JP2007231193A - Polymer, and composition containing the same, as well as phase difference plate and liquid crystal display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer useful for producing stably an optical anisotropy layer, etc. that contribute to the optical compensation of a liquid crystal display. <P>SOLUTION: The polymer comprises a structural unit having at least one sort of substituent group containing a fluorine atom, and a structural unit represented by general formula (A), (wherein Mp represents a trivalent group, L a single bond or a bivalent linking group, and X a disk-like substituent). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymer useful for forming an optically anisotropic layer, a composition containing the polymer, a retardation plate produced using the composition, and a liquid crystal display device having the retardation plate. .

  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 determined by discotic liquid crystal compound (discotic liquid crystal compound) (for example, 2,3,6,7,10,11-hexa {4- (4-acryloyloxy). Hexyloxy) benzoyloxy} triphenylene, etc.), when offset by an optical compensation sheet having an optically anisotropic layer (for example, Patent Document 1), the wavelength dispersion of the rod-like liquid crystal and the discotic liquid crystalline compound is different. Therefore, the phase difference cannot be canceled simultaneously for all the wavelengths of light, and discoloration (such as no black color) may occur.

  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, and thus the alignment angle needs to be controlled.

  However, in the case of a trisubstituted benzene type discotic liquid crystal 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 that can reduce the alignment angle of the 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 discotic liquid crystal compound is not clearly shown, and the conventional technique does not align the alignment. It was insufficient to control the angle to a desired angle (Patent Document 2).

  In addition, regarding the control of the orientation angle, in particular, it is desired that the change in the orientation angle is small even if the temperature during polymerization performed to fix the orientation is changed. The improvement was desired.

  Further, for example, Non-Patent Documents 2 and 3 describe polymers having a triphenylene group as a disc-like substituent in the side chain. These are dendrimers substituted with a block copolymer with styrene or polypropylene imine. A copolymer with a monomer substituted with a fluorine atom that is effective as an orientation controlling agent has not been known.

JP-A-8-50206 JP 2002-129162 A Molecular Crystals and Liquid Crystals, 2001, 370, 391. Macromolecules, 2003, 36, 3432 Journal of American Chemical Society, 2005, 127, 691.

An object of the present invention is to provide a composition useful for stably producing an optically anisotropic layer or the like that contributes to optical compensation of a liquid crystal display device, and a polymer suitably used therefor. In particular, an optically anisotropic layer exhibiting optical anisotropy expressed by hybrid alignment of discotic liquid crystalline compounds is produced without defects (or with reduced defects) due to variations in optical characteristic values, alignment defects, etc. It is an object of the present invention to provide a polymer and a composition useful for the preparation.
It is another object of the present invention to provide a retardation plate useful for optical compensation of a liquid crystal display device and a liquid crystal display device having good display characteristics.

Means for solving the above problems are as follows.
[1] A polymer containing a structural unit having at least one substituent containing a fluorine atom and a structural unit represented by the following general formula (A):

一般式（Ａ）中、Ｍｐは３価の基を表し、Ｌは単結合又は２価の連結基を表し、Ｘは円盤状置換基を表す。 Formula (A)

In general formula (A), Mp represents a trivalent group, L represents a single bond or a divalent linking group, and X represents a discotic substituent.

[2] A polymer having at least one substituent containing a fluorine atom and containing at least one structural unit represented by the following general formula (A):

一般式（Ａ）中、Ｍｐは３価の基を表し、Ｌは単結合又は２価の連結基を表し、Ｘは円盤状置換基を表す。 Formula (A)

In general formula (A), Mp represents a trivalent group, L represents a single bond or a divalent linking group, and X represents a discotic substituent.

[3] The polymer of [1] or [2] having at least one substituent containing a fluorine atom in the side chain.
[4] The polymer of [1], wherein the structural unit having at least one substituent containing a fluorine atom is represented by the following general formula (B):

一般式（Ｂ）中、Ｍｐ'は３価の基を表し、Ｌ'は単結合又は２価の連結基を表し、Ｒｆは少なくとも一つのフッ素原子を含有する置換基を表す。 General formula (B)

In general formula (B), Mp ′ represents a trivalent group, L ′ represents a single bond or a divalent linking group, and Rf represents a substituent containing at least one fluorine atom.

[5] The polymer according to any one of [1] to [4], wherein in the structural unit represented by the general formula (A), X is a triphenylene group.
[6] The polymer according to any one of [1] to [5], which is a polymer exhibiting liquid crystallinity.
[7] The polymer according to any one of [1] or [3] to [6], which is a block copolymer.
[8] A composition comprising at least one liquid crystal compound and at least one polymer selected from any one of [1] to [7].
[9] The composition according to [8], wherein the viscosity of at least one liquid crystal compound is 500 to 1000 mPas at 80 to 150 ° C.
[10] The composition according to [8] or [9], wherein the at least one liquid crystal compound is a compound represented by the following general formula (DI):

一般式（ＤＩ）中、Ｙ¹¹、Ｙ¹²及びＹ¹³はそれぞれ独立に、メチン又は窒素原子を表し；Ｌ¹、Ｌ²及びＬ³はそれぞれ独立に、単結合又は２価の連結基を表し；Ｈ¹、Ｈ²及びＨ³はそれぞれ独立に、下記一般式（ＤＩ−Ａ）又は下記一般式（ＤＩ−Ｂ）で表される基であり；Ｒ¹、Ｒ²及びＲ³はそれぞれ独立に、下記一般式（ＤＩ−Ｒ）で表される基であり；

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 represent a single bond or a divalent linking group. H ¹ , H ² and H ³ are each independently a group represented by the following general formula (DI-A) or the following general formula (DI-B); R ¹ , R ² and R ³ are each independently And a group represented by the following general formula (DI-R);

一般式（ＤＩ−Ａ）中、ＹＡ¹及びＹＡ²はそれぞれ独立に、メチン又は窒素原子を表し；ＸＡは酸素原子、硫黄原子、メチレン又はイミノを表し；＊はＬ¹〜Ｌ³のいずれかと結合する位置を表し；＊＊はＲ¹〜Ｒ³のいずれかと結合する位置を表し；

In 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; * represents any ^one of L ^{1 to} L ³ Represents a bonding position; ** represents a bonding position with any of R ^{1 to} R ³ ;

一般式（ＤＩ−Ｂ）中、ＹＢ¹及びＹＢ²はそれぞれ独立に、メチン又は窒素原子を表し；ＸＢは酸素原子、硫黄原子、メチレン又はイミノを表し；＊はＬ¹〜Ｌ³のいずれかと結合する位置を表し、＊＊はＲ¹〜Ｒ³のいずれかと結合する位置を表し；
一般式（ＤＩ−Ｒ）
＊−（−Ｌ²¹−Ｆ¹）_n1−Ｌ²²−Ｌ²³−Ｑ¹
一般式（ＤＩ−Ｒ）中、＊は一般式（ＤＩ）中のＨ¹、Ｈ²又はＨ³に結合する位置を表し；Ｆ¹は少なくとも１種類の環状構造を有する２価の連結基を表し；Ｌ²¹は単結合又は２価の連結基を表し；ｎ１は０〜４の整数を表し；Ｌ²²は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−、又は−Ｃ≡Ｃ−を表し；Ｌ²³は−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−及び−Ｃ≡Ｃ−ならびにこれらの２個以上を連結して形成される基から選択される２価の連結基を表し、これらの基のうち水素原子を含む基は、該水素原子が置換基で置き換わっていてもよく；Ｑ¹は重合性基又は水素原子を表す。

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; * represents any ^one of L ^{1 to} L ³ Represents a bonding position, and ** represents a bonding position with any of R ^{1 to} R ³ ;
General formula (DI-R)
*-(-L ²¹ -F ¹ ) _n1 -L ²² -L ²³ -Q ¹
In general formula (DI-R), * represents a position bonded to H ¹ , H ² or H ³ in general formula (DI); F ¹ represents a divalent linking group having at least one kind of cyclic structure. It represents; L ²¹ represents a single bond or a divalent linking group; n1 represents an integer of 0 to 4; L ²² is -O -, - O-CO - , - CO-O -, - O-CO- O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—, or —C≡C—; L ²³ represents —O—, —S—, —C ( ═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C≡C— and a divalent group formed by linking two or more thereof. Of these groups, a group containing a hydrogen atom may be replaced by a substituent; Q ¹ represents a polymerizable group or a hydrogen atom.

