JP2008133355A - Polymer, composition, phase difference plate, elliptical polarization plate and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition useful for stably producing optically anisotropic layer having a small orientation angle. <P>SOLUTION: The polymer contains a group represented by at least one kind of formula (A) (wherein, M<SP>01</SP>and M<SP>02</SP>are each independently a divalent linking group such as -C(=O)-O-; R<SP>01</SP>is a hydrogen atom or the like; R<SP>02</SP>is a substituted or nonsubstituted aliphatic hydrocarbon group; and K<SP>01</SP>is a substituted aromatic ring) as a constituent unit. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymer useful for forming an optically anisotropic layer, a composition containing them, and a retardation plate produced using the same.

  A liquid crystal display device is usually provided with a first polarizing plate and a second polarizing plate with a liquid crystal cell interposed therebetween, and the liquid crystal cell has a liquid crystal layer containing a rod-like liquid crystalline compound between a pair of substrates. A phase difference generated in a liquid crystal cell using a rod-like liquid crystal compound is converted into a discotic liquid crystal compound (for example, 2,3,6,7,10,11-hexa {4- (4-acryloyloxyhexyloxy) benzoyloxy. } When the compensation is performed by an optical compensation sheet (for example, Patent Document 1) having an optically anisotropic layer formed from triphenylene or the like, the wavelength dispersion of the rod-like liquid crystalline compound and the discotic liquid crystalline compound is different. In some cases, the phase difference cannot be canceled at the same time with respect to the wavelength of light, and discoloration (such as no black color) may occur.

  A trisubstituted benzene compound having a heterocyclic group has been reported as a discotic liquid crystalline compound (Non-patent Document 1). It is not easy to achieve a low wavelength dispersion by using this compound, and a compound having a smaller wavelength dispersion (Re (short wavelength (for example, 450 nm)) / Re (long wavelength (for example, 650 nm)) is small) Is desired.

  The retardation value Re (λ) of the retardation plate needs to be determined according to the optical properties of the liquid crystal cell to be compensated. Here, the retardation value (Δnd) is the product of the refractive index anisotropy (Δn) of the optically anisotropic layer and the thickness (d) of the optically anisotropic layer. If the rate anisotropy (Δn) is large, the liquid crystal cell can be compensated even if the layer thickness (d) is small. In addition, in a retardation plate prepared by fixing the alignment of liquid crystal, the retardation value Re changes depending on the alignment angle (tilt angle, average tilt angle) of the aligned liquid crystal, and thus the alignment angle needs to be controlled. .

  However, in the case of a 3-substituted benzene type discotic liquid crystalline compound substituted with a heterocyclic group, it is difficult to control the orientation angle, and in particular, it is difficult to perform hybrid orientation at a low orientation angle. There has been a demand for an alignment control agent that can reduce the alignment angle of a discotic liquid crystalline compound to a desired angle.

  On the other hand, a technique for controlling the orientation angle by adding an orientation control agent to the liquid crystalline compound is disclosed, but the effect on the trisubstituted benzene type liquid crystalline compound is not clearly shown. Is insufficient to control the angle to a desired angle (Patent Document 2).

JP-A-8-50206 JP 2002-129162 A Molecular Crystals and Liquid Crystals, 2001, 370, 391.

  An object of the present invention is to provide a composition (liquid crystalline composition) useful for stably producing an optically anisotropic layer having a low orientation angle that contributes to optical compensation of a liquid crystal display device. In particular, it is an object to provide a composition useful for producing an optically anisotropic layer exhibiting optical anisotropy expressed by hybrid orientation of a discotic liquid crystalline compound in a state where orientation defects are small. In particular, it is an object to provide a composition capable of controlling the orientation angle of a tri-substituted benzene type or heterocyclic type liquid crystal. Another object of the present invention is to provide a retardation plate useful for optical compensation of a liquid crystal display device.

（一般式（Ａ）中、Ｍ⁰¹、Ｍ⁰²はそれぞれ独立に−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｒ⁰¹は水素原子またはメチル基を表し、Ｒ⁰²は置換または無置換の脂肪族炭化水素基を表す。Ｋ⁰¹は下記一般式（Ｂ）を表す。）

（一般式（Ｂ）中、Ｂ¹¹、Ｂ¹²、Ｂ¹³、Ｂ¹⁴は、それぞれ独立に水素原子または置換基を表し、Ｂ¹¹、Ｂ¹²、Ｂ¹³、Ｂ¹⁴のうち２つが互いに連結して環を形成していてもよい。）
（２）前記一般式（Ａ）中のＫ⁰¹が、一般式（Ｂ−１）で表される、（１）に記載のポリマー。

（一般式（Ｂ−１）中、Ｂ¹⁵は、置換基を表し、ｎ１１は０〜６の整数を表す。ｎ１１が２以上のとき、それぞれのＢ¹⁵は同じであっても異なっていてもよい。）
（３）前記一般式（Ａ）の少なくとも一種が下記一般式（Ａ−１）で表される基である、（１）または（２）に記載のポリマー。

（一般式（Ａ−１）中、Ｂ¹⁶は、置換基を表し、ｎ１２は０〜６の整数を表す。ｎ１２が２以上のとき、それぞれのＢ¹⁶は同じであっても異なっていてもよい。Ｒ⁰³は置換または無置換の脂肪族炭化水素基を表す。）
（４）一般式（Ａ）の構成単位を含む一般式（Ｐ−Ａ）で表されるポリマー。

（一般式（Ｐ−Ａ）中、Ｒ¹¹、Ｒ¹²はそれぞれ独立に水素原子またはメチル基を表す。Ｇは、−Ｍ⁰¹−Ｋ⁰¹−Ｍ⁰²−Ｒ⁰²を表す（ここで、Ｍ⁰¹、Ｍ⁰²はそれぞれ独立に−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ(Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｒ⁰²は置換または無置換の脂肪族炭化水素基を表す。Ｋ⁰¹は一般式（Ｂ）を表す。）。Ｍ⁴¹は、それぞれ独立に連結基を表す。Ｊ¹は環構造を一つ以上含む基を表す。Ａ¹は構成単位を表す。ａ、ｂ、ｃはそれぞれの構成単位の質量分率（％）を表す。）
（５）少なくとも１種の一般式（Ｄｏ）で表される化合物と、（１）〜（４）のいずれか１項に記載のポリマーを含有する組成物。

（一般式（Ｄｏ）中、Ｙ¹、Ｙ²およびＹ³は、それぞれ独立にメチンまたは窒素原子を表し、Ｒ^a、Ｒ^b、Ｒ^cはそれぞれ独立に置換基を表す。）
（６）前記一般式（Ｄｏ）で表される化合物が、下記一般式（ＤＩ）で表される、（５）に記載の組成物。

（一般式（ＤＩ）中、Ｙ¹¹、Ｙ¹²、Ｙ¹³は、それぞれ独立にメチンまたは窒素原子を表す。Ｌ¹、Ｌ²、Ｌ³は、それぞれ独立に単結合または二価の連結基を表す。Ｈ¹、Ｈ²、Ｈ³はそれぞれ独立に、一般式（ＤＩ−Ａ）または一般式（ＤＩ−Ｂ）を表す。Ｒ¹、Ｒ²、Ｒ³は、それぞれ独立に下記一般式（ＤＩ−Ｒ）を表す。）

（一般式（ＤＩ−Ａ）中、ＹＡ¹、ＹＡ²は、それぞれ独立にメチンまたは窒素原子を表す。ＸＡは酸素原子、硫黄原子、メチレン、またはイミノを表す。＊はＬ¹〜Ｌ³と結合する位置を表し、＊＊はＲ¹〜Ｒ³と結合する位置を表す。）

（一般式（ＤＩ−Ｂ）中、ＹＢ¹、ＹＢ²は、それぞれ独立にメチンまたは窒素原子を表す。ＸＢは酸素原子、硫黄原子、メチレン、またはイミノを表す。＊はＬ¹〜Ｌ³と結合する位置を表し、＊＊はＲ¹〜Ｒ³と結合する位置を表す。）
一般式（ＤＩ−Ｒ）
＊−（−Ｌ²¹−Ｆ¹）_n1−Ｌ²²−Ｌ²³−Ｑ¹
（一般式（ＤＩ−Ｒ）中、＊は一般式（ＤＩ）中のＨ¹、Ｈ²またはＨ³に結合する位置を表す。Ｌ²¹は単結合または二価の連結基を表す。Ｆ¹は少なくとも１種類の環状構造を有する二価の環状連結基を表す。ｎ１は０〜４の整数を表す。Ｌ²²は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｃ=Ｃ−を表す。Ｌ²³は−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｑ¹は重合性基または水素原子を表す。）
（７）前記一般式（Ｄｏ）で表される化合物が、下記一般式（ＤＩＩ）で表される化合物、または、下記一般式（ＤＩＩＩ）で表される化合物である、（５）に記載の組成物。

（一般式（ＤＩＩ）中、Ｙ³¹、Ｙ³²、Ｙ³³はそれぞれ独立にメチンまたは窒素原子を表す。Ｒ³¹、Ｒ³²、Ｒ³³はそれぞれ独立に一般式（ＤＩＩ−Ｒ）で表される。）

（一般式（ＤＩＩ−Ｒ）中、Ａ³¹、Ａ³²は、それぞれ独立にメチンまたは窒素原子を表す。Ｘ³は酸素原子、硫黄原子、メチレン、またはイミノを表す。Ｆ²は、６員環構造を有する二価の環状基を表す。ｎ３は、１〜３整数を表す。Ｌ³¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−または−Ｃ=Ｃ−を表す。Ｌ³²は−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｑ³は重合性基または水素原子を表す。）

（一般式（ＤＩＩＩ）中、Ｙ⁴¹、Ｙ⁴²およびＹ⁴³は、それぞれ独立にメチンまたは窒素原子を表し、Ｒ⁴¹、Ｒ⁴²およびＲ⁴³は、それぞれ独立に一般式（ＤＩＩＩ−Ａ）、一般式（ＤＩＩＩ−Ｂ）、または一般式（ＤＩＩＩ−Ｃ）を表す。）
一般式（ＤＩＩＩ−Ａ）

（一般式（ＤＩＩＩ−Ａ）中、Ａ⁴¹、Ａ⁴²、Ａ⁴³、Ａ⁴⁴、Ａ⁴⁵、Ａ⁴⁶は、それぞれ独立にメチンまたは窒素原子を表し、Ｘ⁴¹は、酸素原子、硫黄原子、メチレンまたはイミノを表し、Ｌ⁴¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−または−Ｃ=Ｃ−を表す。Ｌ⁴²は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｑ⁴は、重合性基または水素原子を表す。）

（一般式（ＤＩＩＩ−Ｂ）中、Ａ⁵¹、Ａ⁵²、Ａ⁵³、Ａ⁵⁴、Ａ⁵⁵、Ａ⁵⁶は、それぞれ独立にメチンまたは窒素原子を表し、Ｘ⁵²は、酸素原子、硫黄原子、メチレンまたはイミノを表し、Ｌ⁵¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−または−Ｃ=Ｃ−を表す。Ｌ⁵²は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｑ⁵は重合性基または水素原子を表す。）

（一般式（ＤＩＩＩ−Ｃ）中、Ａ⁶¹、Ａ⁶²、Ａ⁶³、Ａ⁶⁴、Ａ⁶⁵、Ａ⁶⁶は、それぞれ独立にメチンまたは窒素原子を表し、Ｘ⁶³は、酸素原子、硫黄原子、メチンまたはイミノを表し、Ｌ⁶¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−または−Ｃ=Ｃ−を表す。Ｌ⁶²は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｑ⁶は重合性基または水素原子を表す。）
（８）支持体の上に、配向膜と、（５）〜（７）のいずれか１項に記載の組成物から形成されてなる光学異方性層とを有する位相差板。
（９）前記配向膜がポリビニルアルコール類を含む、（８）に記載の位相差板。
（１０）前記光学異方性層がハイブリッド配向したディスコティック液晶性化合物から形成される（８）または（９）に記載の位相差板。
（１１）（８）〜（１０）のいずれか１項に記載の位相差板と、偏光膜とを有する楕円偏光板。
（１２）（８）〜（１０）のいずれか１項に記載の位相差板を有する液晶表示装置。 Means for solving the above problems are as follows.
(1) A polymer containing at least one group represented by the following general formula (A) as a structural unit.

(In General Formula (A), M ⁰¹ and M ⁰² are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O ) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C═C—, and a combination thereof selected from the group consisting of these, In the case of a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent, R ⁰¹ represents a hydrogen atom or a methyl group, and R ⁰² represents a substituted or unsubstituted aliphatic hydrocarbon group. ⁰¹ represents the following general formula (B).)

(In the general formula (B), B ¹¹ , B ¹² , B ¹³ and B ¹⁴ each independently represent a hydrogen atom or a substituent, and two of B ¹¹ , B ¹² , B ¹³ and B ¹⁴ are linked to each other. And may form a ring.)
(2) The polymer according to (1), wherein K ⁰¹ in the general formula (A) is represented by the general formula (B-1).

(In General Formula (B-1), B ¹⁵ represents a substituent, and n11 represents an integer of 0 to 6. When n11 is 2 or more, each B ¹⁵ may be the same or different. Good.)
(3) The polymer according to (1) or (2), wherein at least one of the general formula (A) is a group represented by the following general formula (A-1).

(In General Formula (A-1), B ¹⁶ represents a substituent, and n12 represents an integer of 0 to 6. When n12 is 2 or more, each B ¹⁶ may be the same or different. R ⁰³ represents a substituted or unsubstituted aliphatic hydrocarbon group.
(4) A polymer represented by the general formula (PA) containing the structural unit of the general formula (A).

(In the general formula (PA), R ¹¹ and R ¹² each independently represents a hydrogen atom or a methyl group. G represents -M ⁰¹ -K ⁰¹ -M ⁰² -R ⁰² (where M ⁰¹ , M ⁰² are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, —SO ₂ —, —NH. —, —CH ₂ —, —CH═CH— and —C (C— represents a divalent linking group selected from the group consisting of a combination thereof, and when the above group is a group containing a hydrogen atom, The hydrogen atom may be substituted with a substituent, R ⁰² represents a substituted or unsubstituted aliphatic hydrocarbon group, K ⁰¹ represents the general formula (B), and M ⁴¹ each independently represents a linking group. J ¹ represents a group containing one or more ring structures, A ¹ represents a structural unit, and a, b, and c represent mass fractions (%) of the respective structural units.
(5) A composition comprising at least one compound represented by the general formula (Do) and the polymer described in any one of (1) to (4).

(In the general formula (Do), Y ¹ , Y ² and Y ³ each independently represent a methine or nitrogen atom, and R ^a , R ^b and R ^c each independently represent a substituent.)
(6) The composition according to (5), wherein the compound represented by the general formula (Do) is represented by the following general formula (DI).

(In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom. L ¹ , L ² and L ³ each independently represents a single bond or a divalent linking group. H ¹ , H ² and H ³ each independently represents the general formula (DI-A) or the general formula (DI-B), and R ¹ , R ² and R ³ each independently represent the following general formula ( DI-R).)

