JP6644932B1 - 光学フィルムおよびその製造方法、偏光板、ならびに画像表示装置 - Google Patents
光学フィルムおよびその製造方法、偏光板、ならびに画像表示装置 Download PDFInfo
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- JP6644932B1 JP6644932B1 JP2019133317A JP2019133317A JP6644932B1 JP 6644932 B1 JP6644932 B1 JP 6644932B1 JP 2019133317 A JP2019133317 A JP 2019133317A JP 2019133317 A JP2019133317 A JP 2019133317A JP 6644932 B1 JP6644932 B1 JP 6644932B1
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Abstract
Description
光学フィルム1は、フィルム基材11の少なくとも一方の面に易滑層15を備える。
フィルム基材11としては透明フィルムが好ましい。透明フィルム基材の全光線透過率は80%以上が好ましく、85%以上がより好ましく、90%以上がさらに好ましい。フィルム基材11を構成する樹脂材料としては、アクリル系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリオレフィン系樹脂、環状ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂等が挙げられる。光学フィルムが光学等方性の偏光子保護フィルムとして用いられる場合は、複屈折が小さいことから、フィルム基材11の樹脂材料として、アクリル系樹脂または環状ポリオレフィン系樹脂が好ましく、アクリル系樹脂が特に好ましい。
フィルム基材11の表面に設けられる易滑層15は、バインダ樹脂および微粒子を含む。易滑層15が微粒子を含むことにより、易滑層15の表面に微細な凹凸が形成され、フィルムの滑り性が向上する。そのため、光学フィルム1のロール搬送時の傷付きの低減や、ロール状に巻き取る際のブロッキング抑制に寄与する。
バインダ樹脂としては、アクリル系フィルム等のフィルム基材との密着性に優れることから、ポリウレタン樹脂、エポキシ樹脂、イソシアネート樹脂、ポリエステル樹脂、分子中にアミノ基を含むポリマー類、オキサゾリン基等の架橋性官能基を有するアクリル樹脂等の反応性基を有する樹脂(ポリマー)が用いられる。易滑層15のバインダ樹脂としては、ポリウレタン樹脂が特に好ましい。ポリウレタン樹脂バインダを含む易滑層15は、フィルム基材11との密着性が高い。
易滑層15に微粒子が含まれることにより、易滑層の表面に微細な凹凸形状が形成され、光学フィルム1の滑り性が向上し、ブロッキングを抑制できる。滑り性向上に寄与する凹凸を形成する観点から、微粒子の粒子径(平均一次粒子径)は、10nm以上が好ましく、15nm以上がより好ましく、20nm以上がさらに好ましい。微粒子の平均一次粒子径は、易滑層の厚みよりも小さいことが好ましい。微粒子の粒子径が易滑層の厚みよりも小さいことにより、易滑層からの微粒子の脱落を抑制できる。微粒子の粒子径は、250nm以下が好ましく、200nm以下がより好ましい。また、微粒子の平均一次粒子径が可視光波長よりも小さいことにより、バインダ樹脂と微粒子との界面での可視光の散乱を抑制できる。透明性向上の観点からは、微粒子の粒子径は100nm以下が好ましく、80nm以下がより好ましく、60nm以下がさらに好ましく、50nm以下が特に好ましい。
微粒子の分散性を高めるために、アミンやアンモニア等のアルカリ成分を用いると、易滑層には不可避的にアルカリ成分が残存する。光学フィルム1を偏光子保護フィルムとして用いた場合、易滑層15の残存アルカリ成分の水分への溶出や、フィルム基材11を透過したアルカリ成分が、偏光子を劣化させ、偏光板の偏光度の低下や、スジ状のムラ等の光学的な欠陥が発生する場合がある。
フィルム基材11の表面への易滑層15の形成方法は特に限定されない。好ましくは、バインダ樹脂および微粒子を含む易滑層形成用組成物(塗液)を、フィルム基材11上に塗布し、加熱することにより、易滑層15が形成される。
