JP5211844B2

JP5211844B2 - Patterned retardation film

Info

Publication number: JP5211844B2
Application number: JP2008129471A
Authority: JP
Inventors: 浩史長谷部; 修山崎; 清文竹内
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2008-05-16
Filing date: 2008-05-16
Publication date: 2013-06-12
Anticipated expiration: 2028-05-16
Also published as: JP2009276664A

Description

本願発明は、液晶ディスプレイ等の光学補償に使用される重合性液晶組成物を用いたパターン化位相差フィルムに関する。 The present invention relates to a patterned retardation film using a polymerizable liquid crystal composition used for optical compensation of a liquid crystal display or the like.

半透過型液晶ディスプレイの性能向上に有用な技術として、パターン化位相差フィルムの利用が提案されている（非特許文献１〜３、特許文献１〜２）。これは、一画素を透過領域と反射領域に分け、一方の領域にのみ位相差フィルムを設けるもので、20〜100μｍ程度の幅で位相差フィルムの有り無しがパターン化された位相差フィルムを使用するものである。 As a technique useful for improving the performance of a transflective liquid crystal display, use of a patterned retardation film has been proposed (Non-Patent Documents 1 to 3, Patent Documents 1 and 2). This is because one pixel is divided into a transmission area and a reflection area, and a retardation film is provided only in one area. A retardation film with a width of about 20 to 100 μm and patterned with or without a retardation film is used. To do.

しかしながら、従来のパターン化位相差フィルムは、パターン断面の側壁角が最適化されていないことに起因する光学特性の悪化によって、当該パターン化位相差フィルムを用い液晶ディスプレイの表示品位が悪い問題があった。 However, the conventional patterned retardation film has a problem in that the display quality of the liquid crystal display using the patterned retardation film is poor due to the deterioration of the optical characteristics caused by the optimization of the sidewall angle of the pattern cross section. It was.

C.Doornkamp, B.M.I. van der Zande, S.J. Roosendaal, L.W.G. Sofmeel, J.J. van Glabbeek, J.T.M. Osenga, J.A.M. Steenbakkers, "Next generation mobile LCDs with in-cell retarders", IDW’03, 685(2003).C.Doornkamp, B.M.I.van der Zande, S.J.Roosendaal, L.W.G.Sofmeel, J.J.van Glabbeek, J.T.M.Osenga, J.A.M.Steenbakkers, "Next generation mobile LCDs with in-cell retarders", IDW’03, 685 (2003). S.J.Roosendaal, B.M.I. van der Zande, A.C.Nieuwkerk, C.A. Renders, J.T.M. Osenga, C. Doornkamp, E.Peeters, J. Bruinink, J.A.M.M. van Haaren and S.Takahashi, "Novel High Performance Transflective LCD with a Patterned Retarder", SID’03, 78(2003).SJRoosendaal, BMI van der Zande, ACNieuwkerk, CA Renders, JTM Osenga, C. Doornkamp, E.Peeters, J. Bruinink, JAMM van Haaren and S. Takahashi, "Novel High Performance Transflective LCD with a Patterned Retarder", SID '03, 78 (2003). C.Doornkamp, S.J.Roosendaal, B.M.I. van der Zande, L.W.G. Stofmeel, J.J. van Glabbeek, J.T.M. Osenga, "Novel Transflective LCD with Ultra-wide Viewing Angle", SID’04, 670(2004).C. Doornkamp, S. J. Roosendaal, B.M.I.van der Zande, L.W.G.Stofmeel, J.J.van Glabbeek, J.T.M.Osenga, "Novel Transflective LCD with Ultra-wide Viewing Angle", SID’04, 670 (2004). 特開２００５−３３８２５６号公報JP 2005-338256 A 特開２００６−９８６２３号公報JP 2006-98623 A

本発明の解決しようとする課題は、液晶ディスプレイ等の光学補償に使用される重合性液晶組成物を用いたパターン化位相差フィルムにおいて、表示のにじみが無く、表示品位を確保できるものを提供することにある。 The problem to be solved by the present invention is to provide a patterned retardation film using a polymerizable liquid crystal composition used for optical compensation of a liquid crystal display or the like, which has no display blur and can ensure display quality. There is.

上記課題を解決するために鋭意検討した結果、パターン化位相差フィルムの断面形状を特定の条件に設定することにより解決できることを見出し、発明の完成に至った。
本願発明は、重合性液晶組成物の硬化物により構成されパターンを有するパターン化位相差フィルムにおける各パターンの断面において、該重合性液晶組成物の硬化時に活性エネルギー線を照射した側を上部、基板側を下部としたとき、上部のサイズ：Ａ、下部のサイズ：Ｂ、パターンの厚さ：Ｔから以下の式（１）
ＳＷＡ（°）＝ｔａｎ^-1｛（Ｂ−Ａ）／２／Ｔ｝式（１）
によって算出される側壁角：ＳＷＡが16°以上であり、重合性液晶組成物が一般式（I） As a result of intensive studies to solve the above-mentioned problems, it has been found that the cross-sectional shape of the patterned retardation film can be set to specific conditions, and the invention has been completed.
In the present invention, in the cross section of each pattern in a patterned retardation film composed of a cured product of the polymerizable liquid crystal composition and having a pattern, the side irradiated with active energy rays at the time of curing of the polymerizable liquid crystal composition is the upper part, the substrate When the side is the lower part, the following formula (1) is derived from the upper part size: A, the lower part size: B, and the pattern thickness: T.
SWA (°) = tan ⁻¹ {(BA) / 2 / T} Equation (1)
Side wall angle calculated by: SWA is 16 ° or more, and the polymerizable liquid crystal composition has the general formula (I)

（式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表し、MGはメソゲン基又はメソゲン性支持基を表し、R¹は、ハロゲン原子、シアノ基又は炭素原子数１〜２５のアルキル基を表すが、該アルキル基は１つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する１つのCH₂基又は隣接していない２つ以上のCH₂基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH₃)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良く、あるいはR¹は一般式（I-a）

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, m represents 0 or 1, MG represents a mesogenic group or a mesogenic support group, and R ¹ represents Represents a halogen atom, a cyano group or an alkyl group having 1 to 25 carbon atoms, and the alkyl group may be substituted by one or more halogen atoms or CN, and one CH ₂ present in the group. Group or two or more non-adjacent CH ₂ groups are each independently of each other such that —O—, —S—, —NH—, —N (CH ₃ ) -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, or R ¹ may be represented by the general formula (Ia)

（式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表す。）で表される構造を表す。）で表される化合物を92.35質量％から96.84質量％含有することを特徴とするパターン化位相差フィルムを提供する。図１にA、B、T、SWAの定義を示す。

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, and m represents 0 or 1). The patterned retardation film is characterized in that it contains 92.35% by mass to 96.84% by mass of the compound represented by formula (1). FIG. 1 shows the definitions of A, B, T, and SWA.

パターン化位相差フィルムを用いた液晶ディスプレイの表示にじみが改善し、表示品位が改善される。 The display blur of the liquid crystal display using the patterned retardation film is improved, and the display quality is improved.

