JP2007272185A - Composition, retardation plate, liquid crystal display device, average tilt angle regulator, and method for regulating average tilt angle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition useful to stably produce an optically anisotropic layer having a low angle of alignment, which contributes to optical compensation of a liquid crystal display device. <P>SOLUTION: The composition contains at least one liquid crystalline compound and a polymer having a ≥2C unsubstituted alkyl group in a side chain as a polymer which regulates the average tilt angle of the liquid crystal compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition useful for forming an optically anisotropic layer, a retardation plate using the composition, and the like.

  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 crystal between a pair of substrates. A phase difference generated in a liquid crystal cell using a rod-like liquid crystal is converted into a discotic liquid crystalline compound (for example, 2,3,6,7,10,11-hexa {4- (4-acryloyloxyhexyloxy) benzoyloxy} triphenylene. In the case of canceling with an optical compensation sheet (for example, Patent Document 1) having an optically anisotropic layer formed from, for example, the wavelength dispersion of the rod-like liquid crystal and the discotic liquid crystalline compound is different, so May not be able to cancel out the phase difference at the same time, and discoloration (such as no black color) may occur.

  On the other hand, a trisubstituted benzene compound having a heterocyclic group has been reported (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 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 (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 refractive index 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 manufactured by fixing the alignment of liquid crystal, the retardation (Re) changes depending on the alignment angle (tilt angle, average tilt angle) of the aligned liquid crystal, so it is necessary to control the alignment angle. is there.

  However, in the case of a trisubstituted 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 tilt angle. An alignment controller capable of adjusting the alignment angle of the discotic liquid crystal compound to a desired angle has been desired.

  On the other hand, an example in which an alignment controller or an alignment accelerator is added to the liquid crystal compound is disclosed, but the effect on the trisubstituted benzene type liquid crystal compound is not clearly shown, and the conventional technique does not provide an alignment angle. It was insufficient to control 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 useful for stably producing an optically anisotropic layer having a low orientation angle, which 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. 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Ｐ−Ａ中、Ｒ⁷¹、Ｒ⁷²はそれぞれ独立に水素原子またはメチル基を表し、Ｌ⁷¹、Ｌ⁷²はそれぞれ独立に連結基を表し、Ｒｆは炭素原子数１〜２０のフッ化アルキル基を表し、Ｒ⁷³は炭素原子数２〜３０の無置換のアルキル基を表し、Ａ⁷は任意の構成単位を表し、ａ、ｂ、ｃはそれぞれの構成単位の質量分率を表す。）
（４）前記一般式Ｐ−Ａで表されるポリマーが下記一般式Ｐ−Ａ２で表される、（３）に記載の組成物。

（一般式Ｐ−Ａ２中、Ｒ⁹¹、Ｒ⁹²はそれぞれ独立に水素原子またはメチル基を表し、Ｌ⁹¹、Ｌ⁹²はそれぞれ独立に−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−のいずれかを表し、Ｒｆは炭素原子数３〜２０のフッ化アルキル基を表し、Ｒ⁹³は炭素原子数２〜２０の無置換のアルキル基を表し、Ａ⁹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。）
（５）さらに、フルオロ脂肪族基含有モノマーより誘導される構成単位を含み、かつ、側鎖に炭素原子数２以上の無置換のアルキル基を含まないポリマーを含有する、（１）〜（４）のいずれか１項に記載の組成物。
（６）前記フルオロ脂肪族基含有モノマーより誘導される構成単位を含み、かつ、側鎖に炭素原子数２以上の無置換のアルキル基を含まないポリマーが、親水性基を含有する、（１）〜（５）のいずれか１項に記載の組成物。
（７）前記フルオロ脂肪族基含有モノマーより誘導される構成単位を含み、かつ、側鎖に炭素原子数２以上の無置換のアルキル基を含まないポリマーが、下記一般式Ｆで表される、（１）〜（５）のいずれか１項に記載の組成物。
（一般式Ｆ）

（一般式Ｆ中、Ｒ¹⁰¹およびＲ¹⁰²はそれぞれ独立に水素原子またはメチル基を表し、Ｌ¹⁰¹、Ｌ¹⁰²は、それぞれ独立に単結合または炭素原子数１〜２０の二価の連結基を表し、Ｒｆ"は炭素原子数３〜２０のフッ化アルキル基を表し、Ｒ¹⁰³は任意の親水性基を表し、Ａ¹⁰は任意の構成単位を表し、ｇ、ｈ、iはそれぞれの構成単位の質量分率を表す。）
（８）（１）〜（７）のいずれか１項に記載の組成物であって、該組成物からなる光学異方性層における液晶性化合物の平均チルト角が、該組成物から前記側鎖に炭素原子数２以上の無置換のアルキル基を有するポリマーであって、前記液晶性化合物の平均チルト角を調整するポリマーを除いた組成物からなる光学異方性層における液晶性化合物の平均チルト角よりも、２〜４５°低減している、（１）〜（７）のいずれか１項に記載の組成物。
（９）前記液晶性化合物は、ディスコティック液晶性化合物である、（１）〜（８）のいずれか１項に記載の組成物。
（１０）前記液晶性化合物の少なくとも１種は、下記一般式（ＤＩ）で表される液晶性化合物である、（１）〜（９）のいずれか１項に記載の組成物。

（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、下記一般式（ＤＩ−Ａ）または下記一般式（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）
＊−（−Ｌ²¹−二価の環状基）_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。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−、を表し、Ｌ²³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。Ｑ¹は重合性基または水素原子を表す。）
（１１）前記液晶性化合物の少なくとも１種は、下記一般式（ＤＩＩ）で表される液晶性化合物および下記一般式（ＤＩＩＩ）で表される液晶性化合物から選択されるものである、（１）〜（９）のいずれか１項に記載の組成物。

（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はそれぞれ独立に下記一般式（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。二価の環状基は、６員環構造を有する基である。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−、−Ｃ≡Ｃ−、を表し、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、それぞれ独立に下記一般式（ＤＩＩＩ−Ａ）、または下記一般式（ＤＩＩＩ−Ｂ）、または下記一般式（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−を表し、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−を表し、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−を表し、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。）
（１２）透明支持体の上に、配向膜と、（１）〜（１１）のいずれか１項に記載の組成物からなる光学異方性層とを有する位相差板。
（１３）前記配向膜がポリビニルアルコール類を含む、（１２）に記載の位相差板。
（１４）前記光学異方性層は、ディスコティック液晶性化合物がハイブリッド配向している、（１２）または（１３）に記載の位相差板。
（１５）（１２）〜（１４）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。
（１６）（１２）〜（１４）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。
（１７）側鎖に炭素原子数２以上の無置換のアルキル基を有するポリマーを含む、液晶性化合物の平均チルト角調整剤。
（１８）前記ポリマーが下記一般式Ｐ−Ａで表される、（１７）に記載の液晶性化合物の平均チルト角調整剤。

（一般式Ｐ−Ａ中、Ｒ⁷¹、Ｒ⁷²はそれぞれ独立に水素原子またはメチル基を表し、Ｌ⁷¹、Ｌ⁷²はそれぞれ独立に連結基を表し、Ｒｆは炭素原子数１〜２０のフッ化アルキル基を表し、Ｒ⁷³は炭素原子数２〜３０の無置換のアルキル基を表し、Ａ⁷は任意の構成単位を表し、ａ、ｂ、ｃはそれぞれの構成単位の質量分率を表す。）
（１９）側鎖に炭素原子数２以上の無置換のアルキル基を有するポリマーを用いることを含む、液晶性化合物の平均チルト角を調整する方法。
（２０）前記ポリマーが下記一般式Ｐ−Ａで表される、（１９）に記載の液晶性化合物の平均チルト角を調整する方法。

（一般式Ｐ−Ａ中、Ｒ⁷¹、Ｒ⁷²はそれぞれ独立に水素原子またはメチル基を表し、Ｌ⁷¹、Ｌ⁷²はそれぞれ独立に連結基を表し、Ｒｆは炭素原子数１〜２０のフッ化アルキル基を表し、Ｒ⁷³は炭素原子数２〜３０の無置換のアルキル基を表し、Ａ⁷は任意の構成単位を表し、ａ、ｂ、ｃはそれぞれの構成単位の質量分率を表す。）
（２１）前記液晶性化合物が、下記一般式（ＤＩ）で表される液晶性化合物である、（１７）または（１８）に記載の液晶性化合物の平均チルト角調整剤。
一般式（ＤＩ）

（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、下記一般式（ＤＩ−Ａ）または下記一般式（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）
＊−（−Ｌ²¹−二価の環状基）_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。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−、を表し、Ｌ²³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。Ｑ¹は重合性基または水素原子を表す。）
（２２）下記一般式（ＤＩ）で表される液晶性化合物用である、（１９）または（２０）に記載の液晶性化合物の平均チルト角を調整する方法。
一般式（ＤＩ）

（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、下記一般式（ＤＩ−Ａ）または下記一般式（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）
＊−（−Ｌ²¹−二価の環状基）_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。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−、を表し、Ｌ²³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。Ｑ¹は重合性基または水素原子を表す。） Means for solving the above problems are as follows.
(1) A composition comprising at least one liquid crystal compound and a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in a side chain, the polymer adjusting the average tilt angle of the liquid crystal compound. .
(2) The polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain, the polymer adjusting the average tilt angle of the liquid crystalline compound further has a fluorinated alkyl group in the side chain The composition according to (1).
(3) A composition comprising at least one liquid crystal compound and a polymer represented by the following general formula PA.

