JP2007065078A - Composition, retardation plate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition and the like useful for stably preparing an optical anisotropic layer in which defects or the like caused by an alignment defect are eliminated or reduced. <P>SOLUTION: The composition contains a liquid crystalline compound and a compound represented by general formula (A). In general formula (A), R<SP>1A</SP>represents a substituent including a hetero-substituent, R<SP>2A</SP>represents a substituent including a hydrogen aliphatic hydrocarbon group, an aryl group or a hetero-substituent, R<SP>3A</SP>and R<SP>4A</SP>represent hydrogen, an aliphatic hydrocarbon group, an aryl group, a hetero-cyclic group, -OR<SP>31A</SP>, -NR<SP>32A</SP>R<SP>33A</SP>or -C(=X)R<SP>34A</SP>, R<SP>31A</SP>, R<SP>32A</SP>, R<SP>33A</SP>and R<SP>34A</SP>represent hydrogen, an aliphatic hydrocarbon group, an aryl group or the like and X represents oxygen or the like. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

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

  On the other hand, a trisubstituted benzene compound having a heterocyclic group has been reported (Non-patent Document 1). However, it is not easy to achieve low wavelength dispersion by using this compound, and the value of smaller wavelength dispersion (Re (short wavelength (eg, 450 nm)) / Re (long wavelength (eg, 650 nm)). Is desired).

  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, 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 crystalline compound having 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 liquid crystal compound to a desired angle has been desired.

  In addition, when the liquid crystalline composition is applied on the alignment film, the wettability of the liquid crystalline composition is poor, and it may become a problem that it remains as a defect after repelling. In the case of a type of discotic liquid crystal compound, it is a problem often seen and improvement has been desired.

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

  An object of the present invention is to provide a composition (particularly a liquid crystalline composition) useful for stably producing an optically anisotropic layer that contributes to optical compensation of a liquid crystal display device, for example. Furthermore, an optically anisotropic layer exhibiting optical anisotropy expressed by hybrid orientation of a discotic liquid crystalline compound (for example, discotic liquid crystalline molecules) can be formed without defects due to poor alignment or repelling (or defects). It is an object to provide a composition that is useful to make (reduced). Another object of the present invention is to provide a retardation plate useful for optical compensation of a liquid crystal display device.

（一般式（Ａ）中、Ｒ^1Aは、ヘテロ原子を含む置換基を表し、Ｒ^2Aは、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基またはヘテロ原子を含む置換基を表し、Ｒ^3AおよびＲ^4Aは、それぞれ、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロ環基、−ＯＲ^31A、−ＮＲ^32AＲ^33Aまたは−Ｃ（＝Ｘ）Ｒ^34Aを表し、Ｒ^31A、Ｒ^32AおよびＲ^33Aは、それぞれ、水素原子、置換もしくは無置換の脂肪族炭化水素基または置換もしくは無置換のアリール基を表し、Ｒ^34Aは水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基または−ＮＲ^35AＲ^36Aを表し、Ｘは酸素原子、硫黄原子またはＮＲ^37Aを表し、Ｒ^35A、Ｒ^36AおよびＲ^37Aは、それぞれ、水素原子、置換もしくは無置換の脂肪族炭化水素基または置換もしくは無置換のアリール基を表す。）
（２）前記一般式（Ａ）において、Ｒ^1Aが−ＯＲ^11A、−ＮＲ^12AＲ^13Aまたは−ＳＲ^14Aを表し、Ｒ^11A、Ｒ^12A、Ｒ^13AおよびＲ^14Aが、それぞれ、水素原子、置換もしくは無置換の脂肪族炭化水素基または置換もしくは無置換のアリール基を表す、（１）に記載の組成物。
（３）前記一般式（Ａ）において、Ｒ^2Aが水素原子である、（１）または（２）に記載の組成物。
（４）前記液晶性化合物が、下記一般式（ＤＩ）で表される、（１）〜（３）のいずれか１項に記載の組成物。
一般式（ＤＩ）

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

（一般式（ＤＩ−Ａ）中、Ｙ^A1およびＹ^A2は、それぞれ、メチンまたは窒素原子を表す。Ｘ^Aは酸素原子、硫黄原子、メチレンまたはイミノを表す。＊はＬ¹〜Ｌ³と結合する位置を表し、＊＊はＲ¹〜Ｒ³と結合する位置を表す。）
一般式（ＤＩ−Ｂ）

（一般式（ＤＩ−Ｂ）中、Ｙ^A1およびＹ^A2は、それぞれ、メチンまたは窒素原子 を表す。Ｘ^Aは、酸素原子、硫黄原子、メチレンまたはイミノを表す。＊はＬ¹ 〜Ｌ³と結合する位置を表し、＊＊はＲ¹〜Ｒ³と結合する位置を表す。）
一般式（ＤＩ−Ｒ）
＊−（−Ｌ¹¹−Ｆ¹）_n1−Ｌ¹²−Ｌ¹³−Ｑ¹
（一般式（ＤＩ−Ｒ）中、＊はＨ¹〜Ｈ³と結合する位置を表す。Ｌ¹¹は単結合または二価の連結基を表す。Ｆ¹は、少なくとも１種類の環状構造を有する二価の環状連結基を表す。ｎ１は０〜４整数を表す。Ｌ¹²は、＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−ＮＨ−、＊−ＳＯ₂−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−、＊−Ｃ≡Ｃ−を表し（＊はＬ¹³と反対側に結合する位置を表す。）、Ｌ¹³は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、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換されていてもよい。Ｑ¹は重合性基または水素原子を表す。））
（５）前記一般式（ＤＩ）で表される液晶性化合物が、下記一般式（ＤＩＩ）で表される液晶性化合物である、（４）に記載の組成物。
一般式（ＤＩＩ）

（一般式(ＤＩＩ)中、Ｙ¹¹、Ｙ¹²およびＹ¹³は、それぞれ、メチンまたは窒素原子を表す。Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ、下記一般式（ＤＩＩ−Ｒ）で表される。
一般式（ＤＩＩ−Ｒ）

（一般式（ＤＩＩ−Ｒ）中、Ｙ^A1およびＹ^A2は、それぞれ、メチンまたは窒素原子を表す。Ｘ^Aは酸素原子、硫黄原子、メチレンまたはイミノを表す。Ｆ¹は、少なくとも１種類の環状構造を有する二価の環状連結基を表す。ｎ２は、１〜３の整数を表す。Ｌ¹²は、＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−ＮＨ−、＊−ＳＯ₂−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−または＊−Ｃ≡Ｃ−を表し（＊はＬ¹³と反対側に結合する位置を表す。）、Ｌ¹³は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、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換されていてもよい。Ｑ¹は重合性基または水素原子を表す。））
（６）支持体上に、配向膜と、（１）〜（５）のいずれか１項に記載の組成物から形成されてなる光学異方性層とを有する位相差板。
（７）前記配向膜が、ポリビニルアルコール類を含む、（６）に記載の位相差板。
（８）前記光学異方性層がハイブリッド配向したディスコティック液晶性化合物を含む、（６）または７に記載の位相差板。
（９）（６）〜（８）のいずれか１項に記載の位相差板と、偏光膜とを有する、楕円偏光板。
（１０）（６）〜（８）のいずれか１項に記載の位相差板を有する液晶表示装置。 Means for solving the above problems are as follows.
(1) A composition containing at least one liquid crystal compound and at least one compound represented by the following general formula (A).
Formula (A)

(In the general formula (A), R ^1A represents a substituent containing a hetero atom, and R ^2A represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group or a hetero atom. R ^3A and R ^4A each represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, —OR ^31A , —NR ^32A R ^33A or —C ( ^═X ) R ^34A , wherein R ^31A , R ^32A and R ^33A are each a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aryl group. R ^34A represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group or —NR ^35A R ^36A , X represents an oxygen atom, a sulfur atom or NR ^37A , R ^35A , R ^{3 6A} and R ^37A each represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aryl group.
(2) In the general formula (A), R ^1A represents —OR ^11A , —NR ^12A R ^13A or —SR ^14A , and R ^11A , R ^12A , R ^13A and R ^14A are each a hydrogen atom, The composition according to (1), which represents an unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aryl group.
(3) The composition according to (1) or (2), wherein, in the general formula (A), R ^2A is a hydrogen atom.
(4) The composition according to any one of (1) to (3), wherein the liquid crystal compound is represented by the following general formula (DI).
General formula (DI)