側壁角は、16度以上が好ましく、35度以上がさらに好ましい。
重合性液晶組成物には3〜5質量%の重合開始剤、0.1〜1.5質量%の重合性禁止剤を含有させることが好ましい。重合開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド等が挙げられる。具体的には、「Irugarue-819」、「Irugarue-651」、「Irugarue-184D」、「Irugarue-1800」、「Irugarue-907」、「Irugarue-369」（以上、チバスペシャリティケミカルズ社製）、「ルシリンTPO」（BASF社製）が挙げられる。これらの中でも、硬化時の雰囲気を窒素置換をしなくても硬化性を確保できる「Irugarue-907」、「Irugarue-369」が好ましく、硬化性が優れる「Irgacure-907」が最も好ましい。

The side wall angle is preferably 16 degrees or more, and more preferably 35 degrees or more .
The polymerizable liquid crystal composition preferably contains 3 to 5% by mass of a polymerization initiator and 0.1 to 1.5% by mass of a polymerizable inhibitor. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Specifically, “Irugarue-819”, “Irugarue-651”, “Irugarue-184D”, “Irugarue-1800”, “Irugarue-907”, “Irugarue-369” (above, manufactured by Ciba Specialty Chemicals) “Lucirin TPO” (manufactured by BASF) may be mentioned. Among these, “Irugarue-907” and “Irugarue-369”, which can ensure curability without replacing the atmosphere during curing with nitrogen, are preferable, and “Irgacure-907” having excellent curability is most preferable.

重合禁止剤としては、例えば、ヒドロキノン、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β−ナフチルアミン類、β−ナフトール類、ニトロソ化合物等が挙げられる。より具体的にはメトキシフェノール、2,6-ジ-tert-ブチルフェノールを挙げることができる。重合開始剤と重合禁止剤の好ましい組み合わせの一例は、重合開始剤として「Irgacure-907」、重合禁止剤として「メトキシフェノール」の組み合わせである。重合禁止剤の添加濃度をC（%）、重合開始剤の濃度をD（%）としたとき、C/D*10000（以後、この値をパラメータEと呼ぶ）が333〜3750になるように設定することが好ましく、600〜2500が更に好ましく、800〜2000が特に好ましい。パラメータEが小さいと解像度と側壁角が悪化する傾向があり、パラメータEが大きいと硬化性が悪化する傾向がある。 Examples of the polymerization inhibitor include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like. More specific examples include methoxyphenol and 2,6-di-tert-butylphenol. An example of a preferable combination of a polymerization initiator and a polymerization inhibitor is a combination of “Irgacure-907” as a polymerization initiator and “methoxyphenol” as a polymerization inhibitor. When the addition concentration of the polymerization inhibitor is C (%) and the concentration of the polymerization initiator is D (%), C / D * 10000 (hereinafter, this value is referred to as parameter E) is 333 to 3750. It is preferable to set, 600 to 2500 is more preferable, and 800 to 2000 is particularly preferable. When the parameter E is small, the resolution and the side wall angle tend to deteriorate, and when the parameter E is large, the curability tends to deteriorate.

一般式（I）において、Spがアルキレン基を表し（該アルキレン基は１つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する１つのCH₂基又は隣接していない２つ以上のCH₂基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH₃)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良い。）、MGが一般式（I-b） In the general formula (I), Sp represents an alkylene group (the alkylene group may be substituted by one or more halogen atoms or CN, and is not adjacent to one CH ₂ group present in the group) Two or more CH ₂ groups are independently of each other, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted.), MG is represented by the general formula (Ib)

（式中、A1、A2及びA3はそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基は置換基として１個以上のF、Cl、CF₃、OCF₃、シアノ基、炭素原子数１〜８のアルキル基、アルコキシ基、アルカノイル基、アルカノイルオキシ基、炭素原子数２〜８のアルケニル基、アルケニルオキシ基、アルケノイル基又はアルケノイルオキシ基を有していても良く、Z0、Z1、Z2及びZ3はそれぞれ独立して、-COO-、-OCO-、-CH₂ CH₂-、-OCH₂-、-CH₂O-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CH₂CH₂COO-、-CH₂CH₂OCO-、-COO CH₂CH₂-、-OCOCH₂CH₂-、-CONH-、-NHCO-又は単結合を表し、nは０、１又は２を表す。）で表される構造を表し、Pが一般式（I-c）、一般式（I-d）及び一般式（I-e） (In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-Dihydrophenanthrene-2,7-diyl group 1,2,3,4,4a, 9,10a- octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group is 1 or more F as _{_{substituents, Cl, CF 3, OCF 3}} , cyano Group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group. , Z0, Z1, Z2 and Z3 are each independently -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -C≡C -, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COO CH ₂ CH _2- , -OCOCH ₂ CH _2- , -CONH-,- NHCO- or a single bond, n represents 0, 1 or 2), and P represents a general formula (Ic), general formula (Id) and general formula (Ie)

（式中、R²¹、R²²、R²³、R³¹、R³²、R³³、R⁴¹、R⁴²及びR⁴³はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１〜５のアルキル基を表し、nは０又は１を表す。）で表される置換基からなる群より選ばれる置換基を表す、で表される化合物を含有するものが好ましい。
ここで、重合性液晶組成物に含有される化合物として、より具体的には一般式（II） (In the formula, R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1) and preferably contains a compound represented by the formula: wherein the substituent is selected from the group consisting of substituents represented by:
Here, the compound contained in the polymerizable liquid crystal composition is more specifically represented by the general formula (II)

（式中、mは０又は１を表し、W¹及びW²はそれぞれ独立的に単結合、-O-、-COO-又は-OCO-を表し、Y¹及びY²はそれぞれ独立的に-COO-又は-OCO-を表し、r及びsはそれぞれ独立的に２〜１８の整数を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良い。）を挙げることができる。
又、一般式（III） Wherein m represents 0 or 1, W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ¹ and Y ² each independently represent — COO- or -OCO- is represented, and r and s each independently represent an integer of 2 to 18, the 1,4-phenylene group present in the formula is an alkyl group or alkoxy group having 1 to 7 carbon atoms , An alkanoyl group, a cyano group, or a halogen atom, which may be substituted one or more times.
In addition, the general formula (III)

（式中、Z¹は水素原子、ハロゲン原子、シアノ基又は炭素原子数１〜２０の炭化水素基を表し、Z²は水素原子又はメチル基を表し、tは０又は1を表し、A、B及びCはそれぞれ独立的に、1,4−フェニレン基、隣接しないCH基が窒素で置換された1,4−フェニレン基、1,4−シクロヘキシレン基、１つ又は隣接しない２つのCH₂基が酸素又は硫黄原子で置換された1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y³及びY⁴はそれぞれ独立的に単結合、-CH₂CH₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH₂）₄-、-CH₂CH₂CH₂O-、-OCH₂CH₂CH₂-、-CH=CHCH₂CH₂-、-CH₂CH₂CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH₂CH₂COO-、-CH₂CH₂OCO-、-COO CH₂CH₂-又は-OCOCH₂CH₂-を表し、Y⁵は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物も挙げることができる。一般式（III）で表される化合物の含有量は30質量％以下が好ましく、20質量％以下が更に好ましい。
又、一般式（IV） (In the formula, Z ¹ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z ² represents a hydrogen atom or a methyl group, t represents 0 or 1, A, B and C are each independently a 1,4-phenylene group, a 1,4-phenylene group in which a non-adjacent CH group is substituted with nitrogen, a 1,4-cyclohexylene group, one or two non-adjacent CH ₂ Represents a 1,4-cyclohexylene group or 1,4-cyclohexenylene group in which the group is substituted with an oxygen or sulfur atom, and the 1,4-phenylene group present in the formula is an alkyl having 1 to 7 carbon atoms Group, an alkoxy group, an alkanoyl group, a cyano group or a halogen atom, and Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, _{-OCH 2 -, - COO -,} - OCO -, - C≡C -, - CH = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH ₂ CH ₂ CH _2- , -CH = CHCH ₂ CH _2- , -CH ₂ _{CH 2 CH = CH -, -} CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH ₂ CH ₂ - and And Y ⁵ represents a single bond, —O—, —COO—, —OCO—, or —CH═CHCOO—). The content of the compound represented by the general formula (III) is preferably 30% by mass or less, and more preferably 20% by mass or less.
In addition, general formula (IV)