(In the general formula PA, R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a methyl group, L ⁷¹ and L ⁷² each independently represent a linking group, and Rf represents a fluorinated carbon atom having 1 to 20 carbon atoms. Represents an alkyl group, R ⁷³ represents an unsubstituted alkyl group having 2 to 30 carbon atoms, A ⁷ represents an arbitrary structural unit, and a, b, and c represent mass fractions of the respective structural units. )
(4) The composition according to (3), wherein the polymer represented by the general formula PA is represented by the following general formula P-A2.

(In the general formula P-A2, R ⁹¹ and R ⁹² each independently represent a hydrogen atom or a methyl group, and L ⁹¹ and L ⁹² each independently represent any of —COO—, —CONH—, and —OCO—. , Rf represents a fluorinated alkyl group having 3 to 20 carbon atoms, R ⁹³ represents an unsubstituted alkyl group having 2 to 20 carbon atoms, A ⁹ represents a structural unit, and d, e, and f are respectively Represents the mass fraction of the structural unit.)
(5) Furthermore, the polymer contains a structural unit derived from a fluoroaliphatic group-containing monomer and does not contain an unsubstituted alkyl group having 2 or more carbon atoms in the side chain. The composition according to any one of items 1).
(6) The polymer containing a structural unit derived from the fluoroaliphatic group-containing monomer and not containing an unsubstituted alkyl group having 2 or more carbon atoms in the side chain contains a hydrophilic group. The composition according to any one of (5) to (5).
(7) A polymer containing a structural unit derived from the fluoroaliphatic group-containing monomer and containing no unsubstituted alkyl group having 2 or more carbon atoms in the side chain is represented by the following general formula F. The composition according to any one of (1) to (5).
(General Formula F)

(In General Formula F, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a methyl group, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a divalent linking group having 1 to 20 carbon atoms. , Rf ″ represents a fluorinated alkyl group having 3 to 20 carbon atoms, R ¹⁰³ represents an arbitrary hydrophilic group, A ¹⁰ represents an arbitrary structural unit, and g, h, and i represent the respective structural units. Represents mass fraction.)
(8) The composition according to any one of (1) to (7), wherein the average tilt angle of the liquid crystalline compound in the optically anisotropic layer comprising the composition is Average of liquid crystalline compounds in an optically anisotropic layer comprising a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the chain and excluding the polymer that adjusts the average tilt angle of the liquid crystalline compound The composition according to any one of (1) to (7), which is reduced by 2 to 45 ° from the tilt angle.
(9) The composition according to any one of (1) to (8), wherein the liquid crystal compound is a discotic liquid crystal compound.
(10) The composition according to any one of (1) to (9), wherein at least one of the liquid crystalline compounds is a liquid crystalline compound 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 represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² , and R ³ each independently represent the following general formula Represents 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 _-divalent cyclic group) _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. 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≡C—, and L ²³ represents —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 when the above group is a group containing a hydrogen atom, the hydrogen atom is a substituent Q ¹ represents a polymerizable group or a hydrogen atom.
(11) At least one of the liquid crystalline compounds is selected from a liquid crystalline compound represented by the following general formula (DII) and a liquid crystalline compound represented by the following general formula (DIII): The composition according to any one of (9) to (9).

(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 following 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. The divalent cyclic group is A group having a 6-membered ring structure, n3 represents an integer of 1 to 3. L ³¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—. , —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—, —C≡C—, L ³² represents —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 following general formula (DIII-A), Or the following general formula (DIII-B) or the following general formula (DIII-C).
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—, and 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 -, —CH═CH— or —C≡C—, and L ⁵² 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 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. , - - -O or an imino, L ⁶¹ is O-CO -, - CO- O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, —CH═CH— or —C≡C—, and 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.)
(12) A retardation plate having an alignment film and an optically anisotropic layer made of the composition according to any one of (1) to (11) on a transparent support.
(13) The retardation film according to (12), wherein the alignment film contains polyvinyl alcohols.
(14) The retardation plate according to (12) or (13), wherein the optically anisotropic layer has a discotic liquid crystalline compound in a hybrid orientation.
(15) An elliptically polarizing plate having the retardation plate according to any one of (12) to (14) and a polarizing film.
(16) A liquid crystal display device having the retardation plate according to any one of (12) to (14).
(17) An average tilt angle adjusting agent for a liquid crystal compound, comprising a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain.
(18) The average tilt angle adjusting agent for liquid crystal compounds according to (17), wherein the polymer is represented by the following general formula PA.

(In the general formula PA, R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a methyl group, L ⁷¹ and L ⁷² each independently represent a linking group, and Rf represents a fluorinated carbon atom having 1 to 20 carbon atoms. Represents an alkyl group, R ⁷³ represents an unsubstituted alkyl group having 2 to 30 carbon atoms, A ⁷ represents an arbitrary structural unit, and a, b, and c represent mass fractions of the respective structural units. )
(19) A method for adjusting an average tilt angle of a liquid crystal compound, comprising using a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in a side chain.
(20) The method for adjusting the average tilt angle of the liquid crystal compound according to (19), wherein the polymer is represented by the following general formula PA.

(In the general formula PA, R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a methyl group, L ⁷¹ and L ⁷² each independently represent a linking group, and Rf represents a fluorinated carbon atom having 1 to 20 carbon atoms. Represents an alkyl group, R ⁷³ represents an unsubstituted alkyl group having 2 to 30 carbon atoms, A ⁷ represents an arbitrary structural unit, and a, b, and c represent mass fractions of the respective structural units. )
(21) The average tilt angle adjusting agent for a liquid crystal compound according to (17) or (18), wherein the liquid crystal compound is a liquid crystal compound represented by the following general formula (DI).
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 represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² , and R ³ each independently represent the following general formula Represents 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 _-divalent cyclic group) _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. 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≡C—, and L ²³ represents —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 when the above group is a group containing a hydrogen atom, the hydrogen atom is a substituent Q ¹ represents a polymerizable group or a hydrogen atom.
(22) A method for adjusting an average tilt angle of a liquid crystal compound according to (19) or (20), which is for a liquid crystal compound represented by the following general formula (DI).
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 represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² , and R ³ each independently represent the following general formula Represents 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 _-divalent cyclic group) _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. 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≡C—, and L ²³ represents —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 when the above group is a group containing a hydrogen atom, the hydrogen atom is a substituent Q ¹ represents a polymerizable group or a hydrogen atom.

  ADVANTAGE OF THE INVENTION According to this invention, the composition useful for producing stably the optically anisotropic layer with a low orientation angle which contributes to the optical compensation of a liquid crystal display device can be provided. According to the present invention, it is particularly useful for producing an optically anisotropic layer exhibiting optical anisotropy expressed by the hybrid orientation of a discotic liquid crystalline compound without or depending on temperature during polymerization. Composition can be provided. Moreover, according to the present invention, a retardation plate useful for optical compensation of a liquid crystal display device can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

  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 carbon atoms, the number of carbon atoms means a number including the number of carbon atoms that the substituent has.

First, details of Re (λ), Rth (λ), tilt angle, and average tilt angle in this specification will be described below.
In this specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth (λ) is the light of wavelength λnm from the direction inclined by + 40 ° with respect to the normal direction of the film, with Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotary axis). And a retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation value measured in three directions in total, the assumed value of the average refractive index, and the input film thickness value. Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. 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).

In this specification, the average tilt angle of the liquid crystal compound molecules 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 axis. The angle formed with the physical target axis of the molecule of the liquid crystalline compound being anisotropic is the tilt angle θ1, and the angle formed with the other surface (the air interface in the retardation plate of the present invention) is the tilt angle θ2. The average value ((θ1 + θ2) / 2) is defined. 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 (the tilt angle of the discotic liquid crystal compound or the rod-like liquid crystal compound is uniform in the layer) constituting it 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 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 retardation plate of the present invention is preferably a discotic having a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in a side chain, which will be described in detail below, and a general formula (DI), which will be described in detail below. An optically anisotropic layer made of a composition containing a liquid crystal compound is contained. Moreover, it is preferable that additives, such as a polymerization initiator and an orientation control agent, are contained in the composition used for the phase difference plate of the present invention in addition to the above compounds. Further, the retardation plate of the present invention preferably has a form in which the optically anisotropic layer is formed on the alignment film on the transparent support.
Hereinafter, a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain contained in the composition used in the retardation plate of the present invention, a liquid crystal compound, and other suitably used additives will be sequentially described. To do. Further, an alignment film and a transparent support that are suitably used for the retardation plate of the present invention will be described in order.

1. Composition (1-1) A polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain, the polymer adjusting the average tilt angle of the liquid crystalline compound. A polymer having a substituted alkyl group that adjusts the average tilt angle of the liquid crystal compound (hereinafter sometimes referred to as “polymer A”) controls the tilt angle of the liquid crystal compound to be low (tilt angle). For the purpose of reducing). Basically, the orientation angle can be lowered by increasing the number of carbon atoms in the alkyl group and increasing the alkyl group content. The number of carbon atoms required to reduce the orientation angle differs depending on the liquid crystal compound, but it is at least about 2 but can be increased as necessary, and can be controlled to an arbitrary orientation angle by such a method. It becomes possible to do.
In particular, in the present invention, when an optically anisotropic layer is formed using the composition of the present invention, the average tilt angle of the liquid crystalline compound is formed using a composition obtained by removing the polymer A from the composition of the present invention. The average tilt angle of the liquid crystalline compound in the optically anisotropic layer is preferably reduced by 2 to 45 °.