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

(In the general formula (DI-A), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene or imino. * Represents a bond to L ^{1 to} L ³ . ** represents a position where R ^{1 to} R ³ are bonded.)
General formula (DI-B)

(In General Formula (DI-B), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene or imino, and * represents L ^{1 to} L ³ . (The bond position is represented, and ** represents the bond position with R ^{1 to} R ^3. )
General formula (DI-R)
*-(-L ¹¹ -F ¹ ) _n1 -L ¹² -L ¹³ -Q ¹
(In the general formula (DI-R), * represents a position bonded to H ^{1 to} H ^3. L ¹¹ represents a single bond or a divalent linking group. F ¹ has at least one kind of cyclic structure. Represents a divalent cyclic linking group, n1 represents an integer of 0 to 4. L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —NH—, * —SO ₂ —, * —CH ₂ —, * —CH═CH—, * —C≡C— (* represents the position on the opposite side of L ¹³⁾ L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C— and When the divalent linking group selected from the group consisting of these combinations is a group containing a hydrogen atom, the hydrogen atom may be substituted with a substituent, and Q ¹ is polymerizable. Group or hydrogen atom Represent.))
(5) The composition according to (4), wherein the liquid crystalline compound represented by the general formula (DI) is a liquid crystalline compound represented by the following general formula (DII).
Formula (DII)

(In general formula (DII), Y ¹¹ , Y ¹² and Y ¹³ each represent a methine or nitrogen atom. R ²¹ , R ²² and R ²³ are each represented by the following general formula (DII-R). The
General formula (DII-R)

(In General Formula (DII-R), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene or imino, and F ¹ represents at least one kind of cyclic group. Represents a divalent cyclic linking group having a structure, n2 represents an integer of 1 to 3. L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—. CO—O—, * —S—, * —NH—, * —SO ₂ —, * —CH ₂ —, * —CH═CH— or * —C≡C— (* is opposite to L ¹³⁾ L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —. C≡C— represents a divalent linking group selected from the group consisting of a combination thereof, and when these groups are groups containing a hydrogen atom, the hydrogen atom is substituted with a substituent. Q ¹ represents a polymerizable group or a hydrogen atom.))
(6) A retardation plate having an alignment film and an optically anisotropic layer formed from the composition according to any one of (1) to (5) on a support.
(7) The retardation plate according to (6), wherein the alignment film contains polyvinyl alcohols.
(8) The retardation plate according to (6) or 7, wherein the optically anisotropic layer contains a discotic liquid crystal compound in which hybrid alignment is performed.
(9) An elliptically polarizing plate having the retardation plate according to any one of (6) to (8) and a polarizing film.
(10) A liquid crystal display device having the retardation plate according to any one of (6) to (8).

  ADVANTAGE OF THE INVENTION According to this invention, the 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, an optically anisotropic layer exhibiting optical anisotropy expressed by hybrid orientation of a discotic liquid crystalline compound is produced without (or reduced) defects caused by orientation failure or repellency. A useful composition can be provided. Moreover, according to the present invention, a retardation plate useful for optical compensation of a liquid crystal display device can be provided.

  Hereinafter, the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

First, details of Re (λ), Rth (λ), tilt angle, and average tilt angle in this specification will be described below.
In this specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRYA1ADH (manufactured by Oji Scientific Instruments). Rth (λ) is Re (λ), and light having a wavelength of λ nm from the direction inclined by + 40 ° with respect to the film normal direction with the in-plane slow axis (determined by KOBRYA1ADH) as the tilt axis (rotation axis). Retardation value measured by making it incident, and retardation measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis) KOBRYA1ADH is calculated based on the retardation value measured in three directions in total, the assumed value of the average refractive index, and the input film thickness value. Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59).

Further, 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 (orientation film surface in the retardation plate of the present invention). The tilt angle θ1 is the angle between the physical target axis of the discotic liquid crystal compound molecule in the optical anisotropy and the angle between the other surface (the air interface in the retardation plate of the present invention) is tilted The angle θ2 is defined as 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 liquid crystalline compound or a rod-like liquid crystalline compound. Further, it is assumed that the minimum unit layer (the tilt angle of the discotic liquid crystal compound or the rod-like liquid crystal compound is uniform in the layer) constituting it is optically uniaxial.
2. It is assumed that the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer.
The specific calculation method is as follows.
(1) In a plane in which the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer, the incident angle of the measurement light to the optically anisotropic layer is changed, and three or more The retardation value is measured at the measurement angle. In order to simplify measurement and calculation, it is preferable to measure the retardation value at three measurement angles of −40 °, 0 °, and + 40 °, with the normal direction to the optically anisotropic layer being 0 °. Such measurements include KOBRYA1ADH and KOBRA-WR (manufactured by Oji Scientific Instruments), transmission-type ellipsometer AEP-100 (manufactured by Shimadzu Corporation), M150 and M520 (manufactured by JASCO Corporation), ABR10A (manufactured by UNIOPT Co., Ltd.) can be used.
(2) In the above model, the refractive index of ordinary light in each layer is no, the refractive index of extraordinary light is ne (ne is the same value in all layers, and no is the same), and the thickness of the entire multilayer body is d. And Further, based on the assumption that the tilt direction of each layer and the uniaxial optical axis direction of the layer coincide with each other, the calculation of the angular dependence of the retardation value of the optically anisotropic layer agrees with the measured value. Fitting is performed using the tilt angle θ1 on one surface of the isotropic layer and the tilt angle θ2 on the other surface as variables, and θ1 and θ2 are calculated.
Here, known values such as literature values and catalog values can be used for no and ne. If the value is unknown, it can also be measured using an Abbe refractometer. The thickness of the optically anisotropic layer can be measured by an optical interference film thickness meter, a cross-sectional photograph of a scanning electron microscope, or the like.

The retardation plate of the present invention has an optically anisotropic layer composed of a composition containing a compound represented by the general formula (A) of the present invention and a liquid crystal compound, which will be described in detail below. In particular, as the liquid crystalline compound contained in the composition of the present invention, a discotic liquid crystalline compound is preferable, and as the discotic liquid crystalline compound, a compound represented by the general formula (DI) shown in detail below is more preferable. Moreover, it is preferable that additives, such as a polymerization initiator and an orientation control agent, are contained in the composition used for the phase difference plate of the present invention in addition to the above compounds. Further, the retardation plate of the present invention preferably has a form in which an optically anisotropic layer is formed on an alignment film provided on a support.
Hereinafter, the compound represented by the general formula (A), the liquid crystal compound, and other suitably used additives contained in the composition used for the retardation plate of the present invention will be sequentially described. Further, an alignment film and a support preferably used for the retardation plate of the present invention will be described in order.

1. Composition (1) Compound represented by general formula (A)

（一般式（Ａ）中、Ｒ^1Aは、ヘテロ原子を含む置換基を表し、Ｒ^2Aは、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基またはヘテロ原子を含む置換基を表し、Ｒ^3AおよびＲ^4Aは、それぞれ、水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロ環基、−ＯＲ^31A、−ＮＲ^32AＲ^33Aまたは−Ｃ（＝Ｘ）Ｒ^34Aを表し、Ｒ^31A、Ｒ^32AおよびＲ^33Aは、それぞれ、水素原子、置換もしくは無置換の脂肪族炭化水素基または置換もしくは無置換のアリール基を表し、Ｒ^34Aは水素原子、置換もしくは無置換の脂肪族炭化水素基、置換もしくは無置換のアリール基または−ＮＲ^35AＲ^36Aを表し、Ｘは酸素原子、硫黄原子またはＮＲ^37Aを表し、Ｒ^35A、Ｒ^36AおよびＲ^37Aは、それぞれ、水素原子、置換もしくは無置換の脂肪族炭化水素基または置換もしくは無置換のアリール基を表す。） Formula (A)

(In the general formula (A), R ^1A represents a substituent containing a hetero atom, and R ^2A represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group or a hetero atom. R ^3A and R ^4A each represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, —OR ^31A , —NR ^32A R ^33A or —C ( ^═X ) R ^34A , wherein R ^31A , R ^32A and R ^33A are each a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aryl group. R ^34A represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group or —NR ^35A R ^36A , X represents an oxygen atom, a sulfur atom or NR ^37A , R ^35A , R ^{3 6A} and R ^37A each represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aryl group.