（式中、Z³は水素原子、ハロゲン原子、シアノ基又は炭素原子数１〜２０の炭化水素基を表し、Z⁴は水素原子又はメチル基を表し、W³は単結合、-O-、-COO-又は-OCO-を表し、vは２〜１８の整数を表し、uは０又は１を表し、D、E及びFはそれぞれ独立的に、1,4−フェニレン基、隣接しないCH基が窒素で置換された1,4−フェニレン基、1,4−シクロヘキシレン基、１つ又は隣接しない２つのCH₂基が酸素又は硫黄原子で置換された1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y⁶及びY⁷はそれぞれ独立的に単結合、-CH₂CH₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH₂）₄-、-CH₂CH₂CH₂O-、-OCH₂CH₂CH₂-、-CH=CHCH₂CH₂-、-CH₂CH₂CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH₂CH₂COO-、-CH₂CH₂OCO-、-COO CH₂CH₂-又は-OCOCH₂CH₂-を表し、Y⁸は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物を挙げることもできる。一般式（III）で表される化合物の含有量は30質量％以下が好ましく、20質量％以下が更に好ましい。一般式（I）で表される化合物の具体例を以下に挙げることができる。 (Wherein Z ³ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z ⁴ represents a hydrogen atom or a methyl group, W ³ represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 2 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, but the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF _{_{-, - (CH 2) 4}} -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH ₂ CH ₂ - represents, Y ⁸ represents a single bond, - And a compound represented by O-, -COO-, -OCO-, or -CH = CHCOO-). The content of the compound represented by the general formula (III) is preferably 30% by mass or less, and more preferably 20% by mass or less. Specific examples of the compound represented by the general formula (I) can be given below.

（式中、j、k、l及びmはそれぞれ独立的に２〜１８の整数を表す。）
又、一般式（II）で表される化合物の具体例を以下に挙げることができる。 (Wherein j, k, l and m each independently represent an integer of 2 to 18)
Specific examples of the compound represented by the general formula (II) can be given below.

（式中、j及びkはそれぞれ独立的に２〜１８の整数を表す。）
又、一般式（III）で表される化合物の具体的な例として、化合物の構造と相転移温度を以下に挙げることができる。 (Wherein j and k each independently represents an integer of 2 to 18)
Specific examples of the compound represented by the general formula (III) include the structure of the compound and the phase transition temperature.

（式中、シクロヘキサン環はトランスシクロヘキサン環を表し、数字は相転移温度を表し、Cは結晶相、Nはネマチック相、Sはスメクチック相、Iは等方性液体相をそれぞれ表す。）
又、一般式（IV）で表される化合物の具体例を以下に挙げることができる。 (In the formula, a cyclohexane ring represents a transcyclohexane ring, a number represents a phase transition temperature, C represents a crystalline phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase.)
Specific examples of the compound represented by the general formula (IV) can be given below.

（式中、X¹は水素原子又はメチル基を表し、Rは炭素原子数１から２０のアルキル基を表す。）
重合性液晶組成物中の重合性液晶については、単官能材料の濃度を20質量％以下にするのが好ましく、10質量％以下にするのが更に好ましい。これによって、位相差フィルムの耐熱性が向上する。 (In the formula, X ¹ represents a hydrogen atom or a methyl group, and R represents an alkyl group having 1 to 20 carbon atoms.)
With respect to the polymerizable liquid crystal in the polymerizable liquid crystal composition, the concentration of the monofunctional material is preferably 20% by mass or less, and more preferably 10% by mass or less. Thereby, the heat resistance of the retardation film is improved.

又、円盤状化合物は、ベンゼン誘導体、トリフェニレン誘導体、トルキセン誘導体、フタロシアニン誘導体又はシクロヘキサン誘導体を分子の中心の母核とし、直鎖のアルキル基、直鎖のアルコキシ基又は置換ベンゾイルオキシ基がその側鎖として放射状に置換した構造であることが好ましく、一般式（V）で表される In addition, the discotic compound has a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative as a mother nucleus at the center of the molecule, and a linear alkyl group, a linear alkoxy group, or a substituted benzoyloxy group is a side chain. It is preferable that the structure is a radially substituted structure represented by the general formula (V).

（式中、R⁵はそれぞれ独立して一般式（V-a）で表される置換基を表す。） (In the formula, each R ⁵ independently represents a substituent represented by the general formula (Va).)

（式中、R⁶及びR⁷はそれぞれ独立的に水素原子、ハロゲン原子又はメチル基を表し、R⁸は炭素原子数１〜２０アルコキシ基を表すが、該アルコキシ基中の水素原子は一般式（V-b）、一般式（V-c）又は一般式（V-d）で表される置換基によって置換されていても良い。） (In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ⁸ represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group represents a general formula. (It may be substituted by a substituent represented by (Vb), general formula (Vc) or general formula (Vd).)

（式中、R⁸¹、R⁸²、R⁸³、R⁸⁴、R⁸⁵、R⁸⁶、R⁸⁷、R⁸⁸及びR⁸⁹はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１〜５のアルキル基を表し、nは０又は１を表す。）で表される構造を有することがさらに好ましく、一般式（V）においてR⁸の内少なくとも一つは一般式（V-b）、一般式（V-c）又は一般式（V-d）で表される置換基によって置換されたアルコキシ基を表すことが好ましく、R⁸の全てが一般式（V-b）、一般式（V-c）又は一般式（V-d）で表される置換基によって置換されたアルコキシ基を表すことが特に好ましい。
さらに、一般式(V-a)は具体的には一般式(V-e) Wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1.) In general formula (V), at least one of R ⁸ is represented by general formula (Vb), general formula (Vc) or It preferably represents an alkoxy group substituted by a substituent represented by the general formula (Vd), and all of R ⁸ are substituted represented by the general formula (Vb), the general formula (Vc) or the general formula (Vd). It is particularly preferred to represent an alkoxy group substituted by a group.
Further, the general formula (Va) specifically represents the general formula (Ve).