  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. Can be preferably used, and can be composed of two or more main chain structures, and the structural unit may be a block or random, and may be a linear polymer. Even if it exists, you may have a branch like a graft polymer or a star polymer.

  Further, when the liquid crystal compound represented by the general formula (DI) is adopted as the liquid crystal compound, the liquid crystal compound has a higher tilt angle on the air interface side, and in order to lower the orientation angle, It is effective to be unevenly distributed on the interface side. By increasing the number of carbon atoms in the alkyl group of the polymer having an alkyl group in the side chain, the surface energy decreases and surface unevenness develops, so increasing the number of carbon atoms in the side chain alkyl group is However, the polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain of the present invention preferably has a lower surface energy. It is preferable to have an alkyl group.

  The polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the present invention is preferably a polymer represented by the following general formula PA.

In the general formula PA, R ⁷¹ and R ⁷² each independently represents a hydrogen atom or a methyl group.
L ⁷¹ and L ⁷² each independently represent a linking group, preferably a linking group having 1 to 20 carbon atoms, and represented by the following general formula (PL-1), general formula (PL-2), and general formula (PL-3). ) Is more preferable.

（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ＲｆまたはＲ⁷³で表される側鎖と結合する部位を表し、Ｌ⁸¹は炭素原子数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原子数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良く、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 Rf or R ⁷³ , and L ⁸¹ represents a carbon atom. Represents a linking group of formulas 1 to 19, 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 the structures may be included. L ⁸¹ may include 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ＲｆまたはＲ⁷³で表される側鎖と結合する部位を表し、Ｌ⁸²は炭素原子数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 Rf or R ⁷³ , and L ⁸² represents a carbon atom. Represents a linking group of formulas 1 to 19, 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ＲｆまたはＲ⁷³で表される側鎖と結合する部位を表し、Ｌ⁸³は炭素原子数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 Rf or R ⁷³ , and L ⁸³ represents a carbon atom. Represents a linking group of formulas 1 to 19, and p is 0 or 1.)
The preferred range of L ⁸³ is the same as L ⁸¹ in the general formula (PL-1).

Rf represents a fluorinated alkyl group having 1 to 20 carbon atoms, preferably a fluorinated alkyl group having 3 to 20 carbon atoms, and more preferably a perfluoroalkyl group. Further, it may be substituted with a substitutable group (for example, an alkoxy group, an acyloxy group, a halogen atom, etc.). A fluorine-containing alkyl group having 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms is preferable, 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.), but 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 alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl) Group, a perfluorocyclopentyl group, or an alkyl group substituted with these).

R ⁷³ represents an unsubstituted alkyl group having 2 to 30 carbon atoms, preferably an unsubstituted alkyl group having 2 to 20 carbon atoms, more preferably an unsubstituted alkyl group having 2 to 15 carbon atoms. It is. The alkyl group of R ⁷³ may have either a saturated bond or an unsaturated bond, and may have any of a linear structure, a branched structure, and a ring structure.

A ⁷ represents an arbitrary structural unit, and is appropriately selected from the viewpoints of the desired orientation angle, affinity with the structural component of the composition to be used, etc., and the constituent monomer is not particularly limited and is a structural unit containing the fluorinated alkyl group Any monomer can be used as long as it can be copolymerized with the monomer constituting the structural unit containing the alkyl group, and the functional group may or may not be contained. Specific examples include functional groups. Olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 3 -Trimethoxysilylpropyl acrylate, acrylate having polyethylene oxide at the ester site, Acrylates having dimethylsiloxane at the ester site), methacrylates (methyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, 3-triethoxysilylpropyl 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, etc.), 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, carboxyl group-containing vinyl monomers are preferred, acrylic acid esters, methacrylic acid esters, Acrylamides, methacrylamides, vinyl ethers and vinyl esters are particularly preferred.

a, b and c represent mass fractions (%) of the respective structural units, and preferably 0 ≦ a ≦ 80, 20 ≦ b ≦ 100, and 0 ≦ c ≦ 80, 10 ≦ a ≦ 80, 20 ≦ b ≦ 90 and 0 ≦ c ≦ 70 are more preferable, and 20 ≦ a ≦ 70, 30 ≦ b ≦ 80, and 0 ≦ c ≦ 50 are particularly preferable.
Each structural unit may be included only in one type, or may be included in two or more types. When two or more types are included, the total amount is the mass fraction (%) of the structural unit represented by a, b, and c.

  The general formula PA is preferably represented by the following general formula P-A2.

（一般式Ｐ−Ａ２中、Ｒ⁹¹、Ｒ⁹²はそれぞれ独立に水素原子またはメチル基を表し、Ｌ⁹¹、Ｌ⁹²はそれぞれ独立に−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−のいずれかを表し、Ｒｆは炭素原子数３〜２０のフッ化アルキル基を表し、Ｒ⁹³は炭素原子数２〜２０の無置換のアルキル基を表し、Ａ⁹はそれぞれの構成単位を表し、ｄ、ｅ、ｆはそれぞれの構成単位の質量分率を表す。）

(In the general formula P-A2, R ⁹¹ and R ⁹² each independently represent a hydrogen atom or a methyl group, and L ⁹¹ and L ⁹² each independently represent any of —COO—, —CONH—, and —OCO—. , Rf represents a fluorinated alkyl group having 3 to 20 carbon atoms, R ⁹³ represents an unsubstituted alkyl group having 2 to 20 carbon atoms, A ⁹ represents each constituent unit, d, e, f Represents the mass fraction of each constituent unit.)

R ⁹¹ and R ⁹² are respectively synonymous with R ⁷¹ and R ⁷² in the general formula PA, and preferred ranges are also synonymous. Rf is more preferably a perfluoroalkyl group. Further, it may be substituted with a substitutable group (for example, an alkoxy group, an acyloxy group, a halogen atom, etc.). Preferably, it is a fluorine-containing alkyl group having 3 to 20 carbon atoms, more preferably 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.), for example, a branched structure (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 alicyclic structures (preferably 5-membered or 6-membered rings such as perfluoro A cyclohexyl group, a perfluorocyclopentyl group, an alkyl group substituted with these, or the like.
R ⁹³ represents an unsubstituted alkyl group having 2 to 20 carbon atoms, and preferably an unsubstituted alkyl group having 2 to 15 carbon atoms. The alkyl group for R ⁹³ may have either a saturated bond or an unsaturated bond, and may have any of a linear structure, a branched structure, and a ring structure.
A ⁹ represents an arbitrary structural unit, and has the same meaning as A ⁷ in the general formula PA, and the preferred range is also the same.
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. Each structural unit may be included only in one type, or may be included in two or more types. When two or more types are included, the total amount is the mass fraction (%) of the structural unit represented by d, e, and f.

  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 ≦ 100000. More preferably it is.

  As described above, the preferred range of the structure of the polymer represented by the general formula PA contained in the composition of the present invention is shown. However, depending on the nature of the liquid crystal compound used and the orientation angle required, Preferred ranges will be determined, and these can be experimentally adjusted and determined based on the following concept.

The ability to control the polymer orientation angle represented by the general formula PA can be adjusted by the number of carbon atoms of the alkyl group represented by R ⁷³ . That is, when the orientation angle is further reduced (for example, when a state close to horizontal orientation is required), the number of carbon atoms in the alkyl chain is increased, and the composition of the structural unit containing this is increased (ie, the value of b). Is effective. On the other hand, when it is desired to slightly reduce the orientation angle, the number of carbon atoms in the alkyl chain is reduced, the composition of this structural unit is reduced, and the component represented by A ⁷ is increased (ie, the value of b). Lowering the value and raising the value of c) is effective. In addition, by having a fluorinated alkyl group having a low surface energy, the property of segregating on the surface becomes strong, and the ability to reduce the orientation angle becomes remarkable. Therefore, when it is required to lower the orientation angle, it is also effective to lengthen the fluorinated alkyl chain and raise the composition of the structural unit containing it.

  The preferable addition amount range of the polymer represented by the general formula PA contained in the composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0.05 to the liquid crystalline compound. It is -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, A single organic organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.
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 preferred examples of the compound represented by the general formula PA contained in the composition of the present invention are shown below, but the present invention is not limited to the following.

(1-2) Other Polymers The composition of the present invention may contain a polymer other than the polymer A described above (hereinafter sometimes referred to as “polymer B”). The polymer B is used for the purpose of adjusting the average tilt angle (relaxing the effect of the polymer A and consequently suppressing the decrease of the average tilt angle), or for the purpose of adjusting the surface tension and viscosity of the composition.
The structure of the polymer B is not particularly defined as long as it can be mixed or dissolved in the composition of the present invention and does not contain an unsubstituted alkyl group having 2 or more carbon atoms in the side chain.

  Preferable examples of such a polymer B include a polymer containing a structural unit derived from a fluoroaliphatic group-containing monomer and not containing an unsubstituted alkyl group having 2 or more carbon atoms in the side chain.