[11] Any of [8] to [10], wherein the at least one liquid crystal compound is a liquid crystal compound represented by the following general formula (DII) or a liquid crystal compound represented by the following general formula (DIII). Some compositions:

一般式（ＤＩＩ）中、Ｙ³¹、Ｙ³²及びＹ³³はそれぞれ独立に、メチン又は窒素原子を表し；Ｒ³¹、Ｒ³²及びＲ³³はそれぞれ独立に、下記一般式（ＤＩＩ−Ｒ）で表される基であり；

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 each independently represent the following general formula (DII-R) A group to be

一般式（ＤＩＩ−Ｒ）中、Ａ³¹及びＡ³²はそれぞれ独立に、メチン又は窒素原子を表し；Ｘ³は酸素原子、硫黄原子、メチレン又はイミノを表し；Ｆ²は６員環状構造を有する２価の環状連結基を表し；ｎ３は、１〜３整数を表し；Ｌ³¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−、又は−Ｃ≡Ｃ−を表し；Ｌ³²は−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−及び−Ｃ≡Ｃ−ならびにこれらの２個以上を連結して形成される基から選択される２価の連結基を表し、これら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いてもよく；Ｑ³は重合性基又は水素原子を表し； General formula (DII-R)

In the general formula (DII-R), A ³¹ and A ³² each independently represent a methine or nitrogen atom; X ³ represents an oxygen atom, a sulfur atom, methylene or imino; F ² has a 6-membered cyclic structure N3 represents an integer of 1 to 3; L ³¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, a divalent cyclic linking group; —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—, or —C≡C—; L ³² represents —O—, —S—, —C (═O) —, —SO _2- , -NH-, -CH _2- , -CH = CH- and -C≡C- and a divalent linking group selected from a group formed by linking two or more thereof, When the group of is a group containing a hydrogen atom, the hydrogen atom may be substituted with a substituent; Q ³ represents a polymerizable group or a hydrogen atom;

一般式（ＤＩＩＩ）中、Ｙ⁴¹、Ｙ⁴²及びＹ⁴³はそれぞれ独立に、メチン又は窒素原子を表し；Ｒ⁴¹、Ｒ⁴²及びＲ⁴³はそれぞれ独立に、下記一般式（ＤＩＩＩ−Ａ）、下記一般式（ＤＩＩＩ−Ｂ）、又は下記一般式（ＤＩＩＩ−Ｃ）で表される基であり；

In the general formula (DIII), Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represent a methine or nitrogen atom; R ⁴¹ , R ⁴² and R ⁴³ each independently represent the following general formula (DIII-A), A group represented by the general formula (DIII-B) or the following general formula (DIII-C);

一般式（ＤＩＩＩ−Ａ）中、Ａ⁴¹、Ａ⁴²、Ａ⁴³、Ａ⁴⁴、Ａ⁴⁵及びＡ⁴⁶はそれぞれ独立に、メチン又は窒素原子を表し；Ｘ⁴¹は、酸素原子、硫黄原子、メチレン又はイミノを表し；Ｌ⁴¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表し；Ｌ⁴²は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−及び−Ｃ≡Ｃ−ならびにこれらの２個以上を連結して形成される基から選択される２価の連結基を表し、これら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く；Ｑ⁴は、重合性基又は水素原子を表し；

In the general formula (DIII-A), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ each independently represents a methine or nitrogen atom; X ⁴¹ represents an oxygen atom, a sulfur atom, methylene or L ⁴¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, — CH═CH— or —C≡C—; L ⁴² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from CH- and -C≡C- and a group formed by linking two or more thereof, and when these groups are groups containing a hydrogen atom, The atom may be replaced by a substituent; Q ⁴ represents a polymerizable group or a hydrogen atom;

一般式（ＤＩＩＩ−Ｂ）中、Ａ⁵¹、Ａ⁵²、Ａ⁵³、Ａ⁵⁴、Ａ⁵⁵及びＡ⁵⁶はそれぞれ独立に、メチン又は窒素原子を表し、Ｘ⁵²は、酸素原子、硫黄原子、メチレン又はイミノを表し；Ｌ⁵¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表し；Ｌ⁵²は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−及び−Ｃ≡Ｃ−ならびにこれらの２個以上を連結して形成される基から選択される２価の連結基を表し、これら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いてもよく；Ｑ⁵は重合性基又は水素原子を表し；

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, and X ⁵² represents an oxygen atom, a sulfur atom, methylene or an imino; L ⁵¹ is -O -, - O-CO - , - CO-O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, - CH = CH— or —C≡C—; L ⁵² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from CH- and -C≡C- and a group formed by linking two or more thereof, and when these groups are groups containing a hydrogen atom, The atom may be replaced by a substituent; Q ⁵ represents a polymerizable group or a hydrogen atom;

一般式（ＤＩＩＩ−Ｃ）中、Ａ⁶¹、Ａ⁶²、Ａ⁶³、Ａ⁶⁴、Ａ⁶⁵及びＡ⁶⁶はそれぞれ独立に、メチン又は窒素原子を表し；Ｘ⁶³は、酸素原子、硫黄原子、メチン又はイミノを表し；Ｌ⁶¹は−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ₂−、−ＣＨ₂−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表し；Ｌ⁶²は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−及び−Ｃ≡Ｃ−ならびにこれらの２個以上を連結して形成される基から選択される２価の連結基を表し、これら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く；Ｑ⁶は重合性基又は水素原子を表す。

In the general formula (DIII-C), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ each independently represents a methine or nitrogen atom; X ⁶³ represents an oxygen atom, a sulfur atom, methine or an imino; L ⁶¹ is -O -, - O-CO - , - CO-O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, - CH═CH— or —C≡C—; L ⁶² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from CH- and -C≡C- and a group formed by linking two or more thereof, and when these groups are groups containing a hydrogen atom, The atom may be replaced by a substituent; Q ⁶ represents a polymerizable group or a hydrogen atom.

[12] A retardation plate having an optically anisotropic layer made of the composition according to any one of [8] to [11].
[13] A liquid crystal display device having the retardation plate of [12].

  ADVANTAGE OF THE INVENTION According to this invention, the polymer and composition useful for producing stably the optically anisotropic layer which contributes to the optical compensation of a liquid crystal display device can be provided. According to the present invention, in particular, the optical anisotropy layer exhibiting optical anisotropy expressed by the hybrid orientation of the discotic liquid crystalline compound has an optical property value variation caused by slight fluctuations in the orientation temperature, the orientation It is possible to provide a composition that is useful for making without or reducing defects caused by defects or the like. Further, according to the present invention, a retardation plate useful for optical compensation of a liquid crystal display device and a liquid crystal display device with good display characteristics can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below. 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.
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) each represent the in-plane retardation and the thickness direction letter at the 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 normal direction of the film with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation value measured in a total of three directions, 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 molecules of the discotic liquid crystalline compound in the optically anisotropic layer refers to one surface of the optically anisotropic layer (for example, the alignment film surface) and the disco in the optically anisotropic layer. The angle formed by the physical target axis of the molecule of the tick liquid crystalline compound is defined as the tilt angle θ1, and the angle formed by the other surface (for example, the air interface) is defined as the tilt angle θ2, and the average value ((θ1 + θ2) / 2). However, it is difficult to directly and accurately measure θ1 and the tilt angle θ2 of the other surface. Therefore, in this specification, θ1 and θ2 are calculated by the following method. Although this method does not accurately represent the actual orientation state, it is effective as a means of expressing the relative relationship between some optical properties of the optical film.
In this method, in order to facilitate calculation, the following two points are assumed and the tilt angle at the two interfaces of the optically anisotropic layer is used.
1. The optically anisotropic layer is assumed to be a multilayer body composed of layers containing a discotic compound or a rod-like compound. Further, it is assumed that the minimum unit layer (assuming that the tilt angle of the discotic compound or rod-shaped compound is uniform in the layer) 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 the 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 include 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 present invention relates to a polymer containing at least one substituent containing a fluorine atom and at least one constituent unit represented by the following general formula (A). The present invention also includes a composition containing at least one kind of the polymer and at least one kind of liquid crystal compound. An optically anisotropic layer can be formed from the composition, and the retardation plate of the present invention having the optically anisotropic layer can be produced. When the liquid crystalline compound is hybrid-aligned in the presence of the polymer of the present invention, a hybrid alignment having a small average tilt angle can be realized. Furthermore, when forming the optically anisotropic layer by fixing the molecules of the liquid crystalline compound in such an alignment state by polymerization, there is a feature that there is no or little change in the tilt angle due to fluctuations in the polymerization temperature. Therefore, according to the present invention, an optically anisotropic layer having desired performance can be stably formed, and the present invention also contributes to the improvement of the production stability of a retardation plate having an optically anisotropic layer. To do.

Hereinafter, the polymer, the composition, and the retardation plate of the present invention will be sequentially described.
(1) Polymer of the Present Invention (1) -1 Structural Unit Represented by General Formula (A) The polymer of the present invention contains at least one structural unit represented by the following general formula (A).

Formula (A)

  In general formula (A), Mp represents a trivalent group, L represents a single bond or a divalent linking group, and X represents a discotic substituent. However, the term “discotic substituent” refers to a discotic substituent in which three or more cyclic substituents are directly or via a linking group in one core group, and a cyclic substituent in the core. Is used to include any of four or more discotic substituents formed by condensing the ring.