（式中ｎは２〜９の整数を表す）で表される構造を有することが特に好ましい。
また、重合性液晶組成物中に一般式（VI）

It is particularly preferable to have a structure represented by the formula (wherein n represents an integer of 2 to 9).
In the polymerizable liquid crystal composition, the general formula (VI)

（式中、R¹、R²、R³及びR⁴はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数1〜２０の炭化水素基を表し、該炭化水素基中の水素原子は１つ以上のハロゲン原子で置換されていても良い。）で表される繰り返し単位を有する重量平均分子量が１００以上である化合物を含有させることが好ましい。これによって重合性液晶分子の配向を水平方向にすることができる。添加量は0.05〜0.3質量％が好ましく、0.06〜0.15質量％が更に好ましい。

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one hydrocarbon atom in the hydrocarbon group. It may be substituted with the above halogen atom.) It is preferable to contain a compound having a repeating unit represented by the following formula and having a weight average molecular weight of 100 or more. Thereby, the alignment of the polymerizable liquid crystal molecules can be made horizontal. The addition amount is preferably 0.05 to 0.3% by mass, and more preferably 0.06 to 0.15% by mass.

一般式（VI）で表される化合物は、例えばポリエチレン、ポリプロピレン、ポリイソブチレン、パラフィン、流動パラフィン、塩素化ポリプロピレン、塩素化パラフィン、又は塩素化流動パラフィンが挙げられる。これ以外にも、フッ素原子が導入された化合物はムラ抑制の観点からも有効である。
一般式（VI）で表される繰り返し単位を有する化合物のうち、好適な構造として、式（VI-a）〜式（VI-f） Examples of the compound represented by the general formula (VI) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin. In addition to this, a compound in which a fluorine atom is introduced is also effective from the viewpoint of suppressing unevenness.
Among the compounds having a repeating unit represented by the general formula (VI), as a preferred structure, the formula (VI-a) to the formula (VI-f)

で表される繰り返し単位を有する化合物が挙げられる。中でも、式（VI-a）〜式（VI-e）で表される構造がより好ましく、式（VI-a）及び式（VI-c）で表される構造が特に好ましい。又、式（VI-a）〜式（VI-f）で表される繰り返し単位を有する化合物を２種以上共重合させた共重合体も好ましい。この場合、式（VI-a）及び式（VI-b）を有する共重合体、式（VI-a）及び式（VI-c）を有する共重合体、式（VI-a）及び式（VI-f）を有する共重合体、及び、式（VI-a）、（VI-b）及び式（VI-f）を有する共重合体がより好ましく、式（VI-a）及び式（VI-b）を有する共重合体、及び、式（VI-a）、（VI-b）及び式（VI-f）を有する共重合体が特に好ましい。 The compound which has a repeating unit represented by these is mentioned. Among these, structures represented by formulas (VI-a) to (VI-e) are more preferable, and structures represented by formulas (VI-a) and (VI-c) are particularly preferable. A copolymer obtained by copolymerizing two or more compounds having a repeating unit represented by formula (VI-a) to formula (VI-f) is also preferable. In this case, a copolymer having the formula (VI-a) and the formula (VI-b), a copolymer having the formula (VI-a) and the formula (VI-c), the formula (VI-a) and the formula ( More preferred are copolymers having VI-f) and copolymers having formulas (VI-a), (VI-b) and formula (VI-f), wherein formula (VI-a) and formula (VI Particularly preferred are copolymers having -b) and copolymers having the formulas (VI-a), (VI-b) and (VI-f).