  Furthermore, the polymer B preferably contains a hydrophilic group. Examples of the hydrophilic group include a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a group having a salt structure thereof, a polyoxyalkylene chain (for example, a polyoxyethylene group, a polyoxypropylene group) And the like having a polyoxyalkylene chain). Among these, a group having a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid machine, or a polyoxyalkylene chain is more preferred, and a group having a hydroxyl group, a carboxylic acid machine, or a polyoxyalkylene chain is particularly preferred.

（一般式Ｆ中、Ｒ¹⁰¹およびＲ¹⁰²はそれぞれ独立に水素原子またはメチル基を表し、Ｌ¹⁰¹、Ｌ¹⁰²は、それぞれ独立に単結合または炭素原子数１〜２０の二価の連結基を表し、Ｒｆ"は炭素原子数３〜２０のフッ化アルキル基を表し、Ｒ¹⁰³は任意の親水性基を表し、Ａ¹⁰は任意の構成単位を表し、ｇ、ｈ、iはそれぞれの構成単位の質量分率を表す。） As a particularly preferred example of the polymer B, a structure represented by the following general formula F can be given.
(General Formula F)

(In General Formula F, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a methyl group, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a divalent linking group having 1 to 20 carbon atoms. , Rf ″ represents a fluorinated alkyl group having 3 to 20 carbon atoms, R ¹⁰³ represents an arbitrary hydrophilic group, A ¹⁰ represents an arbitrary structural unit, and g, h, and i represent the respective structural units. Represents mass fraction.)

R ¹⁰¹ and R ¹⁰² each independently represents a methyl group or a hydrogen atom. Rf ″ is synonymous with Rf in the general formula PA, and the preferred range is also synonymous. L ¹⁰¹ and L ¹⁰² are each synonymous with L in the general formula PA, and the preferred range is also synonymous. R ¹⁰³ represents a hydrophilic group, and is preferably a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid machine, or a group having a polyoxyalkylene chain. ) An ethyleneoxy chain, a poly (oligo) propyleneoxy chain, and a poly (oligo) butyleneoxy chain are preferable, and a copolymer using two or more of these may be used. The degree of polymerization of the polyalkyleneoxy chain is preferably from 1 to 10,000, and more preferably from 1 to 100.
A ¹⁰ represents an arbitrary structural unit, and has the same meaning and the same preferable range as A ⁷ in the general formula PA.

g, h and i represent mass fractions (%) of the respective structural units, and preferably 20 ≦ g ≦ 100, 0 ≦ h ≦ 80, 0 ≦ i ≦ 80, 20 ≦ g ≦ 90, 10 ≦ h ≦ 80 and 0 ≦ i ≦ 70 are more preferable, and 30 ≦ g ≦ 90, 10 ≦ h ≦ 70, and 0 ≦ i ≦ 50 are further preferable.
One type of structural unit may be included, or two or more types of structural units may be included. When two or more types are included, the total amount is the mass fraction (%) of the structural unit represented by g, h, i.

 These copolymers may be random copolymers in which each structural unit is introduced irregularly, or may be block copolymers introduced regularly. Each structural unit in a certain case may be synthesized in any order of introduction, and the same structural component may be used twice or more.

 The polymer B can be used for various applications, and in each case, an optimum composition can be selected from the above-mentioned range. Although typical examples are shown below and the ranges to be selected for the respective compositions are shown, the use of the polymer B is not limited to these examples.

Polymer B can be used for the purpose of adjusting the average tilt angle. That is, when both polymer A and polymer B are used, the average tilt angle can be adjusted to a higher value than when polymer B is not used. In this case, the value of g is usually important. For example, it is preferable that the value of g satisfies the following requirement with the value of a in the polymer represented by the general formula PA (corresponding to the value of d in the general formula PA-2). That means
Δg = g−a (or Δg = g−d)
In this case, 0 ≦ | Δg | ≦ 10 is preferable, and 0 ≦ | Δg | ≦ 5 is more preferable.

 On the other hand, when the polymer B is used for the purpose other than the adjustment of the average tilt angle, for example, when the polymer B is used for the purpose of reducing the surface tension of the composition and improving the wettability, the value of g is, for example, the general formula PA. It is preferable that it is larger than the value a of the polymer represented by the formula (corresponding to the value d in the case of the general formula P-A2). In this case, Δg described above is preferably 10 <Δg ≦ 95, and more preferably 15 ≦ Δg ≦ 90. This is because, firstly, it is useful to lower the surface tension of the entire composition by adding a polymer having a higher fluorine content, and secondly, the polymer A and the polymer B are separated. This is because the change in the tilt angle due to the addition of the polymer B can be suppressed by the fact that the polymer B having a higher fluorine content segregates in the air interface direction.

  The molecular weight range of the polymer B is a weight average molecular weight (Mw), preferably 1000 to 1,000,000, more preferably 2000 to 200,000, and further preferably 3000 to 100,000. Moreover, it is preferable that it is 1-4, and, as for the molecular weight distribution of the polymer used by this invention, it is more preferable that it is 1-3.

  The preferable addition amount range of the polymer B contained in the composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0.05 to 20% by mass with respect to the liquid crystal compound. Preferably, it is 0.1-5 mass%.

  The polymer B used in the present invention can be synthesized by various polymerization methods in the same manner as the polymer represented by the general formula PA. The preferred synthesis method is the same as that of the polymer represented by the general formula PA.

  Specific preferred examples of the compound represented by Formula F contained in the composition of the present invention are shown below, but the present invention is not limited to the following.

(2) Liquid crystalline compound The composition of this invention contains a liquid crystalline compound. The liquid crystalline compound may be a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound, but a discotic liquid crystalline compound is preferable.
Furthermore, it is preferable to include a liquid crystal compound represented by any one of the general formula (DI), the general formula (DII), and the general formula (DIII).

[Compound represented by the general formula (DI)]
The liquid crystalline 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 the present specification, the “divalent cyclic group” means a divalent cyclic group having at least one kind of cyclic structure unless otherwise specified.

In the general 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 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, and a halogen atom. 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 the number of carbon atoms. A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom, and a cyano group are more preferable.

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 a methyl group, ethyl group or hydrogen atom. Is more preferable, and a hydrogen atom is particularly preferable.

The divalent cyclic group represented by L ¹ , L ² and L ³ 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 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 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, carbon An alkyl group substituted with a halogen atom having 1 to 16 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, carbon An acyloxy group having 2 to 16 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 2 to 16 carbon atoms Acylamino groups are included.

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—a divalent cyclic group— or * —C≡C—a divalent cyclic group— is more preferable, and a single bond 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 the 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 represent 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 _-divalent cyclic group) _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 a methyl group, ethyl group or hydrogen atom. Is more preferable, and a hydrogen atom is particularly preferable.

L ²¹ represents a single bond, ** — O—CO—, ** — CO—O—, ** — CH═CH— or ** — C≡C— (where ** represents a general formula (DI—R Represents the left side of L ^{21 in} the formula (A). A single bond is particularly preferable.

  The divalent cyclic group in the general formula (DI-R) is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, More preferably. 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 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 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 1 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 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 1 to 1 carbon atoms 16 alkylthio groups, acyloxy groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, carbamoyl groups substituted with alkyl groups having 2 to 16 carbon atoms, and 2 to 2 carbon atoms 16 acylamino groups are included. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and a halogen-substituted alkyl group having 1 to 6 carbon atoms are preferable. -4 alkyl groups and halogen-substituted alkyl groups having 1 to 4 carbon atoms are preferable, and halogen atoms, alkyl groups having 1 to 3 carbon atoms, and trifluoromethyl groups 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. When n1 is 0, L ²² in the formula (DI-R) is directly bonded to H ^{1 to} H ³ in the general formula (D1). When n1 is 2 or more, each -L ²¹ -divalent cyclic group may be the same or different.

L ²² represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —N (R) —, —CH ₂ —, —CH═CH— or —C≡C— is represented. Preferred is —O—, —O—CO—, —CO—O—, —O—CO—O—, —CH ₂ —, —CH═CH— or —C≡C—, and more preferred. —O—, —O—CO—, —CO—O—, —O—CO—O— or —CH ₂ —.

L ²³ is selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. It is a divalent linking group. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be replaced with other substituents. Examples of other substituents 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, and 1 to 6 carbon atoms. Alkoxy groups having 2 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, acyloxy groups having 2 to 6 carbon atoms, alkoxycarbonyl groups having 2 to 6 carbon atoms, carbamoyl groups, carbon atoms A carbamoyl group substituted with an alkyl group having 2 to 6 carbon atoms and an acylamino group having 2 to 6 carbon atoms are included. 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 compound represented by the general formula (DI) is used as a coating solution.

L ²³ is preferably a linking group selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. 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.

  Further, as the discotic liquid crystalline compound used in the present invention, it is more preferable to use a liquid crystalline compound represented by the following general formula (DII) or a liquid crystalline 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 a 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), a divalent cyclic group represents a divalent cyclic group having a 6-membered cyclic structure. 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 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, carbon An alkynyl group having 2 to 16 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 1 to 1 carbon atoms 16 alkylthio groups, acyloxy groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, carbamoyl groups substituted with alkyl groups having 2 to 16 carbon atoms, and 2 to 2 carbon atoms 16 acylamino groups are included. The substituent of the divalent cyclic group is preferably a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and further, a halogen atom, 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 more preferable.

  n3 represents an integer of 1 to 3. n3 is preferably 1 or 2. When n3 is 2 or more, each divalent cyclic group 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-, and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. A preferred range for L ³¹ is the same as L ^{22 in} formula (DI-R).

