JP7019852B1 - 偏光子保護フィルム - Google Patents
偏光子保護フィルム Download PDFInfo
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- JP7019852B1 JP7019852B1 JP2021042963A JP2021042963A JP7019852B1 JP 7019852 B1 JP7019852 B1 JP 7019852B1 JP 2021042963 A JP2021042963 A JP 2021042963A JP 2021042963 A JP2021042963 A JP 2021042963A JP 7019852 B1 JP7019852 B1 JP 7019852B1
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract
Description
フルオレン系ポリエステル樹脂を含むポリエステル系樹脂層と、
アクリル系樹脂を含むアクリル系樹脂層と、を有し、延伸することで製膜されてなる多層フィルムであり、
前記ポリエステル系樹脂層が全体に占める厚み比率が、1~30%であり、
波長589nmにおける厚み方向の位相差Rth(589)が、-50nm以上50nm以下であり、
波長550nmにおける面内位相差Ro(550)が、0nm以上50nm以下である、
偏光子保護フィルム。
〔2〕
前記フルオレン系ポリエステル樹脂が、下記一般式(1)及び下記一般式(3)で表される繰り返し単位を含む共重合ポリエステル樹脂である、
〔1〕に記載の偏光子保護フィルム。
〔3〕
前記アクリル系樹脂が、下記一般式(4)、(5)又は(6)のいずれかで表される繰り返し単位を含む、
〔1〕又は〔2〕に記載の偏光子保護フィルム。
置換基を示す。]
〔4〕
前記アクリル系樹脂が、ポリメタクリル酸メチルを含む、
〔1〕~〔3〕のいずれか一項に記載の偏光子保護フィルム。
〔5〕
前記ポリエステル系樹脂層と前記アクリル系樹脂層とが、接着を目的とする層を介さずに接している構成である、
〔1〕~〔4〕のいずれか一項に記載の偏光子保護フィルム。
〔6〕
前記多層フィルムの最外層が、前記アクリル系樹脂層であり、前記多層フィルムが3層以上の層を有する、
〔1〕~〔5〕のいずれか一項に記載の偏光子保護フィルム。
〔7〕
前記ポリエステル系樹脂層が、紫外線吸収剤を含有する、
〔1〕~〔6〕のいずれか一項に記載の偏光子保護フィルム。
〔8〕
前記多層フィルムの380nmにおける分光線透過率が10%以下であり、全光線透過率が85%以上である、
〔1〕~〔7〕のいずれか一項に記載の偏光子保護フィルム。
〔9〕
〔1〕~〔8〕のいずれか一項に記載の偏光子保護フィルムと、ポリビニルアルコール系樹脂で形成される偏光子とが、紫外線硬化型接着剤で貼り合わされている、
偏光板。
〔10〕
前記紫外線硬化型接着剤が、9,9-ビス(アリール)フルオレン骨格を有するポリエステルポリオールとジイソシアネート化合物と水酸基含有アクリレート化合物との反応生成物及び単官能アクリレート化合物を含有する組成物である、
〔9〕に記載の偏光板。
〔11〕
〔9〕又は〔10〕に記載の偏光板を備える、
画像表示装置。
〔12〕
〔11〕に記載の画像表示装置を備える、
情報処理装置。
本実施形態の偏光子保護フィルムは、フルオレン系ポリエステル樹脂を含むポリエステル系樹脂層と、アクリル系樹脂を含むアクリル系樹脂層と、を有する多層フィルムである。これにより、ポリエステル系樹脂層による耐久性や機械的強度を偏光子保護フィルムに付与することができる。また、ポリエステル系樹脂層は、紫外線吸収剤との相溶性がよいことから、新たに紫外線吸収性能を付与することもできる。さらにアクリル系樹脂層は、透明性と耐傷つき性を有するため、より機械強度を高めた偏光子保護フィルムを得ることができる。より具体的には、本実施形態の偏光子保護フィルムは、低透湿であり、熱安定性があるため、水分や熱による偏光子の劣化を防ぎ、低レタデーションのため虹むらや光漏れなどを生じ難い。また、ポリエステル系樹脂層は紫外線吸収剤を高濃度で含有してもブリードアウトを抑制できるため、そのような態様では薄膜化しても紫外線による劣化を防ぐことができる。さらに、本実施形態の偏光子保護フィルムは、脆さが抑制されているため、偏光子保護フィルムロールを巻き取るハンドリング性に優れる。また、2軸延伸により薄膜化も可能である。例えば、アクリル系樹脂として汎用ポリメタクリルメチル樹脂を用いるため、溶融押出及び2軸延伸により大量に製造することができる。