重合性液晶組成物に界面活性剤を含有させることは好ましい。これによって、位相差フィルム表面の平坦性が向上する。界面活性剤は、イオン性界面活性剤、非イオン性界面活性剤の区別はない。含有することができる界面活性剤としては、アルキルカルボン酸塩、アルキルリン酸塩、アルキルスルホン酸塩、フルオロアルキルカルボン酸塩、フルオロアルキルリン酸塩、フルオロアルキルスルホン酸塩、ポリオキシエチレン誘導体、フルオロアルキルエチレンオキシド誘導体、ポリエチレングリコール誘導体、アルキルアンモニウム塩、フルオロアルキルアンモニウム塩類、シリコーン誘導体等をあげることができ、特に含フッ素界面活性剤、シリコーン誘導体が好ましい。更に具体的には「ＭＥＧＡＦＡＣＦ−１１０」、「ＭＥＧＡＦＡＣＦ−１１３」、「ＭＥＧＡＦＡＣＦ−１２０」、「ＭＥＧＡＦＡＣＦ−８１２」、「ＭＥＧＡＦＡＣＦ−１４２Ｄ」、「ＭＥＧＡＦＡＣＦ−１４４Ｄ」、「ＭＥＧＡＦＡＣＦ−１５０」、「ＭＥＧＡＦＡＣＦ−１７１」、「ＭＥＧＡＦＡＣＦ−１７３」、「ＭＥＧＡＦＡＣＦ−１７７」、「ＭＥＧＡＦＡＣＦ−１８３」、「ＭＥＧＡＦＡＣＦ−１９５」、「ＭＥＧＡＦＡＣＦ−８２４」、「ＭＥＧＡＦＡＣＦ−８３３」、「ＭＥＧＡＦＡＣＦ−１１４」、「ＭＥＧＡＦＡＣＦ−４１０」、「ＭＥＧＡＦＡＣＦ−４９３」、「ＭＥＧＡＦＡＣＦ−４９４」、「ＭＥＧＡＦＡＣＦ−４４３」、「ＭＥＧＡＦＡＣＦ−４４４」、「ＭＥＧＡＦＡＣＦ−４４５」、「ＭＥＧＡＦＡＣＦ−４４６」、「ＭＥＧＡＦＡＣＦ−４７０」、「ＭＥＧＡＦＡＣＦ−４７１」、「ＭＥＧＡＦＡＣＦ−４７４」、「ＭＥＧＡＦＡＣＦ−４７５」、「ＭＥＧＡＦＡＣＦ−４７７」、「ＭＥＧＡＦＡＣＦ−４７８」、「ＭＥＧＡＦＡＣＦ−４７９」、「ＭＥＧＡＦＡＣＦ−４８０ＳＦ」、「ＭＥＧＡＦＡＣＦ−４８２」、「ＭＥＧＡＦＡＣＦ−４８３」、「ＭＥＧＡＦＡＣＦ−４８４」、「ＭＥＧＡＦＡＣＦ−４８６」、「ＭＥＧＡＦＡＣＦ−４８７」、「ＭＥＧＡＦＡＣＦ−４８９」、「ＭＥＧＡＦＡＣＦ−１７２Ｄ」、「ＭＥＧＡＦＡＣＦ−１７８Ｋ」、「ＭＥＧＡＦＡＣＦ−１７８ＲＭ」、「ＭＥＧＡＦＡＣＲ−０８」、「ＭＥＧＡＦＡＣＲ−３０」、「ＭＥＧＡＦＡＣＦ−４７２ＳＦ」、「ＭＥＧＡＦＡＣＢＬ−２０」、「ＭＥＧＡＦＡＣＲ−６１」、「ＭＥＧＡＦＡＣＲ−９０」、「ＭＥＧＡＦＡＣＥＳＭ−１」、「ＭＥＧＡＦＡＣＭＣＦ−３５０ＳＦ」（以上、DIC株式会社製）、「フタージェント１００」、「フタージェント１００Ｃ」、「フタージェント１１０」、「フタージェント１５０」、「フタージェント１５０ＣＨ」、「フタージェントＡ」、「フタージェント１００Ａ-Ｋ」、「フタージェント５０１」、「フタージェント３００」、「フタージェント３１０」、「フタージェント３２０」、「フタージェント４００ＳＷ」、「ＦＴＸ-４００Ｐ」、「フタージェント２５１」、「フタージェント２１５Ｍ」、「フタージェント２１２ＭＨ」、「フタージェント２５０」、「フタージェント２２２Ｆ」、「フタージェント２１２Ｄ」、「ＦＴＸ-２１８」、「ＦＴＸ-２０９Ｆ」、「ＦＴＸ-２１３Ｆ」、「ＦＴＸ-２３３Ｆ」、「フタージェント２４５Ｆ」、「ＦＴＸ-２０８Ｇ」、「ＦＴＸ-２４０Ｇ」、「ＦＴＸ-２０６Ｄ」、「ＦＴＸ-２２０Ｄ」、「ＦＴＸ-２３０Ｄ」、「ＦＴＸ-２４０Ｄ」、「ＦＴＸ-２０７Ｓ」、「ＦＴＸ-２１１Ｓ」、「ＦＴＸ-２２０Ｓ」、「ＦＴＸ-２３０Ｓ」、「ＦＴＸ-７５０ＦＭ」、「ＦＴＸ-７３０ＦＭ」、「ＦＴＸ-７３０ＦＬ」、「ＦＴＸ-７１０ＦＳ」、「ＦＴＸ-７１０ＦＭ」、「ＦＴＸ-７１０ＦＬ」、「ＦＴＸ-７５０ＬＬ」、「ＦＴＸ-７３０ＬＳ」、「ＦＴＸ-７３０ＬＭ」、「ＦＴＸ-７３０ＬＬ」、「ＦＴＸ-７１０ＬＬ」（以上、ネオス社製）、「ＢＹＫ−３００」、「ＢＹＫ−３０２」、「ＢＹＫ−３０６」、「ＢＹＫ−３０７」、「ＢＹＫ−３１０」、「ＢＹＫ−３１５」、「ＢＹＫ−３２０」、「ＢＹＫ−３２２」、「ＢＹＫ−３２３」、「ＢＹＫ−３２５」、「ＢＹＫ−３３０」、「ＢＹＫ−３３１」、「ＢＹＫ−３３３」、「ＢＹＫ−３３７」、「ＢＹＫ−３４０」、「ＢＹＫ−３４４」、「ＢＹＫ−３７０」、「ＢＹＫ−３７５」、「ＢＹＫ−３７７」、「ＢＹＫ−３５０」、「ＢＹＫ−３５２」、「ＢＹＫ−３５４」、「ＢＹＫ−３５５」、「ＢＹＫ−３５６」、「ＢＹＫ−３５８Ｎ」、「ＢＹＫ−３６１Ｎ」、「ＢＹＫ−３５７」、「ＢＹＫ−３９０」、「ＢＹＫ−３９２」、「ＢＹＫ−ＵＶ３５００」、「ＢＹＫ−ＵＶ３５１０」、「ＢＹＫ−ＵＶ３５７０」、「ＢＹＫ−Ｓｉｌｃｌｅａｎ３７００」（以上、ビックケミー・ジャパン社製）、「ＴＥＧＯＲａｄ２１００」、「ＴＥＧＯＲａｄ２２００Ｎ」、「ＴＥＧＯＲａｄ２２５０」、「ＴＥＧＯＲａｄ２３００」、「ＴＥＧＯＲａｄ２５００」、「ＴＥＧＯＲａｄ２６００」、「ＴＥＧＯＲａｄ２７００」（以上、テゴ社製）等の例をあげることができる。添加量は、重合性液晶組成物中に０．０１〜１質量％含有することが好ましく、０．０２〜０．５質量％含有することがさらに好ましく、０．０３〜０．１質量％含有することが特に好ましい。 It is preferable to include a surfactant in the polymerizable liquid crystal composition. Thereby, the flatness of the retardation film surface is improved. As the surfactant, there is no distinction between an ionic surfactant and a nonionic surfactant. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts, silicone derivatives and the like, and fluorine-containing surfactants and silicone derivatives are particularly preferable. More specifically, “MEGAFAC F-110”, “MEGAFACCF-113”, “MEGAFAC F-120”, “MEGAFAC F-812”, “MEGAFAC F-142D”, “MEGAFAC F-144D”, “MEGAFAC F-” 150 "," MEGAFAC F-171 "," MEGAFACCF-173 "," MEGAFAC F-177 "," MEGAFAC F-183 "," MEGAFAC F-195 "," MEGAFAC F-824 "," MEGAFAC F-833 " , “MEGAFAC F-114”, “MEGAFAC F-410”, “MEGAFAC F-493”, “MEGAFAC F-494”, “MEGAFAC F-443”, “MEGAFAC F-444”, “MEGAFAC F-445”, "ME GAFAC F-446, MEGAFAC F-470, MEGAFAC F-471, MEGAFAC F-474, MEGAFAC F-475, MEGAFAC F-477, MEGAFAC F-478, MEGAFAC F-479, MEGAFAC F-480SF, MEGAFAC F-482, MEGAFAC F-483, MEGAFAC F-484, MEGAFAC F-486, MEGAFAC F-487, MEGAFAC F -489 "," MEGAFAC F-172D "," MEGAFAC F-178K "," MEGAFAC F-178RM "," MEGAFAC R-08 "," MEGAFAC R-30 "," MEGAFAC F-472SF "," MEGAFAC " “BL-20”, “MEGAFAC R-61”, “MEGAFAC R-90”, “MEGAFAC ESM-1”, “MEGAFAC MCF-350SF” (manufactured by DIC Corporation), “Factent 100”, “Factent” 100C "," Factent 110 "," Factent 150 "," Factent 150CH "," Factent A "," Factent 100A-K "," Factent 501, "" Factent 300 "," Factent " 310 "," Factent 320 "," Factent 400SW "," FTX-400P "," Factent 251 "," Factent 215M "," Factent 212MH "," Factent 250 "," Factent 222F " , “Fargent 212 ”,“ FTX-218 ”,“ FTX-209F ”,“ FTX-213F ”,“ FTX-233F ”,“ Factent 245F ”,“ FTX-208G ”,“ FTX-240G ”,“ FTX-206D ”, "FTX-220D", "FTX-230D", "FTX-240D", "FTX-207S", "FTX-211S", "FTX-220S", "FTX-230S", "FTX-750FM", "FTX -730FM "," FTX-730FL "," FTX-710FS "," FTX-710FM "," FTX-710FL "," FTX-750LL "," FTX-730LS "," FTX-730LM "," FTX-730LLL " ”,“ FTX-710LL ”(from Neos),“ BYK-300 ”,“ BYK-302 ”,“ BYK-306 ”,“ BYK-307 ” , “BYK-310”, “BYK-315”, “BYK-320”, “BYK-322”, “BYK-323”, “BYK-325”, “BYK-330”, “BYK-331”, “ "BYK-333", "BYK-337", "BYK-340", "BYK-344", "BYK-370", "BYK-375", "BYK-377", "BYK-350", "BYK-" 352 "," BYK-354 "," BYK-355 "," BYK-356 "," BYK-358N "," BYK-361N "," BYK-357 "," BYK-390 "," BYK-392 " , “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “BYK-Silklean 3700” (above, manufactured by Big Chemie Japan), “TE O Rad2100 "," TEGO Rad2200N "," TEGO Rad2250 "," TEGO Rad2300 "," TEGO Rad2500 "," TEGO Rad2600 "," TEGO Rad2700 "(or more, Tego Co., Ltd.) can be mentioned an example of such. The addition amount is preferably 0.01 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass in the polymerizable liquid crystal composition. It is particularly preferable to do this.