L ³² is composed of —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. When the 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, Particularly preferred are an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a halogen atom and a cyano group.
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 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, more preferably 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 substituents that methine has include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, alkyl groups having 1 to 16 carbon atoms, and alkenyl groups having 2 to 16 carbon atoms. Group, 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, a carbon atom 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, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and 2 to 16 carbon atoms Of the acylamino group. 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, An alkyl group substituted with a halogen 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.
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 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, 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 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, and a halogen atom and an alkyl group having 1 to 4 carbon atoms. 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, or a trifluoromethyl group is 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 represent 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, carbon atom number An alkenyl group having 2 to 16 carbon atoms, 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, and an acyl having 2 to 16 carbon atoms Groups, alkylthio groups having 1 to 16 carbon atoms, acyloxy groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, alkyl-substituted carbamoyl groups having 2 to 16 carbon atoms, and carbon atoms The acylamino group of several 2-16 is contained. 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, An alkyl group substituted with a halogen 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.
X ⁶³ represents an oxygen atom, a sulfur atom, methylene or imino, and 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 —C≡C—. Preferably, -O -, - O-CO -, - CO-O -, - O-CO-O -, - CH 2 -, - CH = CH -, - it is C≡C-, more preferably, -O-, -O-CO-,-
CO—O—, —O—CO—O— or —CH ₂ —. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent.
Examples of such a 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 having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , 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, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls 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 preferred.

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—, —C≡C—, and combinations thereof. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a 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, and an alkoxy having 1 to 6 carbon atoms. Group, 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, and 2 carbon atoms Preferred examples include a carbamoyl group substituted with ~ 6 alkyl 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 preferred.

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. Furthermore, 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).

  Although the specific example of a compound represented by general formula (DI) below is shown, this invention is not limited to these.

  Examples of the liquid crystal phase exhibited by the liquid crystal compound of 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 liquid crystalline compound represented by the general formula (DI) 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 liquid crystalline compound represented by the general formula (DI) used in the present invention can be synthesized by applying a known method.

[Phase difference plate]
The retardation plate of the present invention is characterized by having an optically anisotropic layer made of the composition of the present invention. One aspect of the retardation plate of the present invention includes a transparent support, an alignment film formed on the transparent support, an alignment control by the alignment film, and a fixed composition in the alignment state. And an optically anisotropic layer.
Hereinafter, the optically anisotropic layer, the alignment film, and the transparent support will be sequentially described in detail.

(1) Optically anisotropic layer When the composition of the present invention is used for forming an optically anisotropic layer, the composition of the present invention contains a polymerizable initiator and other additives as desired in addition to the above. You may go out. The optically anisotropic layer is formed by applying such a composition as a coating solution, for example, on the surface of the alignment film of the present invention formed on a transparent support, and aligning and fixing the liquid crystalline compound. be able to. After aligning and fixing the liquid crystalline compound, the transparent support may be peeled off.

(1) -a Forming Method The optically anisotropic layer is formed on a transparent support by applying a coating liquid prepared by dissolving the liquid crystalline compound or the polymer in a solvent capable of dissolving the liquid crystalline compound or the polymer, and has an orientation property. It can produce by apply | coating on the provided alignment film. 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 optically anisotropic layer is formed by drying the solvent used at 25 ° C. to 130 ° C., and simultaneously orienting the molecules of the liquid crystalline compound and fixing the molecules by ultraviolet irradiation or the like. 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 thus formed varies depending on the optimum retardation value depending on the application such as optical compensation, but is preferably 0.1 to 10 μm, preferably 0.5 to 5 μm. More preferably.

  The molecules of the liquid crystalline compound are preferably substantially uniformly oriented in the optically anisotropic layer, more preferably fixed in a substantially uniformly oriented state. Most preferably, the liquid crystal compound is fixed by the reaction.

  The ratio of the liquid crystalline compound represented by the general formula (DI) or the polymer obtained from the liquid crystalline compound in the optically anisotropic layer is preferably 10% by mass to less than 100% by mass, It is more preferable that it is 99 mass%, and it is most preferable that it is 50-99 mass%.

(1) -b Other materials used for forming the optically anisotropic layer The composition of the present invention may contain other materials in addition to the liquid crystalline compound and the polymer. Examples of the additive include a polymerization initiator, an additive for controlling the alignment state of the liquid crystal compound (for example, an onium salt and an air interface vertical alignment agent), a polymerization initiator, a plasticizer, a surfactant, and a polymerizability. A monomer or the like may be contained. These materials are added for various purposes, for example, for the purpose of fixing the orientation, uniformity of the coating film, strength of the film, and improving 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. Photoinitiators are preferred. 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).
It is preferable that the usage-amount of a photoinitiator is 0.01-20 mass% of solid content of a coating liquid, and it is more preferable that it is 0.5-5 mass%.

  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 polymerizable group-containing liquid crystalline compound. Examples thereof include those described in paragraph numbers [0018] to [0020] in JP-A No. 2002-296423. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the liquid crystal compound.

  Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in paragraph numbers [0028] to [0056] of JP-A No. 2001-330725 are exemplified.

  A polymer may be added for the purpose of thickening the coating solution. Examples of such polymers include cellulose esters. Preferable examples of the cellulose ester include those described in JP-A 2000-155216, paragraph [0178]. The addition amount of the polymer is preferably in the range of 0.1 to 10% by mass, and in the range of 0.1 to 8% by mass with respect to the liquid crystal compound so as not to inhibit the alignment of the liquid crystal compound. It is more preferable.

  Furthermore, you may add the additive which improves the adhesiveness with an alignment film to the composition of this invention. As such an additive, an additive that strongly interacts and interacts with a hydroxyl group on the alignment film and also reacts with a polymerizable group of the liquid crystal compound is preferable.

  A compound represented by the following general formula (I) is particularly preferable as an additive (adhesion improving additive) that improves the adhesion to the alignment film.

Formula (I)

（一般式（Ｉ）中、Ｘ¹は二価の連結基を表し、Ｚは重合性基を有する置換基を表し、Ｑは配向膜に吸着して結合が可能な基を表す。）

(In general formula (I), X ¹ represents a divalent linking group, Z represents a substituent having a polymerizable group, and Q represents a group capable of adsorbing and bonding to the alignment film.)

X ¹ represents a single bond, or —O—, —CO—, —NH—, —CO—NH—, —COO—, —O—COO—, a substituted or unsubstituted alkylene group, substituted or unsubstituted. It is preferably selected from an arylene group, a substituted or unsubstituted heteroaryl group, and combinations thereof, and more preferably a substituted or unsubstituted arylene group.

  Z is preferably a group represented by the following general formula (III) or a group having an oxiranyl moiety or an oxetane moiety.

Formula (III)

一般式（ＩＩＩ）中、Ｒ³⁰³は水素原子またはメチル基であり、水素原子が好ましい。
Ｌ³⁰¹は、単結合または−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯ−ＮＨ−、−ＣＯＯ−、−Ｏ−ＣＯＯ−、置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基および置換もしくは無置換のヘテロ環基、ならびに、それらの組み合わせから選ばれる二価の連結基であり、単結合、−ＣＯ−ＮＨ−または−ＣＯＯ−が好ましく、単結合または−ＣＯ−ＮＨ−がより好ましい。

In general formula (III), ^R303 is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
L ³⁰¹ represents a single bond or —O—, —CO—, —NH—, —CO—NH—, —COO—, —O—COO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group. And a divalent linking group selected from a substituted or unsubstituted heterocyclic group and combinations thereof, preferably a single bond, —CO—NH— or —COO—, wherein a single bond or —CO—NH— is More preferred.

  Specifically, Z is preferably an acrylate group, a methacrylate group, a styryl group, a vinyl ketone group, a butadiene group, a vinyl ether group, an oxiranyl group, an aziridinyl group or an oxetane group, and a (meth) acrylate group, a styryl group, an oxiranyl group or an oxetane. A group is more preferable, and a (meth) acrylate group or a styryl group is more preferable.

Q is preferably a group capable of bonding to the hydroxyl group of the alignment film. Q is preferably —SiX ³⁰³ (X ³⁰³ is a halogen atom or an alkoxy group), an aldehyde group, an ester, a carboxyl group, an isocyanate, a boronic acid, or a boronic acid ester.

The general formula (I) is more preferably a compound represented by the general formula (II).
Formula (II)

（一般式（ＩＩ）中、Ｒ³⁰¹およびＲ³⁰²は、それぞれ独立に、水素原子、置換若しくは無置換の脂肪族炭化水素基、置換若しくは無置換のアリール基、または、置換若しくは無置換のヘテロアリール基を表し、置換若しくは無置換のアルキレン連結基または置換若しくは無置換のアリール連結基、あるいは、これらの組み合わせからなる連結基を介して連結してもよい。Ｘ¹は二価の連結基を表し、Ｚは重合性基を有する置換基を表す。）
一般式（ＩＩ）中、Ｒ³⁰¹とＲ³⁰²は結合して環を形成してもよい。

(In General Formula (II), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl. X ¹ represents a divalent linking group, and may be linked via a linking group consisting of a substituted or unsubstituted alkylene linking group, a substituted or unsubstituted aryl linking group, or a combination thereof. Z represents a substituent having a polymerizable group.)
In general formula (II), R ³⁰¹ and R ³⁰² may combine to form a ring.