(In the general formula (DI-A), YA ¹ and YA ² each independently represents a methine or nitrogen atom, XA represents an oxygen atom, a sulfur atom, methylene, or imino, and * represents L ^{1 to} L ³ . (The bond position is represented, and ** represents the bond position with R ^{1 to} R ^3. )

(In the general formula (DI-B), YB ¹ and YB ² each independently represent a methine or nitrogen atom, XB represents an oxygen atom, a sulfur atom, methylene, or imino, and * represents L ^{1 to} L ³ . (The bond position is represented, and ** represents the bond position with R ^{1 to} R ^3. )
General formula (DI-R)
*-(-L ²¹ -F ¹ ) _n1 -L ²² -L ²³ -Q ¹
(In the general formula (DI-R), * represents a position bonded to H ¹ , H ² or H ³ in the general formula (DI). L ²¹ represents a single bond or a divalent linking group. F ¹ Represents a divalent cyclic linking group having at least one cyclic structure, n1 represents an integer of 0 to 4. L ²² represents —O—, —O—CO—, —CO—O—, —O—. CO-O -, - S - , - NH -, - SO 2 -, - CH 2 -, - CH = CH -, - C = the .L ²³ representing the C- -O -, - S -, - C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C═C— and a divalent linking group selected from the group consisting of these, When the group of is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent, and Q ¹ represents a polymerizable group or a hydrogen atom.)
(7) The compound represented by the general formula (Do) is a compound represented by the following general formula (DII) or a compound represented by the following general formula (DIII). Composition.

(In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methine or nitrogen atom. R ³¹ , R ³² and R ³³ are each independently represented by the general formula (DII-R). .)

(In the general formula (DII-R), A ³¹ and A ³² each independently represents a methine or nitrogen atom, X ³ represents an oxygen atom, a sulfur atom, methylene, or imino. F ² represents a 6-membered ring. .n3 representing the divalent cyclic group having the structure, the .L ³¹ representing a 1-3 integer -O -, - O-CO - , - CO-O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, - CH = CH- or -C = .L ³² representing the C- is -O -, - S -, - C (= O) -, - Represents a divalent linking group selected from the group consisting of SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C═C— and combinations thereof, and the above group contains a hydrogen atom. When it is a group, the hydrogen atom may be replaced by a substituent, and Q ³ represents a polymerizable group or a hydrogen atom.)

(In the general formula (DIII), Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represents a methine or nitrogen atom, and R ⁴¹ , R ⁴² and R ⁴³ each independently represents the general formula (DIII-A), Formula (DIII-B) or general formula (DIII-C) is represented.)
General formula (DIII-A)

(In the general formula (DIII-A), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ , A ⁴⁶ each independently represents a methine or nitrogen atom, and X ⁴¹ represents an oxygen atom, a sulfur atom, or methylene. Or L ⁴¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH— or —C═C—, L ⁴² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH Represents a divalent linking group selected from the group consisting of ═CH— and —C═C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is replaced by a substituent. Q ⁴ represents a polymerizable group or a hydrogen atom.)

(In the general formula (DIII-B), A ⁵¹ , A ⁵² , A ⁵³ , A ⁵⁴ , A ⁵⁵ , A ⁵⁶ each independently represents a methine or nitrogen atom, and X ⁵² represents an oxygen atom, a sulfur atom, or methylene. , - - -O or an imino, L ⁵¹ is O-CO -, - CO- O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, .L ⁵² representing a -CH = CH- or -C = C-is, -O -, - S -, - C (= O) -, - SO 2 -, - NH -, - CH 2 -, - CH Represents a divalent linking group selected from the group consisting of ═CH— and —C═C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is replaced by a substituent. Q ⁵ represents a polymerizable group or a hydrogen atom.)

(In the general formula (DIII-C), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ , A ⁶⁶ each independently represents a methine or nitrogen atom, and X ⁶³ represents an oxygen atom, a sulfur atom, or methine. Or L ⁶¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, Represents —CH═CH— or —C═C—, L ⁶² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH; Represents a divalent linking group selected from the group consisting of ═CH— and —C═C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is replaced by a substituent. Q ⁶ represents a polymerizable group or a hydrogen atom.)
(8) A retardation plate having an alignment film and an optically anisotropic layer formed from the composition according to any one of (5) to (7) on a support.
(9) The retardation plate according to (8), wherein the alignment film contains polyvinyl alcohols.
(10) The phase difference plate according to (8) or (9), wherein the optically anisotropic layer is formed from a discotic liquid crystalline compound in which hybrid alignment is performed.
(11) An elliptically polarizing plate having the retardation plate according to any one of (8) to (10) and a polarizing film.
(12) A liquid crystal display device comprising the retardation plate according to any one of (8) to (10).

  According to the present invention, it is possible to provide a composition useful for stably producing an optically anisotropic layer having a low orientation angle, which contributes to optical compensation of a liquid crystal display device. According to the present invention, in particular, an optically anisotropic layer exhibiting optical anisotropy expressed by hybrid orientation of a discotic liquid crystalline compound is produced without (or reduced) defects caused by orientation failure or repellency. It is possible to provide a liquid crystal composition useful for the purpose. In particular, it has become possible to provide a composition comprising an alignment control agent and a liquid crystalline compound effective for reducing the average tilt angle of trisubstituted benzene type or heterocyclic type liquid crystals and reducing alignment defects. Furthermore, according to the present invention, a retardation plate useful for optical compensation of a liquid crystal display device can be provided.

  Hereinafter, the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has.

注記：
上記のＲｅ（θ)は法線方向から角度θ傾斜した方向におけるレターデーション値を表す。
式（１）におけるｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘおよびｎｙに直交する方向の屈折率を表す。 First, details of Re (λ), tilt angle, and average tilt angle in this specification will be described below.
In this specification, Re (λ) represents an in-plane retardation value at a wavelength λ. Re (λ) is measured by making light with a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, the retardation value at a tilt angle larger than the tilt angle. After changing its sign to negative, KOBRA 21ADH or WR calculates.

Note:
The above Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In formula (1), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. .

  In the above measurement, the assumed value of the average refractive index may be the value in the polymer handbook (JOHN WILEY & SONS, INC) and various optical film catalogs. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). By inputting these assumed values of average refractive index and film thickness, KOBRA 21ADH or WR calculates nx, ny, and nz. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

Further, in this specification, the average tilt angle of the discotic liquid crystalline compound in the optically anisotropic layer refers to one surface of the optically anisotropic layer (the surface of the alignment film in the retardation plate of the present invention) and the optical The angle formed by the physical target axis of the molecules of the discotic liquid crystalline compound in the anisotropic layer is defined as the tilt angle θ1, and the angle formed by the other surface (in the retardation plate of the present invention, the air interface). The tilt angle θ2 is defined as an average value ((θ1 + θ2) / 2). However, it is difficult to directly and accurately measure θ1 and the tilt angle θ2 of the other surface. Therefore, in this specification, θ1 and θ2 are calculated by the following method. Although this method does not accurately represent the actual orientation state, it is effective as a means of expressing the relative relationship between some optical properties of the optical film.
In this method, in order to facilitate calculation, the following two points are assumed and the tilt angle at the two interfaces of the optically anisotropic layer is used.
1. The optically anisotropic layer is assumed to be a multilayer body composed of layers containing a discotic liquid crystalline compound or a rod-like liquid crystalline compound. Further, it is assumed that the minimum unit layer (a tilt angle of a discotic liquid crystal compound or a rod-like liquid crystal compound is uniform in the layer) constituting the same is optically uniaxial.
2. It is assumed that the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer.
The specific calculation method is as follows.
(1) In a plane in which the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer, the incident angle of the measurement light to the optically anisotropic layer is changed, and three or more The retardation value is measured at the measurement angle. In order to simplify measurement and calculation, it is preferable to measure the retardation value at three measurement angles of −40 °, 0 °, and + 40 °, with the normal direction to the optically anisotropic layer being 0 °. Such measurements were performed using KOBRA-21ADH and KOBRA-WR (manufactured by Oji Scientific Instruments), transmission type ellipsometer AEP-100 (manufactured by Shimadzu Corporation), M150 and M520 (manufactured by JASCO Corporation). ), ABR10A (manufactured by UNIOPT Co., Ltd.).
(2) In the above model, the refractive index of ordinary light in each layer is no, the refractive index of extraordinary light is ne (ne is the same value in all layers, and no is the same), and the thickness of the entire multilayer body is d. And Further, based on the assumption that the tilt direction of each layer and the uniaxial optical axis direction of the layer coincide with each other, the calculation of the angular dependence of the retardation value of the optically anisotropic layer agrees with the measured value. Fitting is performed using the tilt angle θ1 on one surface of the isotropic layer and the tilt angle θ2 on the other surface as variables, and θ1 and θ2 are calculated.
Here, known values such as literature values and catalog values can be used for no and ne. If the value is unknown, it can also be measured using an Abbe refractometer. The thickness of the optically anisotropic layer can be measured by an optical interference film thickness meter, a cross-sectional photograph of a scanning electron microscope, or the like.

The composition of the present invention comprises at least one polymer containing as a constituent unit a group represented by the general formula (A) of the present invention, which will be described in detail below, and at least one compound represented by the general formula (Do). Including seeds.
The retardation plate of the present invention contains an optically anisotropic layer formed from the composition of the present invention. In particular, at least one of the compounds represented by the general formula (Do) contained in the composition of the present invention is represented by the compound represented by the general formula (DI), the general formula (DII) shown in detail below. Or a compound represented by the general formula (DIII). Moreover, it is preferable that additives, such as a polymerization initiator and an orientation control agent, contain in the composition of this invention.
Furthermore, the retardation plate of the present invention is preferably in a form in which the optically anisotropic layer is formed on an alignment film provided on a support.

  Hereinafter, a polymer containing a group represented by the general formula (A) contained in the composition used for the retardation plate of the present invention as a structural unit, a compound represented by the general formula (Do), and other suitable uses. The additives to be used will be described sequentially. Further, an alignment film and a support that are suitably used for the retardation plate of the present invention will be sequentially described.

(1) A polymer containing a group represented by the general formula (A) as a structural unit.

In general formula (A), M ⁰¹ and M ⁰² are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O). It represents a divalent linking group selected from the group consisting of —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C═C—, and combinations thereof. When M ⁰¹ and M ⁰² are a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent (hereinafter the same for M ⁰¹ and M ⁰² ).
M ⁰¹ and M ⁰² are preferably each independently —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, -C = C- and a divalent linking group selected from the group consisting of these, and more preferably each independently -O-, -C (= O)-, -O-C (= O ) -, - C (= O ) -O -, - a well divalent linking group selected from the group consisting of - CH _2.
Examples of the substituent that may be replaced with a hydrogen atom include those exemplified as the substituent that R ⁰² described later may have, but it is preferable that the substituent does not have a substituent.

R ⁰¹ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.

R ⁰² represents a substituted or unsubstituted aliphatic hydrocarbon group.
The substituent that R ⁰² may have is an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 50 carbon atoms, more preferably 1 to 1 carbon atoms). 18 alkyl groups, for example, methyl group, ethyl group, isopropyl group, tert-butyl group, tert-pentyl group, cyclopropyl group, cyclohexyl group, 2-ethylhexyl group, dodecyl group), alkenyl group (preferably carbon A substituted or unsubstituted alkenyl group having 2 to 50, more preferably a substituted or unsubstituted alkenyl group having 2 to 18, for example, a vinyl group, an alkynyl group (preferably a substituted or unsubstituted group having 2 to 50 carbon atoms). A substituted alkynyl group, more preferably a substituted or unsubstituted alkynyl group of 2 to 18, for example, an ethynyl group), a cycloalkynyl group, A group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, more preferably a substituted or unsubstituted cycloalkyl group having 3 to 18 carbon atoms, such as a cyclohexyl group), an aryl group (preferably having a carbon number) 6 to 50 substituted or unsubstituted aryl groups, more preferably 6 to 25 substituted or unsubstituted aryl groups (for example, phenyl group, naphthyl group, anthryl group),

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acylamino group (preferably an acylamino group having 1 to 50 carbon atoms, more preferably an acylamino group having 1 to 18 carbon atoms, such as an acetylamino group; Butanoylamino group, benzoylamino group, trifluoroacetylamino group, picolinoylamino group), acyloxy group (preferably an acyloxy group having 1 to 50 carbon atoms), for example, acetoxy group, tetradecanoyloxy group, benzoyloxy Group), an acyl group (preferably an acyl group having 1 to 50 carbon atoms, more preferably an acyl group having 1 to 18 carbon atoms, such as formyl group, acetyl group, pivaloyl group, tetradecanoyl group, cyclohexylcarbonyl group, benzoyl group) Group, trifluoroacetyl group), aryloxycarboni A group (preferably an aryloxycarbonyl group having 7 to 50 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 25 carbon atoms, such as a phenoxycarbonyl group or a naphthoxycarbonyl group), a carbamoyl group (preferably having 1 to 50 carbon atoms). Carbamoyl group, more preferably 1-18 carbamoyl group, for example, carbamoyl group, N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N-mesylcarbamoyl group), carbamoyloxy group (preferably having 1 carbon atom) A carbamoyloxy group of -50, more preferably a carbamoyloxy group of 1-18, for example, N, N-dimethylcarbamoyloxy group, a carbonamido group (preferably a carbonamido group having 1-50 carbon atoms, more preferably 1-18 carbonamido groups such as An amide group, an N-methylacetamide group, an acetamide group, an N-methylformamide group, a benzamide group), a sulfonamide group (preferably a sulfonamide group having 1 to 50 carbon atoms, more preferably a sulfonamide group having 1 to 18 carbon atoms). A methanesulfonamide group, a dodecanesulfonamide group, a benzenesulfonamide group, a p-toluenesulfonamide group), an alkoxy group (preferably an alkoxy group having 1 to 50 carbon atoms, more preferably an alkoxy group having 1 to 18 carbon atoms). For example, methoxy group, propoxy group, isopropoxy group, octyloxy group, tert-octyloxy group, dodecyloxy group, 2- (2,4-di-tert-pentylphenoxy) ethoxy group), aryloxy group (preferably Is an aryloxy group having 6 to 50 carbon atoms, more preferably An aryloxy group having 6 to 25, for example, a phenoxy group, a 4-methoxyphenoxy group, a naphthoxy group), a sulfamoyl group (preferably a sulfamoyl group having 0 to 50 carbon atoms, more preferably a sulfamoyl group having 0 to 25 carbon atoms, Sulfamoyl group, N-butylsulfamoyl group, N, N-diethylsulfamoyl group, N-methyl-N- (4-methoxyphenyl) sulfamoyl group),