In general formula (A), Mp is a trivalent group and constitutes the main chain of the polymer of the present invention. As will be described later, the main chain may be composed of other repeating units. Mp is, -CR ₂ -CR ₂ - (R are each a hydrogen atom or a substituent), - CR = CR- (R are each a hydrogen atom or a substituent) and -CC- of any one or more A group consisting only of a structure (for example, a substituted or unsubstituted ethylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted cyclic alkylene group, a substituted or unsubstituted phenylene group, etc.) A group containing an oxygen atom (eg, ether group, acetal group, ester group, carbonate group, etc.), a group containing a nitrogen atom (eg, amino group, imino group, amide group, urethane group, ureido group, imide group, imidazole group) Groups, oxazole groups, pyrrole groups, anilide groups, maleimide groups, etc.), groups containing sulfur atoms (for example, sulfide groups, sulfone groups, thiophene groups, etc.) A group containing a phosphorus atom (for example, a phosphine group, a phosphate ester group, etc.), a group containing a silicon atom (for example, a siloxane group, etc.), and a trivalent group formed by linking two or more of these groups Is included.

  Although the preferable specific example of Mp is shown below, Mp is not limited to this. Moreover, the site | part represented by * in Mp represents the site | part connected with L. FIG.

Mp is preferably any one of -CR ₂ -CR _2- (R is a hydrogen atom or a substituent, respectively), -CR = CR- (R is a hydrogen atom or a substituent, respectively) and -CC-. It is a group consisting of only the above structure, more preferably a group consisting of only a structure of —CR ₂ —CR ₂ — (wherein R is a hydrogen atom or a substituent, respectively), and more preferably a substituted or unsubstituted ethylene. Group, particularly preferably Mp-1 and Mp-2.

Examples of the divalent linking group represented by L in the general formula (A) include a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, a butylene group, an iso group). Propylene group, etc.), alkenylene group having 2 to 20 carbon atoms (eg, vinylene group, butene group, etc.), substituted or unsubstituted arylene group (eg, o-phenylene group, m-phenylene group, p-phenylene group, 1,4-naphthylene group, etc.), —O—, —NR ^a1 —, —S—, ^{—PR a2} —, —Si (R ^a3 ) (R ^a4 ) —, —C (═O) —, —C ( ═O) O—, —C (═O) NR ^a5 —, —OC (═O) O—, —OC (═O) NR ^a6 —, —NR ^a7 C (═O) NR ^a8 —, — (— O) represents ₂ CH- and the like. The above R ^{a1 to} R ^a8 represent substitutable substituents, for example, a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group such as a monocycloalkyl group or a bicycloalkyl group containing one or more ring structures). ), Alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic rings Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfur Famoylamino group, alkyl Rusulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryl Examples include oxycarbonyl group, alkoxycarbonyl group, carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group and silyl group.
Moreover, the coupling group as shown below formed by connecting two or more of the above-mentioned coupling groups may be used. Moreover, the site | part represented by * in L represents the site | part connected with Mp.

More preferably, L in the general formula (A) is —O—, —NR ^a11 — (wherein R ^a11 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a C 6 to 20 carbon atom). Represents an aryl group.), —S—, —C (═O) —, —S (═O) ₂ —, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and 2 It is a divalent linking group selected from a group formed by linking at least one group. Examples of the divalent linking group formed by linking two or more of them include —C (═O) O—, —OC (═O) —, —OC (═O) O—, —C (═O). NH -, - NHC (= O ) -, - C (= O) O (CH 2) ma O- ( where, ma is an integer of 1 to 20), etc.).

Further, when Mp in the general formula (A) represents Mp-1 or Mp-2, L represents —O—, —NR ^a11 — (R ^a11 represents a hydrogen atom, a carbon atom number of 1 to 10 represents an aliphatic hydrocarbon group or an aryl group having 6 to 20 carbon atoms.), —S—, —C (═O) —, —S (═O) ₂ —, and the number of carbon atoms It is preferably a divalent linking group selected from 1 to 20 substituted or unsubstituted alkylene groups and a group formed by linking two or more of these, -O-, -C (= A group selected from O) O—, —C (═O) NH—, and a divalent linking group composed of a combination of one or more of these and an alkylene group is more preferable. For example, the L-1, L-2, L-3 and the like.

  The discotic substituent represented by X in the general formula (A) has at least three or more cyclic substituents (hereinafter referred to as Xd) directly or linked to one core group (hereinafter referred to as Xc). A discotic substituent substituted via a group (hereinafter referred to as XL), or the core group (Xc) is a cyclic substituent, and other cyclic substituents (Xd) are condensed around the core. It is preferable that it is a 4 or more ring-shaped discotic substituent, and each preferable linking method includes the following general formulas X-1 and X-2. However, the site | part connected with L in general formula (A) may be any site | part of Xc, Xd, and XL.

  Examples of the core group (Xc) include methine, a nitrogen atom, 3 to 8 cyclic aliphatic hydrocarbon groups (for example, cyclopropane and cyclohexyl), and 6 to 10 aryl groups (for example, a benzene ring and a naphthalene ring). ) And a heterocyclic group (for example, 1,3,5-triazine ring, 1,3-pyrimidine ring, etc.), preferably a benzene ring.

  In addition, examples of the cyclic substituent (Xd) formed by substitution or condensation on the core include a substituted and unsubstituted cyclic aliphatic hydrocarbon group having 3 to 30 carbon atoms (for example, a substituted cyclohexyl group), substituted and unsubstituted Examples thereof include an unsubstituted aryl group having 6 to 30 carbon atoms (for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, etc.), and the substituted cyclic group is preferably a substituted phenyl group or a substituted naphthyl group. In the case of forming a condensed ring, a benzene ring is preferable.

In addition, as the linking group XL of Xc and Xd, a simple bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, isopropylene group, etc.), Alkenylene group having 2 to 20 carbon atoms (for example, vinylene group, butene group, etc.), —O—, —NR ^x1 —, —C (═O) —, —C (═O) O—, —C (= O) NR ^x2 —, —OC (═O) O—, —OC (═O) NR ^x3 —, — (— O) ₂ CH— and the like. The above R ^{x1 to} R ^x3 represent substitutable substituents, for example, a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group such as a monocycloalkyl group or a bicycloalkyl group containing one or more ring structures). ), Alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic rings Examples include oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group and the like.

  Specific examples of preferred structural units as general formula (A) are shown below, but the present invention is not limited thereto.

  The polymer of the present invention has at least one substituent containing a fluorine atom. The substituent is preferably present in the side chain of the polymer. The substituent containing the fluorine atom may be contained in the structural unit represented by the general formula (A). In such a case, in the linking group L or the discotic substituent X constituting the side chain. It is preferably present as a substituent of When the substituent containing the fluorine atom is contained in the structural unit represented by the general formula (A), the polymer of the present invention may be a homopolymer derived from one kind of monomer. Good. About the preferable example of the substituent containing the fluorine atom contained in the structural unit represented by the said general formula (A), about the substituent containing the fluorine atom which the structural unit represented by the general formula (B) mentioned later has The same as the preferred example.

(1) -2 Constituent Unit Composed of a Group Substituted with a Fluorine Atom One aspect of the polymer of the present invention is a substituent containing a fluorine atom in addition to the constituent unit that is a group represented by the general formula (A). A copolymer having at least one structural unit. As such a structural unit, a structural unit derived from a fluoroaliphatic group-containing monomer is preferable, and a structural unit represented by the following general formula (B) is more preferable. The detail about group represented by general formula (B) below is described.

General formula (B)

  In general formula (B), Mp ′ represents a trivalent group, L ′ represents a single bond or a divalent linking group, and Rf represents a substituent containing at least one fluorine atom.

Mp ′ is synonymous with Mp in the general formula (A), and a preferred range is also synonymous.
L ′ is preferably —O—, —NR ^a11 — (wherein R ^a11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms). , —S—, —C (═O) —, —S (═O) ₂ —, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and a combination of two or more thereof. A divalent linking group selected from the following groups. Examples of the divalent linking group formed by linking two or more of them include —C (═O) O—, —OC (═O) —, —OC (═O) O—, —C (═O). NH -, - NHC (= O ) -, - C (= O) O (CH 2) ma O- ( where, ma is an integer of 1 to 20), and the like.

Furthermore, when Mp ′ in the general formula (B) represents Mp-1 or Mp-2, L ′ represents —O—, —NR ^a11 — (R ^a11 represents a hydrogen atom, 1 carbon atom. Represents an aliphatic hydrocarbon group having 10 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.), -S-, -C (= O)-, -S (= O) _2- , and a carbon atom. It is preferably a divalent linking group selected from a substituted or unsubstituted alkylene group having a number of 1 to 20 and a group formed by linking two or more of these, -O-, -C ( ═O) O— and —C (═O) NH— and a divalent linking group selected from a group consisting of one or more of these and an alkylene group (for example, L-1, L -2 and L-3 etc.) are more preferred.