Preferred examples of the aliphatic hydrocarbon group for R ³⁰² and R ³⁰² include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group.
Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, Eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, A linear, branched, or cyclic alkyl group such as a 2-norbornyl group is preferred.
Examples of the alkenyl group include linear, branched, or cyclic groups such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, and 1-cyclohexenyl group. Are preferred.

As the alkynyl group, an ethynyl group, 1-propynyl group, 1-butynyl group, 1-octynyl group and the like are preferable.
Examples of the aryl group include those in which 1 to 4 benzene rings form a condensed ring, and those in which a benzene ring and an unsaturated five-membered ring form a condensed ring. Specific examples include a phenyl group and naphthyl. Group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, pyrenyl group and the like.

  The heteroaryl group is preferably a heteroaryl group containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and 1 heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. More preferred is a heteroaryl group obtained by removing one hydrogen atom on a heteroaromatic ring containing at least one heteroaromatic ring. Specific examples of the heteroaromatic ring containing one or more heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring , Isoxazole ring, oxadiazole ring, thiazole ring, thiadiazole ring, indole ring, carbazole ring, benzofuran ring, dibenzofuran ring, thianaphthene ring, dibenzothiophene ring, indazolebenzimidazole ring, anthranyl ring, benzisoxazole ring, benzoxazole Ring, benzothiazole ring, purine ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyl Down ring, phenanthroline ring, a pteridine ring and the like.

One or more of the above groups may be substituted with any substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen, halogen atoms (F, Br, Cl, I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, Alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy Group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl Sulfoxy group, arylsulfoxy group, acylthio group, Ruamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′- Diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfo Nyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfur group Famoiru group _{(-SO 2 NHSO 2 (alkyl)} ) and its conjugated base group N- aryl acylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugated base group, N- alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugated base group, N- aryl sulfonyl carbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ), hydroxysilyl group (—Si (OH) ₃ ) And its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ ), alkyl Ariruhosuhono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono (-PO ₃ H (alkyl)) and its conjugated base group, monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugate base group, a phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group, Dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkyl Phosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group, monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group, cyano group, nitro group, aryl group, alkenyl Group and alkynyl group.
In addition, these substituents may combine with each other or with a substituted hydrocarbon group to form a ring, if possible.

Furthermore, R ³⁰¹ and R ³⁰² may be linked to B (boron) via a linking group consisting of a substituted or unsubstituted alkylene linking group, a substituted or unsubstituted aryl linking group, or a combination thereof. Here, the aryl linking group refers to a linking group containing an aryl group, and includes an arylene group.

R ³⁰¹ and R ³⁰² in the general formula (II) are preferably hydrogen atoms.
Moreover, X < ¹ > and Z in general formula (II) are synonymous with X < ¹ > and Z in general formula (I) respectively, and its preferable range is also synonymous.
Specific examples of preferred polymerizable compounds represented by formula (I) are shown below, but the present invention is not limited thereto.

  The solid content concentration of the liquid crystal compound and other additives in the coating solution is preferably 0.1% by mass to 60% by mass, more preferably 0.5% by mass to 50% by mass, and 2% by mass to 40% by mass. % Is more preferable. The viscosity of the 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 in 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 alignment represents a state in which the tilt angle of the liquid crystal compound continuously changes in the film thickness direction.

After the liquid crystalline compound is applied on the transparent support (more preferably on the alignment film), a liquid crystal phase is expressed by, for example, heating. Therefore, the liquid crystalline compound is formed on the transparent support surface or coating film at the interface on the transparent support side. The tilt angle of the interface (or the alignment film interface when an alignment film is provided) (in other words, the direction of the transparent support surface and the disk surface direction of the liquid crystal compound (the liquid crystal compound of the present invention has a disk shape)) At the interface between the air and the tilt angle of the air interface.
By using a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain of the present invention, the average tilt angle of the optically anisotropic layer (the direction of the transparent support surface and the direction of the disc surface of the liquid crystalline compound) Corner) can be adjusted. It is particularly effective to use for the purpose of reducing the average tilt angle. That is, the average tilt angle of the liquid crystalline compound in the optically anisotropic layer made of the composition of the present invention is the average tilt angle of the liquid crystalline compound in the optically anisotropic layer made of the composition obtained by removing the polymer from the composition. It is possible to adjust to an arbitrary average tilt angle that is further reduced. This is because the polymer of the present invention segregates at the air interface and reduces the tilt angle at the air interface. The degree of reduction can be adjusted by the method as described above, and can be reduced by an average tilt angle of 2 to 45 ° as compared with the case where the polymer of the present invention is not used. As a result, the average tilt angle of the optically anisotropic layer (depending on the properties of the liquid crystal compound used and the transparent support) can be controlled to an arbitrary value from about 0 ° (horizontal alignment) to about 80 °. It becomes.

(2) Alignment film An alignment film may be used for producing the retardation plate of the present invention. The alignment film is formed by rubbing a compound (preferably a polymer), oblique deposition of an inorganic compound, forming a layer having a microgroove, or an organic compound (for example, ω-tricosanoic acid, 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 liquid crystal compound. In the present invention, in addition to the function of aligning the liquid crystalline compound, the cross-linking having a function of binding a side chain having a crosslinkable functional group (for example, a double bond) to the main chain or aligning the liquid crystalline compound. It is preferable to introduce a functional functional group 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, a polyvinyl alcohol and a modified polyvinyl alcohol, poly (N-methylolacrylamide) described in paragraph No. [0022] of JP-A-8-338913, Polyester, polyimide, vinyl acetate polymer, carboxymethyl cellulose, polycarbonate and the like are included. 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 aligning the liquid crystal compound generally has a hydrophobic group as a functional group. The specific type of functional group is determined according to the type of liquid crystal compound 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 And hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azilinidyl 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 the side chain having a crosslinkable functional group is bonded to the main chain of the alignment film polymer or the crosslinkable functional group is introduced into the side chain having a function of aligning the liquid crystalline compound, the alignment film polymer and the optically anisotropic film The polyfunctional monomer contained in the conductive 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 paragraph numbers [0080] to [0100] in 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 paragraph numbers [0023] to [0024] in 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 occurrence of reticulation can be obtained.

  The alignment film can be basically formed by coating the transparent film containing the alignment film forming material on the transparent support containing the above-mentioned polymer and a crosslinking agent, followed by drying by heating and crosslinking, and if necessary, a rubbing treatment. it can. As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the transparent 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 optically anisotropic layer reduces significantly.

 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. The film thickness after drying is preferably 0.1 to 10 μm. Heat drying is preferably performed at 20 to 110 degrees. In order to form sufficient cross-linking, 60 ° to 100 ° is more preferable, and 80 ° to 100 ° is more preferable. The drying time can be usually 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 used. In particular, when glutaraldehyde is used, the pH is preferably 4.5 to 5.5, and more preferably 5.

  The alignment film is provided on the transparent support or the undercoat layer. 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 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 liquid crystalline compound on the alignment film, if necessary, the alignment film polymer is reacted with the polyfunctional monomer contained in the optically anisotropic layer, or the alignment film polymer is formed using a crosslinking agent. It may be cross-linked. The thickness of the alignment film is preferably in the range of 0.1 to 10 μm. The coating liquid prepared by dissolving the alignment film polymer in a solvent can be applied to the surface of the transparent support, and the solvent contained in the coating liquid can be dried and removed at 25 ° C to 140 ° C. Moreover, although it can also form by vapor deposition if possible, formation by application | coating is more preferable. The thickness of the alignment film thus formed 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.

The alignment film formed by the above method is preferably one whose surface is rubbed and liquid crystal alignment is imparted. The rubbing treatment can be performed by rubbing the surface of the polymer coating layer several times in a certain direction (usually the longitudinal direction) with paper or cloth. As a method other than rubbing, liquid crystal alignment can be imparted by applying an electric field, applying a magnetic field, or irradiating light. As a method for imparting liquid crystal alignment, an alignment film formed by a rubbing treatment of a polymer is particularly preferable.
(3) Transparent support The retardation plate may have a support. The transparent 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. Moreover, even if it is a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence, the expression of the molecule can be achieved by modifying the molecule as described in, for example, International Publication WO 00/26705 pamphlet. It is also possible to use a material with a reduced value.

Hereinafter, the cellulose ester preferably used as the transparent 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 the cellulose are not evenly distributed by 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 is preferably 30% to 40% and substituted with an acyl group with respect to the total degree of substitution, more preferably 31% or more, and 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 in addition to the acetyl group (for example, propionyl group, butyryl group, valeroyl group, benzoyl group, acryloyl 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 described in Synthesis Example 1 described in Paragraph Nos. 0043 to 0044 of JP-A No. 11-5851, Synthetic Example 2 described in Paragraph Nos. 0048 to 0049 and Paragraph Nos. 0051 to 0052. It can be synthesized with reference to the method of Synthesis Example 3 described.

In order to adjust the retardation value of a polymer film used as a transparent 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). Such retardation increasing agents are disclosed in International Publication WO01 / 88574 pamphlet, International Publication WO00 / 2619 pamphlet, Japanese Unexamined Patent Publication No. 2000-1111914, Japanese Unexamined Patent Publication No. 2000-275434, Japanese Unexamined Patent Publication No. 2002-363343, and the like. Are listed.

  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. 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.