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 50 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 18 carbon atoms such as a cyclohexyloxycarbonyl group, a methoxycarbonyl group, an isopropoxycarbonyl group, a tert-butoxycarbonyl group) An N-acylsulfamoyl group (preferably an N-acylsulfamoyl group having 1 to 50 carbon atoms, more preferably an N-acylsulfamoyl group having 1 to 18 carbon atoms, for example, N-tetradecanoylsulfa A moyl group, an N-benzoylsulfamoyl group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 50 carbon atoms, more preferably an alkylsulfonyl group having 1 to 18 carbon atoms such as a methanesulfonyl group, an isopropylsulfonyl group, A cyclohexylsulfonyl group, A octylsulfonyl group, a 2-methoxyethylsulfonyl group, a 2-hexyldecylsulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 50 carbon atoms, more preferably an arylsulfonyl group having 6 to 25 carbon atoms such as benzene A sulfonyl group, a p-toluenesulfonyl group, a 4-phenylsulfonylphenylsulfonyl group), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 50 carbon atoms, more preferably an alkoxycarbonylamino group having 2 to 18 carbon atoms, Ethoxycarbonylamino group, isopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 50 carbon atoms, more preferably Or an aryloxycarbonylamino group having 7 to 25, for example, a phenoxycarbonylamino group or a naphthoxycarbonylamino group, an amino group (preferably an amino group having 0 to 50 carbon atoms, more preferably an amino group having 0 to 18 carbon atoms). For example, an amino group, a methylamino group, a diethylamino group, a diisopropylamino group, an anilino group), a cyano group, a nitro group, a carboxyl group, a hydroxy group, a sulfo group, a mercapto group, or an alkylsulfinyl group (preferably having a carbon number of 1 to 50 alkylsulfinyl groups, more preferably 1-18 alkylsulfinyl groups such as methanesulfinyl group, octanesulphinyl group, arylsulfinyl group (preferably arylsulfinyl group having 6 to 50 carbon atoms, more preferably 6 to 25 arylsulfinyl Group, for example, benzenesulfinyl group, 4-chlorophenylsulfinyl group, p-toluenesulfinyl group), alkylthio group (preferably alkylthio group having 1 to 50 carbon atoms, more preferably 1 to 18 alkylthio group, for example methylthio group) Group, octylthio group, cyclohexylthio group), arylthio group (preferably an arylthio group having 6 to 50 carbon atoms, more preferably an arylthio group having 6 to 25 carbon atoms, for example, phenylthio group, naphthylthio group), ureido group (preferably carbon A ureido group having a number of 1 to 50, more preferably a ureido group having 1 to 18, such as a 3-methylureido group, a 3,3-dimethylureido group, and a 1,3-diphenylureido group), a heterocyclic group (preferably a carbon Heterocyclic group having 2 to 50, more preferably 2 to 25 heterocyclic group The hetero atom includes, for example, at least one or more of nitrogen, oxygen, sulfur and the like, and is a 3-membered to 12-membered monocyclic or condensed ring such as a 2-furyl group, a 2-pyranyl group, and 2-pyridyl. Group, 2-thienyl group, 2-imidazolyl group, morpholino group, 2-quinolyl group, 2-benzimidazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, 2-quinazolinon-3-yl group, 1, 1-dioxo-1,2,4-benzothiadiazin-3-yl group), a sulfamoylamino group (preferably a sulfamoylamino group having 0 to 50 carbon atoms, more preferably a sulfamoylamino group having 0 to 18 carbon atoms). A famoylamino group, for example, an N-butylsulfamoylamino group, an N-phenylsulfamoylamino group), a silyl group (preferably a silyl group having 3 to 50 carbon atoms, A trimethylsilyl group, a dimethyl-tert-butylsilyl group, a triphenylsilyl group), a phosphonyl group (preferably a phosphonyl group having 1 to 50 carbon atoms, more preferably a phosphonyl group having 1 to 18 carbon atoms such as a phenoxyphosphonyl group, octyloxy A phosphonyl group, a phenylphosphonyl group), an azo group (preferably an azo group having 1 to 50 carbon atoms, more preferably an azo group having 1 to 18 carbon atoms such as a phenylazo group), an imide group (preferably having a carbon number of 1 to 1). 50 imide groups, more preferably 1-18 imide groups, such as N-succinimide group and N-phthalimide group). These substituents may be further substituted with the above substituents and the like.

R ⁰² is preferably an unsubstituted linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aliphatic hydrocarbon group substituted with a fluorine atom having 6 to 20 carbon atoms, and more preferably Is an aliphatic hydrocarbon group substituted with fluorine having 8 to 10 carbon atoms, more preferably a fluorine-containing alkyl group having 3 to 20 carbon atoms, and still more preferably a fluorine-containing alkyl group having 4 to 15 carbon atoms. It is.
These alkyl groups are linear (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.) Even so, a branched structure (for example, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H etc.) And may have an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these). May be.

一般式（Ｂ）中、Ｂ¹¹、Ｂ¹²、Ｂ¹³、Ｂ¹⁴は、それぞれ独立に水素原子または置換基を表し、Ｂ¹¹、Ｂ¹²、Ｂ¹³、Ｂ¹⁴のうち２つが互いに連結して環を形成していてもよい。
置換基は、前記Ｒ⁰²が有していてもよい置換基として挙げた例が好ましい例として挙げられ、 置換基の例としては、前記Ｒ⁰²が有していてもよい置換基として挙げた例が好ましい例として挙げられ、アルキル基、アルケニル基、ハロゲン原子、シアノ基、ニトロ基、カルボキシル基、ヘテロ環基が好ましい。
これらの置換基同士が連結して環を形成する場合、４〜８員環の脂環式の環、または、４〜８員環のヘテロ原子（窒素、酸素、硫黄等）を含む環であることが好ましい。これらの環は、飽和または、不飽和または芳香族性のいずれであってもよい。具体的には、ベンゼン環、シクロヘキサン環、ピリジン環等が挙げられる。 In the general formula (A), K ¹ represents the following general formula (B).

In the general formula (B), B ¹¹ , B ¹² , B ¹³ and B ¹⁴ each independently represent a hydrogen atom or a substituent, and two of B ¹¹ , B ¹² , B ¹³ and B ¹⁴ are connected to each other. A ring may be formed.
Substituents, examples wherein R ⁰² is exemplified as a substituent which may have can be mentioned as preferable examples, examples of the substituents, the R ⁰² is exemplified as a substituent which may have Example Are preferable examples, and an alkyl group, an alkenyl group, a halogen atom, a cyano group, a nitro group, a carboxyl group, and a heterocyclic group are preferable.
When these substituents are connected to form a ring, it is a 4- to 8-membered alicyclic ring or a ring containing a 4- to 8-membered hetero atom (nitrogen, oxygen, sulfur, etc.). It is preferable. These rings may be saturated, unsaturated or aromatic. Specifically, a benzene ring, a cyclohexane ring, a pyridine ring, etc. are mentioned.

In general formula (A), ^K01 is preferably represented by the following general formula (B-1).

一般式（Ｂ−１）中、Ｂ¹⁵は、置換基を表す。該置換基の例としては前記Ｒ⁰²が有していてもよい置換基として挙げた例が好ましい例として挙げられるが、置換基を有さない方が好ましい。
ｎ１１は０〜６の整数を表す。ｎ１１が２以上のとき、それぞれのＢ¹⁵は同じであっても異なっていてもよい。ｎ１１は０〜３の整数が好ましく、０、１または２がより好ましい。

In the general formula (B-1), B ¹⁵ represents a substituent. Examples of the substituent include those exemplified as the substituent that R ⁰² may have, but it is preferable that the substituent does not have a substituent.
n11 represents an integer of 0 to 6. When n11 is 2 or more, each B ¹⁵ may be the same or different. n11 is preferably an integer of 0 to 3, more preferably 0, 1 or 2.

The group represented by the general formula (A) is preferably a group represented by the following general formula (A-1).

In the general formula (A-1), B ¹⁶ represents a substituent. Examples of the substituent include those exemplified as the substituent that R ⁰² may have, but preferred are those having no substituent.
R ⁰³ represents a substituted or unsubstituted aliphatic hydrocarbon group, preferably substituted with an unsubstituted linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms or a fluorine atom having 6 to 20 carbon atoms. More preferably an aliphatic hydrocarbon group substituted with fluorine having 8 to 10 carbon atoms, more preferably a fluorine-containing alkyl group having 3 to 20 carbon atoms, and still more Preferably it is a C4-C15 fluorine-containing alkyl group.
n12 represents the integer of 0-6. When n12 is 2 or more, each B ¹⁶ may be the same or different. n12 is preferably an integer of 0 to 3, and preferably 0, 1 or 2.

  Specific preferred examples of the group represented by the general formula (A) contained in the composition of the present invention are shown below, but the present invention is not limited to the following. Me represents a methyl group.

  The main chain structure of the polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain of the present invention is not particularly limited, and is generally known as long as it can be mixed and dissolved in the composition, for example. Any structure can be preferably used, and it may be composed of two or more main chain structures, and they may be blocks or random.

  Further, the compound represented by the general formula (Do) has a higher tilt angle on the air interface side, and it is effective to be unevenly distributed on the air interface side in order to lower the orientation angle. Increasing the carbon number of the alkyl group of the polymer having an alkyl group in the side chain reduces the surface energy and surface unevenness, so increasing the carbon number of the side chain alkyl group is also oriented from this aspect. Although it is effective for lowering the angle, it is preferable that it is unevenly distributed on the surface, and the polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain of the present invention is a fluorinated alkyl group exhibiting a lower surface energy. It is preferable that it is also provided. This effect of reducing the surface energy is more preferably incorporated into the general formula (A).

In the present invention, the polymer containing a group represented by the general formula (A) as a structural unit may contain two or more groups represented by the general formula (A) as a structural unit.
Furthermore, the polymer containing the group represented by the general formula (A) in the present invention as a structural unit is preferably a polymer represented by the following general formula (PA).

（一般式（Ｐ−Ａ）中、Ｒ¹¹、Ｒ¹²はそれぞれ独立に水素原子またはメチル基を表す。Ｇは、−Ｍ⁰¹−Ｋ⁰¹−Ｍ⁰²−Ｒ⁰²を表す（ここで、Ｍ⁰¹、Ｍ⁰²はそれぞれ独立に−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｒ⁰²は置換または無置換の脂肪族炭化水素基を表す。Ｋ⁰¹は下記一般式（Ｂ）を表す。）。Ｍ⁴¹は、それぞれ独立に連結基を表す。Ｊ¹は環構造を１つ以上含む基である。Ａ¹は構成単位を表す。ａ、ｂ、ｃはそれぞれの構成単位の質量分率（％）を表す。）

（一般式（Ｂ）中、Ｂ¹¹、Ｂ¹²、Ｂ¹³、Ｂ¹⁴は、それぞれ独立に水素原子または置換基を表し、Ｂ¹¹、Ｂ¹²、Ｂ¹³、Ｂ¹⁴のうち２つが互いに連結して環を形成していてもよい。）

(In the general formula (PA), R ¹¹ and R ¹² each independently represents a hydrogen atom or a methyl group. G represents -M ⁰¹ -K ⁰¹ -M ⁰² -R ⁰² (where M ⁰¹ , M ⁰² are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, —SO ₂ —, —NH. Represents a divalent linking group selected from the group consisting of —, —CH ₂ —, —CH═CH— and —C═C—, and combinations thereof, and when the above group is a group containing a hydrogen atom, The hydrogen atom may be substituted with a substituent, R ⁰² represents a substituted or unsubstituted aliphatic hydrocarbon group, K ⁰¹ represents the following general formula (B)), and M ⁴¹ is independently linked. J ¹ represents a group containing one or more ring structures, A ¹ represents a structural unit, and a, b, and c represent mass fractions (%) of the respective structural units.)

(In the general formula (B), B ¹¹ , B ¹² , B ¹³ and B ¹⁴ each independently represent a hydrogen atom or a substituent, and two of B ¹¹ , B ¹² , B ¹³ and B ¹⁴ are linked to each other. And may form a ring.)

In the general formula (PA), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
G represents -M ⁰¹ -K ⁰¹ -M ⁰² -R ⁰² and has the same meaning as M ⁰¹ , K ⁰¹ , M ⁰² and R ⁰² in formula (A), and the preferred range is also the same.
M ⁴¹ each independently represents a linking group, preferably a linking group having 1 to 20 carbon atoms, and any one of the following general formula (PL-1), general formula (PL-2), and general formula (PL-3). It is more preferable that it is group represented by these.

（一般式（ＰＬ−１）中、＊はポリマー主鎖の炭素原子と結合する部位を表し、＊＊はＪ¹で表される側鎖と結合する部位を表し、Ｌ⁸¹は炭素数１〜１９の連結基を表し、ｎは０または１である。）
Ｌ⁸¹は好ましくは１〜１５の連結基を表し、より好ましくは炭素数１〜６の連結基を表し、飽和結合および不飽和結合のいずれを有していてもよく、直鎖構造および分岐構造のいずれを含んでもよい。また、Ｌ⁸¹は環構造を含んでいてもよく、該環構造は、Ｏ、Ｎ、Ｓから選ばれるヘテロ原子を有していても含んでいてもよい。
ｎは０が好ましい。

(In General Formula (PL-1), * represents a site bonded to a carbon atom of the polymer main chain, ** represents a site bonded to a side chain represented by J ¹ , and L ⁸¹ represents 1 to 1 carbon atoms. 19 represents a linking group, and n is 0 or 1.)
L ⁸¹ preferably represents a linking group having 1 to 15 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, which may have either a saturated bond or an unsaturated bond, and has a linear structure and a branched structure Any of these may be included. L ⁸¹ may contain a ring structure, and the ring structure may have a hetero atom selected from O, N, and S.
n is preferably 0.

（一般式（ＰＬ−２）中、＊はポリマー主鎖の炭素原子と結合する部位を表し、＊＊はＪ¹で表される側鎖と結合する部位を表し、Ｌ⁸²は炭素数１〜１９の連結基を表し、ｍは０または１である。）
Ｌ⁸²の好ましい範囲は、一般式（ＰＬ−１）におけるＬ⁸¹と同一である。

(In General Formula (PL-2), * represents a site bonded to a carbon atom of the polymer main chain, ** represents a site bonded to a side chain represented by J ¹ , and L ⁸² represents a carbon number of 1 to 19 represents a linking group, and m is 0 or 1.)
A preferred range for L ⁸² is the same as L ⁸¹ in formula (PL-1).

（一般式（ＰＬ−３）中、＊はポリマー主鎖の炭素原子と結合する部位を表し、＊＊はＪ¹で表される側鎖と結合する部位を表し、Ｌ⁸³は炭素数１〜１９の連結基を表し、ｐは０または１である。）
Ｌ⁸³の好ましい範囲は、一般式（ＰＬ−１）におけるＬ⁸¹と同一である。

(In General Formula (PL-3), * represents a site bonded to a carbon atom of the polymer main chain, ** represents a site bonded to a side chain represented by J ¹ , and L ⁸³ represents 1 to 1 carbon atoms. 19 represents a linking group, and p is 0 or 1.)
A preferred range for L ⁸³ is the same as L ⁸¹ in formula (PL-1).

J ¹ is a group containing one or more ring structures, and the ring structure is preferably a condensed ring between a condensed ring and a non-condensed ring, and the number of rings is 6-membered or 5-membered. A 4-membered ring and a 7-membered ring are preferable, and a 6-membered ring is more preferable. In addition, atoms of the ring structure may be replaced with heteroatoms. The number of rings is preferably 1 to 5, but more preferably 1 to 3, and the ring and the ring may be directly connected, that is, condensed. The ring structure and the group linking the ring structure are preferably a single bond, —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O). —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C (C— and a divalent linking group selected from the group consisting of combinations thereof, more preferably a single bond. , -C (= O) -O-, -C (= O) -NH-, and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. The hydrogen atom connected to the structure may be replaced by a substituent, and is —X (X is a halogen atom), —CN, or —NO ₂ , more preferably a fluorine atom, a chlorine atom, a bromine atom, or —CN.
Examples of J ^1, can be employed a group listed below.

