JP6697625B2 - 粘着剤層、粘着剤層付光学フィルム、光学積層体、および画像表示装置 - Google Patents
粘着剤層、粘着剤層付光学フィルム、光学積層体、および画像表示装置 Download PDFInfo
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- JP6697625B2 JP6697625B2 JP2019206105A JP2019206105A JP6697625B2 JP 6697625 B2 JP6697625 B2 JP 6697625B2 JP 2019206105 A JP2019206105 A JP 2019206105A JP 2019206105 A JP2019206105 A JP 2019206105A JP 6697625 B2 JP6697625 B2 JP 6697625B2
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- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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- 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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- G02F1/13—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 for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/35—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being liquid crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32—LAYERED PRODUCTS
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- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/204—Plasma displays
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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Description
本発明の(メタ)アクリル系ポリマー(A)は、前記アルキル(メタ)アクリレートを主成分として含有する。なお、(メタ)アクリレートは、アクリレートおよび/またはメタクリレートをいい、本発明の(メタ)とは同様の意味である。
前記(メタ)アクリル系ポリマー(A)の製造は、溶液重合、電子線やUVなどの放射線重合、塊状重合、乳化重合などの各種ラジカル重合などの公知の製造方法を適宜選択できる。また、得られる(メタ)アクリル系ポリマー(A)は、ランダム共重合体、ブロック共重合体、グラフト共重合体などのいずれでもよい。
本発明のケイ素化合物(B)は、オルガノポリシロキサン化合物である。前記オルガノポリシロキサン化合物は、変性シリコーンオイルとも呼ばれ、シリコーンオイル(ジメチルシリコーンオイル)の側鎖および/または末端に有機基が導入されている。前記有機基は、分子の両末端に存在していてもよく、片方の末端に存在していてもよい。前記有機基としては、本発明の粘着剤層において、前記インジウム−スズ複合酸化物層の面におけるSi元素の比率が、0.5atomic%以上5atomic%以下となる範囲であれば何ら限定されるものではないが、例えば、(メタ)アクリロイル基、エポキシ基、アミノ基、水酸基、カルボキシ基、カルビノール基、メルカプト基、酸無水物基などの反応性有機基;ポリエーテル変性(オキシアルキレン鎖を有する)、アルキル変性、アラルキル変性、高級脂肪酸アミド変性、高級脂肪酸エステル変性、フッ素変性などの非反応性有機基などが挙げられる。前記ケイ素化合物(B)は単独でまたは組み合わせて使用できる。
(式(bII)中、R1は1価の有機基、R2、R3およびR4はアルキレン基、R5は水素原子または有機基、mは1〜2000の整数を表す。aおよびbは0〜1000の整数を表す(但し、aとbが同時に0になることはない)。)
(式(bIII)中、R1は1価の有機基、R2、R3およびR4はアルキレン基、R5は水素原子または有機基、mは1〜2000の整数を表す。aおよびbは0〜1000の整数を表す(但し、aとbが同時に0になることはない)。)
本発明の粘着剤組成物は、反応性官能基含有シランカップリング剤を含有することができる。前記反応性官能基含有シランカップリング剤は、前記反応性官能基が、エポキシ基、メルカプト基、アミノ基、イソシアネート基、イソシアヌレート基、ビニル基、スチリル基、アセトアセチル基、ウレイド基、チオウレア基、(メタ)アクリル基および複素環基のいずれか1つ以上である。前記反応性官能基含有シランカップリング剤は単独でまたは組み合わせて使用できる。