易滑層形成用組成物は、水を溶媒(および微粒子に対する分散媒)とする水系の組成物であることが好ましい。易滑層形成用組成物における固形分(不揮発成分)の濃度は、1〜30重量%が好ましく、2〜20重量%がより好ましく、3〜15重量%がさらに好ましい。
フィルム基材11上に易滑層形成用組成物を塗布する前に、フィルム基材の表面処理を行ってもよい。表面処理を行うことにより、フィルム基材の濡れ張力を調整し、易滑層15との密着性を向上できる。表面処理としては、コロナ処理、プラズマ処理、オゾン吹き付け、紫外線照射、火炎処理、化学薬品処理等が挙げられる。これらの中でも、コロナ処理またはプラズマ処理が好ましい。
偏光板は、偏光子の一方の面のみに透明保護フィルムを備えるものでもよく、図2Aおよび図2Bに示すように偏光子5の両面に透明保護フィルムを備えるものでもよい。偏光子の一方の面に、偏光子保護フィルムとして上記の光学フィルムを貼り合わせることにより、偏光子の一方の面のみに透明保護フィルムを有する偏光板が形成される。偏光子の両方の面に偏光子保護フィルムを有する偏光板は、偏光子の少なくとも一方の面に、上記の光学フィルムが貼り合わせられていればよい。偏光板は、偏光子の両面に上記の光学フィルムが貼り合わせられたものであってもよい。偏光子5と光学フィルム1とは、接着剤層6を介して貼り合わせられる。
偏光子5としては、ポリビニルアルコールや、部分ホルマール化ポリビニルアルコール等のポリビニルアルコール系フィルムに、ヨウ素や二色性染料等の二色性物質を吸着させて1方向に配向させたポリビニルアルコール(PVA)系偏光子が用いられる。例えば、ポリビニルアルコール系フィルムにヨウ素染色および延伸を施すことにより、PVA系偏光子が得られる。
偏光子5と光学フィルム1との貼り合わせに用いられる接着剤層6は、光学的に透明であれば、その材料は特に制限されず、エポキシ系樹脂、シリコーン系樹脂、アクリル系樹脂、ポリウレタン、ポリアミド、ポリエーテル、ポリビニルアルコール等が挙げられる。接着剤層6の厚みは、例えば、0.01〜20μm程度であり、被着体の種類や接着剤の材料等に応じて適宜に設定される。塗布後の架橋反応により接着性を示す硬化型の接着剤を用いる場合、接着剤層6の厚みは0.01〜5μmが好ましく、0.03〜3μmがより好ましい。
偏光子5の一方の面(第一主面)に、接着剤層6を介して光学フィルム1を貼り合わせることにより偏光板が製造される。光学フィルム1は、図2Aに示すように、易滑層形成面が接着剤層を介して偏光子5と貼り合わせられていてもよく、図2Bに示すように、易滑層非形成面が接着剤層を介して偏光子5と貼り合わせられていてもよい。
偏光子5の第二主面には、接着剤層7を介して透明保護フィルム2が貼り合わせられてもよい。透明保護フィルム2としては、任意の適切な透明フィルムを採用し得る。透明保護フィルム2の厚みは、5〜200μm程度である。機械強度、透明性およびハンドリング性等の観点から、透明保護フィルム2の厚みは10〜100μmが好ましく、15〜60μmがより好ましい。光学フィルム1と透明保護フィルム2の厚みは同一でもよく異なっていてもよい。
偏光板には、液晶セルや有機ELセル等への貼り合わせのための粘着剤層を設けてもよい。粘着剤層を形成する粘着剤としては、アクリル系ポリマー、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系やゴム系等のポリマーをベースポリマーとするものを適宜に選択して用いることができる。特に、光学的透明性に優れ、適度な濡れ性と凝集性を示し、かつ耐候性や耐熱性等に優れることから、アクリル系粘着剤が好ましい。
樹脂成分としてポリエステルウレタンおよびイソホロンジイソシアネートを含み、さらに硬化触媒としてのトリエチルアミンおよび分散媒としてのメチルエチルケトンを含む固形分34%の水系ポリウレタン(第一工業製薬製「スーパーフレックス210R」)20.6重量部、固形分25%のオキサゾリン含有ポリマー水溶液(日本触媒製「エポクロスWS−700」)5.2重量部、1重量%のアンモニア水2.8重量部、平均一次粒子径35nmのコロイダルシリカの20%水分散液(扶桑化学工業製「クォートロンPL−3」)7.5重量部、および純水63.9重量部を混合して、易滑層形成用組成物を調製した。この組成物は、固形分100重量部に対してシリカ粒子を15.3重量部含有する濃度9.8%の水溶液であった。以下の実施例および比較例では、この組成物を用いて易滑層を形成した。