A ¹ represents a structural unit, which is appropriately selected from the viewpoints of the target orientation angle, the affinity with the structural component of the composition to be used, and other structural units constituting the polymer represented by the general formula (PA) Any material can be used as long as it can be copolymerized, and it may or may not contain a functional group.
Specific examples include olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, phenylmaleimide, etc.) and acrylate esters (methyl acrylate, ethyl acrylate, hexyl acrylate) without functional groups. , Phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 3-trimethoxysilylpropyl acrylate, acrylate having polyethylene oxide at ester site, ester polydimethylsiloxane Acrylates etc.), methacrylates (methyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, 3-triethoxysilyl) Propyl methacrylate, methacrylate having polypropylene oxide at the ester site), styrene derivatives (styrene, p-methoxystyrene, etc.), vinyl pyridines (2-vinyl pyridine, 4-vinyl pyridine, etc.) vinyl ethers (methyl vinyl ether, hydroxyethyl) Vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-hydroxyacrylamide, 3-aminopropylacrylamide, etc.), methacrylamides (N-hydroxymethacrylamide) , 3-aminopropylmethacrylamide), acrylonitrile, carboxyl group-containing vinyl monomers (acrylic acid, crotonic acid, maleic acid, itaconic acid, etc.) Among these, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, styrene derivatives, vinyl ethers, vinyl esters, and carboxyl group-containing vinyl monomers are preferred. Particularly preferred are acid esters, acrylamides, methacrylamides, vinyl ethers, and vinyl esters.

a, b, and c represent mass fractions (%) of the respective structural units, represented by 0 <a ≦ 100, 0 ≦ b <100, and 0 ≦ c <100, preferably 10 ≦ a ≦ 90, 10 ≦ b ≦ 90 and 0 ≦ c ≦ 80, and in order to further lower the average tilt angle, 20 <a ≦ 80, 20 ≦ b ≦ 80, and 0 ≦ c ≦ 60 are more preferable.
Each structural unit constituting the polymer represented by the general formula (PA) may include two or more types of structural units. In this case, the total mass of the two or more structural units is calculated as a, b, or c.

（一般式（Ｐ−Ａ２）中、Ｒ²¹、Ｒ²²はそれぞれ独立に水素原子またはメチル基を表し、Ｍ⁵¹はそれぞれ独立に−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−のいずれかを表し、Ｇは、−Ｍ⁰¹−Ｋ⁰¹−Ｍ⁰²−Ｒ⁰²を表す（ここで、Ｍ⁰¹、Ｍ⁰²はそれぞれ独立に−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ=Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、上述の基が水素原子を含む基であるときは、該水素原子は置換基で置き換わってもよい。Ｒ⁰²は置換または無置換の脂肪族炭化水素基を表す。Ｋ⁰¹は下記一般式（Ｂ）を表す。）。Ｊ²は環構造を１つ以上含む基を表し、Ａ²は構成単位を表し、ｄ、ｅ、ｆはそれぞれの構成単位の質量分率を表す。） The general formula (PA) is preferably represented by the following general formula (P-A2).

(In the general formula (P-A2), R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group, M ⁵¹ each independently represents any of —COO—, —CONH—, and —OCO—, G represents -M ⁰¹ -K ⁰¹ -M ⁰² -R ⁰² (where M ⁰¹ and M ⁰² are each independently -O-, -S-, -C (= O)-, -C (= O) —O—, —O—C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C═C— and combinations thereof. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent, and R ⁰² represents a substituted or unsubstituted aliphatic hydrocarbon group. K ⁰¹ represents the following general formula (B).) J ² represents a group containing one or more ring structures, A ² represents a structural unit, and d, e and f represent Represents the mass fraction of each constituent unit.)

M ⁵¹ is synonymous with M ⁴¹ in the general formula (PA), and a preferable range thereof is also synonymous.
G represents ^{-M 01 -K 01 -M 02 -R 02} , have the same meaning as ^{M 01, K 01, M 02} , R 02 in the general formula (A), R ⁰² is a small group of the surface energy It is preferable. R ⁰² is preferably a fluorine-containing alkyl group having 3 to 20 carbon atoms, more preferably a fluorine-containing alkyl group having 4 to 15 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.) and an alicyclic structure (preferably a 5-membered ring or 6 A member ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these.
The preferred ranges of M ⁰¹ , K ⁰¹ and M ⁰² are the same as those in general formula (A).

J ² is a group containing one or more ring structures, and may be substituted with a substitutable group (for example, an alkoxy group, an acyloxy group, a halogen atom, etc.). When there is a substituent on the benzene ring, it is more preferable that there is a substituent at the 4-position. Of these, a cyano group, a halogen group, an alkyl group, and a nitro group are preferable.
A ² represents a structural unit and is synonymous with A ¹ in the general formula (PA), and a preferred range is also synonymous.
d, e, and f represent the mass fraction (%) of each structural unit, and are synonymous with a, b, and c in general formula (PA), and their preferable ranges are also synonymous.

  The molecular weight of the polymer represented by the general formula (PA) is preferably a number average molecular weight (Mn) of 1000 ≦ Mn ≦ 1000000, more preferably 1000 ≦ Mn ≦ 500000, and 2000 ≦ Mn ≦. More preferably, it is 100,000.

  As described above, the preferred range for the structure of the polymer represented by the general formula (PA) contained in the composition of the present invention is shown, but actually, depending on the properties of the liquid crystal compound used and the required orientation angle, The truly preferable ranges are determined, and these can be experimentally adjusted and determined based on the following concept.

  The preferable addition amount range of the polymer represented by the general formula (PA) contained in the composition of the present invention is 0.01 to 50% by mass with respect to the compound represented by the general formula (Do). More preferably, it is 0.05-20 mass%, Most preferably, it is 0.1-5 mass%.

The polymer represented by the general formula (PA) used in the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.
The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.
Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile , Methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more organic solvents such as water, or a mixed solvent with water. .
The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can usually be from 0 ° C. to 100 ° C., but the polymerization is preferably performed in the range of 50 to 100 ° C. .
The reaction pressure can be appropriately selected, but is usually preferably 1 to 100 kg / cm ² , particularly preferably about 1 to 30 kg / cm ² . The reaction time is about 5 to 30 hours. The obtained polymer may be subjected to purification such as reprecipitation.

  Specific examples of preferred compounds represented by formula (PA) contained in the composition of the present invention are shown below, but the present invention is not limited to the following. Et represents an ethyl group, Bu represents a butyl group, n-hex represents a hexyl group, and Ph represents a phenyl group.

(2) Liquid crystalline compound The composition of the present invention includes a compound represented by the following general formula (Do) as the liquid crystalline compound. The compound represented by the general formula (Do) is one or more of a compound represented by the general formula (DI), a compound represented by the general formula (DII), and a compound represented by the general formula (DIII). More preferably.

（一般式（Ｄ₀）中、Ｙ¹、Ｙ²およびＹ³は、それぞれ独立にメチンまたは窒素原子を表し、Ｒ^a、Ｒ^b、Ｒ^cはそれぞれ独立に置換基を表す。）

(In the general formula (D ₀ ), Y ¹ , Y ² and Y ³ each independently represent a methine or nitrogen atom, and R ^a , R ^b and R ^c each independently represent a substituent.)

[Compound represented by the general formula (DI)]
The compound represented by the general formula (DI) used in the present invention preferably exhibits discotic liquid crystallinity, and particularly preferably exhibits a discotic nematic phase.

In formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom. When Y ¹¹ , Y ¹² and Y ¹³ are each methine, the hydrogen atom of methine may be substituted with a substituent. Examples of the substituent that methine may have include, for example, an alkyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, alkylthio group, arylthio group, halogen Mention may be made of atoms and cyano groups. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom, and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 2 to 12 carbon atoms. More preferred are an alkoxycarbonyl group, an acyloxy group having 2 to 12 carbon atoms, a halogen atom and a cyano group.

Y ¹¹ , Y ¹² and Y ¹³ are preferably all methine, and methine is preferably unsubstituted.

In the general formula (DI), L ¹ , L ² and L ³ are each independently a single bond or a divalent linking group. The divalent linking group includes —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C═C—, a divalent cyclic group, and combinations thereof. A divalent linking group selected from the group consisting of R ⁷ is an alkyl group having 1 to ⁷ carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and further preferably a methyl group, an ethyl group or a hydrogen atom. Particularly preferred is a hydrogen atom.

When L ¹ , L ² and L ³ are a divalent cyclic group, it is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, More preferably, it is a ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring. The cyclic group preferably contains an aromatic ring and a heterocyclic ring.

  Of the divalent cyclic group, the cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic group having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group.

The divalent cyclic group represented by L ¹ , L ² or L ³ may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, and a carbon number of 1 An alkyl group substituted with -16 halogen atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms Group, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group substituted with an alkyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms.

L ¹ , L ² and L ³ are each a single bond, * —O—CO—, * —CO—O—, * —CH═CH—, * —C═C—, * —divalent cyclic group— * -O-CO-divalent cyclic group-, * -CO-O-divalent cyclic group-, * -CH = CH-divalent cyclic group-, * -C = C-divalent cyclic group. Group-, * -divalent cyclic group-O-CO-, * -divalent cyclic group-CO-O-, * -divalent cyclic group-CH = CH- or * -divalent cyclic group- C = C- is preferred. In particular, a single bond, * -CH = CH-, * -C = C-, * -CH = CH-divalent cyclic group- or * -C = C-divalent cyclic group- is more preferable. Is more preferable. Here, * represents the position bonded to the 6-membered ring containing Y ¹¹ , Y ¹² and Y ¹³ in the general formula (I).

In the general formula (DI), H ¹ , H ² and H ³ each independently represent the following general formula (DI-A) or the following general formula (DI-B).

In general formula (DI-A), YA ¹ and YA ² each independently represents a methine or a nitrogen atom. At least one of YA ¹ and YA ² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. XA represents an oxygen atom, a sulfur atom, methylene or imino. XA is preferably an oxygen atom. * Represents a position where L ^{1 to} L ³ are bonded, and ** represents a position where R ^{1 to} R ³ are bonded.

In the general formula (DI-B), YB ¹ and YB ² each independently represents a methine or a nitrogen atom. At least one of YB ¹ and YB ² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. XB represents an oxygen atom, a sulfur atom, methylene or imino. XB is preferably an oxygen atom. * Represents a position where L ^{1 to} L ³ are bonded, and ** represents a position where R ^{1 to} R ³ are bonded.

R ¹ , R ² and R ³ each independently represents the following general formula (DI-R).
General formula (DI-R)
*-(-L ²¹ -F ¹ ) _n1 -L ²² -L ²³ -Q ¹

In the general formula (DI-R), * represents a position bonded to H ¹ , H ² or H ³ in the general formula (DI). L ²¹ represents a single bond or a divalent linking group. When L ²¹ is a divalent linking group, it consists of —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C═C—, and combinations thereof. A divalent linking group selected from the group is preferred. R ⁷ is an alkyl group having 1 to ⁷ carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and further preferably a methyl group, an ethyl group or a hydrogen atom. Particularly preferred is a hydrogen atom.

L ²¹ is a single bond, **-O-CO-, **-CO-O-, **-CH = CH- or **-C = C- (where ** is a general formula (DI-R Represents the left side of L ^{21 in} the formula (A), and a single bond is more preferable.

F ¹ represents a divalent cyclic linking group having at least one cyclic structure. The divalent cyclic linking group is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and even more preferably a 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

  Of the divalent cyclic linking groups, the cyclic linking group having a benzene ring is preferably a 1,4-phenylene group or a 1,3-phenylene group. Examples of the cyclic linking group having a naphthalene ring include naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2, A 6-diylnaphthalene-2,7-diyl group is preferred. The cyclic linking group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic linking group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic linking group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. As the divalent cyclic linking group, a 1,4-phenylene group, a 1,3-phenylenenaphthalene-2,6-diyl group and a 1,4-cyclohexylene group are particularly preferable.

  The divalent cyclic linking group may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 1 to 16 carbon atoms, and 2 carbon atoms. -16 alkynyl group, alkyl group substituted with a halogen atom having 1 to 16 carbon atoms, alkoxy group having 1 to 16 carbon atoms, acyl group having 2 to 16 carbon atoms, alkylthio group having 1 to 16 carbon atoms, carbon number Examples include an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group substituted with an alkyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. As the substituent of the divalent cyclic linking group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms are preferable. An alkyl group having 1 to 4 carbon atoms and an alkyl group substituted with a halogen atom having 1 to 4 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are particularly preferable.

n1 represents an integer of 0 to 4. As n1, the integer of 1-3 is preferable and 1 or 2 is preferable. In the case of n1 is 0, L ²² in formula (DI-R) directly binds to H ¹ to H ³ in the general formula (D1). When n1 is 2 or more, each -L ²¹ -F ¹ may be the same or different.

L ²² represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH. -Or -C = C- is represented. L ²² is preferably —O—, —O—CO—, —CO—O—, —O—CO—O—, —CH ₂ —, —CH═CH— or —C═C—, More preferred is —O—, —O—CO—, —CO—O—, —O—CO—O— or —CH ₂ —.

L ²³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C═C— and combinations thereof. A divalent linking group selected from the group consisting of When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon Substituted by an acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, or an alkyl group having 2 to 6 carbon atoms. Carbamoyl groups and acylamino groups having 2 to 6 carbon atoms. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable. By being substituted by these substituents, the solubility of the compound represented by the general formula (DI) in the solvent can be improved. That is, it is preferable when a composition containing a compound represented by the general formula (DI) is used as a coating solution.

L ²³ is a divalent linking group selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C═C—, and combinations thereof. Is preferred. L ²³ preferably contains 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. Furthermore, L ²³ is -CH ₂ - preferably contains 1 to 16 a, -CH ₂ - and more preferably a containing 2-12.

Q ¹ is a polymerizable group or a hydrogen atom. When the compound represented by the general formula (DI) is used for production of an optical film or the like that requires that the phase difference does not change due to heat like an optical compensation film, Q ¹ represents a polymerizable group. It is preferable that The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

  Furthermore, the polymerizable group is particularly preferably a functional group capable of addition polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.

  Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).

  In formula (M-3) and formula (M-4), R represents a hydrogen atom or an alkyl group. R is preferably a hydrogen atom or a methyl group. Among the above (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is more preferable.

  The ring-opening polymerizable group is preferably a cyclic ether group, and more preferably an epoxy group or an oxetanyl group, and most preferably an epoxy group.

Next, the compound represented by general formula (DII) is demonstrated.

In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methine or nitrogen atom. Y ³¹ , Y ³² and Y ³³ are respectively the same as the definitions of Y ¹¹ , Y ¹² and Y ^{13 in} the general formula (DI), and preferred ranges are also synonymous.

R ³¹ , R ³² and R ³³ are each independently represented by the general formula (DII-R).

In the general formula (DII-R), A ³¹ and A ³² each independently represents a methine group or a nitrogen atom. As A ³¹ and A ³² , at least one is preferably a nitrogen atom, and most preferably both are nitrogen atoms.
X ³ represents an oxygen atom, a sulfur atom, methylene, or imino. X ³ is preferably an oxygen atom.