Rf is a substituent containing at least one fluorine atom, and preferred examples thereof include an aliphatic hydrocarbon group having 1 to 30 carbon atoms substituted with at least one fluorine atom (for example, a trifluoroethyl group, Perfluorohexylethyl group, perfluorohexylethoxyethyl group, perfluorohexylpropyl group, perfluorobutylethyl group, perfluorooctylethyl group, etc.), an aryl group having 6 to 20 carbon atoms substituted by at least one fluorine atom (For example, 4-trifluoromethylphenyl group, 4- (perfluorohexylethoxy) ethoxyphenyl group, etc.) are included. Rf preferably has a CF ₃ group or a CF ₂ H group at the terminal, and more preferably has a CF ₃ group.

Rf in the general formula (B) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 4 to 16 carbon atoms, and an alkyl group having 4 to 8 carbon atoms. More preferably.
Rf is more preferably an alkyl group having a CF ₃ group at the terminal or an alkyl group having a CF ₂ group at the terminal. The alkyl group having a CF ₃ group at the terminal is an alkyl group in which some or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. An alkyl group in which 50% or more of the hydrogen atoms in the alkyl group having a CF ₃ group at the terminal are substituted with fluorine atoms is preferred, an alkyl group in which 60% or more is substituted is more preferred, and 70% or more is substituted. Particularly preferred are alkyl groups. The remaining hydrogen atoms may be further substituted with the substituents exemplified as the substituent group D described later.
The alkyl group having a CF ₂ H group at the terminal is an alkyl group in which some or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. 50% or more of the hydrogen atoms in the alkyl group having a CF ₂ H group at the terminal are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and 70% or more are substituted. It is particularly preferable. The remaining hydrogen atoms may be further substituted with the substituents exemplified as the substituent group D described later.

Substituent group D
In the present specification, the substituent group D includes an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. , Methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably An alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group. Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms). Nyl group, for example, propargyl group, 3-pentynyl group, etc., aryl group (preferably 6-30 carbon atoms, more preferably 6-20 carbon atoms, particularly preferably 6-6 carbon atoms). 12 aryl groups such as a phenyl group, a p-methylphenyl group, and a naphthyl group, and a substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 carbon atoms). -10, particularly preferably an amino group having 0 to 6 carbon atoms, such as an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group).

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group. An aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyloxy group and 2-naphthyl group. An oxy group, etc.), an acyl group (preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably an acyl group having 1-12 carbon atoms, for example, acetyl group, benzoyl Group, formyl group, pivaloyl group, etc.), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably carbon An alkoxycarbonyl group having 2 to 16 children, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group, and an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms). More preferably an aryloxycarbonyl group having 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as a phenyloxycarbonyl group), an acyloxy group (preferably having 2 to 2 carbon atoms). 20, more preferably an acyloxy group having 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group).

Acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group) An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group) An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms). Oxycarbonylamino group), sulfonylamino group Preferably, it is a sulfonylamino group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group. ), A sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, Dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). Groups such as unsubstituted carbamoyl, methylcarbamoyl, Bamoiru group, phenylcarbamoyl group),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group). An arylthio group (preferably an arylthio group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), a sulfonyl group ( Preferably they are C1-C20, More preferably, it is C1-C16, Most preferably, it is C1-C12 sulfonyl group, for example, a mesyl group, a tosyl group etc. are mentioned), a sulfinyl group ( Preferably, it is a sulfo having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Nyl group, for example, methanesulfinyl group, benzenesulfinyl group, etc.), ureido group (preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-1 carbon atoms). 12 ureido groups, for example, an unsubstituted ureido group, a methylureido group, a phenylureido group and the like, and a phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1 carbon atom). 16, particularly preferably a phosphoric acid amide group having 1 to 12 carbon atoms, such as a diethylphosphoric acid amide group and a phenylphosphoric acid amide group, a hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom) , Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group A sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms such as a nitrogen atom, an oxygen atom, a sulfur atom, etc. For example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group), a silyl group (preferably A silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group) It is. These substituents may be further substituted with these substituents. Further, when two or more substituents are present, they may be the same or different. If possible, they may be bonded to each other to form a ring.

Examples of an alkyl group having a CF ₃ group at the terminal or an alkyl group having a CF ₂ H group at the terminal are shown below.
R1: n-C ₈ F _{17-
R2: n-C 6 F 13} -
_{R3: n-C 4 F 9} -
_{R4: n-C 8 F 17} - (CH 2) 2 -
_{R5: n-C 6 F 13} - (CH 2) 2 -
_{R6: n-C 4 F 9} - (CH 2) 2 -
_{R7: H- (CF 2) 8} -
_{R8: H- (CF 2) 6} -
_{R9: H- (CF 2) 4} -
_{R10: H- (CF 2) 8} - (CH 2) -
R11: H— (CF ₂ ) ₆ — (CH ₂ ) —
_{R12: H- (CF 2) 4} - (CH 2) -
_{R13: n-C 4 F 9} - (CH 2) 2 -O- (CH 2) 3 -O-
_{R14: n-C 6 F 13} - (CH 2) 2 -O-
_{R15: n-C 4 F 9} - (CH 2) 2 -O-

  Specific examples of preferable repeating units derived from the fluoroaliphatic group-containing monomer are shown below, but the present invention is not limited to the following specific examples.

In addition to the structural unit containing the structure represented by the general formula (A) and the structural unit substituted with a fluorine atom, the polymer of the present invention includes a monomer copolymerizable with the monomer forming these structural units. You may contain the structural unit induced | guided | derived more.
There is no restriction | limiting in particular as a monomer which can be copolymerized. Preferred monomers include, for example, hydrocarbon polymers (for example, polyethylene, polypropylene, polystyrene, polymaleimide, polyacrylic acid, polyacrylic acid ester, polyacrylamide, polyacrylanilide, etc.), polyether, polyester, polycarbonate , A monomer constituting polyamide, polyamic acid, polyimide, polyurethane and polyureide.
Furthermore, the structural unit whose main chain structure becomes the same as what the group represented by general formula (A) comprises is preferable.

  Specific examples of the copolymerizable structural unit are shown below, but the present invention is not limited to the following specific examples.

In the polymer of the present invention, the content of the structural unit represented by the general formula (A) is preferably 1 to 90% by mass, and more preferably 5 to 80% by mass.
As a content rate of the structural unit (preferably group represented by general formula (B)) which has a substituent containing a fluorine atom in the polymer of this invention, 5-90 mass% is preferable, and 10-80% is preferable. More preferred.
As a content rate of structural units other than said 2 types, 60 mass% or less is preferable, and 50 mass% or less is more preferable.

These copolymers may be random copolymers in which each constituent 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.
Moreover, the group represented by general formula (A), the group represented by general formula (B), etc. may be only one type, and may be two or more types. In the case of two or more types, the content is the total content.

  Furthermore, the molecular weight range of the polymer of this invention is a weight average molecular weight (Mw), Preferably it is 1000-1 million, More preferably, it is 2000-200000, More preferably, it is 3000-100,000. Further, the molecular weight distribution of the polymer of the present invention is preferably 1 to 4, and more preferably 1 to 3.

  The addition amount range of the polymer of the present invention is preferably 0.001 to 10% by mass, more preferably 0.005 to 5.0% by mass, further preferably 0 to the liquid crystal compound. 0.01 to 1.0% by mass.

The polymer of the present invention is preferably a liquid crystalline polymer exhibiting liquid crystallinity. Further, it is more preferably a liquid crystalline polymer exhibiting liquid crystallinity between 25 ° C and 250 ° C.
Liquid crystal as used herein refers to a state of high viscosity and fluidity between the crystal and the liquid, which is either thermotropic liquid crystal that changes its state thermally or lyotropic liquid crystal that changes its state depending on the concentration. However, the former thermotropic liquid crystal property is preferable. Further, the thermotropic liquid crystallinity includes nematic liquid crystallinity and smectic liquid crystallinity depending on the alignment state. In the present invention, any alignment liquid crystal may be used, but nematic liquid crystallinity is preferable.

  Specific examples of the polymer of the present invention are shown in Table 1 below.

  The synthesis of the polymer of the present invention can be carried out by applying a known method. The polymer of the present invention can be synthesized by any of addition, condensation, and substitution reaction or a combination thereof. Although there is no particular limitation, when the polymer contains an ethylenic repeating unit, it is convenient and preferable to synthesize using a radical polymerization reaction of an ethylenically unsaturated compound corresponding to the repeating unit.