本発明の位相差フィルムは例えば、図１〜３に示すように、配向膜付き基板（３、４）、もしくは基板上（４）に重合性液晶組成物を坦持させて重合性液晶組成物層を形成する第一工程、重合性液晶組成物層にマスク（６）を介して活性エネルギー線（５）を照射することにより露光部を硬化させる第二工程、未硬化部を除去する第三工程を含む製造工程を適用することによって製造することができる。 The retardation film of the present invention is, for example, as shown in FIGS. 1 to 3, a polymerizable liquid crystal composition by carrying a polymerizable liquid crystal composition on a substrate with an alignment film (3, 4) or on a substrate (4). A first step of forming a layer, a second step of curing the exposed portion by irradiating the polymerizable liquid crystal composition layer with an active energy ray (5) through a mask (6), and a third step of removing the uncured portion. It can manufacture by applying the manufacturing process containing a process.

基板に重合性液晶組成物を坦持させて重合性液晶組成物層を形成する第一工程としては、例えば、重合性液晶組成物を溶媒に溶解させ、これを基板上に塗布し、さらに溶媒を揮発させる方法を挙げることができる。重合性液晶を溶剤に溶解させないで、そのまま、基板上に塗布することも可能である。好適な有機溶媒として例えばトルエン、キシレン、クメンなどのアルキル置換ベンゼンやプロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、シクロヘキサノン、シクロペンンタノン等を挙げることができる。さらにこれらの溶媒にジメチルホルムアミド、γ−ブチロラクトン、N-メチルピロリジノン、メチルエチルケトン、酢酸エチル等を添加しても良い。溶媒を揮発させる方法としては60〜150℃、さらに好ましくは80℃〜120℃での加熱を、15〜120秒、さらに好ましくは30〜90秒の間行う方法を例示することができる。この加熱の他に、減圧乾燥を組み合わせることもできる。塗布の方法としては、スピンコーティング、ダイコーティング、エクストルージョンコーティング、ロールコーティング、ワイヤーバーコーティング、グラビアコーティング、スプレーコーティング、ディッピング、プリント法等を挙げることができる。 As the first step of forming the polymerizable liquid crystal composition layer by supporting the polymerizable liquid crystal composition on the substrate, for example, the polymerizable liquid crystal composition is dissolved in a solvent, applied onto the substrate, The method of volatilizing can be mentioned. It is also possible to apply the polymerizable liquid crystal directly onto the substrate without dissolving it in the solvent. Suitable organic solvents include, for example, alkyl-substituted benzenes such as toluene, xylene, cumene, propylene glycol monomethyl ether acetate, butyl acetate, cyclohexanone, cyclopentanone and the like. Further, dimethylformamide, γ-butyrolactone, N-methylpyrrolidinone, methyl ethyl ketone, ethyl acetate and the like may be added to these solvents. Examples of the method for volatilizing the solvent include a method in which heating at 60 to 150 ° C., more preferably 80 to 120 ° C. is performed for 15 to 120 seconds, more preferably 30 to 90 seconds. In addition to this heating, vacuum drying can be combined. Examples of the application method include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing.

活性エネルギー線としては紫外線を使用することが好ましい。照射量は50〜900mJ/cm²が好ましく、60〜500mJ/cm²が更に好ましく、80〜300mJ/cm²が特に好ましい。照射量が少ないと、得られる位相差フィルムの機械的特性や耐熱性が悪化する傾向がある。一方、照射量が多いと機械的特性や耐熱性は良くなるものの、解像度が悪くなり、細かいパターンを形成することが困難になる傾向や、側壁角が小さくなってしまう傾向がある。また、紫外線の強度の設定も重要である。紫外線強度は2〜100mW/cm²が好ましく、10〜50mW/cm²が更に好ましい。紫外線強度が弱いとマスク露光に必要な時間が長くなり生産性が悪化する傾向がある。紫外線強度が強いと、解像度や側壁角が小さくなってしまう傾向がある。マスクと重合性液晶組成物層との距離ｄは、150μｍ以下が好ましく、100ミクロン以下が更に好ましく、80μｍ以下が特に好ましい。50μｍ以下にすれば更に良い結果が得られるものの、距離ｄをあまり小さくするとマスクと重合性液晶組成物層が接触してしまうので、実用上は10μｍ以上にすることが好ましい。 It is preferable to use ultraviolet rays as the active energy rays. Irradiation dose is preferably 50~900mJ / cm ^2, more preferably ^{60~500mJ / cm 2, 80~300mJ / cm} 2 is particularly preferred. If the irradiation amount is small, the mechanical properties and heat resistance of the resulting retardation film tend to deteriorate. On the other hand, when the irradiation amount is large, the mechanical properties and heat resistance are improved, but the resolution is deteriorated, and it tends to be difficult to form a fine pattern, and the side wall angle tends to be small. The setting of the intensity of ultraviolet rays is also important. The ultraviolet intensity is preferably ² to 100 mW / cm ^2, more preferably 10 to 50 mW / cm ² . If the intensity of ultraviolet rays is weak, the time required for mask exposure tends to be long and productivity tends to deteriorate. When the ultraviolet intensity is strong, the resolution and the side wall angle tend to be small. The distance d between the mask and the polymerizable liquid crystal composition layer is preferably 150 μm or less, more preferably 100 μm or less, and particularly preferably 80 μm or less. Although better results are obtained when the thickness is 50 μm or less, the mask and the polymerizable liquid crystal composition layer come into contact if the distance d is too small.

未硬化部を除去する工程としては、溶剤を用いて溶解洗浄する方法を挙げることができる。溶剤としては、重合性液晶材料組成物を溶解し、かつ硬化した重合性液晶組成物にダメージを与えない有機溶媒を選択することが好ましい。有機溶媒としては、トルエン、キシレン、クメンなどのアルキル置換ベンゼンやプロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、シクロヘキサノン、シクロペンンタノン等を挙げることができる。溶媒に接触させる時間は10秒以上が好ましく、20秒以上が好ましい。溶媒の中に浸漬させて良いし、溶媒をシャワー状に吹きかけても良い。溶媒に接触させる時間が短いと、未硬化部分が残存する傾向があり、5分以上溶媒に接触させると、得られた位相差フィルムが溶媒を含んで膨潤する傾向が強くなる。 Examples of the step of removing the uncured part include a method of dissolving and cleaning using a solvent. As the solvent, it is preferable to select an organic solvent that dissolves the polymerizable liquid crystal material composition and does not damage the cured polymerizable liquid crystal composition. Examples of the organic solvent include alkyl-substituted benzene such as toluene, xylene, cumene, propylene glycol monomethyl ether acetate, butyl acetate, cyclohexanone, cyclopentanone and the like. The time for contacting with the solvent is preferably 10 seconds or longer, and more preferably 20 seconds or longer. It may be immersed in a solvent, or the solvent may be sprayed in a shower shape. When the time of contact with the solvent is short, an uncured portion tends to remain, and when the contact with the solvent for 5 minutes or more, the obtained retardation film tends to swell with the solvent.