In General Formula (DII-R), F ² represents a divalent cyclic group having a 6-membered cyclic structure. The ring contained in the divalent cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic linking group may be an aromatic ring, an aliphatic ring, or a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene anthracene ring, and a phenanthrene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

  Of the divalent cyclic groups, the cyclic group having a benzene ring is preferably a 1,4-phenylene group or a 1,3-phenylene group. As the cyclic group having a naphthalene ring, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6 -Diyl groups and naphthalene-2,7-diyl groups are preferred. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. As the divalent cyclic group, 1,4-phenylene group, 1,3-phenylene group, naphthalene-2,6-diyl group and 1,4-cyclohexylene group are particularly preferable.

  The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, and 2 carbon atoms. -16 alkynyl group, alkyl group substituted with a halogen atom having 1 to 16 carbon atoms, alkoxy group having 1 to 16 carbon atoms, acyl group having 2 to 16 carbon atoms, alkylthio group having 1 to 16 carbon atoms, carbon number Examples include an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group substituted with an alkyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms are preferable. An alkyl group having 1 to 4 alkyl groups and an alkyl group substituted with a halogen atom having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.

n3 represents an integer of 1 to 3. n3 is preferably 1 or 2. When n3 is 2 or more, each F ² may be the same or different.

L ³¹ is —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—. , -C = C-. A preferred range for L ³¹ is the same as L ^{22 in} formula (DI-R).

L ³² consists of —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C═C— and combinations thereof. When a divalent linking group selected from the group is represented and the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. A preferred range for L ³² is the same as L ^{23 in} formula (DI-R).

Q ³ represents a polymerizable group or a hydrogen atom, and a preferred range is the same as Q ¹ in the general formula (DI-R).

 Next, the detail of the compound represented by general formula (DIII) is described.

In the general formula (DIII), Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represent a methine or nitrogen atom, and when Y ⁴¹ , Y ⁴² and Y ⁴³ are each methine, the hydrogen atom of methine is a substituent. May be substituted. Examples of the substituent that methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom, and A cyano group can be mentioned as a preferred example. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom and a cyano group are particularly preferred.
Y ⁴¹ , Y ⁴² and Y ⁴³ are more preferably methine, and methine is more preferably unsubstituted.

R ⁴¹ , R ⁴² and R ⁴³ each independently represent the following general formula (DIII-A), the following general formula (DIII-B), or the following general formula (DIII-C).
In the case of producing a retardation plate or the like having a small wavelength dispersion, R ⁴¹ , R ⁴² and R ⁴³ are each preferably represented by the general formula (DIII-A) or the general formula (DIII-C). What is represented by general formula (DIII-A) is more preferable.

In the general formula (DIII-A), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ , A ⁴⁶ each independently represents a methine or nitrogen atom. At least one of A ⁴¹ and A ⁴² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ are preferably methine, and more preferably all methine. When A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ are each methine, the hydrogen atom of methine may be substituted with a substituent. Examples of the substituent that methine has include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, An alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and an alkylthio group having 1 to 16 carbon atoms , An acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group substituted with an alkyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom. An alkyl group substituted with 4 to 4 halogen atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ⁴¹ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

In the general formula (DIII-B), A ⁵¹ , A ⁵² , A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ each independently represents a methine or nitrogen atom. At least one of A ⁵¹ and A ⁵² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ are preferably methine, more preferably methine. When A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ are each methine, the hydrogen atom of methine may be substituted with a substituent. Examples of the substituent that methine may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, and 2 to 16 carbon atoms. An alkenyl group, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and an alkyl group having 1 to 16 carbon atoms Includes an alkylthio group, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group substituted with an alkyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms It is. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number An alkyl group substituted with 1 to 4 halogen atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ⁵² represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

In the general formula (DIII-C), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ each independently represents a methine or nitrogen atom. At least one of A ⁶¹ and A ⁶² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ are preferably methine, more preferably methine. When A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ³⁶ are each methine, the hydrogen atom of the methine may be substituted with a substituent. Examples of the substituent that methine may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, and 2 to 2 carbon atoms. 16 alkenyl groups, alkynyl groups having 2 to 16 carbon atoms, alkyl groups substituted with halogen having 1 to 16 carbon atoms, alkoxy groups having 1 to 16 carbon atoms, acyl groups having 2 to 16 carbon atoms, 1 to 1 carbon atoms 16 alkylthio groups, C2-C16 acyloxy groups, C2-C16 alkoxycarbonyl groups, carbamoyl groups, carbamoyl groups substituted with C2-C16 alkyl groups, and C2-C16 acylamino groups Is included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number An alkyl group substituted with 1 to 4 halogen atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ⁶³ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

L ^{41 in} the general formula (DIII-A), L ^{51 in} the general formula (DIII-B), and L ⁶¹ in the general formula (DIII-C) are each independently —O— or —O—CO—. , -CO-O -, - O -CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, - CH = CH- or an -C = C-. Preferably, -O -, - O-CO -, - CO-O -, - O-CO-O -, - CH 2 -, - CH = CH -, - C = a C-, more preferably, —O—, —O—CO—, —CO—O—, —O—CO—O— or —CH ₂ —.

L ^{42 in} the general formula (DIII-A), L ^{52 in} the general formula (DIII-B), and L ⁶² in the general formula (DIII-C) are each independently —O—, —S—, — It represents a divalent linking group selected from the group consisting of C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C═C— and combinations thereof. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. As such a substituent, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon Substituted by an acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, or an alkyl group having 2 to 6 carbon atoms. Preferred examples include a carbamoyl group and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable.

L ⁴² , L ⁵² and L ⁶² are each independently selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH— and —C═C— and combinations thereof. It is preferable to be selected. L ⁴² , L ⁵² and L ⁶² each independently preferably contain 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. Further, L ⁴² , L ⁵² and L ⁶² each independently preferably contain 1 to 16 —CH ₂ —, and more preferably ₂ to 12 —CH ₂ —.

Formula (DIII-A) in Q ^4, the general formula (DIII-B) Q ⁵ and the general formula in (DIII-C) Q ⁶ in each independently represents a polymerizable group or a hydrogen atom . These preferable ranges are the same as Q < ¹ > in general formula (DI-R).

  Specific examples of the compound represented by the general formula (Do) are shown below, but the present invention is not limited thereto.

  Examples of the liquid crystal phase expressed by the liquid crystal compound used in the present invention include a columnar phase and a discotic nematic phase (ND phase). Among these liquid crystal phases, a discotic nematic phase (ND phase) exhibiting good monodomain properties is preferable.

  The compound represented by the general formula (Do) preferably exhibits a liquid crystal phase in the range of 20 ° C to 300 ° C. More preferably, it is 40 degreeC-280 degreeC, Most preferably, it is 60 degreeC-250 degreeC. Here, the expression of the liquid crystal phase at 20 ° C. to 300 ° C. means that the liquid crystal temperature range crosses 20 ° C. (specifically, for example, 10 ° C. to 22 ° C.) or 300 ° C. (specifically, for example, 298). ° C to 310 ° C). The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.

  The synthesis of the compound represented by the general formula (Do) used in the present invention can be easily produced by using a general organic synthetic chemical technique. For example, it can be easily synthesized by appropriately selecting and combining the methods described in Organic Synthesis, Organic Reactions, Experimental Chemistry Course (published by Maruzen Co., Ltd.) and the like. The directional group heterocycle can be synthesized according to the description in pages 95 to 96 of the new edition of heterocyclic compounds (Kodansha Scientific), and appropriately described in the pages of Journal of Medicinal Chemistry 1972 1198 to 1200. Synthetic methods can be used.

[Phase difference plate]
The retardation plate of the present invention has an optically anisotropic layer formed from the composition of the present invention. In one embodiment of the retardation plate of the present invention, a support (usually a transparent support), an alignment film formed on the support, an alignment control by the alignment film, and the alignment state are fixed. It is an aspect which has an optically anisotropic layer which consists of a composition of this invention.
Hereinafter, the optically anisotropic layer, the alignment film, and the support will be sequentially described in detail.

(1) Optically anisotropic layer The optically anisotropic layer of the present invention is composed of a composition containing a compound represented by the general formula (Do) and a polymer containing a group represented by the general formula (A) as structural units. Become. In addition to this, the optically anisotropic layer may further contain a polymerizable initiator and other additives as desired. The coating liquid containing these can be formed, for example, by coating the surface of the alignment film of the present invention formed on a support and aligning and fixing the compound represented by the general formula (Do). After aligning and fixing the compound represented by the general formula (Do), the support and the alignment film may be peeled off.

(1) -a Formation Method The optically anisotropic layer is dissolved in a solvent capable of dissolving a compound represented by the general formula (Do) and a polymer represented by the general formula (A) as a structural unit. The coating solution (composition of the present invention) prepared in this manner can be produced by coating on an alignment film formed on a support. Further, if possible, formation by vapor deposition may be used, but formation by coating is preferably used. Application methods include curtain coating, dip coating, spin coating, print coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, wire bar method, etc. A well-known coating method is mentioned. Next, the solvent used at 25 ° C. to 130 ° C. is dried, and at the same time, the molecules of the compound represented by the general formula (Do) are oriented, and further fixed by ultraviolet irradiation or the like, whereby the optically anisotropic layer is formed. It is formed. It is preferable to use ultraviolet rays for light irradiation for polymerization. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the optically anisotropic layer formed in this manner varies depending on the application and the optimum retardation value, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm. preferable.

  In the optically anisotropic layer, the compound represented by the general formula (Do) is preferably substantially uniformly oriented, and is preferably fixed in a substantially uniformly oriented state. More preferably, the compound represented by the general formula (Do) is most preferably immobilized by a polymerization reaction.

  The proportion of the compound represented by the general formula (Do) or the polymer obtained from the compound in the optically anisotropic layer is preferably 10 to 100% by mass, and preferably 30 to 99% by mass. More preferred is 50 to 99% by mass.

(1) -b Other materials used for forming the optically anisotropic layer The composition of the present invention comprises a compound represented by the general formula (Do) and a group represented by the general formula (A) as a structural unit. Other materials (components) may be added in addition to the containing polymer. Examples of the additive include a polymerization initiator, an additive for controlling the alignment state of the compound represented by the general formula (Do) (for example, an onium salt and an air interface vertical alignment agent), a polymerization initiator, and a plasticizer. , Surfactants, polymerizable monomers and the like. These materials are added for various purposes, for example, for the purpose of fixing the orientation, improving the uniformity of the coating film, the strength of the film, and the orientation of the liquid crystal compound. These materials are preferably compatible with the liquid crystal compound used in combination and do not inhibit the alignment.

As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator may be used, but a photopolymerization initiator is preferable. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).
The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.

  Examples of the orientation control agent include onium salts described in JP-A No. 2002-37777, onium salts described in JP-A No. 2005-196015 or JP-A No. 2005-196015, carboxyl groups, sulfo groups, and the like. And a fluorine-containing polymer containing a copolymer component.

  Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in paragraph numbers [0018] to [0020] of JP-A No. 2002-296423. The addition amount of the polymerizable monomer is generally 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the compound represented by the general formula (Do).

  As the surfactant, conventionally known ones can be widely used, and fluorine compounds are preferable. Specific examples include compounds described in paragraph numbers [0028] to [0056] of JP-A No. 2001-330725.

  The polymer used together with the compound represented by the general formula (Do) is preferably capable of thickening the coating solution. Examples of such polymers include cellulose esters. Preferable examples of the cellulose ester include those described in paragraph No. [0178] of JP-A No. 2000-155216. The amount of the polymer added is preferably in a range in which the orientation of the compound represented by the general formula (Do) is hardly inhibited, and is usually 10% by mass or less with respect to the compound represented by the general formula (Do). More preferably, it is more preferably 8% by mass or less. The lower limit is not particularly defined, but is, for example, 0.1% by mass or more.

  As a solid content concentration of the compound represented by the general formula (Do), the polymer containing the group represented by the general formula (A) as a structural unit, and other additives in the composition (coating liquid) of the present invention. Is preferably 0.1% by mass to 60% by mass, more preferably 0.5% by mass to 50% by mass, and even more preferably 2% by mass to 40% by mass. The viscosity of the composition (coating solution) is preferably 0.01 cp to 100 cp, and more preferably 0.1 cp to 50 cp.

(1) -c Alignment State When the optically anisotropic layer of the present invention is used as a phase difference plate in a liquid crystal display mode such as TN (Twisted Nematic), the state where the discotic nematic phase is hybrid-aligned is fixed. Is preferable. Here, the hybrid orientation represents a state in which the tilt angle of the compound represented by the general formula (Do) is continuously changed in the film thickness direction.

The compound represented by the general formula (Do) is applied on the support (more preferably on the alignment film), and then, for example, is heated to develop a liquid crystal phase. Therefore, the compound represented by the general formula (Do) Is the tilt angle (for example, the direction of the support surface and the disc surface direction of the compound represented by the general formula (Do) of the support surface or the coating film interface (or the alignment film interface when an alignment film is provided) at the support side interface. At the interface between the air and the tilt angle of the air interface.
In the present invention, the average tilt angle of the optically anisotropic layer (the angle formed by the direction of the support surface and the direction of the disk of the compound represented by the general formula (Do)) is preferably 10 to 70 °, and preferably 15 to 40 °. Is more preferable, and 20 to 32 ° is more preferable.
The tilt angle at each interface is a combination of the tilt angle at the air interface of 0 to 50 ° and the tilt angle of the support side interface of 20 to 90 °, or the tilt angle of the support side interface of 0 to 50 ° and the air. A combination in which the tilt angle of the interface is 20 to 90 ° is preferable. In particular, a combination in which the tilt angle of the air interface is 0 to 40 ° and the tilt angle of the support side interface is 40 to 80 °, or the tilt angle of the support side interface is 0 to 40 ° and the tilt angle of the air interface is 40 to 40 °. A combination of 80 ° is preferred.

(2) Alignment film An alignment film may be used for producing the retardation plate of the present invention. The alignment film is composed of an organic compound (for example, ω-tricosanoic acid, rubbed treatment of a compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.

  In principle, the polymer used for the alignment film has a molecular structure having a function of aligning the compound represented by the general formula (Do). In the present invention, in addition to the function of orienting the compound represented by the general formula (Do), a side chain having a crosslinkable functional group (for example, a double bond) is bonded to the main chain, or the general formula ( It is preferable to introduce a crosslinkable functional group having a function of orienting the compound represented by Do) into the side chain. As the polymer used in the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.

  Examples of the polymer include, for example, a methacrylate polymer, a styrene polymer, a polyolefin, polyvinyl alcohol, modified polyvinyl alcohol (polyvinyl alcohols), poly (poly (vinyl alcohol) described in JP-A-8-338913, paragraph [0022]. N-methylolacrylamide), polyester, polyimide, vinyl acetate polymer, carboxymethylcellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are most preferable. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization.

  The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. It is preferable that the polymerization degree of polyvinyl alcohol is 100-5000.

The side chain having the function of orienting the compound represented by the general formula (Do) generally has a hydrophobic group as a functional group. The specific type of functional group is determined according to the type of compound represented by the general formula (Do) and the required alignment state.
For example, the modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of modifying groups include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, fluorine atoms Examples include substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy groups, dialkoxy groups, monoalkoxy groups), and the like. Specific examples of these modified polyvinyl alcohol compounds include, for example, paragraph numbers [0022] to [0145] in JP-A No. 2000-155216 and paragraph numbers [0018] to [0022] in JP-A No. 2002-62426. And the like.