(2) Composition of the present invention The composition of the present invention contains at least one polymer of the present invention and at least one liquid crystal compound. Hereinafter, the liquid crystal compound suitably used for the composition of the present invention will be described.
(2) -1 Liquid crystalline compound The liquid crystalline compound used in the present invention is not particularly defined, but is preferably a compound exhibiting discotic liquid crystallinity, and more preferably a compound exhibiting a discotic nematic phase. .
Examples of the liquid crystalline compound used in the present invention include those represented by the general formula (DI).

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

In 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, for example, alkyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, alkylthio group, arylthio group, halogen Mention may be made of atoms and cyano groups. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 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. Further, 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 include a single bond, * —O—CO—, * —CO—O—, * —CH═CH—, * —C≡C—, * -2 valent cyclic group— * -O-CO-2 valent cyclic group-, * -CO-O-2 valent cyclic group-, * -CH = CH-2 valent cyclic group-, * -C≡C-2 valent cyclic. Group-, * -2 valent cyclic group-O-CO-, * -2 valent cyclic group-CO-O-, * -2 valent cyclic group-CH = CH-, or * -2 valent cyclic group- C≡C— is preferred. In particular, a single bond, * -CH = CH-, * -C≡C-, * -CH = CH-2 valent cyclic group- or * -C≡C-2 valent cyclic group- is more preferable, Is more preferable. Here, * represents a position bonded to a 6-membered ring including 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 formula (DI-A), YA ¹ and YA ² each independently represent a methine group 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 bonded to L to L ^3, and ** represents a position bonded to R ^{1 to} R ³ .

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 bonded to L to L ^3, and ** represents a position bonded to R ^{1 to} R ³ .

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

In the general formula (DI-R), * represents a position bonded to H ¹ , H ² or H ³ in the general formula (DI). F ¹ represents a divalent linking group having at least one cyclic structure. 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 preferable. 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.

F ¹ in the general formula (DI-R) represents a divalent cyclic linking group having at least one cyclic structure. The cyclic structure 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, and even more preferably a 6-membered ring. The cyclic structure may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. Further, 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 F ¹ , those having a benzene ring are preferably a 1,4-phenylene group or a 1,3-phenylene group. Those 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-2,6- A diylnaphthalene-2,7-diyl group is preferred. Those having a cyclohexane ring are preferably 1,4-cyclohexylene groups. Pyridine-2,5-diyl groups are preferred as those having a pyridine ring. As a compound having a pyrimidine ring, a pyrimidine-2,5-diyl group is preferable. F ¹ is particularly preferably a 1,4-phenylene group, a 1,3-phenylenenaphthalene-2,6-diyl group, and a 1,4-cyclohexylene group.

F ¹ 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. The substituent 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 a halogen atom or an alkyl having 1 to 4 carbon atoms. Group, an alkyl group substituted with a halogen atom having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are 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 -F ¹ may be the same or different.

L ²² represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH. -Or -C≡C- is represented. 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 —.
Here, when it is a group containing a hydrogen atom among the above, the hydrogen atom may be replaced by a substituent. 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 group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group, carbon atom 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.

L ²³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and two of these. A divalent linking group selected from the groups formed by linking the above. 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 group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group, carbon atom 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 with these substituents, the solubility of the compound represented by the general formula (DI) in the solvent can be improved, and the composition of the present invention can be easily prepared 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.

  Furthermore, it is more preferable to use the liquid crystalline compound represented by the following general formula (DII) or the liquid crystalline compound represented by the following general formula (DIII) as the discotic liquid crystalline compound used in the present invention.

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).

General formula (DII-R)

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

In General Formula (DII-R), F ² represents a divalent cyclic linking group having a 6-membered cyclic structure. The 6-membered ring contained in F ² may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The 6-membered ring contained in F ² 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.

  Among 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.

F ² 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. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms are preferable. An alkyl group having 1 to 4 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 F ² may be the same or different.

L ³¹ is —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—. , -C≡C-, 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 represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, or two or more thereof. Represents a divalent linking group selected from the group formed by linking 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 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 represents a methine or nitrogen atom. When Y ⁴¹ , Y ⁴² and Y ⁴³ are each methine, the hydrogen atom of the 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 all 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 general formula (DIII-A) or general formula (DIII-C), What is represented by general formula (DIII-A) is more preferable.

In General Formula (DIII-A), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ , and A ⁴⁶ each independently represent 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 possessed by methine include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, and alkenyl group 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, a carbamoyl group and a carbon atom substituted with an alkyl group having 2 to 16 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 ⁴¹ represents an oxygen atom, a sulfur atom, methylene or imino, and 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, and preferably an oxygen atom.

In the general formula (DIII-C), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ each independently represents a methine or nitrogen atom. At least one of A ⁶¹ and A ⁶² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ are preferably methine, more preferably methine. When A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ³⁶ are each methine, the hydrogen atom of the methine may be substituted with a substituent. Examples of the substituent that methine may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, 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 Group, 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, and a carbamoyl substituted with an alkyl group having 2 to 16 carbon atoms Groups and acylamino groups of 2 to 16 carbon atoms are 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 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, 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 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 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—, — Selected from C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C≡C— and groups formed by linking two or more thereof. Represents a divalent linking group. 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 each independently connect —O—, —C (═O) —, —CH ₂ —, —CH═CH— and —C≡C— and two or more thereof. It is preferable that it is a bivalent coupling group selected from the group formed in this way. 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 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), general formula (DII), and general formula (DIII) below is shown, this invention is not limited to these.

  The compounds represented by formula (DIII) are shown below.

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

  The compound represented by the general formula (DI) preferably exhibits a liquid crystal phase in a range of 20 ° C to 300 ° C, more preferably in a range of 40 ° C to 280 ° C, and 60 ° C to 250 ° C. It is more preferable to express in the range of. 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 compound represented by the general formula (DI) used in the present invention can be synthesized by applying a known method.

  The viscosity of the liquid crystalline compound used in the present invention is preferably 500 to 1000 mPa · s at 80 to 150 ° C., and more preferably (600 to 900) mPa · s at the same temperature.

(3) Phase difference plate of this invention The phase difference plate of this invention has an optically anisotropic layer which consists of a composition of this invention, It is characterized by the above-mentioned. One aspect of the retardation plate of the present invention comprises a support, an alignment film formed on the support, and the composition of the present invention, the alignment of which is controlled by the alignment film and fixed in the alignment state. It is an aspect which has an optically anisotropic layer.
Hereinafter, the optically anisotropic layer, the alignment film, and the support will be sequentially described in detail.

(3) -1 Optically Anisotropic Layer The optically anisotropic layer is composed of the composition of the present invention, preferably at least one liquid crystalline compound represented by the general formula (DI), and It consists of a composition containing at least one polymer. The composition may further contain a polymerization initiator and other additives as desired. The composition of the present invention may be prepared as a coating solution, for example, applied to the surface of an alignment film formed on a support, and after aligning the liquid crystalline compound, it may be formed by immobilization. After aligning and fixing the liquid crystalline compound, the support may be peeled off.

(3) -1-a Forming Method The optically anisotropic layer is formed on a support and coated with a coating solution prepared by dissolving the liquid crystalline compound and the polymer of the present invention in a solvent that can be dissolved. It can produce by apply | coating on the orientation film | membrane to which the property was provided. 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 may be formed by drying the solvent used at 25 ° C. to 130 ° C., and simultaneously orienting the molecules of the liquid crystalline compound and fixing them by ultraviolet irradiation or the like. It is preferable to use ultraviolet rays for light irradiation for polymerization. The irradiation energy is preferably 20 mJ / cm ^{2 to} 50 J / cm ² , and more preferably 100 mJ / cm ^{2 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. More preferably, the liquid crystal compound is fixed by the reaction.

  The content of the liquid crystalline compound or the polymer of the liquid crystalline compound in the composition used for forming the optically anisotropic layer is preferably 10 to 100% by mass, and 30 to 99% by mass. Is more preferable, and it is further more preferable that it is 50-99 mass%.

(3) -1-b Other materials used for forming the optically anisotropic layer The liquid crystalline compound is preferably fixed while maintaining the alignment state, and the fixing is a polymerizable group introduced into the liquid crystalline compound. The polymerization reaction is preferably performed. For that purpose, it is preferable to contain a polymerization initiator in the composition. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and EB curing using an electron beam. Among these, photopolymerization reaction (photocuring) and EB curing are preferable. Examples of polymerization initiators that generate radicals by the action of light include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670) and acyloin ethers (described in US Pat. No. 2,448,828). , Α-hydrocarbon substituted aromatic acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), triarylimidazole dimer and p-aminophenyl Combinations with ketones (described in U.S. 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. 4,221,970) Acetophenone) Compounds, benzoin ether compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, and the like are preferable. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy -2-methyl-propiophenone, p-dimethylaminoacetone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like. Examples of the benzyl compound include benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, 1-hydroxycyclohexyl phenyl ketone and the like. Examples of the benzoin ether compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, and benzoin isobutyl ether. Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and the like. Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. Among such photosensitive radical polymerization initiators composed of aromatic ketones, acetophenone compounds and benzyl compounds are particularly preferable in terms of curing characteristics, storage stability, odor, and the like. The photosensitive radical polymerization initiators composed of these aromatic ketones can be used alone or in combination of two or more according to the desired performance. In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like.