Dope is made from raw 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 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 direction of travel of the transparent 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 particularly 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-35-1907073, JP-A-35-194789, JP-A-35-271471, and JP-A-36-107854.
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 preventing deterioration can be further enhanced. 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, the temperature of the cellulose acetate film in these treatments is preferably Tg (glass transition temperature) or less, specifically 150 ° C. or less.

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, 18 ° 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 manufactured 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 protective film described above with respect to elliptically polarized light can be used. TN mode liquid crystal cell retardation plates (optical compensation sheets) are described in JP-A-6-214116, US Pat. No. 5,583,679, US Pat. No. 5,646,703, and German Patent Publication 3911620A1. 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 Diid Liquid CrystaD), OCB (OpticDyDenHyDenTwN) 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 in TN (Twisted Nematic) and OCB (OpticaDDy Compensatory Bend) modes.

  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 D3-12]
Synthesis was performed according to the following scheme 1.

(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 ° 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 ° 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 ° 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 °, and an isotropic liquid exceeded 142 °. It turned into a phase. That is, it was found that D3-12 exhibits a discotic nematic liquid crystal phase between 86 ° and 142 °.

 D3-11 and D3-15 used in the following examples were also synthesized by the same method by changing 5-chloro-1-pentanol as a raw material to the corresponding compound.

Synthesis Example 2 [Synthesis of P-57]
Synthesized according to the following scheme

To a 200 ml three-necked flask equipped with a stirrer and a condenser tube, 7.68 g of methyl ethyl ketone was added and heated to 78 ° C. under a nitrogen atmosphere. Here, 16.32 g of methyl ethyl ketone was added to 1.32 g of dimethyl 2,2′-azobisisobutyrate, A solution in which 12.8 g of 2-perfluorohexylethyl acrylate, 16.0 g of n-butyl acrylate, and 3.2 g of Blemmer AE90 (manufactured by NOF Corporation) was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.1 g of dimethyl 2,2′-azobisisobutyrate in 1.0 g of methyl ethyl ketone was added and further heated for 4 hours. The obtained reaction solution was reprecipitated twice in a large excess amount of methanol, and the precipitated polymer was dried to obtain 31 g of P-57.
The composition of the obtained polymer was confirmed by ¹ HNMR, and the number average molecular weight (Mn) determined by GPC was 12000.

Synthesis Example 3 [Synthesis of P-1]
Except for changing 12.8 g of 2-perfluorohexylethyl acrylate, 16.0 g of n-butyl acrylate, and 3.2 g of Bremmer AE90 (manufactured by NOF Corporation) to 32.0 g of n-butyl acrylate in Synthesis Example 2 above. Were synthesized under the same conditions to obtain 30 g of P-1.
The number average molecular weight determined from GPC of the obtained polymer was 12,800.

Synthesis Example 4 [Synthesis of P-3]
Synthesis was carried out under the same conditions except that 16.0 g of n-butyl acrylate and 3.2 g of Bremer AE90 (manufactured by NOF Corporation) were changed to 19.2 g of n-butyl acrylate in Synthesis Example 2 above. 28 g of 3 was obtained.
The composition of the obtained polymer was confirmed by ¹ HNMR, and the number average molecular weight (Mn) determined by GPC was 11,000.

Synthesis Example 5 [Synthesis of P-49]
In Synthesis Example 2, all except that 1-6.0 g of n-butyl acrylate and 3.2 g of Bremer AE90 (manufactured by NOF Corporation) were changed to 17.6 g of n-butyl acrylate and 1.6 g of 2-hydroxyethyl acrylate. Synthesis was performed under the same conditions to obtain 29 g of P-49.
The composition of the obtained polymer was confirmed by ¹ HNMR, and the number average molecular weight (Mn) determined by GPC was 11,300.

Synthesis Example 6 [Synthesis of P-60]
The synthesis was performed under the same conditions except that 3.2 g of Blemmer AE90 (manufactured by NOF Corporation) was replaced with 3.2 g of BLEMMER AP400 (manufactured by NOF Corporation), and P-60 was used. 30 g was obtained.
The composition of the obtained polymer was confirmed by ¹ HNMR, and the number average molecular weight (Mn) determined by GPC was 10900.

Synthesis Example 7 [Synthesis of F-6]
Synthesized according to the following scheme.

To a 200 ml three-necked flask equipped with a stirrer and a condenser tube, 7.68 g of methyl ethyl ketone was added and heated to 78 ° C. under a nitrogen atmosphere. A solution in which 12.8 g of 2-perfluorohexylethyl acrylate and 19.3 g of Bremer AP400 (manufactured by NOF Corporation) was dissolved was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.1 g of dimethyl 2,2′-azobisisobutyrate in 1.0 g of methyl ethyl ketone was added and further heated for 4 hours. The obtained reaction solution was reprecipitated twice in a large excess amount of n-hexane, and the precipitated polymer was dried to obtain 30 g of F-6.
The composition of the obtained polymer was confirmed by ¹ HNMR, and the number average molecular weight determined by GPC was 11,000.

Synthesis Example 8 [Synthesis of F-10]
In the synthesis example 7, 12.8 g of 2-perfluorohexylethyl acrylate and 19.3 g of Bremer AP400 (manufactured by NOF Corporation) were changed to 16.0 g of 2-perfluorohexylethyl acrylate and 16.0 g of acrylic acid. The synthesis was performed under the same conditions except that 28 g of F-10 was obtained.
The composition of the obtained polymer was confirmed by ¹ HNMR, and the number average molecular weight (Mn) determined by GPC was 10,000.

[Example 1: Preparation of composition (LM-1) of the present invention]
The liquid crystal compound (D3-12) represented by the general formula (D1) and the polymer (P-57) represented by the general formula PA (manufactured by Tokyo Chemical Industry Co., Ltd.) at the composition ratio shown below. ), Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, and diethylthioxanthone as a photosensitizer were weighed and dissolved in methyl ethyl ketone to prepare a composition (LM-1).

Composition of composition (LM-1)-Liquid crystalline compound represented by general formula (D1): D3-12 100 parts by mass-Polymer represented by general formula PA: P-57 0.6 parts by mass- Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.) 3.0 parts by mass, 1.0 part by weight of diethylthioxanthone, 250 parts by weight of methyl ethyl ketone

[Example 2: Preparation of the composition of the present invention (LM-2 to LM-16)]
In Example 1, the types of the polymer and / or liquid crystal compound represented by the general formula PA were as shown in Table 1, and the others were carried out in the same manner to obtain the compositions (LM-2) to (LM-10). ) Was produced. Further, in Example 1, the type of the polymer and / or liquid crystal compound represented by the general formula PA is as shown in Table 1, and the compound represented by the general formula F is added as shown in Table 1. Thus, (LM-11) to (LM-16) were produced.

[Comparative Example 1: Preparation of comparative compositions (LH-1 to LH-5)]
In the compositions (LM-1), (LM-6), and (LM-7) in Examples 1 and 2, all were the same except that the polymer represented by the general formula PA was not added. Comparative compositions (LH-1), (LH-2), and (LH-3) were prepared.
Further, in the composition (LM-7) in Example 2, the polymer (P-57) represented by the general formula PA was changed to (F-6), and the others were similarly changed to (LH-4). (LH-5) was adjusted in the same manner except that the polymer represented by the general formula PA in (LM-1) in Example 1 was changed to (F-10).

[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 in a state where the solvent content is 70% by mass, both ends in the width direction of the film are fixed with a pin tenter, and an interval in which the stretch rate in the width direction is 3% is maintained in a region where the solvent content is 3 to 5% by mass. While drying. Thereafter, the film is further dried by being conveyed between rolls of a heat treatment apparatus. In a region exceeding 120 ° C., the stretching ratio in the machine direction is substantially 0%, and the ratio between the stretching ratio in the width direction and the stretching ratio in the machine direction is 0.00. A cellulose acetate film having a thickness of 100 μm was prepared by adjusting to 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 first undercoat 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.

―――――――――――――――――――――――――――――――――――
Composition of the second undercoat coating solution ―――――――――――――――――――――――――――――――――――
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 ――――――――――――――― ―――――――――――――――――――

(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 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.

※添え字はｍｏｌ分率を表す

* Subscript indicates mol fraction

This solution was applied onto the second undercoat layer, dried with hot air at 100 ° C. for 120 seconds, and then rubbed 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)
On the rubbing process surface of the alignment film produced above, the coating liquid of the composition (LM-1) prepared in Example 1 was applied using a wire bar. The film coated with the optically anisotropic layer was oriented in a constant temperature bath at 120 ° C. and irradiated with 200 mJ / cm ² of ultraviolet light to fix the orientation state of the optically anisotropic layer. 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 1.0 μm.

[Example 4: Production of retardation plate (RM-2 to RM-16) of the present invention]
In Example 3, except that the composition (LM-1) was changed to the compositions (LM-2) to (LM-16), the retardation plates (RM-2) to (RM-) were changed in the same manner. 16) was produced.

[Comparative Example 2: Production of comparative retardation plates (RH-1 to RH-5)]
In Example 3, the phase difference plate (RH-2) was the same except that the composition (LH-1) was changed to the comparative compositions (LH-2) to (LH-5). To (RH-5) were prepared.