When a side chain having a crosslinkable functional group is bonded to the main chain of the alignment film polymer or a crosslinkable functional group is introduced into a side chain having a function of aligning the compound represented by the general formula (Do), the alignment is performed. The polymer of the film and the polyfunctional monomer contained in the optically anisotropic layer can be copolymerized. As a result, not only between the polyfunctional monomer and the polyfunctional monomer, but also between the alignment film polymer and the alignment film polymer and between the polyfunctional monomer and the alignment film polymer is firmly bonded by a covalent bond. Therefore, the strength of the retardation plate can be remarkably improved by introducing a crosslinkable functional group into the alignment film polymer.
The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specific examples include those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216.

Apart from the crosslinkable functional group, the alignment film polymer can also be crosslinked using a crosslinking agent.
Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraphs [0023] to [0024] of JP-A No. 2002-62426. Aldehydes having high reaction activity, particularly glutaraldehyde are preferred.

  0.1-20 mass% is preferable with respect to a polymer, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable. The amount of the unreacted crosslinking agent remaining in the alignment film is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. By adjusting in this way, even if the alignment film is used for a long time in a liquid crystal display device or left in a high-temperature and high-humidity atmosphere for a long time, sufficient durability without generation of reticulation can be obtained.

  The alignment film can basically be formed by applying the above-mentioned polymer as an alignment film forming material and a support containing a crosslinking agent, followed by drying by heating (crosslinking) and, if necessary, rubbing treatment. it can. As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating liquid is preferably a mixed solvent of an organic solvent (for example, methanol) having a defoaming action and water. The ratio by mass is water: methanol greater than 0 and 99 or less: less than 100, preferably 1 or more, and more preferably greater than 0 and 91 or less: less than 100, 9 or more. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an alignment film and also an optical anisotropic layer reduces remarkably.

  The coating method used for forming the alignment film is preferably a spin coating method, a dip coating method, a curtain coating method, an extrusion coating method, a rod coating method or a roll coating method. A rod coating method is particularly preferable. Moreover, it is preferable that the film thickness after drying is 0.1-10 micrometers. Drying can be performed at 20 to 110 degrees, for example. From the viewpoint of forming more sufficient cross-linking, the drying is preferably 60 ° to 100 °, more preferably 80 ° to 100 °. The drying time can be, for example, 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is also preferably set to an optimum value for the crosslinking agent to be used. For example, when glutaraldehyde is used as the crosslinking agent, the pH is 4.5 to 5.5, and 5 is particularly preferable.

  The alignment film is provided on the support or an undercoat layer provided on the support. The alignment film can be obtained by cross-linking the polymer layer as described above and, if necessary, rubbing the surface.

  For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of a liquid crystal display device (LCD) can be applied. That is, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.

  After aligning the compound represented by the general formula (Do) on the alignment film, if necessary, the polymer contained in the alignment film and the polyfunctional monomer contained in the optically anisotropic layer are reacted, or The alignment film polymer may be crosslinked using a crosslinking agent. The thickness of the alignment film is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

  Examples of the solvent used for the preparation of the alignment film forming coating solution include water, alcohols (eg, methanol, ethanol, isopropanol, etc.), amides (eg, N, N-dimethylformamide, etc.), acetonitrile, acetone. , Methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and the like, and water, alcohols and a mixed solvent thereof are preferable. The concentration of the alignment film polymer in the coating solution is preferably 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 20% by mass, and 2% by mass to 10% by mass. % Is more preferable. The viscosity of the coating solution is preferably 0.1 cp to 100 cp, and more preferably 0.5 cp to 50 cp.

  In addition to the alignment film polymer, an additive may be appropriately added to the coating solution. For example, when the alignment film polymer is difficult to dissolve in a water-soluble solvent, a basic compound (for example, sodium hydroxide, lithium hydroxide, triethylamine) or an acidic compound (for example, hydrochloric acid, acetic acid, succinic acid, etc.) ) May be added to promote dissolution.

(3) Support The retardation plate may have a support, and the support is preferably a transparent support. The support is not particularly limited as long as it is optically isotropic and has a light transmittance of 80% or more, but a polymer film is preferable. Specific examples of the polymer include cellulose esters (for example, cellulose diacetate, cellulose triacetate), norbornene-based polymers, poly (meth) acrylate esters, and the like, and many commercially available polymers are preferably used. Is possible. Among these, cellulose esters are preferable from the viewpoint of optical performance, and lower fatty acid esters of cellulose are more preferable. The lower fatty acid is a fatty acid having 6 or less carbon atoms, and preferably having 2, 3, or 4 carbon atoms. Specific examples include cellulose acetate, cellulose propionate, and cellulose butyrate. Among these, cellulose triacetate is particularly preferable. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used. Further, even a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence is used by reducing the expression by modifying the molecule described in International Publication WO00 / 26705. You can also.

Hereinafter, the cellulose ester preferably used as the support will be described in detail.
As the cellulose ester, it is preferable to use cellulose acetate having an acetylation degree of 55.0 to 62.5%. In particular, the acetylation degree is preferably 57.0 to 62.0%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). The viscosity average polymerization degree (DP) of the cellulose ester is preferably 250 or more, and more preferably 290 or more. The cellulose ester used in the present invention preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.
In the cellulose ester, the hydroxyl groups at the 2nd, 3rd and 6th positions of cellulose are not evenly distributed to 1/3 of the total substitution degree, and the substitution degree of the 6th hydroxyl group tends to be small. It is preferable that the substitution degree of the 6-position hydroxyl group of cellulose is larger than the 2-position and 3-position. The hydroxyl group at the 6-position with respect to the total substitution degree is preferably substituted with an acyl group at 30 to 40%, more preferably 31% or more, particularly preferably 32% or more. The substitution degree at the 6-position is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with an acyl group having 3 or more carbon atoms (for example, propionyl group, butyryl group, valeroyl group, benzoyl group, acryloyl group) in addition to the acetyl group. The degree of substitution at each position can be determined by NMR. Cellulose esters having a high degree of substitution at the 6-position hydroxyl group are synthesis examples 1 described in paragraphs [0043] to [0044] of JP-A No. 11-5851, and synthesis examples described in paragraphs [0048] to [0049]. 2. It can be synthesized with reference to the method of Synthesis Example 3 described in paragraphs [0051] to [0052].

In order to adjust the retardation value of a polymer film used as a support, particularly a cellulose acetate film, an aromatic compound having at least two aromatic rings may be used as a retardation increasing agent. When such a retardation increasing agent is used, the retardation increasing agent is preferably used in a range of 0.01 to 20 parts by mass with respect to 100 parts by mass of cellulose acetate, and 0.05 to 15 parts by mass. More preferably, it is used in the range of 0.1 to 10 parts by mass. Further, two or more aromatic compounds may be used in combination as a retardation increasing agent.
The aromatic ring of an aromatic compound here is the meaning containing an aromatic heterocyclic ring other than an aromatic hydrocarbon ring.

  The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). The aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring. As the aromatic ring, benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring are preferable, More preferred are a benzene ring and a 1,3,5-triazine ring. It is particularly preferred that the aromatic compound has at least one 1,3,5-triazine ring.

  The number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 8, and most preferably 2 to 6. . The bonding relationship between two aromatic rings can be classified into (a) when a condensed ring is formed, (b) when directly linked by a single bond, and (c) when linked via a linking group (for aromatic rings). , Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c). As for such a retardation increasing agent, International Publication WO 01/88574 pamphlet, International Publication WO 00/2619 pamphlet, JP 2000-1111914 A, JP 2000-275434 A, JP 2002-363343 A. It is described in gazettes.

  The cellulose acetate film is preferably produced from the prepared cellulose acetate solution (dope) by a solvent cast method. The above-mentioned retardation increasing agent may be added to the dope. The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. The surface of the drum or band is preferably finished in a mirror state. The casting and drying methods in the solvent casting method are described in U.S. Pat. Nos. 2,336,310, 2,367,603, 2,429,078, 2,429,297, 2,429,978, 2,607,704, 2,273,069, 2,273,070 and British Patent 6,407,331. No. 736892, JP-B 45-4554, JP-B 49-5614, JP-A 60-176834, JP-A 60-203430, JP-A 62-1115035. There is a description. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

Dopes are made from raw material flakes such as halogenated hydrocarbons (dichloromethane, etc.), alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. Dissolve in the solvent. A typical solvent for dissolving cellulose acylate is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means, for example, that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass).
A cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, hereinafter published Technical Report 2001- No. 1745).

  It is also possible to form a film by casting two or more layers of dope using the prepared cellulose acetate solution (dope). The dope is cast on a drum or band and the solvent is evaporated to form a film. The dope before casting is preferably adjusted in concentration so that the solid content is 10 to 40%. The surface of the drum or band is preferably finished in a mirror state. When casting a plurality of cellulose acetate solutions, a solution is prepared by casting a solution containing cellulose acetate from a plurality of casting openings provided at intervals in the traveling direction of the support, and laminating them. May be. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. Alternatively, the cellulose acetate solution may be cast from two casting ports to form a film. For example, each of JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104413, JP-A-61-158413, and JP-A-6-134933. The method described in the publication can be used. Further, a cellulose acetate film casting method in which a flow of a high-viscosity cellulose acetate solution is wrapped with a low-viscosity cellulose acetate solution and the high-viscosity and low-viscosity cellulose acetate solutions are simultaneously extruded as described in JP-A-56-162617. A method may be used.

  The retardation value of the cellulose acetate film can be further adjusted by a stretching treatment. The draw ratio is preferably in the range of 0 to 100%. When stretching the cellulose acetate film used in the present invention, tenter stretching is preferably used, and in order to control the slow axis with high accuracy, the difference between the left and right tenter clip speeds, separation timing, etc. should be made as small as possible. Is preferred.

  A plasticizer can be added to the cellulose ester film in order to improve mechanical properties or increase the drying speed. As the plasticizer, phosphoric acid ester or carboxylic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCP). Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalates include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and di-2-ethylhexyl phthalate (DEHP). . Examples of citrate esters include triethyl o-acetylcitrate (OACTE) and o-acetylcitrate, tributyl (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred. The addition amount of the plasticizer is preferably 0.1 to 25% by mass of the amount of cellulose ester, more preferably 1 to 20% by mass, and further preferably 3 to 15% by mass.

Degradation inhibitors (for example, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose ester film. The deterioration preventing agents are described in JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854.
The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared, and more preferably 0.01 to 0.2% by mass. By making the addition amount 0.01% by mass or more, the effect of the deterioration preventing agent tends to become more prominent. By setting the addition amount to 1% by mass or less, bleeding out (bleeding) of the deterioration preventing agent to the film surface can be more effectively suppressed. As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. The ultraviolet ray preventing agent is described in JP-A-7-11056.

  The cellulose acetate film is preferably subjected to a surface treatment. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is preferable to provide an undercoat layer. From the viewpoint of maintaining the flatness of the film, it is preferable that the temperature of the cellulose acetate film in these treatments is not higher than the glass transition temperature (Tg), specifically 150 ° C. or lower.

As for the surface treatment of the cellulose acetate film, it is particularly preferable to carry out an acid treatment or an alkali treatment, that is, a saponification treatment for cellulose acetate, from the viewpoint of adhesion to an alignment film or the like.
Hereinafter, the alkali saponification treatment will be specifically described as an example.
The alkali saponification treatment is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution. The specified concentration of hydroxide ions is preferably in the range of 0.1 to 3.0N, and more preferably in the range of 0.5 to 2.0N. The alkaline solution temperature is preferably in the range of room temperature (for example, 25 ° C.) to 90 ° C., more preferably in the range of 40 to 70 ° C.

The surface energy of the cellulose acetate film is preferably 55 mN / m or more, and more preferably in the range of 60 to 75 mN / m.
The thickness of the cellulose acetate film is preferably in the range of 5 to 500 μm, more preferably in the range of 20 to 250 μm, further preferably in the range of 30 to 180 μm, and most preferably in the range of 30 to 110 μm.

  The retardation plate can be used for an elliptical polarizing plate in combination with a polarizing film. Furthermore, it contributes to an increase in viewing angle by being applied to a transmissive, reflective, and transflective liquid crystal display device in combination with a polarizing film. Hereinafter, an elliptically polarizing plate and a liquid crystal display device using a retardation plate will be described.

[Elliptically polarizing plate]
An elliptically polarizing plate can be produced by laminating a retardation plate and a polarizing film. By using the retardation plate, an elliptically polarizing plate that can expand the viewing angle of the liquid crystal display device can be provided. Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film. The polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film.

  The polarizing film is laminated on the optically anisotropic layer side of the retardation plate. It is preferable to form a protective film on the surface opposite to the side on which the retardation film of the polarizing film is laminated. The protective film is preferably a transparent protective film having a light transmittance of 80% or more. As the transparent protective film, generally a cellulose ester film, preferably a triacetyl cellulose film is used. The cellulose ester film is preferably formed by a solvent cast method. The thickness of the protective film is preferably 20 to 500 μm, and more preferably 50 to 200 μm.

[Liquid Crystal Display]
The retardation plate of the present invention contributes to the expansion of the viewing angle of the liquid crystal display device. A liquid crystal display device usually has a liquid crystal cell, a polarizing element, and a retardation plate (optical compensation sheet). The polarizing element generally comprises a polarizing film and a protective film, and the polarizing film and the protective film may be those described for the elliptically polarizing plate. TN mode liquid crystal cell retardation plates (optical compensation sheets) are described in JP-A-6-214116, US Pat. Nos. 5,583,679, 5,646,703, and German Patent 3,911,620A1. In addition, a IPS mode or FDC mode liquid crystal cell retardation plate is described in JP-A-10-54982. Furthermore, a retardation plate for an OCB mode or HAN mode liquid crystal cell is described in US Pat. No. 5,805,253 and International Publication WO 96/37804. Furthermore, a retardation plate for an STN mode liquid crystal cell is described in JP-A-9-26572. A VA mode liquid crystal cell retardation plate is described in Japanese Patent No. 2866372.

  In the present invention, liquid crystal cell retardation plates (optical compensation sheets) of various modes can be prepared with reference to the above-mentioned publications. The phase difference plate is composed of TN (Twisted Nematic), IPS (In-PDane Switching), FDC (Ferroelectric Liquid Liquid Crystal), OCB (Optical Compensation Bend), STN (Super Tender Vend). The liquid crystal display device can be used in various display modes such as a (Nematic) mode. The retardation plate is particularly effective for optical compensation of a liquid crystal display device of TN (Twisted Nematic) or OCB (Optically Compensatory Bend) mode.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Synthesis Example 1 [Synthesis of D3-10]
Synthesized according to the following scheme.

(Synthesis of D3-10A)
2.5 g of 3-cyanobenzoic acid chloride was dissolved in 20 ml of tetrahydrofuran (THF), 1.3 ml of 3-chloro-1-propanol and 3.0 ml of diisopropylethylamine (DIPEA) were added, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure. The residue was dissolved in 100 ml of methanol (MeOH), and 2.8 ml of 50% hydroxylamine solution was added, followed by stirring at 40 ° C. for 1 hour. After cooling, water was added to the reaction solution, and the precipitated crystals were separated by filtration and dried to obtain 3.4 g of D3-10A.