In general formula (A), R ^1A preferably represents —OR ^11A , —NR ^12A R ^13A , or —SR ^14A , more preferably —OR ^11A or —NR ^12A R ^13A , and more preferably Represents —OR ^11A .
R ^11A , R ^12A , R ^13A and R ^14A each represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aryl group.
Examples of the aliphatic hydrocarbon group represented by R ^11A , R ^12A , R ^13A and R ^14A include a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group) Tert-butyl group, hydroxyethyl group, cyclohexyl group, etc.), C 3-30 aralkyl groups (eg, allyl group, benzyl group, etc.) and the like.
Examples of the aryl group represented by R ^11A , R ^12A , R ^13A and R ^14A include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms (for example, unsubstituted phenyl group, tolyl group, naphthyl group, etc.). Can be mentioned.
R ^11A , R ^12A , R ^13A and R ^14A are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, most preferably Is a methyl group.

In the general formula (A), the aliphatic hydrocarbon group represented by R ^2A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert group, -Butyl group, hydroxyethyl group, cyclohexyl group, etc.), C3-C30 aralkyl groups (e.g., allyl group, benzyl group, etc.) and the like. As the aryl group, substituted or unsubstituted C6-C30 Examples include substituted aryl groups (for example, unsubstituted phenyl group, tolyl group, naphthyl group, etc.). The substituent containing a hetero atom represented by R ^2A is the same as R ^1A , and the preferred range is also the same.
R ^2A is preferably a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted aryl group, more preferably a hydrogen atom.

In the general formula (A), the aliphatic hydrocarbon groups represented by R ^3A and R ^4A are each a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (for example, methyl group, ethyl group, propyl group). Isopropyl group, tert-butyl group, hydroxyethyl group, cyclohexyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, etc.), aralkyl groups having 3 to 30 carbon atoms (for example, allyl group, benzyl group, etc.) Can be mentioned.
Examples of the aryl group represented by R ^3A and R ^4A include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms (eg, unsubstituted phenyl group, tolyl group, naphthyl group, etc.).
Examples of the heterocyclic group represented by R ^3A and R ^4A include a substituted or unsubstituted heterocyclic group having 1 to 30 carbon atoms (for example, a pyridine ring group, an imidazole ring group, a pyrimidine ring group, a pyrazine ring group, Triazine ring group, morpholine ring group, etc.).
The substituted or unsubstituted aliphatic hydrocarbon group represented by R ^31A , R ^32A , R ^33A R ^35A , R ^36A and R ^37A and the substituted or unsubstituted aryl group are the same as the above R ^11A , R ^12A , R It is synonymous with ^13A and ^R14A , and its preferable range is also synonymous.

R ^3A and R ^4A may be linked to form a ring. In this case, it is preferably a heterocyclic group, more preferably a heterocyclic ring containing at least one nitrogen atom. The heterocyclic group includes a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrrole ring, morpholine ring, piperidine ring, triazole ring, oxadiazole ring, thiadiazole ring, thiazolidine ring, or imidazolidine ring. (For example, 2-oxaimidazolidine) etc. are mentioned, Preferably it is an imidazolidine ring.

R ^3A is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom, a hydroxymethyl group, or a methoxymethyl group.
R ^4A is preferably an aryl group having 6 to 15 carbon atoms, a heterocyclic group, or —C ( ^═X ) R ^34A , more preferably a heterocyclic group or —C (═O) NR. ^35A R ^36A , and most preferably a heterocyclic group (for example, a triazine ring).

The compound represented by the general formula (A) of the present invention is preferably the following general formula (A1), general formula (A2), or general formula (A3).

General formula (A1)

In general formula (A1), R ^11A has the same meaning as R ^1A in general formula (A), and Q represents a heterocycle formed by linking R ^3A and R ^{4A in} general formula (A).
R ^11A is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
The heterocyclic ring containing Q is a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrrole ring, morpholine ring, piperidine ring, triazole ring, oxadiazole ring, thiadiazole ring, thiazolidine ring, or imidazolidine. A ring (for example, 2-oxaimidazolidine) is preferable, and an imidazolidine ring is more preferable.

General formula (A2)

In formula (A2), R ^11A has the same meaning as R ^1A in the general formula (A), R ^3A and R ^35A are Zorezore, is R ^3A same meaning as in formula (A) .
R ^11A is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
R ^3A and R ^35A are preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and R ^3A and R ^35A are linked to each other to contain a ureido group (for example, 2-oxaimidazo It is also preferable to form a lysine ring or the like.

一般式（Ａ３）中、Ｒ^11Aは、一般式（Ａ）中のＲ^1Aと同義であり、Ｒ^3Aは、一般式（Ａ）中のＲ^3Aと同義である。Ｒ^41Aはヘテロ環基である。
Ｒ^11Aは、好ましくは、水素原子またはメチル基であり、より好ましくはメチル基である。
Ｒ^3Aは、好ましくは、水素原子または炭素数１〜１０の置換もしくは無置換のアルキル基であり、より好ましくは、水素原子、アルキルオキシメチル基またはヒドロキシメチル基であり、さらに好ましくはメトキシメチル基である。
Ｒ^41Aは、トリアジン環基またはピリミジン環基が好ましく、トリアジン環基がより好ましい。 General formula (A3)

In formula (A3), R ^11A has the same meaning as R ^1A in the general formula (A), R ^3A has the same meaning as R ^3A in the general formula (A). R ^41A is a heterocyclic group.
R ^11A is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
R ^3A is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyloxymethyl group or a hydroxymethyl group, still more preferably a methoxymethyl group. It is.
R ^41A is preferably a triazine ring group or a pyrimidine ring group, and more preferably a triazine ring group.

  A preferable addition amount range of the compound represented by the general formula (A) contained in the composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0 to the liquid crystalline compound. It is 1-30 mass%, More preferably, it is 1-20 mass%.

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

  The compound represented by the general formula (A) of the present invention is easily available or can be easily produced by applying a known method. More specifically, it can be synthesized by reacting an aldehyde compound such as formalin with a urea or nitrogen-containing heterocyclic compound in a solvent such as alcohol.

(2) Liquid crystalline compound The liquid crystalline compound used in the present invention is preferably a rod-like liquid crystalline compound or a discotic liquid crystalline compound, and more preferably a discotic liquid crystalline compound. The liquid crystalline compound is preferably substantially uniformly aligned, more preferably fixed in a substantially uniformly aligned state, and the liquid crystalline compound is fixed by a polymerization reaction. Is more preferable.

As the rod-like liquid crystal compound, a polymerizable rod-like liquid crystal compound substituted with a polymerizable group is preferable, and examples of the polymerizable rod-like liquid crystal compound include those described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. Nos. 4,683,327, 5,622,648, 5,770,107, International Publications WO95 / 22586, 95/24455, Nos. 97/00600, 98/23580, 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and JP-A-11-80081. The compounds described in JP 2001-328773 A can be used.

  Although the example of a rod-shaped liquid crystalline compound is shown below, this invention is not limited to these.

As the discotic liquid crystalline compound, various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by the Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J Am. Chem. Soc., VoL116, page 2655 (1994)) can be widely adopted. The polymerization of the discotic liquid crystalline compound is described in, for example, JP-A-8-27284. In order to fix the discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline compound. However, when the polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, a compound in which a linking group is introduced between the discotic core and the polymerizable group is preferable.