本発明の粘着剤組成物は、架橋剤を含有することができる。前記架橋剤としては、有機系架橋剤、多官能性金属キレートなどを用いることができる。前記有機系架橋剤としては、例えば、イソシアネート系架橋剤、過酸化物系架橋剤、エポキシ系架橋剤、イミン系架橋剤などが挙げられる。前記多官能性金属キレートは、多価金属が有機化合物と共有結合または配位結合しているものである。前記多価金属原子としては、Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Tiなどが挙げられる。共有結合または配位結合する有機化合物中の原子としては酸素原子などが挙げられ、有機化合物としてはアルキルエステル、アルコール化合物、カルボン酸化合物、エーテル化合物、ケトン化合物などが挙げられる。前記架橋剤は単独でまたは組み合わせて使用できる。
本発明の粘着剤組成物は、イオン性化合物を含有することができる。前記イオン性化合物としては、特に限定されるものではなく、本分野において用いられるものを好適に用いることができる。例えば、特開2015−4861号公報に記載されているものを挙げることができ、それらの中でも、(ペルフルオロアルキルスルホニル)イミドリチウム塩が好ましく、ビス(トリフルオロメタンスルホニルイミド)リチウムがより好ましい。また、前記イオン性化合物の割合は、特に限定されるものではなく、本発明の効果を損なわない範囲とすることができるが、例えば、前記(メタ)アクリル系ポリマー(A)100重量部に対して、10重量部以下が好ましく、5重量部以下がより好ましく、3重量部以下がさらに好ましく、1重量部以下が特に好ましい。
前記粘着剤組成物により、粘着剤層を形成するが、粘着剤層の形成にあたっては、架橋剤全体の添加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。
本発明の粘着剤層付光学フィルムは、光学フィルムの少なくとも一方の面に前記粘着剤層を有することを特徴とする。なお、前記粘着剤層の形成方法は、前述の通りである。
本発明の粘着剤層付光学フィルムは、透明基材上に透明導電層を有する透明導電性基材の前記透明導電層に貼り合せて、光学積層体として用いることができる。
本発明の画像表示装置は、前記光学積層体を備える液晶セルや有機ELセルを含む画像表示装置であって、前記粘着剤層付光学フィルムの粘着剤層が、前記液晶セルや有機ELセルの少なくとも片面に貼り合わされて用いられる。
(メタ)アクリル系ポリマー(A)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。Mw/Mnについても、同様に測定した。
・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
<合成例1〜2>
特開2013−129809号公報記載の実施例1に準じ、表1に記載の組成を有するオルガノポリシロキサン化合物(B1)および(B2)を合成して得る。
オルガノポリシロキサン化合物の組成は、以下条件の1H−NMR測定により確認した。
・分析装置:Bruker Biospin社製、AVANCEIII 600 with Cryo Probe
・観測周波数:600MHz(1H)
・測定溶媒:CDCl3
・測定温度:300K
・化学シフト基準:測定溶媒[1H:7.25ppm]
厚さ80μmのポリビニルアルコールフィルムを、速度比の異なるロール間において、30℃、0.3%濃度のヨウ素溶液中で1分間染色しながら、3倍まで延伸した。その後、60℃、4%濃度のホウ酸、10%濃度のヨウ化カリウムを含む水溶液中に0.5分間浸漬しながら総合延伸倍率が6倍まで延伸した。次いで、30℃、1.5%濃度のヨウ化カリウムを含む水溶液中に10秒間浸漬することで洗浄した後、50℃で4分間乾燥を行い、厚さ30μmの偏光子を得た。当該偏光子の両面に、けん化処理した厚さ80μmのトリアセチルセルロースフィルムをポリビニルアルコール系接着剤により貼り合せて偏光フィルムを作成した。
<アクリル系ポリマー(A1)の調製>
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76.9部、ベンジルアクリレート18部、アクリル酸5部、4−ヒドロキシブチルアクリレート0.1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)195万、Mw/Mn=3.9のアクリル系ポリマー(A1)の溶液を調製した。
上記で得られたアクリル系ポリマー(A1)の溶液の固形分100部に対して、イソシアネート架橋剤(東ソー社製、商品名「コロネートL」、トリメチロールプロパン/トリレンジイソシアネート付加物)0.4部、過酸化物架橋剤(日本油脂社製、商品名「ナイパーBMT」)0.1部、および合成例1で合成したオルガノポリシロキサン化合物(B1)0.05部を配合して、アクリル系粘着剤組成物の溶液を調製した。
