JP2018184598A - セパレータ付き粘着剤層、その製造方法およびセパレータ付きの粘着剤層付き光学フィルム - Google Patents
セパレータ付き粘着剤層、その製造方法およびセパレータ付きの粘着剤層付き光学フィルム Download PDFInfo
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- JP2018184598A JP2018184598A JP2018100303A JP2018100303A JP2018184598A JP 2018184598 A JP2018184598 A JP 2018184598A JP 2018100303 A JP2018100303 A JP 2018100303A JP 2018100303 A JP2018100303 A JP 2018100303A JP 2018184598 A JP2018184598 A JP 2018184598A
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- separator
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- sensitive adhesive
- pressure
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- 229960005055 sodium ascorbate Drugs 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- PHBSBOANHONSDB-UHFFFAOYSA-N triethoxy(7-oxabicyclo[4.1.0]heptan-5-yl)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCC2OC12 PHBSBOANHONSDB-UHFFFAOYSA-N 0.000 description 1
- 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
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
また、粘着剤層付き偏光フィルムとして、偏光フィルムと粘着剤層の間に導電性ポリマーにより帯電防止層を設けること提案されている(特許文献3)。
前記セパレータは、基材フィルムに、オリゴマー防止層、離型層がこの順で設けられており、かつ、前記離型層は表面抵抗値が1.0×1013Ω/□以上であり、
前記粘着剤層は、ベースポリマーおよびイオン性化合物を含有する粘着剤組成物から形成されており、前記セパレータの離型層に設けられていることを特徴とするセパレータ付き粘着剤層、に関する。
基材フィルムに、オリゴマー防止層、離型層がこの順で設けられており、かつ、前記離型層は表面抵抗値が1.0×1013Ω/□以上のセパレータの当該離型層に、ベースポリマーおよびイオン性化合物を含有する粘着剤組成物の溶液を塗布する工程、および、
前記塗布された粘着剤組成物の溶液を、140℃以上の温度で加熱する工程、
を有することを特徴とするセパレータ付き粘着剤層の製造方法、に関する。
前記セパレータ付き粘着剤層が貼り合わせていることを特徴とする、セパレータ付きの粘着剤層付き光学フィルム、に関する。
Y−R−Si−(X)3 ……(III)
(上記一般式(III)中、Yはアミノ基、Rはメチレン、エチレン、プロピレン等のアルキレン基、Xはメトキシ基、エトキシ基等のアルコキシ基、アルキル基、またはこれらの基を有する有機官能基を表す)。
アルカリ金属塩のカチオン部を構成するアルカリ金属イオンとしては、リチウム、ナトリウム、カリウムの各イオンが挙げられる。これらアルカリ金属イオンのなかでもリチウムイオンが好ましい。
(1):(CnF2n+1SO2)2N− (但し、nは1〜10の整数)、
(2):CF2(CmF2mSO2)2N− (但し、mは1〜10の整数)、
(3):−O3S(CF2)lSO3 − (但し、lは1〜10の整数)、
(4):(CpF2p+1SO2)N−(CqF2q+1SO2)、(但し、p、qは1〜10の整数)、で表わされるものなどが用いられる。特に、フッ素原子を含むアニオン部は、イオン解離性の良いイオン化合物が得られることから好ましく用いられる。無機塩を構成するアニオン部としては、Cl−、Br−、I−、AlCl4 −、Al2Cl7 −、BF4 −、PF6 −、ClO4 −、NO3 −、AsF6 −、SbF6 −、NbF6 −、TaF6 −、(CN)2N−、などが用いられる。アニオン部としては、(CF3SO2)2N−、(C2F5SO2)2N−、等の前記一般式(1)で表わされる、(ペルフルオロアルキルスルホニル)イミドが好ましく、特に(CF3SO2)2N−、で表わされる(トリフルオロメタンスルホニル)イミドが好ましい。