  The discotic liquid crystalline compound used in the present invention is preferably a triphenylene compound substituted with at least one polymerizable group as described in JP-A-8-27284, or represented by the following general formula (DI). Are preferred. The compounds represented by the general formula (DI) are described in detail below.

[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.

General formula (DI)

In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each represent methine or a nitrogen atom. When Y ¹¹ , Y ¹² and Y ¹³ are each methine, the methine may have a substituent (hereinafter the same). Examples of the substituent that methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, and a halogen atom. Mention may be made of atoms and cyano groups. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom, and a cyano group are more preferable. The alkyl group has 1 to 12 carbon atoms, the alkoxy group has 1 to 12 carbon atoms, and the carbon number is A 2-12 alkoxycarbonyl group, carbon number 2-12 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 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, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and preferably a methyl group, an ethyl group or a hydrogen atom. More preferably, it is a hydrogen atom.

The divalent cyclic group 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 most preferably a 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring 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.
Among the divalent cyclic groups, 1,4-phenylene is preferable as the cyclic group having a benzene ring. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.
The divalent cyclic group 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 Halogen-substituted alkyl group having 1 to 16 atoms, alkoxy group having 1 to 16 carbon atoms, acyl group having 2 to 16 carbon atoms, alkylthio group having 1 to 16 carbon atoms, and 2 carbon atoms An acyloxy group having ˜16, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms.

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

Each in the formula, H ^1, H ² and H ³ denote the following general formula (DI-A) or the following general formula (DI-B).

General formula (DI-A)

In general formula (DI-A), Y ^A1 and Y ^A2 each represent a methine group or a nitrogen atom. At least one of Y ^A1 and Y ^A2 is preferably a nitrogen atom, and more preferably both are nitrogen atoms. X ^A represents an oxygen atom, a sulfur atom, methylene or imino. X ^A is preferably an oxygen atom. * Represents a position where L ^{1 to} L ³ are bonded, and ** represents a position where R ^{1 to} R ³ are bonded.

（一般式（ＤＩ−Ｂ）中、Ｙ^A1およびＹ^A2は、それぞれ、メチンまたは窒素原子を表す。Ｘ^Aは、酸素原子、硫黄原子、メチレンまたはイミノを表す。＊はＬ¹〜Ｌ³と結合する位置を表し、＊＊はＲ¹〜Ｒ³と結合する位置を表す。） General formula (DI-B)

(In General Formula (DI-B), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene, or imino. * Represents L ^{1 to} L ³ . (The bond position is represented, and ** represents the bond position with R ^{1 to} R ^3. )

In the general formula (DI-B), Y ^A1 , Y ^A2 and X ^A are the same as those in the general formula (DI-A), respectively, and the preferred range is also the same.

R ¹ , R ² and R ³ each represent the following general formula (DI-R).
General formula (DI-R)
*-(-L ¹¹ -F ¹ ) _n1 -L ¹² -L ¹³ -Q ¹
(In the general formula (DI-R), * represents a position bonded to H ^{1 to} H ^3. L ¹¹ represents a single bond or a divalent linking group. F ¹ has at least one kind of cyclic structure. Represents a divalent cyclic linking group, n1 represents an integer of 0 to 4. L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —NH—, * —SO ₂ —, * —CH ₂ —, * —CH═CH—, * —C≡C— (* represents the position on the opposite side of L ¹³⁾ L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C— and When the divalent linking group selected from the group consisting of these combinations is a group containing a hydrogen atom, the hydrogen atom may be substituted with a substituent, and Q ¹ is polymerizable. Group or hydrogen atom Represent.)

When L ¹¹ is a divalent linking group, it consists of —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C≡C—, and combinations thereof. A divalent linking group selected from the group is preferred. R ⁷ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and preferably a methyl group, an ethyl group or a hydrogen atom. More preferably, it is a hydrogen atom.

L ¹¹ is a single bond, ** — O—CO—, ** — CO—O—, ** — CH═CH— or ** — C≡C— (where ** is on the opposite side of F ¹ ) Represents the bonding position). 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 divalent cyclic linking group preferably has a 5-membered ring, 6-membered ring, or 7-membered ring structure, more preferably has a 5-membered ring or 6-membered ring structure, and further has a 6-membered ring structure. More preferred. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

Among the divalent cyclic linking groups represented by F ¹ , 1,4-phenylene is preferable as the cyclic linking group having a benzene ring. Examples of the cyclic linking group having a naphthalene ring include naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-2,5-diyl, naphthalene-2,6-diylnaphthalene. -2,7-diyl is preferred. The cyclic linking group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic linking group having a pyridine ring, pyridine-2,5-diyl is preferred. The cyclic linking group having a pyrimidine ring is preferably pyrimidine-2,5-diyl. As the divalent cyclic linking group, 1,4-phenylene, naphthalene-2,6-diyl and 1,4-cyclohexylene are particularly preferable.

The divalent cyclic linking group represented by 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, and alkenyl group having 2 to 16 carbon atoms. , An alkynyl group having 2 to 16 carbon atoms, a halogen-substituted alkyl group 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 the number of carbon atoms Is an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and the number of carbon atoms Includes from 2 to 16 acylamino groups. The substituent of the divalent cyclic group is preferably a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or a halogen-substituted alkyl group having 1 to 6 carbon atoms, and further, a halogen atom or a carbon atom An alkyl group having 1 to 4 carbon atoms and a halogen-substituted alkyl group having 1 to 4 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are particularly preferable.

n1 represents an integer of 0 to 4. As n1, the integer of 1-3 is preferable and 1 or 2 is preferable. When n1 is 0, L ¹² is directly bonded to H ^{1 to} H ³ in the formula (D1).

L ¹² is preferably * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —CH ₂ —, * —CH═CH— or * —. C≡C—, more preferably * —O—, * —O—CO—, * —O—CO—O— or * —CH ₂ —.

The hydrogen atom in L ¹³ may be substituted with another substituent. Examples of the substituent in this case include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, carbon A halogen-substituted alkyl group having 1 to 6 atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and 2 carbon atoms -6 acyloxy groups, alkoxycarbonyl groups having 2 to 6 carbon atoms, carbamoyl groups, alkyl-substituted carbamoyl groups having 2 to 6 carbon atoms and acylamino groups 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 ¹³ is preferably a linking group selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, C≡C—, and combinations thereof. L ¹³ preferably contains 1 to 20 carbon atoms, and preferably 2 to 14 carbon atoms. Further, L ¹³ preferably contains 1 to 16 —CH ₂ —, and particularly preferably ₂ to 12 —CH ₂ —.

Q ¹ is a polymerizable group or a hydrogen atom. When the composition of the present invention is used for production of an optical film or the like that requires that the magnitude of the retardation does not change due to heat, such as an optical compensation film, Q ¹ is preferably a polymerizable group. . 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 the above (M-3) and (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 most 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.

  Among the compounds represented by the general formula (DI), a compound represented by the following general formula (DII) is preferable, and a compound represented by the following general formula (DIII) is more preferable.

Formula (DII)

In the general formula (DII), Y ¹¹ , Y ¹² and Y ¹³ each represent methine or a nitrogen atom. Y ¹¹ , Y ¹² and Y ¹³ are synonymous with these in the general formula (DI), and preferred ranges are also synonymous.

In the general formula (DII), R ²¹ , R ²² and R ²³ are each represented by the following general formula (DII-R).