  Multiple photopolymerization initiators may be combined, and the amount used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.05 to 5% by mass, based on the solid content of the coating solution. It is preferable to use ultraviolet rays for light irradiation for polymerization of the liquid crystalline compound.

  As the solvent used for preparing the coating liquid for forming the optically anisotropic layer, an organic solvent is preferable. Examples of organic solvents include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg toluene, hexane) alkyl halides (eg Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane), and the like. . Of these, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

The solid content concentration of the liquid crystal compound and other additives in the composition of the present invention is preferably 0.1% by mass to 60% by mass, more preferably 0.5% by mass to 50% by mass, and 2% by mass. -40 mass% is further more preferable.
The viscosity of the composition of the present invention is preferably 0.01 cp to 100 cp, and more preferably 0.1 cp to 50 cp.

(3) -1-c Alignment State An optically anisotropic layer formed from the composition of the present invention is discotic when used as a phase difference plate in a liquid crystal display mode such as TN (Twisted Nematic). It is preferable to fix the state in which the nematic phase is hybrid-oriented. Here, the hybrid alignment represents a state in which the tilt angle of the liquid crystal compound continuously changes in the film thickness direction.

The liquid crystalline compound is applied on the support (more preferably on the alignment film) and then, for example, heated to develop a liquid crystal phase. Therefore, the liquid crystalline compound is formed on the support surface or the coating film interface (alignment film) at the support side interface. Is aligned at the tilt angle of the alignment film interface) (for example, when a discotic liquid crystal compound is used, the angle formed by the direction of the support surface and the disk surface direction of the liquid crystal compound), and at the interface with air Orientation is performed at the tilt angle of the air interface.
In the present invention, the average tilt angle of the optically anisotropic layer (for example, the angle formed by the direction of the support surface and the disc surface direction of the discotic liquid crystalline compound) is preferably 10 to 70 °, more preferably 20 to 60 °. .
The tilt angle at each interface is a combination of the tilt angle at the air interface of 0 to 50 ° and the tilt angle of the support side interface of 20 to 90 °, or the tilt angle of the support side interface of 0 to 50 °. A combination in which the tilt angle of the air interface is 20 to 90 ° is preferable. In particular, a combination in which the tilt angle of the air interface is 0 to 40 ° and the tilt angle of the support side interface is 40 to 80 °, or the tilt angle of the support side interface is 0 to 40 ° and the tilt angle of the air interface is 40 to 40 °. A combination of 80 ° is preferred.

(3) -2 Alignment Film An alignment film may be used for producing the retardation plate of the present invention. The alignment film is an organic compound (for example, ω-tricosanoic acid, rubbed treatment of a compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.

  In principle, the polymer used for the alignment film has a molecular structure having a function of aligning the liquid crystal compound. In the present invention, in addition to the function of aligning the liquid crystalline compound, the crosslinking having the 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 for 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 methacrylate polymer, styrene polymer, polyolefin, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), polyester described in paragraph No. [0022] of JP-A-8-338913, for example. , Polyimide, vinyl acetate polymer, carboxymethyl cellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are more 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 kind of specific functional group is determined according to the kind of liquid crystalline 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 Atom-substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy groups, dialkoxy groups, monoalkoxy groups) and the like can be mentioned. Specific examples of these modified polyvinyl alcohol compounds include, for example, paragraphs [0022] to [0145] of JP-A No. 2000-155216 and paragraphs [0018] to [0022] of 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 paragraphs [0080] to [0100] of JP-A No. 2000-155216.

Apart from the crosslinkable functional group, the alignment film polymer can also be crosslinked using a crosslinking agent.
Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraph numbers [0023] to [0024] of JP-A-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 when 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 basically be formed by coating the support material containing the above-mentioned polymer as the alignment film forming material and a crosslinking agent, followed by drying by heating and crosslinking, and if necessary, a rubbing treatment. . As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating liquid is preferably a mixed solvent of an organic solvent (for example, methanol) having a defoaming action and water. The ratio by mass is water: methanol greater than 0 and 99 or less: less than 100, preferably 1 or more, and more preferably greater than 0 and 91 or less: less than 100, 9 or more. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an alignment film and also an optically anisotropic layer can be reduced 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. The heat drying can be performed at 20 ° C. to 110 ° C., for example. In order to form sufficient cross-linking, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is more preferable. The drying time can be, for example, 1 minute to 36 hours, and preferably 1 minute to 30 minutes. The pH is also preferably set to an optimum value for the crosslinking agent to be used. When glutaraldehyde is used, pH 4.5 to 5.5 is preferable, and 5 is more preferable.

  The alignment film is provided on the support or on 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. In general, it is carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are flocked 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. It can be produced by applying a coating solution prepared by dissolving the polymer for alignment film in a solvent to the support surface and drying and removing the solvent contained in the coating solution 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, preferably water, alcohols and a mixed solvent thereof. 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 given a liquid crystal alignment by rubbing the surface. 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) -3 Support The retardation plate of the present invention may have a support, and the support is preferably a transparent support. The support is not particularly limited as long as it is optically isotropic and has a light transmittance of 80% or more, but a polymer film is preferable. Specific examples of the polymer include cellulose esters (for example, cellulose diacetate, cellulose triacetate), norbornene-based polymers, poly (meth) acrylate esters, and the like, and many commercially available polymers are preferably used. Is possible. Among these, cellulose esters are preferable from the viewpoint of optical performance, and lower fatty acid esters of cellulose are more preferable. The lower fatty acid is a fatty acid having 6 or less carbon atoms, and preferably having 2, 3, or 4 carbon atoms. Specific examples include cellulose acetate, cellulose propionate, and cellulose butyrate. Among these, cellulose triacetate is particularly preferable. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used. Further, even a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence is used by reducing the expression by modifying the molecule described in International Publication WO00 / 26705. You can also.

Hereinafter, the cellulose ester preferably used as the support will be described in detail.
As the cellulose ester, it is preferable to use cellulose acetate having an acetylation degree of 55.0 to 62.5%. In particular, the acetylation degree is preferably 57.0 to 62.0%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). The viscosity average polymerization degree (DP) of the cellulose ester is preferably 250 or more, and more preferably 290 or more. The cellulose ester used in the present invention preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and further preferably 1.4 to 1.6. preferable.
In the cellulose ester, the hydroxyl groups at the 2nd, 3rd and 6th positions of cellulose are not evenly distributed 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. It is preferable that the hydroxyl group at the 6-position with respect to the total substitution degree is 30% to 40% and is substituted with an acyl group. The rate of substitution with an acyl group is preferably 31% or more, and more 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 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, A benzene ring and a 1,3,5-triazine ring are more preferable. More preferably, 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 particularly preferably 2 to 6. . The bonding relationship between two aromatic rings can be classified into (a) when forming a condensed ring, (b) when directly connecting with a single bond, and (c) when connecting 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-62-115035 There are descriptions in each publication. 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 by high-temperature air whose temperature is changed successively 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 material flakes such as halogenated hydrocarbons (dichloromethane, etc.), alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. Dissolve in the solvent. A typical solvent for dissolving cellulose acylate is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass).
A cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, hereinafter published Technical Report 2001- No. 1745).

  It is also possible to form a film by casting two or more layers of dope using the prepared cellulose acetate solution (dope). The dope is cast on a drum or band and the solvent is evaporated to form a film. The dope before casting is preferably adjusted in concentration so that the solid content is 10 to 40%. The surface of the drum or band is preferably finished in a mirror state. When casting a plurality of cellulose acetate solutions, a solution is prepared by casting a solution containing cellulose acetate from a plurality of casting openings provided at intervals in the traveling direction of the support, and laminating them. May be. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. Alternatively, the cellulose acetate solution may be cast from two casting ports to form a film. For example, 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. Also, a cellulose acetate film casting method in which a flow of a high-viscosity cellulose acetate solution is wrapped in 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 phthalate esters 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 most preferably 3 to 15% by mass.

Degradation inhibitors (for example, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose ester film. The deterioration preventing agents are described in JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854.
The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared, and more preferably 0.01 to 0.2% by mass. By making the addition amount 0.01% by mass or more, the effect of the deterioration preventing agent is hardly recognized. When the addition amount exceeds 1% by mass, bleed-out (bleeding) of the deterioration preventing agent to the film surface may be observed. 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.

