021-01-27 |
US11008485B2 (en) | 2021-05-18 |
KR20190028458A (ko) | 2019-03-18 |
US20190338167A1 (en) | 2019-11-07 |
JP2020050879A (ja) | 2020-04-02 |
CN109415610B (zh) | 2021-04-09 |
US20210284875A1 (en) | 2021-09-16 |
CN109415610A (zh) | 2019-03-01 |
KR102314549B1 (ko) | 2021-10-19 |
TW201821573A (zh) | 2018-06-16 |
TWI735614B (zh) | 2021-08-11 |
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