（一般式（ＤＩＩ−Ｒ）中、Ｙ^A1およびＹ^A2は、それぞれ、メチンまたは窒素原子を表す。Ｘ^Aは酸素原子、硫黄原子、メチレンまたはイミノを表す。Ｆ¹は、少なくとも１種類の環状構造を有する二価の環状連結基を表す。ｎ２は、１〜３の整数を表す。Ｌ¹²は、＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−ＮＨ−、＊−ＳＯ₂−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−または＊−Ｃ≡Ｃ−を表し（＊はＬ¹³と反対側に結合する位置を表す。）、Ｌ¹³は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、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換されていてもよい。Ｑ¹は重合性基または水素原子を表す。） General formula (DII-R)

(In General Formula (DII-R), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene or imino, and F ¹ represents at least one kind of cyclic group. Represents a divalent cyclic linking group having a structure, n2 represents an integer of 1 to 3. L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—. CO—O—, * —S—, * —NH—, * —SO ₂ —, * —CH ₂ —, * —CH═CH— or * —C≡C— (* is opposite to L ¹³⁾ L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —. C≡C— represents a divalent linking group selected from the group consisting of a combination thereof, and when these groups are groups containing a hydrogen atom, the hydrogen atom is substituted with a substituent. Q ¹ represents a polymerizable group or a hydrogen atom.)

In the general formula (DII-R), Y ^A1 , Y ^A2 and X ^A have the same meanings as those in the general formula (DI-A), and the preferred ranges are also the same. In General Formula (DII-R), F ¹ has the same meaning as those in General Formula (DI-R), and the preferred range is also the same.
In General Formula (DII-R), n2 represents an integer of 1 to 3. n2 is preferably 1 or 2.
L < ¹² > in general formula (DII-R) is the same as the definition of L < ¹² > in general formula (DI-R), and its preferable range is also the same. L < ¹³ > in general formula (DII-R) is the same as the definition of L < ¹³ > in general formula (DI-R), and its preferable range is also the same. Q < ¹ > in general formula (DII-R) is the same as the definition of Q < ¹ > in general formula (DI-R), and its preferable range is also the same.

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

（一般式（ＤＩＩＩ）中、Ｙ¹¹、Ｙ¹²およびＹ¹³は、それぞれメチンまたは窒素原子を表し、Ｒ³¹、Ｒ³²およびＲ³³は、それぞれ、下記一般式（ＤＩＩＩ−Ａ）、下記一般式（ＤＩＩＩ−Ｂ）または下記一般式（ＤＩＩＩ−Ｃ）を表す。 Formula (DIII)

(In the general formula (DIII), Y ¹¹ , Y ¹² and Y ¹³ each represent methine or a nitrogen atom, and R ³¹ , R ³² and R ³³ represent the following general formula (DIII-A) and the following general formula, respectively. (DIII-B) or the following general formula (DIII-C) is represented.

In General Formula (DIII), Y ¹¹ , Y ¹² and Y ¹³ have the same meanings as those in General Formula (DI), and the preferred ranges are also the same.

R ³¹ , R ³² and R ³³ represent the following general formula (DIII-A), the following general formula (DIII-B) or the following general formula (DIII-C), respectively. In the case of producing a retardation plate having a small wavelength dispersion, R ³¹ , R ³² and R ³³ are groups represented by the general formula (DIII-A) or the general formula (DIII-C), respectively. Are preferable, and a group represented by the general formula (DIII-A) is more preferable.

（一般式（ＤＩＩＩ−Ａ）中、Ｙ^A1、Ｙ^A2、Ａ¹³、Ａ¹⁴、Ａ¹⁵およびＡ¹⁶は、それぞれ、メチンまたは窒素原子を表し、Ｘ^Aは、酸素原子、硫黄原子、メチレンまたはイミノを表し、Ｌ¹²は＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−ＮＨ−、＊−ＳＯ₂−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−、＊−Ｃ≡Ｃ−を表し、Ｌ¹³は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、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換されていてもよい。Ｑ¹は、重合性基または水素原子を表す。） General formula (DIII-A)

(In the general formula (DIII-A), Y ^A1 , Y ^A2 , A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ each represents a methine or nitrogen atom, and X ^A represents an oxygen atom, a sulfur atom, methylene or Represents imino, and L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —NH—, * —SO ₂ —. , * —CH ₂ —, * —CH═CH—, * —C≡C—, and L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH. Represents a divalent linking group selected from the group consisting of —, —CH ₂ —, —CH═CH— and —C≡C—, and combinations thereof, and when these groups are groups containing a hydrogen atom, (The hydrogen atom may be substituted with a substituent. Q ¹ represents a polymerizable group or a hydrogen atom.)

In general formula (DIII-A), Y ^A1 , Y ^A2 and X ^A are the same as those in general formula (DI-A), respectively, and the preferred range is also the same.
A ^13, A ^14, A ¹⁵ and A ¹⁶ are preferably at least three of these methine groups, more preferably, all of them are methine. When A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ are each methine, the methine may have a substituent, but preferably has no 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 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 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. 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.
L < ¹² >, L < ¹³ > and Q < ¹ > are synonymous with those in the general formula (DI-R), and preferred ranges are also synonymous.

（一般式（ＤＩＩＩ−Ｂ）中、Ｙ^A1、Ｙ^A2、Ａ¹³、Ａ¹⁴、Ａ¹⁵およびＡ¹⁶は、それぞれ、メチンまたは窒素原子を表し、を表し、Ｘ^Aは、酸素原子、硫黄原子、メチレンまたはイミノを表し、Ｌ¹²は＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−ＮＨ−、＊−ＳＯ₂−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−、＊−Ｃ≡Ｃ−を表し、Ｌ¹³は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、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換されていてもよい。Ｑ¹は、重合性基または水素原子を表す。） General formula (DIII-B)

(In General Formula (DIII-B), Y ^A1 , Y ^A2 , A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ each represents a methine or nitrogen atom, and X ^A represents an oxygen atom or a sulfur atom. , Methylene or imino, and L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —NH—, * —. SO ₂ —, * —CH ₂ —, * —CH═CH—, * —C≡C—, and L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —. , —NH—, —CH ₂ —, —CH═CH—, —C≡C— and a divalent linking group selected from the group consisting of these, and these groups are groups containing a hydrogen atom In some cases, the hydrogen atom may be substituted with a substituent, and Q ¹ represents a polymerizable group or a hydrogen atom.)

In General Formula (DIII-B), Y ^A1 , Y ^A2 and X ^A are the same as those in General Formula (DI-A), respectively, and the preferred range is also the same.
A < ¹³ >, A < ¹⁴ >, A < ¹⁵ > and A < ¹⁶ > are respectively synonymous with those in the general formula (DIII-A), and preferred ranges are also synonymous.
L < ¹² >, L < ¹³ > and Q < ¹ > are respectively synonymous with those in the general formula (DI-R), and preferred ranges are also synonymous.

（一般式（ＤＩＩＩ−Ｃ）中、Ｙ^A1、Ｙ^A2、Ａ¹³、Ａ¹⁴、Ａ¹⁵およびＡ¹⁶は、それぞれ、メチンまたは窒素原子を表し、を表し、Ｘ^Aは、酸素原子、硫黄原子、メチレンまたはイミノを表し、Ｌ¹²は＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−ＮＨ−、＊−ＳＯ₂−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−、＊−Ｃ≡Ｃ−を表し、Ｌ¹³は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＳＯ₂−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、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換されていてもよい。Ｑ¹は、重合性基または水素原子を表す。） General formula (DIII-C)

(In General Formula (DIII-C), Y ^A1 , Y ^A2 , A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ each represents a methine or nitrogen atom, and X ^A represents an oxygen atom or a sulfur atom. , Methylene or imino, L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —NH—, * —. SO ₂ —, * —CH ₂ —, * —CH═CH—, * —C≡C—, and L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —. , —NH—, —CH ₂ —, —CH═CH—, —C≡C— and a divalent linking group selected from the group consisting of these, and these groups are groups containing a hydrogen atom In some cases, the hydrogen atom may be substituted with a substituent, and Q ¹ represents a polymerizable group or a hydrogen atom.)

In General Formula (DIII-C), Y ^A1 , Y ^A2 and X ^A are the same as those in General Formula (DI-A), respectively, and the preferred range is also the same.
A < ¹³ >, A < ¹⁴ >, A < ¹⁵ > and A < ¹⁶ > are respectively synonymous with those in the general formula (DIII-A), and preferred ranges are also synonymous.
L < ¹² >, L < ¹³ > and Q < ¹ > are respectively synonymous with those in the general formula (DI-R), and preferred ranges are also synonymous.