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

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

  The retardation plate of the present invention can be used for an elliptically polarizing plate in combination with a polarizing film. Furthermore, it contributes to the expansion of the 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.

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

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

(5) Liquid crystal display device 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, U.S. Pat. Further, a retardation plate for liquid crystal cells in IPS mode or FDC mode is described in JP-A-10-54982. Further, 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 (OpticaDyDenHyDV) 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 D3-10 and D3-10]
Synthesized according to the following scheme.

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

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

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

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

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

(Synthesis Example 2)
[Synthesis Example of Polymer (AD-1)]
Polymer AD-1 was synthesized according to the following scheme.

(Synthesis of A-1 ′)
Hydroxybutyl acrylate (Tokyo Kasei) was methanesulfonylated in acetonitrile with methanesulfonyl chloride, then reacted with 4-hydroxybenzaldehyde (Wako Pure Chemical Industries) in N, N-dimethylacetamide, and 4- (4-acryloxy) Butoxy) phenylaldehyde was obtained. The obtained aldehyde was oxidized with sodium chlorate to obtain 4- (4-acryloxybutoxy) benzoic acid. Hexahydroxytriphenylene (Tokyo Chemicals) was obtained in N-methylpyrrolidone with pentyl bromide and sodium carbonate to obtain hexapentyloxytriphenylene, and then in methylene chloride with B-bromocatecholborane (Tokyo Chemicals). Monohydroxypentapentyloxytriphenylene was obtained by removing the pentyl group.
This benzoic acid and monohydroxypentapentyloxytriphenylene were condensed in tetrahydrofuran by a mixed acid anhydride method using methanesulfonyl chloride and triethylamine to obtain A-1 ′ in an overall yield of 35%.

(Synthesis of AD-1)
Methyl ethyl ketone (5 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A methyl ethyl ketone (20 ml) solution of A-1 ′ (12 g), B-3 ′ (manufactured by Daikin Industries, 8 g) and a polymerization initiator (V-65, 200 mg, manufactured by Wako Pure Chemical Industries, Ltd.) was taken for 3 hours. And dripped. After completion of dropping, the reaction was allowed to proceed for 3 hours at the same temperature. Thereafter, the reaction system was returned to room temperature, and then slowly poured into stirred hexane (500 mL), and the precipitated polymer was taken out by suction filtration and further dried. In this way, 12.8 g of the polymer (AD-1) of the present invention was obtained. The ratio of the obtained polymer was confirmed by ¹ H-NMR, and the molecular weight was confirmed by GPC.

(Synthesis Example 3)
[Synthesis Example of Polymer (AD-5)]
Polymer AD-5 was synthesized according to the following scheme.

(Synthesis of A-5 ′)
4- (4-acryloxybutoxy) benzoic acid was synthesized in the same manner as A-1 ′. Fine oxocol 2000 (manufactured by Nissan Chemical Co., Ltd., C10H21 (C8H17) CHCH2OH) was mesylated with methanesulfonyl chloride, reacted with 2-hydroxynaphthoic acid methyl ester, and further hydrolyzed to give 2- (3 -Octyl) dodecyloxynaphthoic acid was obtained. The obtained benzoic acid and naphthoic acid were condensed at a ratio of 1: 2 to pyrogallol (Tokyo Chemicals) by the mixed acid anhydride method using methanesulfonyl chloride and triethylamine, and A-5 was obtained by silica gel column chromatography. 'Was fractionated to obtain an overall yield of 25%.

(Synthesis of AD-5)
N-methylethylketone (5 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A solution of A-5 ′ (12 g), B-3 ′ (manufactured by Daikin Industries, 8 g) and a polymerization initiator (V-65, 200 mg, manufactured by Wako Pure Chemical Industries, Ltd.) over 3 hours was added over 3 hours. And dripped. After completion of dropping, the reaction was allowed to proceed for 3 hours at the same temperature. Thereafter, the reaction system was returned to room temperature, and then slowly poured into stirred hexane (500 mL), and the precipitated polymer was taken out by suction filtration and further dried. In this way, 11.5 g of the polymer (AD-5) of the present invention was obtained. The ratio of the obtained polymer was confirmed by ¹ H-NMR, and the molecular weight was confirmed by GPC.

(Synthesis Example 4)
[Synthesis Example of (AD-12)]
Polymer AD-12 was synthesized according to the following scheme.

N-methylpyrrolidone (5 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A-1 ′ (6 g), B-3 ′ (8 g), C-12 ′ (manufactured by NOF Corporation, Bunlemmer AP-400, 6 g), polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V- 65, 200 mg) of N-methylpyrrolidone (15 ml) was added dropwise over 3 hours. After completion of dropping, the reaction was allowed to proceed for 3 hours at the same temperature. Then, after returning the reaction system to room temperature, it was slowly poured into a stirred methanol-water mixed solution (800 mL), and the precipitated polymer was taken out by suction filtration and further dried. In this way, 10.2 g of the polymer (AD-12) of the present invention was obtained. The ratio of the obtained polymer was confirmed by ¹ H-NMR.

[Synthesis Example of Polymer (AD-17)]
Polymer AD-17 was synthesized according to the following scheme.

(Synthesis of A-22 ′)
Hydroxybutyl acrylate (Tokyo Kasei) was methanesulfonylated in acetonitrile with methanesulfonyl chloride, then reacted with 4-hydroxybenzaldehyde (Wako Pure Chemical Industries) in N, N-dimethylacetamide, and 4- (4-acryloxy) Butoxy) phenylaldehyde was obtained. The obtained aldehyde was oxidized with sodium chlorate to obtain 4- (4-acryloxybutoxy) benzoic acid. Further, hexahydroxytriphenylene (Tokyo Chemicals) was hexahydroxyethylated with ethylene carbonate in N, N-dimethylacetamide, and hexamethanesulfonyloxyethoxytriphenylene was obtained with methanesulfonyl chloride. Next, hexa (2- (perfluorohexyl) ethoxyethoxy) triphenylene was obtained with 2-perfluorohexyl) ethanol (manufactured by Daikin Industries, A-1620) and sodium carbonate, and then B-bromocatecholborane ( Monohydroxypenta (2- (perfluorohexyl) ethoxyethoxy) triphenylene was obtained by removing one 2- (perfluorohexyl) ethoxyethoxy group at Tokyo Chemicals.
This benzoic acid and monohydroxypenta (2- (perfluorohexyl) ethoxyethoxy) triphenylene are condensed by a mixed acid anhydride method using methanesulfonyl chloride and triethylamine in tetrahydrofuran to completely collect A-21 ′. Obtained at a rate of 25%.

(Synthesis of AD-17)
Methyl ethyl ketone (5 g) was placed in a 100 mL three-necked flask and heated to 78 ° C. while flowing nitrogen at a flow rate of 35 ml / min. A methyl ethyl ketone (10 ml) solution of A-21 ′ (10 g) and a polymerization initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd., 200 mg) was added dropwise over 3 hours. After completion of dropping, the reaction was allowed to proceed for 3 hours at the same temperature. Then, after returning the reaction system to room temperature, it was slowly poured into stirred hexane (300 mL), and the precipitated polymer was taken out by suction filtration and further dried. In this way, 7.5 g of the polymer (AD-17) of the present invention was obtained. The ratio of the obtained polymer was confirmed by ¹ H-NMR, and the molecular weight was confirmed by GPC.

[Example 1: Preparation of composition (LM-1) of the present invention]
Liquid crystal compound (D3-10), polymer of the present invention (AD-1), photopolymerization initiator Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.), and The composition (LM-1) of the present invention was prepared by weighing each diethyl thioxanthone as a sensitizer and dissolving it in methyl ethyl ketone.

Composition of composition (LM-1)-Liquid crystalline compound: D3-10 100 parts by mass-Polymer of the present invention: AD-1 0.4 part by mass-Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.) 3.0 Parts by mass, diethylthioxanthone 1.0 parts by mass, methyl ethyl ketone 250 parts by mass

[Example 2: Preparation of the composition of the present invention (LM-2 to LM-6)]
In Example 1, compositions (LM-2) to (LM-6) of the present invention were prepared in the same manner except that the polymer (AD-1) was changed to the polymers shown in Table 2 below, and the others were the same.
[Example 3: Preparation of the composition of the present invention (LM-7 to LM-8)]
In Example 1, the composition (LM-7) of this invention which added 0.5 mass part of following surfactant (W-1) was prepared. Further, in the composition (LM-7), the polymer (AD-1) was changed to (AD-12), and the composition (LM-8) of the present invention was prepared in the same manner.

Surfactant (W-1)

[Comparative Example 1: Preparation of comparative compositions (LH-1, LH-2)]
A comparative composition (LH-1) was prepared in the same manner as the composition (LM-1) of Example 1 except that the polymer (AD-1) was not added. Further, a comparative composition (LH-2) was prepared in the same manner as the composition (LM-7) of Example 3 except that the polymer (AD-1) was not added.