次いで、上記で得られたアクリル系粘着剤組成物の溶液を、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(三菱化学ポリエステルフィルム製、商品名「MRF38」、セパレータフィルム)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(23℃55%RHにおける水分率が0.45%)を形成した。次いで、上記で作成した偏光フィルムに、セパレータフィルム上に形成した粘着剤層を転写して、粘着剤層付偏光フィルムを作製した。
実施例1において、表3に示すように、アクリル系ポリマーの調製に用いたモノマーの種類、その使用割合を変え、また製造条件を制御して、表3に記載のポリマー性状(重量平均分子量、Mw/Mn)のアクリル系ポリマーの溶液を調製した。
粘着剤層付偏光フィルムを、後述する接着力測定に使用したITO付きガラスに貼り付け、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、粘着剤層付偏光フィルムをITOガラスから剥離し、X線光電子分光法(ESCA)を用い、ITO表面についてワイドスキャン測定し、定性分析を行った。さらに、炭素、窒素、酸素、ケイ素、インジウム、スズの各元素についてナロースキャン測定を行い、これらの元素に対するSi元素の比率(atomic%)の算出を行った。なお、粘着剤層付偏光フィルムを貼り合せていないITOガラスの表面を測定した場合、Si元素は検出下限値である0.2atomic%未満だった。
・装置:ULVAC−PHI製、Quantum 2000
・X線源:モノクロAlKα・Xray Setting:200μmφ[15kV、30W]
・光電子取り出し角:試料表面に対して45度
・結合エネルギーの補正:C1sスペクトルのC−C結合由来のピークを285.0eVに補正
・中和条件:中和銃とArイオン銃(中和モード)の併用
粘着剤層付偏光フィルムを、150×25mm幅の大きさに裁断し、被着体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後、かかるサンプルの接着力を測定した。接着力は、かかるサンプルを引張り試験機(オートグラフSHIMAZU AG−1 1OKN)にて、剥離角度90°、剥離速度300mm/minで引き剥がす際の力(N/25mm、測定時80m長)を測定することにより求めた。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。
被着体として、厚さ0.7mmの無アルカリガラス(コーニング社製、商品名「EG−XG」)および、無アルカリガラスにITOをスパッタ成膜したITO付きガラスを用い、無アルカリガラスおよびITOに対する接着力をそれぞれ測定した。ITOはSn比率3wt%のものを使用した。なお、ITOのSn比率は、Sn原子の重量/(Sn原子の重量+In原子の重量)から算出した。
接着力測定に使用したITO付きガラスと同様のものを被着体として用いた。300×220mmの大きさに切断した粘着剤層付き偏光フィルムを、ラミネーターでITOガラスに貼合した。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ITO付きガラスに密着させた。かかる処理の施されたサンプルに、95℃、または105℃の各雰囲気下で500時間処理を施した後(加熱試験)、また、65℃/95%RHの雰囲気下で500時間処理を施した後(加湿試験)、偏光フィルムと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、剥がれなどの外観上の変化が全くなし。
○:わずかながら端部に剥がれ、または発泡があるが、実用上問題なし。
△: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。
接着力測定に使用したITO付きガラスと同様のものを被着体として用いた。粘着剤層付偏光フィルムを、縦420mm×横320mmに裁断し、ITO付きガラスに、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後、人の手によりITO付きガラスから粘着剤層付偏光フィルムを剥離した。評価は、上記手順で3回繰り返し実施し、下記基準でリワーク性を評価した。
◎:3枚とも糊残りやフィルムの破断がなく良好に剥離可能。
○:3枚中一部はフィルムが破断したが、再度の剥離によって剥がせた。
△:3枚ともフィルム破断したが、再度の剥離によって剥がせた。
×:3枚とも糊残りが生じるか、または何度は剥離してもフィルムが破断して剥がせなかった。
BAは、ブチルアクリレート;
BzAは、ベンジルアクリレート;
NVPは、N−ビニル−ピロリドン;
AAは、アクリル酸;
HBAは、4−ヒドロキシブチルアクリレート;を示す。
X−41−1056は、エポキシ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);
X−41−1810は、メルカプト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);
PDMSは、ポリジメチルシロキサン(信越化学工業社製、商品名「KF−96−20CS」);