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

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

  The compound represented by the general formula (DI) preferably exhibits a liquid crystal phase in the range of 20 ° C to 300 ° C. More preferably, it is 40 degreeC-280 degreeC, More preferably, it is 60 degreeC-250 degreeC. Here, the expression of the liquid crystal phase at 20 ° C. to 300 ° C. also means that the liquid crystal temperature range extends over 20 ° C. (for example, 10 ° C. to 22 ° C.) or 300 ° C. (for example, 298 ° C. to 310 ° C.). It is a purpose to include. 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.

[Phase difference plate]
The retardation plate of the present invention has an optically anisotropic layer made of the composition of the present invention. 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.

(1) Optically anisotropic layer The optically anisotropic layer of this invention consists of a composition containing a liquid crystalline compound and the compound represented by general formula (A). In addition to this, the optically anisotropic layer optionally contains a polymerizable initiator and other additives. The coating liquid containing these can be formed, for example, by coating the surface of the alignment film of the present invention formed on a support, and aligning and fixing the liquid crystalline compound. After aligning and fixing the liquid crystalline compound, the support may be peeled off.

(1) -a Formation Method The optically anisotropic layer can be formed by, for example, the following method. That is, by applying a coating solution prepared by dissolving the liquid crystalline compound or the compound represented by the general formula (A) in a solvent capable of being dissolved on the support, the alignment is imparted with orientation. It can be produced by coating on a film. Further, if possible, formation by vapor deposition may be used, but formation by coating is preferably used. Application methods include curtain coating, dip coating, spin coating, print coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, wire bar method, etc. A well-known coating method is mentioned. Next, the optically anisotropic layer is formed by drying the solvent used at 25 ° C. to 130 ° C., and simultaneously orienting the molecules of the liquid crystalline compound and fixing the molecules by ultraviolet irradiation or the like. It is preferable to use ultraviolet rays for light irradiation for polymerization. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the optically anisotropic layer thus formed varies depending on the optimum retardation value depending on the application such as optical compensation, but is preferably 0.1 to 10 μm, preferably 0.5 to 5 μm. More preferably.

  In the optically anisotropic layer, the liquid crystalline compound is preferably substantially uniformly oriented, more preferably fixed in a substantially uniformly oriented state, by polymerization reaction. Most preferably, the liquid crystal compound is fixed.

  The proportion of the polymer obtained from the compound represented by the general formula (DI) or the compound represented by the general formula (DI) occupying the optically anisotropic layer is preferably 10 to 100% by mass, More preferably, it is 30-99 mass%, and it is most preferable that it is 50-99 mass%.

(1) -b Other materials used for forming the optically anisotropic layer The composition of the present invention includes other materials (additives) in addition to the liquid crystalline compound and the compound represented by the general formula (A). ) May be included. Examples of the additive include a polymerization initiator, an additive for controlling the alignment state of the liquid crystal compound (for example, an onium salt and an air interface vertical alignment agent), a polymerization initiator, a plasticizer, a surfactant, and a polymerizability. A monomer or the like may be contained. These additives are added for various purposes, for example, for the purpose of fixing the alignment, improving the uniformity of the coating film, the strength of the film, and the orientation of the liquid crystal compound.

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

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

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

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

  The polymer used together with the liquid crystal compound is preferably capable of thickening the coating solution. A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph No. [0178] of JP-A No. 2000-155216. The addition amount of the polymer is preferably in the range of 0.1 to 10% by mass, and in the range of 0.1 to 8% by mass with respect to the liquid crystal compound so as not to inhibit the alignment of the liquid crystal compound. It is more preferable.

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

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

The liquid crystalline compound is coated on the support (more preferably on the alignment film) and then, for example, heated to develop a liquid crystal phase. Therefore, the liquid crystal compound is formed on the support surface or the coating film interface (alignment film) at the support side interface. Is provided at a tilt angle (in other words, an angle formed by the direction of the support surface and the disk surface direction of the liquid crystal compound (the liquid crystal compound of the present invention has a disk shape)). At the interface 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 (angle formed between the direction of the support surface and the direction of the disc surface of the liquid crystal compound) is preferably 10 to 70 °, more preferably 20 to 60 °, and more preferably 20 to 35. More preferred is °.
The tilt angle at each interface is a combination of the tilt angle at the air interface of 0 to 50 ° and the tilt angle of the support side interface of 20 to 90 °, or the tilt angle of the support side interface of 0 to 50 ° and the air. A combination in which the tilt angle of the interface is 20 to 90 ° is preferable. In particular, a combination in which the tilt angle of the air interface is 0 to 40 ° and the tilt angle of the support side interface is 40 to 80 °, or the tilt angle of the support side interface is 0 to 40 ° and the tilt angle of the air interface is 40 to 40 °. A combination of 80 ° is preferred.

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

  In principle, the polymer used for the alignment film has a molecular structure having a function of aligning the liquid crystal compound. In the present invention, in addition to the function of aligning the liquid crystalline compound, the cross-linking having a function of binding a side chain having a crosslinkable functional group (for example, a double bond) to the main chain or aligning the liquid crystalline compound. It is preferable to introduce a functional functional group into the side chain. As the polymer used 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, for example, a methacrylate polymer, a styrene polymer, a polyolefin, a polyvinyl alcohol and a modified polyvinyl alcohol, poly (N-methylolacrylamide) described in paragraph No. [0022] of JP-A-8-338913, Polyester, polyimide, vinyl acetate polymer, carboxymethyl cellulose, polycarbonate and the like are included. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are 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 specific type of functional group is determined according to the type of liquid crystal compound and the required alignment state.
For example, the modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of modifying groups include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, fluorine atoms Substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, monoalkoxy) and the like can be mentioned. Specific examples of these modified polyvinyl alcohol compounds include those described in, for example, paragraph numbers [0022] to [0145] of JP-A No. 2000-155216 and paragraph numbers [0018] to [0022] of JP-A No. 2002-62426. Etc.

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 the function of aligning the liquid crystalline compound, the polymer of the alignment film and the optically anisotropic layer Can be copolymerized with the polyfunctional monomer contained in. As a result, not only between the polyfunctional monomer and the polyfunctional monomer, but also between the alignment film polymer and the alignment film polymer and between the polyfunctional monomer and the alignment film polymer is firmly bonded by a covalent bond. Therefore, the strength of the retardation plate can be remarkably improved by introducing a crosslinkable functional group into the alignment film polymer.
The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specific examples include those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216.

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

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

  The alignment film can basically be formed by applying the above-mentioned polymer as an alignment film forming material and a support containing a crosslinking agent, followed by drying by heating (crosslinking) and, if necessary, rubbing treatment. it can. As described above, the crosslinking reaction can be carried out at any 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 more effectively 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. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form a sufficient crosslink, 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, for example, the pH is 4.5 to 5.5, and the pH 5 is preferable.

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

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

  After aligning the liquid crystalline compound on the alignment film, if necessary, the alignment film polymer and the polyfunctional monomer contained in the optically anisotropic layer are reacted or the alignment film polymer is crosslinked using a crosslinking agent. May be. The thickness of the alignment film is preferably in the range of 0.1 to 10 μm. It can be prepared by applying a coating solution prepared by dissolving the polymer for alignment film in a solvent to the surface of the support, and drying and removing the solvent in the coating solution at 25 to 140 ° C. Moreover, although it can also form by vapor deposition if possible, formation by application | coating is more preferable. The thickness of the alignment film thus formed is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

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

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

  The alignment film formed by the above method is preferably 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 orientation 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) Support The retardation plate may have a support, and the support is preferably a transparent support. The support is not particularly limited as long as it is optically isotropic and has a light transmittance of 80% or more, but a polymer film is preferable. Specific examples of the polymer include cellulose esters (for example, cellulose diacetate, cellulose triacetate), norbornene-based polymers, poly (meth) acrylate esters, and the like, and many commercially available polymers are preferably used. Is possible. Among these, cellulose esters are preferable from the viewpoint of optical performance, and lower fatty acid esters of cellulose are more preferable. The lower fatty acid is a fatty acid having 6 or less carbon atoms, and the number of carbon atoms is preferably 2, 3, or 4. Specific examples include cellulose acetate, cellulose propionate, and cellulose butyrate. Among these, cellulose triacetate is particularly preferable. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used. Moreover, even if it is a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence, its expression is reduced by modifying the molecule as described in International Publication WO 00/26705 pamphlet. Can also be used.