(Synthesis of D3-10B)
3.4 g of D3-10A was dissolved in 10 ml of dimethylacetamide (DMAc), 1.2 ml of pyridine and 1.2 g of trimesic acid chloride were added, and the mixture was stirred at 120 ° C. for 1 hour. After cooling, methanol was added, and the precipitated crystals were collected by filtration and dried to obtain 3.9 g of D3-10B.

(Synthesis of D3-10)
3.9 g of D3-10B was dissolved in 50 ml of dimethylacetamide, 3.7 g of potassium carbonate, 2.0 g of sodium iodide and 1.9 ml of acrylic acid were added, followed by stirring at 100 ° C. for 3 hours. Water was added to the reaction solution, and the precipitated crystals were collected by filtration. Purification was performed by column chromatography to obtain 3.0 g of D3-10. The NMR spectrum of the obtained D3-10 is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 2.30 (6H, q), 4.40 (6H, t), 4.55 (6H, t), 5. 85 (3H, dd), 6.15 (3H, dd), 6.45 (3H, dd), 7.65 (3H, t), 8.25 (3H, d), 8.45 (3H, d ), 8.90 (3H, s), 9.30 (3H, s)

  When the phase transition temperature of the obtained D3-10 was measured by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase at around 115 ° C, and an isotropic liquid exceeded 178 ° C. It turned into a phase. That is, it was found that D3-10 exhibits a discotic nematic liquid crystal phase between 115 ° C. and 178 ° C.

Synthesis Example 2 [Synthesis of D3-12]
Synthesized according to the following scheme.

(Synthesis of D3-12A)
2.5 g of 3-cyanobenzoic acid chloride was dissolved in 20 ml of tetrahydrofuran (THF), 5.7 g of 5-chloro-1-pentanol and 3.0 ml of diisopropylethylamine (DIPEA) were added, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure. The residue was dissolved in 100 ml of methanol (MeOH), and 2.8 ml of 50% hydroxylamine solution was added, followed by stirring at 40 ° C. for 1 hour. After cooling, water was added to the reaction solution, and the precipitated crystals were separated by filtration and dried to obtain 3.7 g of D3-12A.

(Synthesis of D3-12B)
3.7 g of D3-12A was dissolved in 10 ml of dimethylacetamide (DMAc), 1.2 ml of pyridine (Pyridine) and 1.1 g of trimesic acid chloride were added, and the mixture was stirred at 120 ° C. for 1 hour. After cooling, methanol was added, and the precipitated crystals were collected by filtration and dried to obtain 3.9 g of D3-12B.

(Synthesis of D3-12)
3.9 g of D3-12B was dissolved in 50 ml of dimethylacetamide (DMAc), 3.7 g of potassium carbonate, 2.0 g of sodium iodide and 1.9 ml of acrylic acid were added, followed by stirring at 100 ° C. for 3 hours. Water was added to the reaction solution, and the precipitated crystals were collected by filtration. Purification was performed by column chromatography to obtain 3.0 g of D3-12. The NMR spectrum of the obtained D3-12 is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 1.60 (6H, m), 1.80-1.90 (12H, m), 4.25 (6H, t ), 4.45 (6H, t), 5.80 (3H, dd), 6.15 (3H, dd), 6.40 (3H, dd), 7.65 (3H, t), 8.25. (3H, d), 8.45 (3H, d), 8.90 (3H, s), 9.30 (3H, s)

  When the phase transition temperature of the obtained D3-12 was measured by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase around 86 ° C. It turned into a phase. That is, it was found that D3-12 exhibits a discotic nematic liquid crystal phase between 86 ° C and 142 ° C.

Synthesis Example 3 [Synthesis of D3-15]
Synthesized according to the following scheme.

(Synthesis of D3-15)
The synthesis was performed in the same manner as in Synthesis Example 1 except that 3-chloro-1-propanol in Synthesis Example 1 was changed to 3-chloro-2-methyl-1-propanol, and 3.0 g of D3-15 was obtained. The NMR spectrum of the obtained D3-15 was as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 1.15 (9H, d), 2.43 to 2.52 (3H, m), 4.25 (6H, d ), 4.38 (6H, d), 5.83 (3H, d), 6.15 (3H, dd), 6.43 (3H, d), 7.67 (3H, t), 8.24 (3H, d), 8.46 (3H, d), 8.90 (3H, s), 9.30 (3H, s)

  When the phase transition temperature of the obtained D3-15 was measured by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase in the vicinity of 90 ° C. It turned into a phase. That is, it was found that D3-15 exhibits a discotic nematic liquid crystal phase between 90 ° C. and 153 ° C.

Synthesis Example 4 [Synthesis of A-2B]
Synthesized according to the following scheme.

(Synthesis of A-2A)
1,3.6 g of 2,3-naphthalenedicarboxylic anhydride, 25.0 g of 2- (perfluorohexyl) ethanol, and 40 mg of dimethylaminopyridine (DMAP) were added to 50 ml of pyridine (Pyridine) and stirred at 70 ° C. for 3 hours. . After adding 10 ml of water and stirring at 40 ° C. for 30 minutes, 50 ml of hydrochloric acid was added and extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid, sodium bicarbonate, dilute hydrochloric acid, and brine, and then dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 29.9 g of Compound A-2A.

(Synthesis of A-2B)
64.15 g of compound A-2A was dissolved in 200 ml of toluene (Toluene), 65 ml of SOCl ₂ and 1 ml of catDMF were added dropwise, and the mixture was stirred at 60 ° C. for 1 hour. Then, the solvent was removed by distillation under reduced pressure, 300 ml of THF and 13.2 ml of 2-hydroxyethyl acrylate were added, and 39.8 ml of diisopropylethylamine (i-Pr ₂ NEt), 4-dimethylaminopyridine ( (DMAP) 0.70 g was added and stirred at room temperature for 3 hours. 1N aqueous hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate, washed with brine, and dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 53.20 g of A-2B. The NMR spectrum of the obtained A-2B was as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 2.70 to 2.56 (2H, m), 4.52 (2H, t), 4.60 (2H, t ), 4.65 (2H, t), 5.87 (1H, d), 6.17 (1H, dd), 6.47 (1H, d), 7.68-7.60 (2H, m) 7.98-7.90 (2H, m) 8.23 (1H, s), 8.30 (1H, s)

Synthesis Example 5 [Synthesis of A-1B]
Synthesized according to the following scheme.

(Synthesis of A-1B)
The synthesis was performed in the same manner as in Synthesis Example 4 except that 2- (perfluorohexyl) ethanol in Synthesis Example 4 was changed to 2- (perfluorobutyl) ethanol, and 50.5 g of A-1B was obtained. The NMR spectrum of the obtained A-1B was as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 2.74 to 2.56 (2H, m), 4.54 (2H, t), 4.60 (2H, t ), 4.65 (2H, t), 5.87 (1H, d), 6.17 (1H, dd), 6.47 (1H, d), 7.68-7.60 (2H, m) 7.98-7.90 (2H, m), 8.23 (1H, s), 8.30 (1H, s)

Synthesis Example 6 [Synthesis of P-1]
Synthesized according to the following scheme.

(Synthesis of P-1)
Methyl ethyl ketone (MEK) (4 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A methyl ethyl ketone (MEK) (8 g) solution of A-2A (16.0 g) and a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-601, 600 mg) was added dropwise over 3 hours. After completion of the dropping, the reaction was allowed to proceed for 4 hours at the same temperature to obtain 15.0 g of polymer (P-1). The molecular weight was 17000.

Synthesis Example 7 [Synthesis of P-3]
Synthesized according to the following scheme.

(Synthesis of P-3)
The synthesis was conducted in the same manner as in Synthesis Example 5 except that A-2A in Synthesis Example 6 was changed to A-1A, and 50.7 g of polymer (P-3) was obtained. The molecular weight was 18,000.

Synthesis Example 8 [Synthesis of P-14]
Synthesized according to the following scheme.

(Synthesis of P-14)
Methyl ethyl ketone (MEK) (4 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A methyl ethyl ketone (MEK) (8 g) solution of A-2A (10.4 g), ethyl acrylate (5.6 g), and a polymerization initiator (Wako Pure Chemical Industries, Ltd., V-601, 600 mg) was added for 3 hours. It was hung and dropped. After completion of the dropwise addition, the mixture was reacted at the same temperature for 4 hours to obtain 15.0 g of polymer (P-14). The molecular weight was 20000.

Synthesis Example 9 [Synthesis of P-16, P-17, P-19, P-21, P-22]
Synthesized according to the following scheme.

(Synthesis of P-16, P-17, P-19, P-21, P-22)
The ethyl acrylate of Synthesis Example 8 was changed to hexyl acrylate, benzyl acrylate, phenoxyethyl acrylate, AE-90 (manufactured by NOF Corporation, Bunlemmer AE-90), AP-400 (manufactured by NOF Corporation, Bunlenmer AP-400), Others were synthesized in the same manner as in Synthesis Example 8, and P-16 was 15.0 g, P-17 was 15.6 g, P-19 was 15.3 g, P-21 was 14.9 g, P-22, respectively. 15.2 g was obtained. The molecular weights were 16000, 17000, 20000 and 19000, respectively.

Synthesis Example 10 [Synthesis of P-31D]
Synthesized according to the following scheme.

(Synthesis of P-31D)
Hydroxybutyl acrylate (Tokyo Chemicals) was methanesulfonylated with methanesulfonyl chloride (MsCl) in acetonitrile (AR) and then reacted with 4-hydroxybenzaldehyde (Wako Pure Chemical Industries) in K ₂ CO ₃ and DMAc. 4- (4-acryloxybutoxy) phenylaldehyde was obtained. The obtained aldehyde was oxidized with sodium chlorate (NaClO ₂ ) under H ₂ O ₂ to obtain 4- (4-acryloxybutoxy) benzoic acid. This benzoic acid and 4-hydroxybenzonitrile (Tokyo Chemicals) were condensed by the mixed acid anhydride method using MsCl and triethylamine (Et ₃ N) in THF to give 1-cyano-4- (4 ′ -41 g of acryloyloxybutoxy) benzoic acid) benzene (P-31D), 75% overall yield. The NMR spectrum of the obtained P-31D was as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 1.90 (4H, m), 4.10 (2H, t), 4.25 (2H, t), 5. 85 (1H, dd), 6.15 (1H, dd), 6.45 (1H, dd), 6.95 (2H, d), 7.35 (2H, d), 7.75 (2H, d ), 8.12 (2H, d)

Synthesis Example 11 [Synthesis of P-31]
Synthesized according to the following scheme.

(Synthesis of P-31)
Methyl ethyl ketone (MEK) (4 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A-2A (6.4 g), P-31D (3.2 g), AP-400 (manufactured by NOF Corporation, Bunlemmer AP-400, 6.4 g), polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.) , V-601, 600 mg) in methyl ethyl ketone (MEK) (8 g) was added dropwise over 3 hours. After completion of the dropping, the reaction was allowed to proceed for 4 hours at the same temperature to obtain 15.2 g of polymer (P-31). The molecular weight was 18,000.

Synthesis Example 12 [Synthesis of P-32D]
Synthesized according to the following scheme.

(Synthesis of P-32D)
The 4-cyanophenol of Synthesis Example 10 was changed to 4-cyano-3-fluoro-phenol, and the others were synthesized in the same manner as in Synthesis Example 10 to obtain 3.5 g of P-32D. The NMR spectrum of the obtained P-32D is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 1.90 (4H, m), 4.10 (2H, t), 4.26 (2H, t), 5. 85 (1H, dd), 6.15 (1H, dd), 6.45 (1H, dd), 6.96 (2H, d), 7.20 (2H, m), 7.68 (1H, t ), 8.10 (2H, d)

Synthesis Example 13 [Synthesis of P-32]
Synthesized according to the following scheme.

(Synthesis of P-32)
Methyl ethyl ketone (MEK) (4 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. There, A-2A (6.4 g), P-32D (3.2 g), AP-400 (manufactured by NOF Corporation, Bunlemmer AP-400, 6.4 g), polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.) , V-601, 600 mg) in methyl ethyl ketone (MEK) (8 g) was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was reacted at the same temperature for 4 hours to obtain 15.4 g of polymer (P-32). The molecular weight was 19000.

Synthesis Example 14 [Synthesis of P-45B]
Synthesized according to the following scheme.

(Synthesis of P-45B)
Hydroxybutyl acrylate (Tokyo Kasei) was methanesulfonylated in acetonitrile with methanesulfonyl chloride (MsCl) and then reacted with 4-cyanophenol (Wako Pure Chemical Industries) in DMAc to yield 50 g of P-45B, overall yield. Obtained at 90%. The NMR spectrum of the obtained P-45B is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 1.90 (4H, m), 4.10 (2H, t), 4.25 (2H, t), 5. 85 (1H, dd), 6.15 (1H, dd), 6.45 (1H, dd), 6.95 (2H, d), 7.35 (2H, d), 7.75 (2H, d ), 8.12 (2H, d)

Synthesis Example 15 [Synthesis of P-45]
Synthesized according to the following scheme.

(Synthesis of P-45)
Methyl ethyl ketone (MEK) (4 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A-2A (6.4 g), P-45B (6.4 g), AP-400 (manufactured by NOF Corporation, Bunlemmer AP-400, 3.2 g), polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.) , V-601, 600 mg) in methyl ethyl ketone (MEK) (8 g) was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was reacted at the same temperature for 4 hours to obtain 15.4 g of polymer (P-45). The molecular weight was 17000.

Synthesis Example 16 [Synthesis of P-47B]
Synthesized according to the following scheme.

(Synthesis of P-47B)
4-cyanophenol of the synthesis example 14 was changed into 4-chlorophenol, and others were synthesize | combined by the method similar to the synthesis example 14, and 3.5g of P-47B was obtained. The NMR spectrum of the obtained P-47B was as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 1.85 (4H, m), 3.95 (2H, t), 4.23 (2H, t), 5. 82 (1H, dd), 6.13 (1H, dd), 6.40 (1H, dd), 6.82 (2H, m), 7.23 (2H, m)

Synthesis Example 17 [Synthesis of P-47]
Synthesized according to the following scheme.

(Synthesis of P-47)
Methyl ethyl ketone (MEK) (4 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A-1A (6.4 g), P-47B (6.4 g), AMP-20G (manufactured by NOF Corporation, 3.2 g), polymerization initiator (manufactured by Wako Pure Chemical Industries, V-601), 600 mg) of methyl ethyl ketone (MEK) (8 g) was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was reacted at the same temperature for 4 hours to obtain 15.3 g of polymer (P-47). The molecular weight was 19000.

[Example 1: Preparation of liquid crystal composition (LM-1) of the present invention]
In the proportion of the composition shown below, the compound represented by the general formula (Do) of the present invention, the polymer containing the group represented by the general formula (A) of the present invention as a structural unit, and Irgacure 907 as a photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd.) and the photosensitizer diethylthioxanthone were weighed and dissolved in methyl ethyl ketone to prepare the composition (LM-1) of the present invention.