本実施形態で使用するポリエステル系樹脂層は、下記に示すフルオレン系ポリエステル樹脂を含む。前記フルオレン系ポリエステル樹脂としては、9,9-ビスアリールフルオレン骨格を有するものが好ましく、例えば、下記一般式(1)及び下記一般式(3)で表される繰り返し単位を含む共重合ポリエステル樹脂が好ましい。このようなポリエステル系樹脂を用いることにより、耐久性や機械的強度がより向上する傾向にある。また、一般にポリエステル樹脂は延伸することで延伸方向の複屈折が増大するが、本実施形態のフルオレン系ポリエステル樹脂は側鎖に含まれる9,9-ビスアリールフルオレン骨格が、延伸方向と直交する方向への位相差を増大させる働きを有しているため、ポリマー全体として位相差を低減させたポリエステル樹脂の設計が可能となる。
フルオレン系ポリエステル樹脂を構成するジオール成分としては、特に限定されないが、例えば、下記一般式(7)で表されるフルオレンジオール成分(A1)を用いることが好ましく、必要に応じて、他のジオール成分(A2)を用いてもよい。以下、各ジオール成分について詳説する。
上記一般式(1)のジオール部分を構成するフルオレンジオール成分(A1)は、下記一般式(7)で表すことができる。
ジオール成分(A)は少なくともフルオレンジオール成分(A1)を含んでいればよく、フルオレンジオール成分(A1)と、他のジオール成分(A2)を含有させ、共重合ポリエステル樹脂を形成してもよい。上記一般式(3)のジオール部分を構成する他のジオール成分(A2)としては、特に限定されないが、例えば、脂肪族ジオール、脂環族ジオール及び芳香族ジオールから選択された少なくとも一種が挙げられる。
フルオレン系ポリエステル樹脂を構成するジカルボン酸成分としては、特に限定されないが、例えば、下記一般式(8)で表されるフルオレンジカルボン酸成分(B1)を用いることが好ましく、必要に応じて、他のジカルボン成分(B2)を用いてもよい。以下、各ジカルボン成分について詳説する。
本実施形態で使用するポリエステル樹脂を構成し得る単量体の1種であるフルオレンジカルボン酸成分(B1)は、下記一般式(8)で表すことができる。
ジカルボン酸成分(B)は、脂肪族ジカルボン酸、脂環族ジカルボン酸及び芳香族ジカルボン酸から選択された少なくとも一種のジカルボン酸(B2)を含んでいてもよい。
偏光子保護フィルムにおいて用いるポリエステル系樹脂はジオール成分(A)とジカルボン酸成分(B)との反応により調製できる。ポリエステル樹脂の製造方法は特に限定されず、慣用の方法、例えば、エステル交換法、直接重合法などの溶融重合法、溶液重合法、界面重合法などで調製してもよく、重合反応では、エステル交換触媒、重縮合触媒、熱安定剤、光安定剤、重合調整剤などを使用してもよい。
本実施形態に使用されるアクリル系樹脂は、(メタ)アクリル酸エステル由来の構成単位を含む重合体であり、好ましくは(メタ)アクリル酸エステルを主体とする重合体である。アクリル系樹脂は、(メタ)アクリル酸エステルの単独重合体であってもよいし、他の重合性単量体との共重合体であってもよい。
本実施形態の偏光子保護フィルムは、前記ポリエステル系樹脂層及び前記アクリル系樹脂層以外の樹脂層を設けても良い。前記ポリエステル系樹脂層及び前記アクリル系樹脂層以外の樹脂層は、接している樹脂層に密着可能な材料であればよく特に限定されない。そのような樹脂層に含まれる樹脂としては、透明性などの光学的特性に優れたアセチルセルロース系樹脂、シクロオレフィン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂などが好ましく、その中でも延伸後のレタデーションの発現が少ないアセチルセルロース系樹脂がより好ましい。本実施形態の偏光子保護フィルムにハードコート性を付与する表面層(以下、「ハードコート層」とする。)を設けることもできる。