[Example 4: 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 ―――――――――――――――――――――― ――――――――――――――

Retardation increasing agent (1)

Retardation increasing agent (2)

  The obtained dope was cast from a casting port onto a drum cooled to 0 ° C. The film is peeled off at a solvent content of 70% by mass, both ends in the width direction of the film are fixed with a pin tenter, and the stretch rate in the width direction (direction perpendicular to the machine direction) is in a region where the solvent content is 3 to 5% by mass. Was dried while maintaining an interval of 3%. 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 support.

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

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

――――――――――――――――――――――――――――――――――――
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 ――――――――――――――― ――――――――――――――――――――

Anionic polymer

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

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

This solution was applied onto the second undercoat layer, 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)
The coating liquid of the composition (LM-1) of the present invention prepared in Example 1 was applied onto the rubbing treated surface of the alignment film prepared above using a wire bar. The film coated with the optically anisotropic layer was oriented in a constant temperature bath at 120 ° C., and irradiated with 200 mJ / cm ² of ultraviolet rays at the same temperature 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 5: Production of retardation plate (RM-2 to RM-8) of the present invention]
In Example 4, except that the composition (LM-1) was changed to the compositions (LM-2) to (LM-8), the retardation plates (RM-2) to (RM-) were changed in the same manner. 8) was produced.

[Comparative Example 2: Production of comparative retardation plate (RH-1, RH-2)]
In Example 4, except that the composition (LM-1) was changed to the compositions (LH-1) and (LH-2), the same was made in the same manner, and a retardation plate (RH-1) for comparison and (RH-2) was produced.

[Example 6: 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 a wavelength λ, respectively. Re (589 nm) of the retardation plates obtained in Examples 4 and 5 and Comparative Example 2 was measured by making light having a wavelength of 589 nm incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth (589 nm) is light having a wavelength of λ nm from the direction inclined by + 40 ° with respect to the film normal direction, with Re (589 nm) and the in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). And a retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the normal direction of the film with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH was calculated based on the retardation values measured in a total of three directions.

(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 angle 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 4 and 5 and Comparative Example 2 was prepared using a microtome, and the section was observed with a polarizing microscope. In the retardation plates RM-1 to RM-8 of the present invention and the optically anisotropic layers of RH-1 and RH-2 of Comparative Example 2, it was confirmed that the liquid crystal molecules were hybrid aligned.

(Temperature dependence of average tilt angle)
In the formation of the optically anisotropic layer, after the temperature was lowered to 100 ° C. after the orientation, a retardation plate was prepared in the same manner except that the orientation state was cured by ultraviolet rays, and then the average tilt angle was measured. The difference in average tilt angle when the orientation is fixed at 100 ° C. is shown in Table 3 below as the average tilt angle temperature dependency.

From the results of Table 3, the retardation plates (RM-1) to (RM-8) of the present invention have an average tilt angle as compared with the retardation plates (RH-1) and (RH-2) of the comparative examples. And the temperature dependency of the average tilt angle was confirmed to be small.
From these results, by using the composition containing the polymer of the present invention, it is possible to hybridally align the discotic liquid crystal with little or no temperature dependence of the tilt angle; and in the production process It is confirmed that a retardation plate can be obtained without causing fluctuations in performance due to fluctuations in temperature (particularly the polymerization temperature for forming an optically anisotropic layer) (or reducing fluctuations in performance). It was.

Claims (13)

A polymer comprising a structural unit having at least one substituent containing a fluorine atom and a structural unit represented by the following general formula (A):
Formula (A)

In general formula (A), Mp represents a trivalent group, L represents a single bond or a divalent linking group, and X represents a discotic substituent. A polymer having at least one substituent containing a fluorine atom and containing at least one structural unit represented by the following general formula (A):
Formula (A)

In general formula (A), Mp represents a trivalent group, L represents a single bond or a divalent linking group, and X represents a discotic substituent. The polymer of Claim 1 or 2 which has at least 1 type of substituent containing a fluorine atom in a side chain. The polymer according to claim 1, wherein the structural unit having at least one substituent containing a fluorine atom is represented by the following general formula (B):
General formula (B)

In general formula (B), Mp ′ represents a trivalent group, L ′ represents a single bond or a divalent linking group, and Rf represents a substituent containing at least one fluorine atom. The polymer according to any one of claims 1 to 4, wherein in the structural unit represented by the general formula (A), X is a triphenylene group. The polymer according to any one of claims 1 to 5, which is a polymer exhibiting liquid crystallinity. The polymer according to claim 1, which is a block copolymer. The composition containing at least 1 type of liquid crystalline compound and at least 1 type of the polymer of any one of Claims 1-7. The composition according to claim 8, wherein the viscosity of the at least one liquid crystalline compound is 500 to 1000 mPas at 80 to 150 ° C. The composition according to claim 8 or 9, wherein the at least one liquid crystalline compound is a 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 represent a single bond or a divalent linking group. H ¹ , H ² and H ³ are each independently a group represented by the following general formula (DI-A) or the following general formula (DI-B); R ¹ , R ² and R ³ are each independently And a group represented by the following general formula (DI-R);

In 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; * represents any ^one of L ^{1 to} L ³ Represents a bonding position; ** represents a bonding position with any of 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; * represents any ^one of L ^{1 to} L ³ Represents a bonding position, and ** represents a bonding position with any of R ^{1 to} R ³ ;
General formula (DI-R)
*-(-L ²¹ -F ¹ ) _n1 -L ²² -L ²³ -Q ¹
In general formula (DI-R), * represents a position bonded to H ¹ , H ² or H ³ in general formula (DI); F ¹ represents a divalent linking group having at least one kind of cyclic structure. It represents; L ²¹ represents a single bond or a divalent linking group; n1 represents an integer of 0 to 4; L ²² is -O -, - O-CO - , - CO-O -, - O-CO- O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—, or —C≡C—; L ²³ represents —O—, —S—, —C ( ═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C≡C— and a divalent group formed by linking two or more thereof. Of these groups, a group containing a hydrogen atom may be replaced by a substituent; Q ¹ represents a polymerizable group or a hydrogen atom. The at least one liquid crystalline compound is a liquid crystalline compound represented by the following general formula (DII) or a liquid crystalline compound represented by the following general formula (DIII). Composition of:

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 each independently represent the following general formula (DII-R) A group to be
General formula (DII-R)

In the general formula (DII-R), A ³¹ and A ³² each independently represent a methine or nitrogen atom; X ³ represents an oxygen atom, a sulfur atom, methylene or imino; F ² has a 6-membered cyclic structure N3 represents an integer of 1 to 3; L ³¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, a divalent cyclic linking group; —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—, or —C≡C—; L ³² represents —O—, —S—, —C (═O) —, —SO _2- , -NH-, -CH _2- , -CH = CH- and -C≡C- and a divalent linking group selected from a group formed by linking two or more thereof, When the group of is a group containing a hydrogen atom, the hydrogen atom may be substituted with a substituent; Q ³ represents a polymerizable group or a hydrogen atom;

In the general formula (DIII), Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represent a methine or nitrogen atom; R ⁴¹ , R ⁴² and R ⁴³ each independently represent the following general formula (DIII-A), A group represented by the general formula (DIII-B) or the following general formula (DIII-C);

In the general formula (DIII-A), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ each independently represents a methine or nitrogen atom; X ⁴¹ represents an oxygen atom, a sulfur atom, methylene or L ⁴¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, — CH═CH— or —C≡C—; L ⁴² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from CH- and -C≡C- and a group formed by linking two or more thereof, and when these groups are groups containing a hydrogen atom, The atom may be 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 and A ⁵⁶ each independently represents a methine or nitrogen atom, and X ⁵² represents an oxygen atom, a sulfur atom, methylene or an imino; L ⁵¹ is -O -, - O-CO - , - CO-O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, - CH = CH— or —C≡C—; L ⁵² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from CH- and -C≡C- and a group formed by linking two or more thereof, and when these groups are groups containing a hydrogen atom, The atom may be 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 and A ⁶⁶ each independently represents a methine or nitrogen atom; X ⁶³ represents an oxygen atom, a sulfur atom, methine or an imino; L ⁶¹ is -O -, - O-CO - , - CO-O -, - O-CO-O -, - S -, - NH -, - SO 2 -, - CH 2 -, - CH═CH— or —C≡C—; L ⁶² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from CH- and -C≡C- and a group formed by linking two or more thereof, and when these groups are groups containing a hydrogen atom, The atom may be replaced by a substituent; Q ⁶ represents a polymerizable group or a hydrogen atom. A phase difference plate having an optically anisotropic layer made of the composition according to claim 8. A liquid crystal display device comprising the retardation plate according to claim 12.