Composition of composition (LM-1)-Compound represented by general formula (Do): D3-12 100 parts by mass-Polymer containing group represented by general formula (A) as structural unit: P-1. 0 parts by mass, Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.)
3.0 parts by mass, diethylthioxanthone 1.0 parts by mass, methyl ethyl ketone 250 parts by mass

[Example 2: Preparation of the composition of the present invention (LM-2 to LM-14)]
The polymer containing the group represented by the general formula (A) as a structural unit and the compound represented by the general formula (Do) are those shown in Table 1 below, and the others are performed in the same manner. LM-2) to (LM-14) were prepared.

[Comparative Example 1: Preparation of comparative compositions (LH-1 to LH-3)]
The composition (LM-9) of Example 1 and (LM-13) of Example 2 except that the polymer (P-31) containing the group represented by formula (A) as a structural unit was not added. In the same manner as (LM-14) and (LM-14), comparative compositions (LH-1), (LH-2), and (LH-3) were prepared, respectively.

[Example 3: Production of retardation plate (RM-1) of the present invention]
(Preparation of transparent support)
The following components were put into a mixing tank and heated and stirred to prepare a cellulose acetate solution (hereinafter sometimes referred to as a dope).
―――――――――――――――――――――――――――――――――
Cellulose acetate solution composition ――――――――――――――――――――――――――――――――――
Cellulose acetate having an acetylation degree of 60.9% 100 parts by mass Triphenyl phosphate 6.5 parts by mass Biphenyl diphenyl phosphate 5.2 parts by mass The following retardation increasing agent (1) 0.1 part by mass The following retardation increasing agent ( 2) 0.2 parts by mass Methylene chloride 310.25 parts by mass Methanol 54.75 parts by mass 1-butanol 10.95 parts by mass ―――――――――――――――――――――― ―――――――――――

  The obtained dope was cast from a casting port onto a drum cooled to 0 ° C. The film is peeled off at a solvent content of 70% by mass, both ends in the width direction of the film are fixed with a pin tenter, and the stretch rate in the width direction (direction perpendicular to the machine direction) is in a region where the solvent content is 3 to 5% by mass. Was dried while maintaining an interval of 3%. Then, it is further dried by transporting between the rolls of the heat treatment apparatus, and the stretching ratio in the machine direction is substantially 0% in the region exceeding 120 ° C. (in consideration of 4% stretching in the machine direction when stripping). A cellulose acetate film having a thickness of 100 μm was prepared by adjusting the ratio of the stretching ratio in the width direction to the stretching ratio in the machine direction to be 0.75. When the retardation value of the produced film was measured at a wavelength of 632.8 nm, the retardation value in the thickness direction was 40 nm, and the in-plane retardation value was 4 nm. The produced cellulose acetate film was used as a transparent support.

(Formation of first undercoat layer)
On the transparent support, a coating solution having the following composition was applied at 28 mD / m ² and dried to form a first undercoat layer.
――――――――――――――――――――――――――――――――
Composition of the first undercoat layer coating solution ――――――――――――――――――――――――――――――――
Gelatin 5.44 parts by mass Formaldehyde 1.38 parts by mass Salicylic acid 1.62 parts by mass Acetone 391 parts by mass Methanol 158 parts by mass Methylene chloride 406 parts by mass Water 12 parts by mass ――――――――――――――― ―――――――――――――――――

(Formation of second undercoat layer)
On the first undercoat layer, a coating solution having the following composition was applied at 7 mD / m ² and dried to form a second undercoat layer.

────────────────────────────────
Second undercoat layer coating solution composition ――――――――――――――――――――――――――――――――
The following anionic polymers 0.77 parts by mass Citric acid monoethyl ester 10.1 parts by mass Acetone 200 parts by mass Methanol 877 parts by mass Water 40.5 parts by mass ――――――――――――――― ――――――――――――――――

アニオン性ポリマー

Anionic polymer

(Formation of back layer)
On the opposite surface of the transparent support, a coating solution having the following composition was applied at 25 mD / m ² and dried to form a back layer.
――――――――――――――――――――――――――――――――
Back layer coating solution composition ――――――――――――――――――――――――――――――――
Cellulose diacetate with an acetylation degree of 55% 6.56 parts by mass Silica matting agent (average particle size: 1 μm) 0.65 parts by mass Acetone 679 parts by mass Methanol 104 parts by mass ――――――――――― ――――――――――――――――――――

(Formation of alignment film)
The following modified polyvinyl alcohol and glutaraldehyde (5% by mass of the modified polyvinyl alcohol) were dissolved in a methanol / water mixed solvent (volume ratio = 20/80) to prepare a 5% by mass solution.

  This solution was applied onto the second undercoat layer and dried with hot air at 100 ° C. for 120 seconds, followed by a rubbing treatment to form an alignment film. The thickness of the obtained alignment film was 0.5 μm. The rubbing direction of the alignment film was parallel to the casting direction of the transparent support.

(Formation of optically anisotropic layer)
The coating liquid of the composition (LM-1) of the present invention prepared in Example 1 was applied onto the rubbing treated surface of the alignment film prepared above using a wire bar. The film coated with the optically anisotropic layer is oriented in a constant temperature bath at 120 ° C. and lowered to 80 ° C., and then irradiated with ultraviolet rays of 200 mJ / cm ² to change the orientation state of the optically anisotropic layer. Fixed. The solution was allowed to cool to room temperature to produce a retardation plate (RM-1) of the present invention. The thickness of the formed optically anisotropic layer was about 0.7 μm.

[Example 4: Production of retardation plate (RM-2 to RM-14) of the present invention]
The composition (LM-1) of the present invention used in the production of the phase difference plate (RM-1) of the present invention described in Example 3 was used as the composition (LM-2) to (LM-14) of the present invention. The retardation plates (RM-2) to (RM-14) of the present invention were produced in the same manner except that the above were changed.

[Comparative Example 2: Production of comparative retardation plates (RH-1 to RH-3)]
The composition (LM-1) of the present invention used in the production of the retardation plate (RM-1) of the present invention described in Example 3 was used as the comparative composition (LH-1) to (LH-). Comparative retardation plates (RH-1) to (RH-3) were produced in the same manner except that they were changed to 3).

[Example 5: Evaluation of retardation plate]
(Measurement of average tilt angle)
Re (589 nm) represents in-plane retardation at the wavelength λ. Re (589 nm) of the phase difference plates obtained in Examples 3 and 4 and Comparative Example 2 was measured by using KOBRA 21ADH (manufactured by Oji Scientific Instruments) in order to simplify the measurement and calculation. The normal direction with respect to the layer was set to 0 °, and light having a wavelength of 589 nm was incident in the normal direction of the film at three measurement angles of −40 °, 0 °, and + 40 °, and the retardation value was measured.
The refractive index of ordinary light of each layer is no, the refractive index of extraordinary light is ne (ne is the same value in all layers, and the same is no), the thickness of the entire multilayer body is d, and the tilt in each layer The direction of the optically anisotropic layer is calculated so that the calculation of the angular dependence of the retardation value of the optically anisotropic layer matches the measured value under the assumption that the direction of the optical axis matches the direction of the uniaxial optical axis of the layer. Fitting was performed using the tilt angle θ1 on one surface and the tilt angle θ2 on the other surface as variables, and θ1 and θ2 were calculated.
The average tilt angle was determined from the average value of these values ((θ1 + θ2) / 2).

  Moreover, the ultrathin section of the cross section of the phase difference plate obtained in Examples 3 and 4 and Comparative Example 2 was prepared using a microtome, and the section was observed with a polarizing microscope. It was confirmed that the retardation films RM-1 to RM-14 of the present invention and the optically anisotropic layers of RH-1 to RH-1 of Comparative Example 2 were hybrid aligned.

(Average tilt angle)
The average tilt angle is listed in Table 2 below.

  From the results in Table 2, the retardation plates (RM-1) to (RM-14) prepared from the liquid crystal composition of the present invention are retardation plates (RH-1) to (RH-3) which are comparative examples. In comparison, it was found that a retardation plate having a small average tilt angle can be produced.

Claims (12)

A polymer comprising at least one group represented by the following general formula (A) as a structural unit.

(In General Formula (A), M ⁰¹ and M ⁰² are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O ) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C═C—, and a combination thereof selected from the group consisting of these, In the case of a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent, R ⁰¹ represents a hydrogen atom or a methyl group, and R ⁰² represents a substituted or unsubstituted aliphatic hydrocarbon group. ⁰¹ represents the following general formula (B).)

(In the general formula (B), B ¹¹ , B ¹² , B ¹³ and B ¹⁴ each independently represent a hydrogen atom or a substituent, and two of B ¹¹ , B ¹² , B ¹³ and B ¹⁴ are linked to each other. And may form a ring.) The polymer according to claim 1, wherein K ⁰¹ in the general formula (A) is represented by the general formula (B-1).

(In General Formula (B-1), B ¹⁵ represents a substituent, and n11 represents an integer of 0 to 6. When n11 is 2 or more, each B ¹⁵ may be the same or different. Good.) The polymer according to claim 1 or 2, wherein at least one of the general formula (A) is a group represented by the following general formula (A-1).

(In General Formula (A-1), B ¹⁶ represents a substituent, and n12 represents an integer of 0 to 6. When n12 is 2 or more, each B ¹⁶ may be the same or different. R ⁰³ represents a substituted or unsubstituted aliphatic hydrocarbon group. The polymer represented by the general formula (PA) containing the structural unit of the general formula (A).

(In the general formula (PA), R ¹¹ and R ¹² each independently represents a hydrogen atom or a methyl group. G represents -M ⁰¹ -K ⁰¹ -M ⁰² -R ⁰² (where M ⁰¹ , M ⁰² are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, —SO ₂ —, —NH. —, —CH ₂ —, —CH═CH— and —C (C— represents a divalent linking group selected from the group consisting of a combination thereof, and when the above group is a group containing a hydrogen atom, The hydrogen atom may be substituted with a substituent, R ⁰² represents a substituted or unsubstituted aliphatic hydrocarbon group, K ⁰¹ represents the general formula (B), and M ⁴¹ each independently represents a linking group. J ¹ represents a group containing one or more ring structures, A ¹ represents a structural unit, and a, b, and c represent mass fractions (%) of the respective structural units. The composition containing the polymer of any one of Claims 1-4 and the compound represented by at least 1 type of general formula (Do).

(In the general formula (Do), Y ¹ , Y ² and Y ³ each independently represent a methine or nitrogen atom, and R ^a , R ^b and R ^c each independently represent a substituent.) The composition according to claim 5, wherein the compound represented by the general formula (Do) is represented by the following general formula (DI).

(In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom. L ¹ , L ² and L ³ each independently represents a single bond or a divalent linking group. H ¹ , H ² and H ³ each independently represents the general formula (DI-A) or the general formula (DI-B), and R ¹ , R ² and R ³ each independently represent the following general formula ( DI-R).)

(In the general formula (DI-A), YA ¹ and YA ² each independently represents a methine or nitrogen atom, XA represents an oxygen atom, a sulfur atom, methylene, or imino, and * represents L ^{1 to} L ³ . (The bond position is represented, and ** represents the bond position with R ^{1 to} R ^3. )

(In the general formula (DI-B), YB ¹ and YB ² each independently represent a methine or nitrogen atom, XB represents an oxygen atom, a sulfur atom, methylene, or imino, and * represents L ^{1 to} L ³ . (The bond position is represented, and ** represents the bond position with R ^{1 to} R ^3. )
General formula (DI-R)
*-(-L ²¹ -F ¹ ) _n1 -L ²² -L ²³ -Q ¹
(In the general formula (DI-R), * represents a position bonded to H ¹ , H ² or H ³ in the general formula (DI). L ²¹ represents a single bond or a divalent linking group. F ¹ Represents a divalent cyclic linking group having at least one cyclic structure, n1 represents an integer of 0 to 4. L ²² represents —O—, —O—CO—, —CO—O—, —O—. CO-O -, - S - , - NH -, - SO 2 -, - CH 2 -, - CH = CH -, - C = the .L ²³ representing the C- -O -, - S -, - C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C═C— and a divalent linking group selected from the group consisting of these, When the group of is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent, and Q ¹ represents a polymerizable group or a hydrogen atom.) The composition according to claim 5, wherein the compound represented by the general formula (Do) is a compound represented by the following general formula (DII) or a compound represented by the following general formula (DIII).

(In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methine or nitrogen atom. R ³¹ , R ³² and R ³³ are each independently represented by the general formula (DII-R). .)

(In the general formula (DII-R), A ³¹ and A ³² each independently represents a methine or nitrogen atom, X ³ represents an oxygen atom, a sulfur atom, methylene, or imino. F ² represents a 6-membered ring. .n3 representing the divalent cyclic group having the structure, the .L ³¹ representing a 1-3 integer -O -, - O-CO - , - CO-O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, - CH = CH- or -C = .L ³² representing the C- is -O -, - S -, - C (= O) -, - Represents a divalent linking group selected from the group consisting of SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C═C— and combinations thereof, and the above group contains a hydrogen atom. When it is a group, the hydrogen atom may be replaced by a substituent, and Q ³ represents a polymerizable group or a hydrogen atom.)

(In the general formula (DIII), Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represents a methine or nitrogen atom, and R ⁴¹ , R ⁴² and R ⁴³ each independently represents the general formula (DIII-A), Formula (DIII-B) or general formula (DIII-C) is represented.)
General formula (DIII-A)

(In the general formula (DIII-A), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ , A ⁴⁶ each independently represents a methine or nitrogen atom, and X ⁴¹ represents an oxygen atom, a sulfur atom, or methylene. Or L ⁴¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH— or —C═C—, L ⁴² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH Represents a divalent linking group selected from the group consisting of ═CH— and —C═C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is replaced by a substituent. Q ⁴ represents a polymerizable group or a hydrogen atom.)

(In the general formula (DIII-B), A ⁵¹ , A ⁵² , A ⁵³ , A ⁵⁴ , A ⁵⁵ , A ⁵⁶ each independently represents a methine or nitrogen atom, and X ⁵² represents an oxygen atom, a sulfur atom, or methylene. , - - -O or an imino, L ⁵¹ is O-CO -, - CO- O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, .L ⁵² representing a -CH = CH- or -C = C-is, -O -, - S -, - C (= O) -, - SO 2 -, - NH -, - CH 2 -, - CH Represents a divalent linking group selected from the group consisting of ═CH— and —C═C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is replaced by a substituent. Q ⁵ represents a polymerizable group or a hydrogen atom.)

(In the general formula (DIII-C), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ , A ⁶⁶ each independently represents a methine or nitrogen atom, and X ⁶³ represents an oxygen atom, a sulfur atom, or methine. Or L ⁶¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, Represents —CH═CH— or —C═C—, L ⁶² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH; Represents a divalent linking group selected from the group consisting of ═CH— and —C═C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is replaced by a substituent. Q ⁶ represents a polymerizable group or a hydrogen atom.)   A phase difference plate having an alignment film and an optically anisotropic layer formed from the composition according to claim 5 on a support.   The retardation film according to claim 8, wherein the alignment film contains polyvinyl alcohols.   The phase difference plate according to claim 8 or 9, wherein the optically anisotropic layer is formed from a discotic liquid crystalline compound with hybrid alignment.   The elliptically polarizing plate which has a phase difference plate of any one of Claims 8-10, and a polarizing film.   The liquid crystal display device which has a phase difference plate of any one of Claims 8-10.