本発明で用いられる有機カチオン−アニオン塩は、カチオン成分とアニオン成分とから構成されており、前記カチオン成分は有機物からなるものである。カチオン成分として、具体的には、ピリジニウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、ピロリン骨格を有するカチオン、ピロール骨格を有するカチオン、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオンなどが挙げられる。
(1):(CnF2n+1SO2)2N− (但し、nは1〜10の整数)、
(2):CF2(CmF2mSO2)2N− (但し、mは1〜10の整数)、
(3):−O3S(CF2)lSO3 − (但し、lは1〜10の整数)、
(4):(CpF2p+1SO2)N−(CqF2q+1SO2)、(但し、p、qは1〜10の整数)、で表わされるものなどが用いられる。なかでも特に、フッ素原子を含むアニオン成分は、イオン解離性の良いイオン化合物が得られることから好ましく用いられる。特に、アニオン成分は、フッ素含有イミドアニオンが好ましい。
前記フッ素含有イミドアニオンとしては、例えば、ペルフルオロアルキル基を有するイミドアニオンを例示できる。
具体的には、前記例示のアニオン成分のなかの、(CF3SO2)(CF3CO)N−、や前記一般式(1)、(2)、(4)、
(1):(CnF2n+1SO2)2N− (但し、nは1〜10の整数)、
(2):CF2(CmF2mSO2)2N− (但し、mは1〜10の整数)、
(4):(CpF2p+1SO2)N−(CqF2q+1SO2)、(但し、p、qは1〜10の整数)、で表わされるものなどが用いられる。これらフッ素含有イミドアニオンは、イオン解離性の良いイオン性化合物が得られることから好ましく用いられる。また、前記フッ素含有イミドアニオンは、炭素数1〜4のフッ化アルキル基またはフッ化アルキレン基を有するものが、表面抵抗値を小さく制御でき静電気ムラを抑えるうえで好ましい。前記フッ素含有イミドアニオンとしては、(CF3SO2)2N−、(C2F5SO2)2N−、等の前記一般式(1)で表わされる、(ペルフルオロアルキルスルホニル)イミドが好ましく、特に(CF3SO2)2N−、で表わされる(トリフルオロメタンスルホニル)イミドが好ましい。
前記オニウム−アニオン塩におけるカチオン部を構成するオニウムとしては、オニウムイオンになる原子がプロトン化したものである。また、本発明のオニウムは、二重結合、三重結合等の不飽和結合によってオニウム塩を形成していないものが偏光子劣化の抑制の点から好ましい。即ち、本発明のオニウムとしては、有機基等による置換によってオニウムイオンを形成した有機オニウムが好ましい。
(メタ)アクリル系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。
・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
<アクリル系ポリマー(A)の調製>
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、ブチルアクリレート99部および4−ヒドロキシブチルアクリレート1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60℃付近に保って7時間重合反応を行った。その後、得られた反応液に、酢酸エチルを加えて、固形分濃度30%に調整した、重量平均分子量160万のアクリル系ポリマー(A)の溶液を調製した。
<アクリル系ポリマー(B)の調製>
製造例1において、モノマー混合物として、ブチルアクリレート96部、アクリル酸3部および4−ヒドロキシブチルアクリレート1部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量160万のアクリル系ポリマー(B)の溶液を調製した。
<粘着剤組成物の調製>