偏光子保護フィルムはヨウ素の紫外線による劣化を防ぐため、波長380nm以下の紫外線を遮断する必要がある。偏光子保護フィルムでは、380nmの透過率で10%以下、好ましくは8%以下にする必要があるとされている。この要求を満足させるためには紫外線吸収剤の添加が有効であるが、フィルムの膜厚が薄くなると、高濃度で紫外線吸収剤を分散させないと所定の透過率が得られなくなる。一般的に、後述するアクリル系樹脂では紫外線吸収剤の溶解度が低く、薄膜になると必要量の紫外線吸収剤が添加できないためフィルムの薄膜化に限度がある。
ポリエステル系樹脂層及び/又は他の樹脂層は、紫外線吸収剤以外に、必要に応じて、各種の添加剤を含有してもよい。このような添加剤としては、特に限定されないが、例えば、帯電防止剤、耐光剤、難燃剤、熱安定剤、酸化防止剤、ゲル化防止剤、界面活性剤等が挙げられる。
上記ではフルオレン系ポリエステル樹脂を含むポリエステル系樹脂層とアクリル系樹脂を含むアクリル系樹脂層とを必須とする偏光子保護フィルムについて記載したが、他の態様として、フルオレン系ポリエステル樹脂を含むポリエステル系樹脂層に代えて、ポリカーボネート樹脂を含むポリカーボネート樹脂層を用いてもよい。本明細書において、「ポリエステル系樹脂層」は、上記「ポリカーボネート樹脂層」をも包含する。
本実施形態の共押出法による多層フィルムの製造方法について説明する。まず、ポリエステル系樹脂及びそれ以外の層に使用する樹脂のペレットを乾燥器によって、水分率が100ppm未満となるように乾燥する。次いで、各樹脂ペレットと添加剤を計量し、混合して押出機に供給し、多層フィードブロックを用いて各層を合流させ、スリット状のダイからシート状に溶融押出を行う。さらに、溶融状態のシートを、静電印加法を用いてキャスティングロールに密着させて冷却固化し、多層フィルムを得る。あるいは多層フィードブロックを用いる代わりにマルチマニホールドダイを用いてもよい。
次に、図2A及び2Bを参照して、本実施形態の偏光板について説明する。この偏光板は、上記の偏光子保護フィルムを含むものである。図2A及び2Bは、偏光板の一態様を概略的に図示した断面図である。
偏光子保護フィルムと偏光子を貼り合わせるのに使用される接着剤として、従来、TACフィルムで使用される水系接着剤、例えば、ポリビニルアルコール、ポリビニルブチラールなどは、ポリエチレンテレフタレート樹脂やアクリル系樹脂フィルムでは透湿性が低いため水の乾燥速度が遅く、生産性の観点から使用することができない。そのため、紫外線硬化型接着剤を使用することが考えられる。
次に、図3A及び3Bを参照して、本実施形態の画像表示装置について説明する。本実施形態の画像表示装置は、上記偏光板を備えるものであれば、特に限定されないが、例えば、有機エレクトロルミネッセンス(EL)表示装置及び液晶表示装置が挙げられる。また、画像表示装置は、それが単体として最終製品として市場に流通する装置に限らず、後述する情報処理装置、例えばスマートフォン等の一部であってもよい。図3Aは、本実施形態の一態様の有機EL表示装置を概略的に図示した断面図であり、図3Bは、本実施形態の一態様の液晶表示装置を概略的に図示した断面図である。
次に、図5を参照して、本実施形態の情報処理装置について説明する。同図は、本実施形態の情報処理装置60を概略的に示す斜視図である。情報処理装置60は、上記偏光板を有する上記画像表示装置を備える。情報処理装置60は、画像表示装置61を備えたスマートフォンである。画像表示装置61には、例えば、上述の有機EL表示装置40又は液晶表示装置50の構成を採用することができる。
(ガラス転移温度(Tg))
示差走査熱量計(セイコーインスツル(株)製「DSC 6220」)を用い、アルミパンに試料を入れ、JIS K 7121に準拠して、30℃から200℃の範囲でTgを測定した。
ゲル浸透クロマトグラフィ(東ソー(株)製、「HLC-8120GPC」)を用い、試料をクロロホルムに溶解させ、ポリスチレン換算で、重量平均分子量Mwを測定した。