溶融押出製膜装置、グラビアコーター、テンター式同時二軸延伸装置、および巻取り装置を備えるフィルム製造装置を用いて、光学フィルムを作製した。アクリル系樹脂として、特開2017−26939号の実施例に記載の「透明保護フィルム1A」の作製に用いたものと同一のイミド化MS樹脂(ガラス転移温度:120℃)のペレットを用いた。アクリル系樹脂をTダイから溶融押出して160μmの厚みで製膜し、フィルムの一方の面にグラビアコーターにて上記の組成物を約9μmのウェット厚みで塗布し、温度140℃の加熱炉内で同時二軸延伸テンターにより長手方向(MD)および幅方向(TD)にそれぞれ2倍に延伸して、厚み40μmのアクリル系フィルムの一方の面に厚み50nmの易滑層を備える光学フィルムを得た。
易滑層形成用組成物の塗布厚みを変更したこと以外は、実施例1と同様にして、光学フィルムを得た。易滑層の厚み(延伸後)は、表2に示す通りであった。
テンター延伸時の炉内温度(延伸温度)を表2に示すように変更した。延伸温度を変更したこと以外は、実施例1と同様にして、光学フィルムを得た。
(偏光子の作製)
厚み45μmのポリビニルアルコール(PVA)系樹脂フィルム(クラレ製「PE4500」)の長尺ロールを、ロール延伸機により長手方向に5.9倍になるように長手方向に一軸延伸しながら、表1に示す膨潤浴、染色浴、架橋浴1、架橋浴2、および洗浄浴を順に搬送し、70℃で5分間乾燥させて厚み18μmの偏光子を作製した。染色浴におけるヨウ素濃度およびヨウ化カリウム濃度は、偏光子の単体透過率が43.4%になるように調整した。
N−ヒドロキシエチルアクリルアミド40重量部およびアクリロイルモルホリン60重量部を硬化性成分として含み、さらに重合開始剤として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製「イルガキュア819」)3重量部を含む紫外線硬化型接着剤を調製した。
片面の偏光子保護フィルムとして、各実施例および比較例の光学フィルムを用い、他方の面の偏光子保護フィルムとして二軸延伸環状ポリオレフィンフィルム(日本ゼオン製「ゼオノアフィルムZF−14」)を用いた。光学フィルムの易滑層形成面およびゼオノアフィルムの表面に、上記の紫外線硬化型接着剤を約1μmの厚みで塗布し、ロールラミネータで偏光子に貼り合わせた後、積算光量1000/mJ/cm2の紫外線を照射して接着剤を硬化させ、偏光子の一方の面にアクリル系フィルム(光学フィルム)、他方の面にゼオノアフィルムを備える偏光板を得た。
<易滑層の残存アルカリ量>
易滑層に残存するトリエチルアミンおよびアンモニアの量を定量した。トリエチルアミンの残存量は光学フィルムの表面から易滑層を削り出した粉末を秤量してメタノールに溶解し、溶液のガスクロマトグラフィー質量分析(GC/MS)法により定量した。アンモニアの残存量は、光学フィルムを25℃の純水に浸漬した後、120℃の乾燥機にて60分間の加熱抽出を行い、水中に溶出したアンモニアをイオンクロマトグラフィーにより定量した。トリエチルアミンの量とアンモニアの量の合計を残存アルカリ量とした。
光学フィルムの易滑層形成面に、粘着テープ(日東電工製「No.31B」)を線圧8kg/m、圧着速度0.3m/分で圧着し、50℃で48時間保存した後、粘着テープの先端を把持して引張速度30m/分で180°ピール試験を行い、下記の基準により易滑層の密着性を判定した。
〇:アクリル系フィルムから易滑層が剥離せず粘着テープと易滑層との界面で剥離したもの
×:アクリル系フィルムと易滑層との界面で剥離が生じたもの
光学フィルムの表面を目視にて観察し、シリカ粒子の凝集による局所的な濁り(ヘイズ上昇)の有無、および易滑層非形成面における傷の有無を評価した。
〇:シリカ粒子の凝集がなく面内の均一性が良好であり、傷が認められなかったもの
△:シリカ粒子の凝集による濁りは見られなかったものの、易滑層非形成面に深さ1μm以下の傷が認められたもの
×:シリカ粒子の凝集による濁り、および易滑層非形成面の傷が認められたもの
光学フィルムの断面を透過型電子顕微鏡(TEM)により観察し、アクリル系フィルムと易滑層との界面において、易滑層中の粒子がアクリル系フィルムに埋設している領域(界面層)の有無を確認した。実施例3(界面層あり)のTEM観察像を図3、比較例4(界面層なし)のTEM観察像を図4に示す。