上記で得られたアクリル系ポリマー(A)溶液の固形分100部に対して、架橋剤として、トリメチロールプロパンキシリレンジイソシアネート(三井化学社製:タケネートD110N)0.1部と、ジベンゾイルパーオキサイド0.3部と、γ−グリシドキシプロピルメトキシシラン(信越化学工業社製:KBM−403)0.2部、さらにイオン性化合物として、1−エチル−1−メチルピロリジニウム・トリフルオロメタンスルホニルイミド1部を配合して、粘着剤組成物の溶液を得た。
≪オリゴマー防止層の形成≫
オルガノシロキサン(エチルシリケート48:コルコート社)をイソプロピルアルコールで固形分濃度1%に希釈して塗布液を調製した。当該塗布液を、厚さ38μmのポリエチレンテレフタレートフィルム(基材フィルム:PETフィルム)の片面に、乾燥後の厚みが50nmになるようにグラビアコーターにより塗布した後、120℃で乾燥して、オリゴマー防止層を形成した。
シリコーン樹脂(KS−847H:信越化学製):20重量部および硬化剤(PL−50T:信越化学製):0.2重量部を、メチルエチルケトン/トルエン混合溶媒(混合比率は1:1)350重量部で希釈して、シリコーン系離型剤の溶液を調製した。当該シリコーン系離型剤の溶液を、上記オリゴマー防止層に、乾燥後の厚みが100nmになるようにグラビアコーターにより塗布した後、120℃で乾燥して、離型層を形成して、基材フィルム/オリゴマー防止層/離型層の構成を有するセパレータを得た。
上記で調製した粘着剤組成物の溶液を、上記セパレータの離型層上にファウンテンコータで均一に塗布した後、150℃の空気循環式恒温オーブンで60秒間乾燥して、前記離型層の表面に厚さ20μmの粘着剤層を形成して、セパレータ付き粘着剤層を得た。
薄型偏光子を作製するため、まず、非晶性PET基材に9μm厚のPVA層が製膜された積層体を延伸温度130℃の空中補助延伸によって延伸積層体を生成し、次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度65度のホウ酸水中延伸によって総延伸倍率が5.94倍になるように非晶性PET基材と一体に延伸された4μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によって非晶性PET基材に製膜されたPVA層のPVA分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光子を構成する、厚さ4μmのPVA層を含む光学フィルム積層体を生成することができた。更に、当該光学フィルム積層体の偏光子の表面にポリビニルアルコール系接着剤を塗布しながら、けん化処理した80μm厚のトリアセチルセルロースフィルムを貼合せたのち、非晶性PET基材を剥離し、薄型偏光子を用いた偏光フィルムを作製した。
次いで、上記偏光フィルムの薄型偏光子に、上記セパレータ付き粘着剤層を貼り合わせ、粘着剤層を移着させて、セパレータ付きの粘着剤層付き偏光フィルムを得た。
実施例1において、<粘着剤組成物の調製>にあたり、アクリル系ポリマーの種類、イオン性化合物の種類、配合量を;≪オリゴマー防止層の形成≫にあたり、オリゴマー防止層の形成剤の種類を;<セパレータ付き粘着剤層の作成>にあたり加熱条件(温度、時間)を、それぞれ、表1に示すように変えたこと以外は実施例1と同様にして、セパレータ付き粘着剤層の作成し、さらに、セパレータ付きの粘着剤層付偏光フィルムを作製した。
セパレータ付き粘着剤層から、粘着剤層を約0.2gを採取し、予め重量を測定したフッ素樹脂(TEMISH NTF-1122日東電工(株)製)(Wa)に包み、当該粘着剤層が漏れないように縛った後、重量(Wb)を測定し、サンプル瓶に入れた。酢酸エチルを40cc加えて7日間放置した。その後、フッ素樹脂を取り出し、アルミカップ上で130℃、2時間乾燥させ、サンプルを含むフッ素樹脂の重量(Wc)を測定し、次式(I)によりゲル分率を求めた。
ゲル分率(重量%)=(Wc−Wa)/(Wb−Wa)×100
セパレータの離型層の表面の表面抵抗値(Ω/□)を三菱化学アナリテック社製MCP−HT450を用いて測定した。
作製された粘着剤層付偏光フィルムを100mm×100mmの大きさに切断し、液晶パネルに貼り付けた。このパネルを10000cdの輝度を持つバックライト上に置き、静電気発生装置であるESD(SANKI社製,ESD−8012A)を用いて5kvの静電気を発生させることで液晶の配向乱れを起こした。その配向不良による表示不良の回復時間(秒)を、瞬間マルチ測光検出器(大塚電子社製,MCPD−3000)を用いて測定し、下記基準で評価した。
○:表示不良が1秒以上10秒未満で消失した。
×:表示不良が10秒以上で消失した。