リタデーション測定装置(大塚電子(株)製「RETS-100」)を用いて、測定温度20℃で、フィルムの波長550nmにおける面内位相差Ro(550)、波長589nmにおける厚み方向の位相差Rth(589)を測定した。
測厚計((株)ミツトヨ製「マイクロメーター」)を用いて、フィルムの長手方向に対して、チャック間を等間隔に3点測定し、その平均値を算出した。
15mm×30mmに切り出したフィルムを折り曲げ試験機(ユアサシステム機器(株)製、「DMLHP-CS」)にて、23℃の室温下で屈曲半径2mm、屈曲速度30回/分、屈曲角度180°の折り曲げ試験に供した。屈曲回数20万回まで実施し、完全に破断するまでの折り曲げ回数を計測することで、下記のとおり耐屈曲性を評価した。
◎:20万回以上
〇:1万回以上20万回未満
×:1万回未満
各実施例で作製した偏光子保護フィルムの表面に後述する紫外線硬化型接着剤を5μmの厚さとなるように塗布した。次いでPVA水溶液(日本酢ビ・ポバール(株)製「JC-40」)を適切な基材上で塗布・乾燥させることでPVAフィルムを作製し、これを該接着剤層の上からラミネーターで貼り付けた。その後、積算光量が300(mJ/cm2)となるよう、高圧水銀ランプで紫外線を照射して接着剤の硬化を行い、試験片を作製した。
○:180度剥離強度が3(N/25mm)以上
×:180度剥離強度が3(N/25mm)未満
「U-3010」(HITACHI製)を用いて、380nmにおける分光線透過率を測定した。
(合成例1:FDPM:9,9-ビス(2-メトキシカルボニルエチル)フルオレン[9,9-ビス(2-カルボキシエチル)フルオレン(又はフルオレン-9,9-ジプロピオン酸)のジメチルエステル])
1,4-ジオキサン200mL、フルオレン33.2g(0.2モル)を反応器に入れ、攪拌することによってフルオレンを溶解させた後、10℃に冷却した状態で水酸化トリメチルベンジルアンモニウムの40質量%メタノール溶液(東京化成(株)製「トリトンB40」)3.0mLを滴下し、30分攪拌した。次に、アクリル酸メチル37.9g(0.44モル)を加えて、約3時間攪拌した。反応終了後、トルエン200mL、0.5N塩酸50mLを加えて洗浄した。水層を除去した後、有機層を蒸留水30mLで3回洗浄した。溶媒を留去することにより、9,9-ビス(プロピオン酸t-ブチル)フルオレン[9,9-ビス{2-(t-ブトキシカルボニル)エチル}フルオレン]84.0g(収率99%)を得た。さらに、70℃のイソプロピルアルコール300mLに溶解させた後、10℃まで冷却することにより再結晶させた結果、9,9-ビス(2-メトキシカルボニルエチル)フルオレンを得た。
BPEF:9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン、大阪ガスケミカル(株)製
EG :エチレングリコール
DMN :2,6-ナフタレンジカルボン酸ジメチル
PMMA:ポリアクリル酸メチル、パラペットGR-01240、(株)クラレ製
紫外線吸収剤:アデカスタブLA-F70[2,4,6-トリス(2-ヒドロキ-4-ヘキシルオキシ-3-メチルフェニル)-1,3,5-トリアジン]、ADEKA(株)製
特開2018-087284号公報の実施例に記載のウレタンアクリレートオリゴマーA1-1(下記一般式(9))70質量部と、フェノキシエチルアクリレート(共栄社化学(株)製)30質量部と、重合開始剤(イルガキュア184 、BASFジャパン(株)製)5質量部と、を混合して組成物を得た。
[製造例1]
FDPM1.00モル、BPEF0.80モル、EG2.20モルに、エステル交換触媒として酢酸マンガン・4水和物2×10-4モル及び酢酸カルシウム・1水和物8×10-4モルを加え、撹拌しながら徐々に加熱溶融した。230℃まで昇温した後、トリメチルホスフェート14×10-4モル、酸化ゲルマニウム20×10-4モルを加え、270℃、0.13kPa以下に到達するまで、徐々に昇温、減圧しながらEGを除去した。所定の撹拌トルクに到達後、内容物を反応器から取り出し、フルオレン系ポリエステルのペレット(樹脂I)を調製した。