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%. The acetylation degree is more 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. The hydroxyl group at the 6-position is preferably substituted with an acyl group at a ratio of 30% to 40% with respect to the total degree of substitution, more preferably 31% or more, and more preferably 32% or more. More preferably it is substituted. The substitution degree at the 6-position is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with an acyl group having 3 or more carbon atoms (for example, propionyl group, butyryl group, valeroyl group, benzoyl group, acryloyl group) in addition to the acetyl group. The degree of substitution at each position can be determined by NMR. Cellulose esters having a high degree of substitution at the 6-position hydroxyl group are 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, More preferred are a benzene ring and a 1,3,5-triazine ring. It is particularly preferred that the aromatic compound has at least one 1,3,5-triazine ring.

  The number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 8, and most preferably 2 to 6. . The bonding relationship between two aromatic rings can be classified into (a) when 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). Examples of such retardation increasing agents include, for example, International Publication WO01 / 88574, International Publication WO00 / 2619, JP2000-11914A, 2000-275434, and JP2002-363343A. It is described in.

  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. Regarding casting and drying methods in the solvent cast method, U.S. Pat. Nos. 2,336,310, 2,367,603, 2,429,078, 2,429,297, 2,429,978, 2,607,704, 2,739,69, U.S. 2,739,070, British Patent 6,407,331, No. 736892, JP-B Nos. 45-4554, 49-5614, JP-A-60-176834, No. 60-203430, and No. 62-1115035. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in, for example, 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, for example, that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass).
The cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and the production method thereof are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, pp., Published on March 15, 2001; (Abbreviated as No. 2001-1745).

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

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

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

Degradation inhibitors (for example, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose ester film. As the deterioration preventing agent, for example, those described in JP-A-3-199201, 5-1907073, 5-194789, 5-271471, and 6-107854 can be employed.
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. When the addition amount is 0.01 mass or more, the effect of the deterioration preventing agent is effective, and when the addition amount is 1 mass% or less, the deterioration preventing agent bleeds out to the film surface more effectively. Can be suppressed. As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. As the ultraviolet ray preventing agent, for example, those described in JP-A-7-11056 can be employed.

  The cellulose acetate film is preferably subjected to a surface treatment. Specific examples of the method include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, saponification treatment, and ultraviolet irradiation treatment. For example, as described in JP-A-7-333433, it is also preferable to provide an undercoat layer.

For the undercoat layer, see, for example, Dr. K. Various methods are known in Science and Technology-ology (VCH, 1993) edited by Keller. In addition, various contrivances have been made for the constitution of the undercoat layer, and a layer that adheres well to the polymer film (hereinafter abbreviated as the first undercoat layer) is provided as the first layer, and the second layer is provided thereon. A so-called multi-layer method in which a hydrophilic resin layer (hereinafter referred to as an undercoat second layer) that adheres well to the alignment film is applied, and a single layer in which only a single resin layer containing both a hydrophobic group and a hydrophilic group is applied. There is a layer method.

In the undercoat first layer in the multilayer method, for example, in addition to a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, Polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, polyvinyl bromide, polyvinyl fluoride, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-ethylene copolymer, chlorinated Vinyl-propylene copolymer, vinyl chloride-styrene copolymer, isobutylene chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile Copolymer, vinyl chloride-butadiene copolymer, salt Vinyl-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer , Vinyl methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, vinylidene chloride-methacrylate copolymer, vinylidene chloride -Halogen-containing synthetic resins such as acrylonitrile copolymer, vinylidene chloride-acrylic acid ester copolymer, chloroethyl vinyl ether-acrylic acid ester copolymer, polychloroprene, polyethylene, polypropylene, polybutene, poly-3-methylbutene, poly -1,2 Α-olefin copolymer such as butadiene, ethylene-propylene copolymer, ethylene-vinyl ether copolymer, ethylene-propylene-1,4-hexadiene copolymer, ethylene-vinyl acetate copolymer, butene-1- Propylene copolymer, butadiene-acrylonitrile copolymer and blends of these copolymers with halogen-containing resins, acrylic acid methyl ester-acrylonitrile copolymer, acrylic acid ethyl ester-styrene copolymer, methacrylic acid methyl ester -Acrylonitrile copolymer, polymethacrylic acid methyl ester, methacrylic acid methyl ester-styrene copolymer, methacrylic acid butyl ester-styrene copolymer, polymethyl acrylate, poly-α-methyl chloroacrylate, polymethacrylic acid methoxy ester Ester, polyacrylic acid glycidyl ester, polyacrylic acid butyl ester, polyacrylic acid methyl ester, polyacrylic acid ethyl ester acrylic acid-butyl acrylate copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester- Acrylic resin such as butadiene-styrene copolymer, polystyrene, poly-α-methylstyrene, styrene-dimethyl fumarate copolymer, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, styrene-butadiene -Acrylonitrile copolymer, poly-2,6-dimethylphenylene oxide, styrene-acrylonitrile copolymer, polyvinylcarbazole, poly-p-xylylene, polyvinyl formal, polyvinyl acetal, polyvinyl Tyral, polyvinyl phthalate, cellulose triacetate, cellulose butyrate, cellulose butyrate, cellulose phthalate, nylon 6, nylon 66, nylon 12, methoxymethyl-6-nylon, nylon 6, 10 polycapramide, poly-N-butyl-nylon-6 Polyethylene sebacate, polybutylene glutarate, polyhexamethylene adipate, polybutylene isophthalate, polyethylene terephthalate, polyethylene adipate, polyethylene adipate terephthalate, polyethylene-2,6-naphthalate, polydiethylene glycol terephthalate, polyethylene oxybenzoate, bisphenol A-isophthalate , Polyacrylonitrile, bisphenol A-adipate, polyhexamethylene-m-benzenedi Ruhon'amido, polytetramethylene hexamethylene carbonate, polydimethylsiloxane, polyethylene methylene bis-4-diphenylene carbonate, and the like oligomers or polymers such as bisphenol A- polycarbonate. Further, those described in EHImmergut “Polymer Handbook” IV 187-231, Intersciense Pub. New York (1966) can also be employed. Etc.)
On the other hand, gelatin is preferred for the second subbing layer.

In the single layer method, good adhesion is achieved by expanding the polymer film and interfacial mixing with the hydrophilic undercoat polymer. Examples of the hydrophilic undercoat polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers, and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer and the like. Examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylate ester-containing copolymer, a vinyl acetate-containing copolymer, and a butadiene-containing copolymer. Of these, gelatin is most preferred. As the gelatin, any of those generally used in this kind of field such as so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin can be preferably used. Of these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used. These gelatins contain various impurities in the production process, for example, 0.01 to 20000 ppm of metals (Na, K, Li, Rb, Ca, Mg, Ba, Ce, Fe, Sn, Pb, Al, Si, Ti , Metals such as Au, Ag, Zn, Ni, and ions thereof) and ions (F, Cl, Br, I, sulfate ions, nitrate ions, acetate ions, ammonium ions, etc.). In particular, it is known that lime-processed gelatin contains Ca ions and Mg ions, and the content thereof is also known to be very wide as 10 to 3000 ppm. Among these, 1000 ppm or less is preferable from the viewpoint of improving the coating performance of the undercoat layer, and 500 ppm or less is more preferable.

From the viewpoint of maintaining the flatness of the film, it is preferable that the temperature of the cellulose acetate film in these treatments is not higher than the glass transition temperature (Tg), specifically 150 ° C. or lower.

As for the surface treatment of the cellulose acetate film, it is particularly preferable to perform a saponification treatment (acid treatment or alkali treatment) 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 most preferably in the range of 30 to 110 μm.