以下、実施例を挙げて本願発明を更に詳述するが、本願発明はこれらの実施例に限定されるものではない。実施例の述べるパターン化位相差フィルムの解像度、幅、側壁角はレーザー顕微鏡（キーエンス社製VK-9510）によって測定した。
（参考例１）
式(a)の化合物40質量% EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. The resolution, width, and sidewall angle of the patterned retardation film described in the examples were measured with a laser microscope (VK-9510 manufactured by Keyence Corporation).
(Reference Example 1)
40% by mass of the compound of the formula (a)

式(b)の化合物20質量%

20% by mass of the compound of the formula (b)

式（c）の化合物25質量%

25% by mass of the compound of the formula (c)

式（d）の化合物5質量％

5% by mass of the compound of the formula (d)

式（e）の化合物10質量%

からなる重合性液晶組成物（A）を調整した。重合性液晶組成物（A）93.35質量％に、光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）5.0質量%、重量平均分子量600の流動パラフィン（関東化学社製）を0.1質量%、ＦＴＸ−７３０ＬＳ（ネオス社製）0.05質量%、重合禁止剤4-メトキシフェノールを0.5質量％添加した重合性液晶組成物（A1）を調製した。

10% by mass of the compound of formula (e)

A polymerizable liquid crystal composition (A) comprising: Polymerizable liquid crystal composition (A) 93.35% by mass, photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) 5.0% by mass, liquid paraffin having a weight average molecular weight of 600 (manufactured by Kanto Chemical Co., Ltd.) 0.1% by mass, FTX A polymerizable liquid crystal composition (A1) to which 0.05 mass% of -730LS (manufactured by Neos) and 0.5 mass% of a polymerization inhibitor 4-methoxyphenol were added was prepared.

（参考例２）
重合性液晶組成物（A）94.35質量％に、光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）5.0質量%、重量平均分子量600の流動パラフィン（関東化学社製）を0.1質量%、ＦＴＸ−７３０ＬＳ（ネオス社製）0.05質量%、重合禁止剤4-メトキシフェノールを500ppm添加した重合性液晶組成物（A2）を調製した。 (Reference Example 2)
94.35% by mass of the polymerizable liquid crystal composition (A), 5.0% by mass of photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals), 0.1% by mass of liquid paraffin having a weight average molecular weight of 600 (manufactured by Kanto Chemical), FTX A polymerizable liquid crystal composition (A2) was prepared by adding 0.05% by mass of -730LS (manufactured by Neos) and 500 ppm of a polymerization inhibitor 4-methoxyphenol.

（実施例１）
重合性液晶組成物（A1）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。これをラビング処理を施したポリイミド配向膜が形成されたITO付きガラス基板にスピンコート（1200回転/分、15秒）した。スピンコートした基板を70℃で2分間乾燥した。このようにして形成した重合性液晶組成物層に、100μｍの間隔をもってマスク（クロム遮光マスク。ラインが40μｍ幅、スペースが40μｍ幅）設置し、その上から平行度2度のUV光源を照射してマスク露光を行った。UV光源の強度は20mW/cm²に設定し、3秒間照射することにより60mJ/cm²のエネルギー量は照射した。次に基板をプロピレングリコールモノメチルエーテルアセテートに30秒浸漬することにより、未硬化部を除去した。この処理を行った基板に付着している溶剤をエアブローで揮発させることにより、パターン化位相差フィルムを得た。このようにして得られたパターン化位相差フィルムの上部のサイズＡは38.6μｍ、下部のサイズＢは40.7μｍ、厚さＴは0.8μｍ、側壁角は３７度であった。位相差フィルムの位相差は137nmであった。 Example 1
A propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (A1) was prepared. This was spin-coated (1200 rotations / minute, 15 seconds) on a glass substrate with ITO on which a polyimide alignment film subjected to rubbing treatment was formed. The spin-coated substrate was dried at 70 ° C. for 2 minutes. The polymerizable liquid crystal composition layer thus formed is placed with a mask (chrome shading mask, line is 40 μm wide, space is 40 μm wide) with an interval of 100 μm, and a UV light source with a parallelism of 2 degrees is irradiated from above. Then, mask exposure was performed. The intensity of the UV light source was set to 20 mW / cm ^2, and an energy amount of 60 mJ / cm ² was irradiated by irradiating for 3 seconds. Next, the uncured portion was removed by immersing the substrate in propylene glycol monomethyl ether acetate for 30 seconds. The solvent adhering to the substrate subjected to this treatment was volatilized by air blow to obtain a patterned retardation film. The size A of the upper part of the patterned retardation film thus obtained was 38.6 μm, the size B of the lower part was 40.7 μm, the thickness T was 0.8 μm, and the side wall angle was 37 degrees. The retardation of the retardation film was 137 nm.

得られたパターン化位相差フィルム付き基板を用いて図５の構成を有する半透過型液晶セルを作成した。基板は1.6μｍの間隔を持って対向させた。これによってパターン化位相差フィルムの上部と対向基板との距離は、0.8μｍに設定される。このような液晶セルに、Δｎ=0.18、Δεが5の液晶を挟持させた。位相差フィルムの光軸（遅相軸）は紙面に対して、垂直方向になるように設定し、上下偏光フィルムの偏光軸は位相差フィルムの遅相軸に対して45度をなすようにして直交させた（クロスニコル）。上下基板ともラビング方向は、位相差フィルムの遅相軸と一致させた。この液晶セルにＩＴＯ透明電極を通じて電圧を印加したところ、にじみのない白黒表示が得られた。
（比較例１）
実施例１において、重合性液晶組成物（A1）に変えて重合性液晶組成物（A2）を用いた以外は、実施例１と同様にしてパターン化位相差フィルムを作製した。のようにして得られたパターン化位相差フィルムの上部のサイズＡは39.5μｍ、下部のサイズＢは46.4μｍ、厚さＴは0.8μｍ、側壁角は１３度であった。位相差フィルムの位相差は137nmであった。 A transflective liquid crystal cell having the configuration of FIG. 5 was prepared using the obtained substrate with a patterned retardation film. The substrates were opposed to each other with an interval of 1.6 μm. Thereby, the distance between the upper part of the patterned retardation film and the counter substrate is set to 0.8 μm. In such a liquid crystal cell, a liquid crystal having Δn = 0.18 and Δε = 5 was sandwiched. The optical axis (slow axis) of the retardation film is set to be perpendicular to the paper surface, and the polarization axis of the upper and lower polarizing films is 45 degrees to the slow axis of the retardation film. Orthogonalized (Cross Nicol). The rubbing direction of both the upper and lower substrates was matched with the slow axis of the retardation film. When a voltage was applied to the liquid crystal cell through the ITO transparent electrode, a black and white display without blur was obtained.
(Comparative Example 1)
A patterned retardation film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition (A2) was used instead of the polymerizable liquid crystal composition (A1). The upper size A of the patterned retardation film thus obtained was 39.5 μm, the lower size B was 46.4 μm, the thickness T was 0.8 μm, and the sidewall angle was 13 degrees. The retardation of the retardation film was 137 nm.