原材料をFDPM0.70モル、DMN0.30モル、BPEF0.85モル、EG2.15モルとしたこと以外は製造例1と同様にして反応させ、表1に示す割合で各成分由来の単位が導入されたポリエステル樹脂IIを得た。
乾燥した樹脂Iのペレット90質量部と、紫外線吸収剤10質量部とをドライブレンドした原料を、二軸押出装置((株)テクノベル製、型番「KZW 15/45」、スクリュー径D=15mm、L/D=32)に供給して、スクリュー温度280℃、回転速度200rpmで混練し、ペレット(樹脂III)を調製した。
また、原材料の樹脂Iを樹脂IIに変更したこと以外は上記と同様の方法によって紫外線吸収剤を添加することで、ペレット(樹脂IV)を調製した。
(製膜工程)
80℃で一晩熱風乾燥した樹脂I、IIIもしくはIVと、PMMAとを原料として、押出機3基を有するTダイ押出成形機を用いて共押出成形し、表1に記載の層構成、厚み比及び総厚みを有する2種3層の多層光学フィルムを調製した。なお、シリンダー温度は、樹脂I、III及びIV側:280~300℃、PMMA側:250℃に設定した。各層の厚み比は、各押出機のスクリュー回転数を調整して制御した。
上記製膜工程で得た各多層フィルムは、表1に記載の延伸条件により、テンター延伸装置を用いて、同時2軸延伸した。なお、表1において、延伸倍率は、縦方向(流れ方向)及び横方向(幅方向)に延伸した倍率を示す。得られた延伸フィルムの各種物性測定を行った。結果を表1に示す。
樹脂Iを使用し、Tダイ押出成形機を用いてフルオレン系ポリエステル樹脂I単層フィルムを製膜し、上記実施例と同様に延伸を実施した。得られた延伸フィルムの各種物性測定を行った。結果を表1に示す。
(株)クラレ製アクリル系樹脂フィルム「PARAPURE HI-50」(厚み75μm)の各種物性測定を行った。結果を表1に示す
Claims (12)
- フルオレン系ポリエステル樹脂を含むポリエステル系樹脂層と、
アクリル系樹脂を含むアクリル系樹脂層と、を有し、延伸することで製膜されてなる多層フィルムであり、
前記ポリエステル系樹脂層が全体に占める厚み比率が、1~30%であり、
波長589nmにおける厚み方向の位相差Rth(589)が、-50nm以上50nm以下であり、
波長550nmにおける面内位相差Ro(550)が、0nm以上50nm以下である、
偏光子保護フィルム。 - 前記フルオレン系ポリエステル樹脂が、下記一般式(1)及び下記一般式(3)で表される繰り返し単位を含む共重合ポリエステル樹脂である、
請求項1に記載の偏光子保護フィルム。
- 前記アクリル系樹脂が、下記一般式(4)、(5)又は(6)のいずれかで表される繰り返し単位を含む、
請求項1又は2に記載の偏光子保護フィルム。
- 前記アクリル系樹脂が、ポリメタクリル酸メチルを含む、
請求項1~3のいずれか一項に記載の偏光子保護フィルム。 - 前記ポリエステル系樹脂層と前記アクリル系樹脂層とが、接着を目的とする層を介さずに接している構成である、
請求項1~4のいずれか一項に記載の偏光子保護フィルム。 - 前記多層フィルムの最外層が、前記アクリル系樹脂層であり、前記多層フィルムが3層以上の層を有する、
請求項1~5のいずれか一項に記載の偏光子保護フィルム。 - 前記ポリエステル系樹脂層が、紫外線吸収剤を含有する、
請求項1~6のいずれか一項に記載の偏光子保護フィルム。 - 前記多層フィルムの380nmにおける分光線透過率が10%以下であり、全光線透過率が85%以上である、
請求項1~7のいずれか一項に記載の偏光子保護フィルム。 - 請求項1~8のいずれか一項に記載の偏光子保護フィルムと、ポリビニルアルコール系樹脂で形成される偏光子とが、紫外線硬化型接着剤で貼り合わされている、
偏光板。 - 前記紫外線硬化型接着剤が、9,9-ビス(アリール)フルオレン骨格を有するポリエステルポリオールとジイソシアネート化合物と水酸基含有アクリレート化合物との反応生成物及び単官能アクリレート化合物を含有する組成物である、
請求項9に記載の偏光板。 - 請求項9又は10に記載の偏光板を備える、
画像表示装置。 - 請求項11に記載の画像表示装置を備える、
情報処理装置。
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