セパレータ付きの粘着剤層付偏光フィルムを60℃、90%RHの条件下で500時間放置した後、セパレータを除去した。粘着剤層付偏光フィルムから、粘着剤層(サンプル)を約0.025g採取して、クロロホルム1mlを加え室温で18時間振とうした後、アセトニトリルを5ml加え抽出を行い、3時間振とうした。得られた溶液を0.45mlメンブランフィルターでろ過し試料を調製した。3量体のPETオリゴマーの標準品を一定濃度に調整し、検量線を作成し、その検量線を用いて粘着剤中に含まれるPETオリゴマー量(ppm)を求めた。検量線は、PETオリゴマー濃度(ppm)が分かっているサンプルを用いて、HPLCで測定して作成した。
HPLC装置:Agilent Technologies製 1200シリーズ
測定条件
カラム:Agilent Technologies製ZORBAX SB-C18
カラム温度:40℃
カラム流量:0.8ml/min
溶離液組成:水/アセトニトリル逆相グラジエント条件
注入量:5μl
検出器:PDA
定量方法:PETオリゴマー3量体の標準試料をクロロホルムで溶解後、アセトニトリルで希釈し一定の濃度で標品を調製した。そのHPLC面積と調整濃度から検量線を作成し、サンプルのPETオリゴマー量を求めた。
「*1」は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;
「*2」はトリブチルメチルアンモニウム・ビス(トリフルオロメタンスルホニル)イミド;
「*3」はリチウムビス(トリフルオロメタンスルホニル)イミド、を示す。
オリゴマー防止層における「シリカ系」は、実施例1で用いたオリゴマー防止層の形成剤と同じであり、「4級アンモニウム塩」は、2−ヒドロキシ−3−メタクリルオキシプロピルトリメチルアンモニウム塩をモノマー単位として含有するアクリルポリマー(対イオン:メチルスルホネート塩)60部、ポリエチレングリコール含有アクリレートポリマー30部およびオキサゾリン架橋剤(エポクロスWS500,株式会社日本触媒製)10部の混合物である。
Claims (6)
- 偏光フィルムの少なくとも片面に、セパレータ付き粘着剤層が貼り合わせているセパレータ付きの粘着剤層付き偏光フィルムであって、
前記偏光フィルムは、厚みが10μm以下である偏光子の少なくとも片面に、透明保護フィルムを有し、
前記セパレータ付き粘着剤層は、セパレータ上に粘着剤層を有し、
前記セパレータは、基材フィルムに、オリゴマー防止層、離型層がこの順で設けられており、かつ、前記離型層は表面抵抗値が1.0×1013Ω/□以上であり、
前記基材フィルムは、ポリエステルフィルムであり、
前記オリゴマー防止層は、シラン化合物および/またはシロキサン化合物により形成された層であり、
前記離型層は、シリコーン系離型剤から得られた層であり、
前記粘着剤層は、ベースポリマーおよびイオン性化合物を含有する粘着剤組成物から形成されており、前記セパレータの離型層に設けられていることを特徴とするセパレータ付きの粘着剤層付き偏光フィルム。 - 前記イオン性化合物が、アルカリ金属塩及び/または有機カチオン−アニオン塩であることを特徴とする請求項1記載のセパレータ付きの粘着剤層付き偏光フィルム。
- 前記ベースポリマーが、(メタ)アクリル系ポリマーであることを特徴とする請求項1または2記載のセパレータ付きの粘着剤層付き偏光フィルム。
- 前記(メタ)アクリル系ポリマーが、モノマー単位として、アルキル(メタ)アクリレートおよびヒドロキシル基含有モノマーを含有することを特徴とする請求項3記載のセパレータ付きの粘着剤層付き偏光フィルム。
- 前記(メタ)アクリル系ポリマーが、モノマー単位として、アルキル(メタ)アクリレートおよびカルボキシル基含有モノマーを含有することを特徴とする請求項3または4記載のセパレータ付きの粘着剤層付き偏光フィルム。
- 請求項1〜5のいずれかに記載のセパレータ付きの粘着剤層付き偏光フィルムの製造方法であって、
基材フィルムに、オリゴマー防止層、離型層がこの順で設けられており、かつ、前記離型層の表面抵抗値が1.0×1013Ω/□以上のセパレータの当該離型層に、ベースポリマーおよびイオン性化合物を含有する粘着剤組成物の溶液を塗布する工程、および
前記塗布された粘着剤組成物の溶液を、140℃以上の温度で加熱する工程、
を有する工程によりセパレータ付き粘着剤層を製造する工程と、
さらに、得られたセパレータ付き粘着剤層を、前記偏光フィルムの少なくとも片面に、貼り合わせる工程を含むことを特徴とするセパレータ付きの粘着剤層付き偏光フィルムの製造方法。
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