得られたパターン化位相差フィルム付き基板を用いて、実施例１と同様の半透過型液晶セルを作製した。この液晶セルにＩＴＯ透明電極を通じて電圧を印加したところ、表示に周期的なモアレ状のにじみが発生した。 A transflective liquid crystal cell similar to that of Example 1 was produced using the obtained substrate with a patterned retardation film. When a voltage was applied to the liquid crystal cell through the ITO transparent electrode, periodic moire-like bleeding occurred in the display.

半透過型液晶ディスプレイ用のパターン化位相差フィルムとして有用である。 It is useful as a patterned retardation film for a transflective liquid crystal display.

本願発明のパターン化位相差フィルムの断面を示す図である。It is a figure which shows the cross section of the patterned retardation film of this invention. 重合性液晶組成物の層の形成をした断面図である。It is sectional drawing which formed the layer of the polymeric liquid crystal composition. マスク露光の断面図である。It is sectional drawing of mask exposure. 未硬化部を除去した断面図である。It is sectional drawing which removed the uncured part. 本願発明のパターン化位相差フィルムを用いた半透過型液晶セルを示す図である。It is a figure which shows the transflective liquid crystal cell using the patterned retardation film of this invention.

Explanation of symbols

１重合性液晶分子
２重合性液晶組成物の層
３配向膜
４基板
５ UV（紫外線）
６マスク
７パターン化位相差フィルム
８ポリイミド配向膜が形成されたＩＴＯ透明電極
９ガラス基板
１０アルミ蒸着膜
１１偏光フィルム
１２液晶層
１３バックライト 1 Polymerizable liquid crystal molecule 2 Polymerizable liquid crystal composition layer 3 Alignment film 4 Substrate 5 UV (ultraviolet)
6 Mask 7 Patterned Retardation Film 8 ITO Transparent Electrode 9 with Polyimide Orientation Film 9 Glass Substrate 10 Aluminum Deposition Film 11 Polarizing Film 12 Liquid Crystal Layer 13 Backlight

Claims

In the cross section of each pattern in a patterned retardation film composed of a cured product of a polymerizable liquid crystal composition and having a pattern, the side irradiated with active energy rays at the time of curing of the polymerizable liquid crystal composition is the upper side, and the substrate side is the lower side When the upper size is A, the lower size is B, and the pattern thickness is T, the following formula (1)
SWA (°) = tan ⁻¹ {2T / (BA)} formula (1)
Side wall angle calculated by: SWA is 16 ° or more, and the polymerizable liquid crystal composition has the general formula (I)

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, and m represents 0 or 1). ) Is contained from 92.35% to 96.84% by weight, contains a polymerization initiator and a polymerization inhibitor, the concentration of the polymerization inhibitor is C (%), and the concentration of the polymerization initiator is D (%). The patterned retardation film is characterized in that C / D * 10000 is 333 to 3750 .

The patterned retardation film according to claim 1, wherein the polymerizable liquid crystal composition contains 3% by mass to 5% by mass of a polymerization initiator and 0.1% by mass to 1.5% by mass of a polymerization inhibitor.

In the general formula (I), Sp represents an alkylene group (the alkylene group may be substituted by one or more halogen atoms or CN, and is not adjacent to one CH ₂ group present in the group) Two or more CH ₂ groups are independently of each other, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted.), MG is represented by the general formula (Ib)

(In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-Dihydrophenanthrene-2,7-diyl group 1,2,3,4,4a, 9,10a- octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group is 1 or more F as _{_{substituents, Cl, CF 3, OCF 3}} , cyano Group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group. , Z0, Z1, Z2 and Z3 are each independently -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -C≡C -, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COO CH ₂ CH _2- , -OCOCH ₂ CH _2- , -CONH-,- NHCO- or a single bond, n represents 0, 1 or 2), and P represents a general formula (Ic), general formula (Id) and general formula (Ie)

(In the formula, R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. 2 represents a substituent selected from the group consisting of substituents represented by the following formula: n represents 0 or 1. The patterned retardation film according to claim 1, comprising a compound represented by:

The polymerizable liquid crystal composition has the general formula (II)

Wherein m represents 0 or 1, W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ¹ and Y ² each independently represent — COO- or -OCO- is represented, and r and s each independently represent an integer of 2 to 18, the 1,4-phenylene group present in the formula is an alkyl group or alkoxy group having 1 to 7 carbon atoms Or a alkanoyl group, a cyano group, or a halogen atom, which may be substituted by one or more.) The method for producing a patterned retardation film according to claim 1.

The polymerizable liquid crystal composition has the general formula (III)

(In the formula, Z ¹ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z ² represents a hydrogen atom or a methyl group, t represents 0 or 1, A, B and C are each independently a 1,4-phenylene group, a 1,4-phenylene group in which a non-adjacent CH group is substituted with nitrogen, a 1,4-cyclohexylene group, one or two non-adjacent CH ₂ Represents a 1,4-cyclohexylene group or 1,4-cyclohexenylene group in which the group is substituted with an oxygen or sulfur atom, and the 1,4-phenylene group present in the formula is an alkyl having 1 to 7 carbon atoms Group, an alkoxy group, an alkanoyl group, a cyano group or a halogen atom, and Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, _{-OCH 2 -, - COO -,} - OCO -, - C≡C -, - CH = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH ₂ CH ₂ CH _2- , -CH = CHCH ₂ CH _2- , -CH ₂ _{CH 2 CH = CH -, -} CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH ₂ CH ₂ - and The patterned retardation film according to claim 1, comprising a compound represented by: Y ⁵ represents a single bond, —O—, —COO—, —OCO—, or —CH═CHCOO—.

The polymerizable liquid crystal composition has the general formula (IV)

(Wherein Z ³ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z ⁴ represents a hydrogen atom or a methyl group, W ³ represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 2 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, but the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF _{_{-, - (CH 2) 4}} -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH ₂ CH ₂ - represents, Y ⁸ represents a single bond, - The patterned retardation film according to claim 1, comprising a compound represented by: O—, —COO—, —OCO— or —CH═CHCOO— .

The polymerizable liquid crystal composition has a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative as a mother nucleus at the center of the molecule, and a linear alkyl group, a linear alkoxy group, or a substituted benzoyloxy group as its side chain. The patterned retardation film according to claim 1, comprising a discotic liquid crystal compound having a radially substituted structure.

The patterned retardation film according to claim 1, wherein the discotic liquid crystal compound comprises the polymerizable liquid crystal composition according to claim 7 represented by the general formula (V).

(In the formula, each R ⁵ independently represents a substituent represented by the general formula (Va).)

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ⁸ represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group represents a general formula. (It may be substituted by a substituent represented by (Vb), general formula (Vc) or general formula (Vd).)

Wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1.)