偏光板を320mm×240mmのサイズに切り出し、環状ポリオレフィンフィルム側の面を、厚み20μmのアクリル系粘着剤を介してガラス上に貼り合わせた。この試料を、温度60℃、相対湿度90%(条件1)の恒温恒湿槽、または温度85℃、相対湿度85%(条件2)の恒温恒湿槽に入れ、500時間保持して加熱・加湿耐久試験を実施した。
◎:条件1および条件2のいずれの耐久試験後の試料もスジムラが観察されない
〇:条件1の耐久試験後の試料にはスジムラが観察されず、条件2の耐久試験後の試料では僅かなスジムラが視認される
△:条件1および条件2の耐久試験後の両方の試料において僅かなスジムラが視認される
×:条件1および条件2の耐久試験後の両方の試料においてスジムラがはっきりと視認される
11 フィルム基材
15 易滑層
2 透明フィルム
5 偏光子
6,7 接着剤層
100,101 偏光板
Claims (18)
- 透明フィルム基材の表面に易滑層を備える光学フィルムであって、
前記易滑層は、バインダ樹脂、および無機微粒子を含有し、
前記易滑層のアミンおよびアンモニアの含有量の合計が5〜75ppmである、光学フィルム。 - 前記易滑層の厚みが40〜280nmである、請求項1に記載の光学フィルム。
- 前記透明フィルム基材と前記易滑層との界面において、前記無機微粒子が前記透明フィルム基材に埋設している領域が存在する、請求項1または2に記載の光学フィルム。
- 前記無機微粒子の平均一次粒子径が10〜250nmである、請求項1〜3のいずれか1項に記載の光学フィルム。
- 前記易滑層中の前記無機微粒子の含有量が3〜50重量%である、請求項1〜4のいずれか1項に記載の光学フィルム。
- 前記透明フィルム基材がアクリル系フィルムである、請求項1〜5のいずれか1項に記載の光学フィルム。
- 前記易滑層の前記バインダ樹脂がウレタン系樹脂である、請求項1〜6のいずれか1項に記載の光学フィルム。
- 請求項1〜7のいずれか1項に記載の光学フィルムを製造する方法であって、
透明フィルム基材の表面に、バインダ樹脂またはその前駆物質、無機微粒子、アミンおよびアンモニアからなる群から選択される1種以上のアルカリ成分、ならびに溶媒を含有する易滑層形成用組成物を塗布し、
前記透明フィルム基材のガラス転移温度よりも10℃以上高い温度で前記易滑層形成用組成物を加熱して、前記溶媒および前記アルカリ成分を揮発させる、光学フィルムの製造方法。 - 前記アルカリ成分が、前記無機微粒子の分散促進作用を有する、請求項8に記載の光学フィルムの製造方法。
- 前記易滑層形成用組成物は、前記バインダ樹脂の前駆物質としてポリウレタン前駆物質を含有し、前記アルカリ成分として第三級アミンを含む、請求項8または9に記載の光学フィルムの製造方法。
- 前記易滑層形成用組成物が、前記アルカリ成分として、沸点が150℃以下のアミンを含む、請求項8〜10のいずれか1項に記載の光学フィルムの製造方法。
- 前記透明フィルム基材のガラス転移温度よりも10℃以上高い温度で前記易滑層形成用組成物を加熱しながら、前記易滑層形成用組成物を塗布した前記透明フィルム基材を少なくとも1方向に延伸する、請求項8〜11のいずれか1項に記載の光学フィルムの製造方法。
- 第一主面および第二主面を有するポリビニルアルコール系偏光子、および前記偏光子の第一主面に接着剤層を介して貼り合わせられた透明フィルムを備え、
前記透明フィルムが請求項1〜7のいずれか1項に記載の光学フィルムである、偏光板。 - 前記光学フィルムの易滑層非形成面が、前記偏光子の第一主面に貼り合わせられている、請求項13に記載の偏光板。
- 前記光学フィルムの易滑層非形成面が、光カチオン重合性の接着剤、または光カチオン重合と光ラジカル重合のハイブリッド型接着剤を介して、前記偏光子の第一主面に貼り合わせられている、請求項14に記載の偏光板。
- 前記光学フィルムの易滑層形成面が、前記偏光子の第一主面に貼り合わせられている、請求項13に記載の偏光板。
- 前記光学フィルムの易滑層非形成面が、光ラジカル重合性の接着剤を介して前記偏光子の第一主面に貼り合わせられている、請求項16に記載の偏光板。
- 画像表示セルと、請求項13〜17のいずれか1項に記載の偏光板とを有する、画像表示装置。
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