[Example 5: Evaluation of retardation plate]
(Measurement of Re and Rth)
Re (589 nm) and Rth (589 nm) represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. Re (589 nm) of the retardation plate obtained in Examples 3 and 4 and Comparative Example 2 was measured by using KOBRA 21ADH (manufactured by Oji Scientific Instruments) and making light of wavelength 589 nm incident in the film normal direction. did. Rth (589 nm) was calculated using KOBRA 21ADH (manufactured by Oji Scientific Instruments) by the method described in [0011] above.

(Measurement of average tilt angle)
The tilt angle θ1 on one surface of the optically anisotropic layer and the tilt angle θ2 on the other surface are used as variables so that the calculation of the angular dependence of the retardation value of the optically anisotropic layer matches the measured value. Fitting was performed, 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, RM-2, RM-4 to RM-6 of the present invention and the optically anisotropic layers of RH-1 to RH-3 of Comparative Example 2 were hybrid aligned. It was also confirmed that RM3 was almost horizontally oriented.

From the results of Table 3, the retardation plates (RM-1) to (RM-16) prepared from the composition of the present invention do not contain a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain. It was confirmed that a retardation plate having a low average tilt angle can be produced as compared with the retardation plates (RH-1) to (RH-5) produced in 1. It was also confirmed that the average tilt angle can be arbitrarily controlled by adjusting the content of the side chain alkyl group and fluorinated alkyl group.
Moreover, (RM-11)-(RM-13) is derived from the fluoroaliphatic group-containing monomer contained in each polymer among the retardation plates prepared from the composition containing both polymer A and polymer B. Depending on the content of the constituent unit, it is possible to obtain a different average tilt angle from the corresponding retardation plates (RM-3) to (RM-5) prepared from the composition not containing the polymer B.
On the other hand, when the content of the structural unit derived from the fluoroaliphatic group-containing monomer contained in the polymer B is higher than that of the polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain (Table 2 (RH-14) to (RH-16)), the value of the average tilt angle is almost smaller than that of the corresponding polymer B not included (respectively (RH-8) to (RH-10)). It was confirmed that it did not change.
From these results, it was confirmed that the polymer can be further adjusted to the average tilt angle according to the purpose by adding polymer B separately. It was also confirmed that a surfactant can be used in combination without changing the average tilt angle. These are determined by the difference between the content of the structural unit derived from the fluoroaliphatic group-containing monomer contained in the polymer B and the content of the structural unit derived from the fluoroaliphatic group-containing monomer contained in the polymer A. It was confirmed that

From these results, in the retardation plate prepared from the composition of the present invention containing a polymer containing an alkyl group in the side chain, the discotic liquid crystal is hybrid-aligned at various average tilt angles depending on the purpose. It was confirmed that a phase difference plate can be obtained.

Claims (22)

A composition comprising at least one liquid crystal compound and a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in a side chain and adjusting an average tilt angle of the liquid crystal compound. The polymer having an unsubstituted alkyl group having 2 or more carbon atoms in the side chain, wherein the polymer for adjusting the average tilt angle of the liquid crystal compound further has a fluorinated alkyl group in the side chain. 2. The composition according to 1. A composition comprising at least one liquid crystal compound and a polymer represented by the following general formula PA.

(In the general formula PA, R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a methyl group, L ⁷¹ and L ⁷² each independently represent a linking group, and Rf represents a fluorinated carbon atom having 1 to 20 carbon atoms. Represents an alkyl group, R ⁷³ represents an unsubstituted alkyl group having 2 to 30 carbon atoms, A ⁷ represents an arbitrary structural unit, and a, b, and c represent mass fractions of the respective structural units. ) The composition according to claim 3, wherein the polymer represented by the general formula PA is represented by the following general formula P-A2.

(In the general formula P-A2, R ⁹¹ and R ⁹² each independently represent a hydrogen atom or a methyl group, and L ⁹¹ and L ⁹² each independently represent any of —COO—, —CONH—, and —OCO—. , Rf represents a fluorinated alkyl group having 3 to 20 carbon atoms, R ⁹³ represents an unsubstituted alkyl group having 2 to 20 carbon atoms, A ⁹ represents a structural unit, and d, e, and f are respectively Represents the mass fraction of the structural unit.) Furthermore, it contains a polymer that contains a structural unit derived from a fluoroaliphatic group-containing monomer and does not contain an unsubstituted alkyl group having 2 or more carbon atoms in the side chain. The composition according to item. The polymer containing a structural unit derived from the fluoroaliphatic group-containing monomer and not containing an unsubstituted alkyl group having 2 or more carbon atoms in the side chain contains a hydrophilic group. The composition of any one of these. The polymer containing a structural unit derived from the fluoroaliphatic group-containing monomer and not containing an unsubstituted alkyl group having 2 or more carbon atoms in the side chain is represented by the following general formula F: The composition of any one of -5.
(General Formula F)

(In General Formula F, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a methyl group, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a divalent linking group having 1 to 20 carbon atoms. , Rf ″ represents a fluorinated alkyl group having 3 to 20 carbon atoms, R ¹⁰³ represents an arbitrary hydrophilic group, A ¹⁰ represents an arbitrary structural unit, and g, h, and i represent the respective structural units. Represents mass fraction.) The composition according to any one of claims 1 to 7, wherein an average tilt angle of the liquid crystalline compound in the optically anisotropic layer made of the composition is the number of carbon atoms in the side chain from the composition. More than the average tilt angle of the liquid crystalline compound in the optically anisotropic layer comprising a composition excluding the polymer that adjusts the average tilt angle of the liquid crystalline compound, the polymer having two or more unsubstituted alkyl groups, The composition according to claim 1, which is reduced by 2 to 45 °. The composition according to claim 1, wherein the liquid crystal compound is a discotic liquid crystal compound. The composition according to any one of claims 1 to 9, wherein at least one of the liquid crystal compounds is a liquid crystal compound 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 represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² , and R ³ each independently represent the following general formula Represents 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 _-divalent cyclic group) _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. 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≡C—, and L ²³ represents —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 when the above group is a group containing a hydrogen atom, the hydrogen atom is a substituent Q ¹ represents a polymerizable group or a hydrogen atom. At least one of the liquid crystal compounds is selected from a liquid crystal compound represented by the following general formula (DII) and a liquid crystal compound represented by the following general formula (DIII). The composition of any one of these.

(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 following 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. The divalent cyclic group is A group having a 6-membered ring structure, n3 represents an integer of 1 to 3. L ³¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—. , —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—, —C≡C—, L ³² represents —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 following general formula (DIII-A), Or the following general formula (DIII-B) or the following general formula (DIII-C).
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—, and 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 -, —CH═CH— or —C≡C—, and L ⁵² 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 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. , - - -O or an imino, L ⁶¹ is O-CO -, - CO- O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, —CH═CH— or —C≡C—, and 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 retardation plate having an alignment film and an optically anisotropic layer made of the composition according to any one of claims 1 to 11 on a transparent support. The phase difference plate according to claim 12, wherein the alignment film contains polyvinyl alcohols. The retardation plate according to claim 12 or 13, wherein the optically anisotropic layer has a discotic liquid crystalline compound in a hybrid orientation. The elliptically polarizing plate which has a phase difference plate of any one of Claims 12-14, and a polarizing film. The liquid crystal display device which has a phase difference plate of any one of Claims 12-14. An average tilt angle adjusting agent for a liquid crystal compound, comprising a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in a side chain. The average tilt angle adjusting agent for a liquid crystal compound according to claim 17, wherein the polymer is represented by the following general formula PA.

(In the general formula PA, R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a methyl group, L ⁷¹ and L ⁷² each independently represent a linking group, and Rf represents a fluorinated carbon atom having 1 to 20 carbon atoms. Represents an alkyl group, R ⁷³ represents an unsubstituted alkyl group having 2 to 30 carbon atoms, A ⁷ represents an arbitrary structural unit, and a, b, and c represent mass fractions of the respective structural units. ) A method for adjusting an average tilt angle of a liquid crystal compound, comprising using a polymer having an unsubstituted alkyl group having 2 or more carbon atoms in a side chain. The method for adjusting the average tilt angle of the liquid crystalline compound according to claim 19, wherein the polymer is represented by the following general formula PA.

(In the general formula PA, R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a methyl group, L ⁷¹ and L ⁷² each independently represent a linking group, and Rf represents a fluorinated carbon atom having 1 to 20 carbon atoms. Represents an alkyl group, R ⁷³ represents an unsubstituted alkyl group having 2 to 30 carbon atoms, A ⁷ represents an arbitrary structural unit, and a, b, and c represent mass fractions of the respective structural units. ) The average tilt angle adjusting agent for a liquid crystal compound according to claim 17 or 18, wherein the liquid crystal compound is a liquid crystal compound represented by the following general formula (DI).
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 represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² , and R ³ each independently represent the following general formula Represents 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 _-divalent cyclic group) _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. 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≡C—, and L ²³ represents —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 when the above group is a group containing a hydrogen atom, the hydrogen atom is a substituent Q ¹ represents a polymerizable group or a hydrogen atom. The method for adjusting the average tilt angle of a liquid crystal compound according to claim 19 or 20, which is for a liquid crystal compound represented by the following general formula (DI).
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 represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² , and R ³ each independently represent the following general formula Represents 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 _-divalent cyclic group) _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. 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≡C—, and L ²³ represents —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 when the above group is a group containing a hydrogen atom, the hydrogen atom is a substituent Q ¹ represents a polymerizable group or a hydrogen atom.