イソシアネートは、イソシアネート架橋剤(東ソー社製、商品名「コロネートL」、トリメチロールプロパン/トリレンジイソシアネート付加物);
過酸化物は、過酸化物架橋剤(日本油脂社製、商品名「ナイパーBMT」);を示す。
2 視認側透明保護フィルム
3 偏光子
4 液晶セル側透明保護フィルム
5 粘着剤層
6 透明導電層
7 透明基材
8 液晶層
9 透明基材
10 粘着剤層
11 液晶セル側透明保護フィルム
12 偏光子
13 光源側透明保護フィルム
Claims (7)
- 透明基材と透明導電層を有する透明導電性基材の前記透明導電層に、粘着剤層付光学フィルムの粘着剤層が貼り合わされた光学積層体であり、
前記粘着剤層付光学フィルムは、光学フィルムと粘着剤層を有し、
前記粘着剤層は、モノマー単位として、少なくとも、アルキル(メタ)アクリレートを含有する(メタ)アクリル系ポリマー(A)と、ケイ素化合物(B)と、架橋剤を含有する粘着剤組成物から形成され、
前記(メタ)アクリル系ポリマー(A)は、モノマー単位として、前記(メタ)アクリル系ポリマー(A)を形成する全モノマー成分において15重量%以下のカルボキシル基含有モノマーを含有し、
前記ケイ素化合物(B)は、分子内に酸性基または酸性基に由来する酸無水物基を有するオルガノポリシロキサン化合物であり、
前記(メタ)アクリル系ポリマー(A)100重量部に対して、前記ケイ素化合物(B)が、0.05〜10重量部であり、
透明基材とインジウム−スズ複合酸化物層を有する透明導電性基材上の前記インジウム−スズ複合酸化物層に、前記粘着剤層と偏光フィルムを有する粘着剤層付偏光フィルムの粘着剤層が貼り合わされた積層体を、50℃、5気圧の条件で、15分間オートクレーブ処理した後、当該粘着剤層を剥離した際の前記インジウム−スズ複合酸化物層の面において、X線光電子分光分析により検出される、炭素、窒素、酸素、ケイ素、インジウム、スズの元素量の合計に対するケイ素元素の比率が、0.5atomic%以上5atomic%以下であることを特徴とする光学積層体。 - 前記粘着剤組成物が、反応性官能基含有シランカップリング剤を含有し、
前記反応性官能基が、エポキシ基、メルカプト基、アミノ基、イソシアネート基、イソシアヌレート基、ビニル基、スチリル基、アセトアセチル基、ウレイド基、チオウレア基、(メタ)アクリル基および複素環基のいずれか1つ以上であることを特徴とする請求項1記載の光学積層体。 - 前記(メタ)アクリル系ポリマー(A)100重量部に対して、前記反応性官能基含有シランカップリング剤が、0.01〜10重量部であることを特徴とする請求項2記載の光学積層体。
- 前記(メタ)アクリル系ポリマー(A)が、モノマー単位として、さらに、芳香族含有(メタ)アクリレート、アミド基含有モノマー、およびヒドロキシル基含有モノマーからなる群より選ばれる1つ以上の共重合モノマーを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光学積層体。
- 前記カルボキシル基含有モノマーが、前記(メタ)アクリル系ポリマー(A)を形成する全モノマー成分において、0.1重量%以上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光学積層体。
- 前記粘着剤層は、インジウム−スズ複合酸化物層に対する接着力が、剥離角度90°、剥離速度300mm/分の条件下で、15N/25mm以下であることを特徴とする請求項1〜5のいずれかに記載の光学積層体。
- 請求項1〜6のいずれかに記載の光学積層体を用いたことを特徴とする画像表示装置。
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TW201910470A (zh) | 2019-03-16 |
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JP2020059280A (ja) | 2020-04-16 |
KR20200035373A (ko) | 2020-04-03 |
JP2020143287A (ja) | 2020-09-10 |
JP6789432B2 (ja) | 2020-11-25 |
KR20210018547A (ko) | 2021-02-17 |
TW202134379A (zh) | 2021-09-16 |
JP6697637B2 (ja) | 2020-05-20 |
JP6789431B2 (ja) | 2020-11-25 |
KR20220146697A (ko) | 2022-11-01 |
WO2019031486A1 (ja) | 2019-02-14 |
JPWO2019031486A1 (ja) | 2019-11-07 |
KR102683203B1 (ko) | 2024-07-10 |
JP2020144381A (ja) | 2020-09-10 |
KR102217094B1 (ko) | 2021-02-18 |
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