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

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

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

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

  In the present invention, liquid crystal cell retardation plates (optical compensation sheets) of various modes can be produced with reference to the description in the above publication. The phase difference plate is composed of TN (Twisted Nematic), IPS (In-PDane Switching), FDC (Ferroelectric Diid Liquid CrystaD), OCB (OpticDyDenHyDenTwN) The liquid crystal display device can be used in various display modes such as a (Nematic) mode. The retardation plate is particularly effective for optical compensation of a liquid crystal display device in TN (Twisted Nematic) and OCB (OpticaDDy Compensatory Bend) modes.

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

Synthesis Example 1 [Synthesis of D3-10]
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, 2.8 ml of 50% hydroxylamine solution was added, and the mixture was stirred 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)
14 g of D3-10A was dissolved in 10 ml of dimethylacetamide (DMAc), 1.2 ml of pyridine (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 confirmed that D3-10 exhibits a discotic nematic liquid crystal phase between 115 ° C. and 178 ° C.

[Example 1: Preparation of composition (LM-1) of the present invention]
Liquid crystal compound (D3-10) represented by general formula (D1) and compound (A-1) represented by general formula (A) (manufactured by Tokyo Chemical Industry Co., Ltd.) at the composition ratio shown below. ), A photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 907), and diethylthioxanthone as a photosensitizer are each weighed and dissolved in methyl ethyl ketone to obtain the composition (LM-1) of the present invention. ) Was prepared.

Composition (LM-1) Liquid crystalline compound represented by general formula (D1): D3-10 100 parts by mass Compound represented by general formula (A): A-1 10 parts by mass Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.) 3.0 parts by weight diethylthioxanthone 1.0 part by weight methyl ethyl ketone 250 parts by weight

[Example 2: Preparation of the composition of the present invention (LM-2 to LM-6)]
Except having each changed the said compound (A-1) into the compound of the following Table 1, it is the same as the composition (LM-1) of Example 1, and is the composition (LM-2)- (LM-4) was prepared. Moreover, except having changed the liquid crystalline compound from said D3-10 into the following DLC-1, it is the same as that of the composition (LM-1) of Example 1, and the composition (LM-5) of this invention is carried out. Prepared. Furthermore, the present invention was carried out in the same manner as in the composition (LM-1) of Example 1 except that 0.4 parts by mass of the following polymer (surfactant) (W-1) was added as a surfactant. A composition (LM-6) was prepared.

Liquid crystalline compound (DLC-1)

Polymer (surfactant) (W-1)

[Comparative Example 1: Preparation of comparative compositions (LH-1 to LH-3)]
Except that the compound (A-1) was not added, the composition (LM-1) of Example 1 and (LM-5) and (LM-6) of Example 2 were all used in the same manner for comparison. Compositions (LH-1), (LH-2), and (LH-3) were prepared, respectively.

  These results are shown in Table 1.

[Example 3: Production of retardation plate (RM-1) of the present invention]
(Production of 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%. Then, it is further dried by transporting between the rolls of the heat treatment apparatus, considering that the stretching ratio in the machine direction is substantially 0% in a region exceeding 120 ° C., that is, 4% is stretched in the machine direction at the time of peeling. A cellulose acetate film having a thickness of 100 μm was prepared by adjusting the ratio of the stretching ratio in the width direction to the stretching ratio in the machine direction to be 0.75. When the retardation value of the produced film was measured at a wavelength of 632.8 nm, Re was 40 nm and Rth was 4 nm. The produced cellulose acetate film was used as a support.

(Formation of first undercoat layer)
On the 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 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 and dried with hot air at 100 ° C. for 120 seconds, followed by a rubbing treatment to form an alignment film. The thickness of the obtained alignment film was 0.5 μm. The rubbing direction of the alignment film was parallel to the casting direction of the 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 thermostatic bath, and irradiated with 200 mJ / cm ² of ultraviolet rays to fix the orientation state of the optically anisotropic layer. The solution was allowed to cool to room temperature to produce a retardation plate (RM-1) of the present invention. The thickness of the formed optically anisotropic layer was about 1.0 μm.

[Example 4: Production of retardation plate (RM-2 to RM-6) of the present invention]
The composition (LM-1) of the present invention used in the production of the phase difference plate (RM-1) of the present invention described in Example 3 was replaced with the compositions (LM-2) to (LM-6) of the present invention. The retardation plates (RM-2) to (RM-6) of the present invention were produced in the same manner except that the above were changed.

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

[Example 5: Evaluation of retardation plate]
(Measurement of Re and Rth)
Re (589 nm) and Rth (589 nm) represent in-plane retardation and retardation in the thickness direction at a wavelength of 589 nm, respectively. Re and Rth obtained in Examples 3 and 4 and Comparative Example 2 were measured by the method described above.

(Measurement of average tilt angle)
The tilt angle θ1 on one surface of the optically anisotropic layer and the tilt angle θ2 on the other surface are used as variables so that the calculation of the angular dependence of the retardation value of the optically anisotropic layer matches the measured value. Fitting was performed, and θ1 and θ2 were calculated.
The average tilt angle was determined from the average value of these values ((θ1 + θ2) / 2).

  Moreover, the ultrathin section of the cross section of the phase difference plate obtained in Examples 3 and 4 and Comparative Example 2 was prepared using a microtome, and the section was observed with a polarizing microscope. It was confirmed that the retardation films RM-1 to RM-6 of the present invention and the optically anisotropic layers of RH-1 to RH-3 of Comparative Example 2 were hybrid aligned.

(Measurement of orientation defects)
The retardation plate before being used as a polarizing plate was observed under a polarizing microscope to evaluate alignment defects. Evaluation under the microscope, carried out by the number of alignment defects observed in the range of 1.0 mm ² (point-like defects due to cissing and schlieren orientation), 1.0 mm point number of defects ² range where the average more than two A 3 to 5 cases were compared as B, 6 to 10 cases as C, 11 to 20 as D, and 21 or more as E. The evaluation of the alignment defect of each retardation plate evaluated in this manner is shown in Table 2 below.

From the results in Table 2, retardation plates prepared from the composition of the present invention (RM-1 to RM-6 are retardation plates manufactured without containing the compound represented by the general formula (A) of the present invention ( It can be seen that a retardation plate with fewer alignment defects can be produced as compared with RH-1 to R-3), and the effect is particularly great when a liquid crystalline compound represented by the general formula (DI) is used. It was remarkable.
From these results, in the phase difference plate produced from the composition containing the compound represented by the general formula (A) of the present invention, the phase difference plate in which the discotic liquid crystalline compound is hybrid-aligned with few alignment defects. It can be seen that can be obtained.

[Example 6: Production of retardation plates (RM-7) and (RM-8) of the present invention and retardation plates (RH-4) and (RH-5) of comparative examples]
In the phase difference plate (RM-1) of the present invention described in Example 3, the composition of the present invention (LM-1) used was as shown in Table 3, and the composition of the present invention (LM-7) and Retardation plates (RM-7) and (RM-8) of the present invention were produced in the same manner except for changing to (LM-8). Further, in the same manner using the comparative compositions (LH-4) and (LH-5) obtained by removing the compound (A-1) represented by the general formula (A) of the present invention from the two kinds of compositions. Comparative retardation plates (RH-4) and (RH-5) were produced. In the obtained four types of samples, all the rod-like liquid crystalline compounds used were aligned parallel to the rubbing direction and horizontally to the substrate of the alignment film. Further, the optical property values (Re, Rth) and thicknesses of these four kinds of samples were respectively equivalent to LM-1, LM-6, LH-1, and LH-3.

Liquid crystalline compound (V-1)

[Example 7: Evaluation of retardation plate]
(Measurement of orientation defects)
The retardation plate before being used as a polarizing plate was observed under a polarizing microscope to evaluate alignment defects. Evaluation under the microscope, carried out by the number of alignment defects observed in the range of 1.0 mm ² (point-like defects due to cissing and schlieren orientation), 1.0 mm point number of defects ² range where the average more than two A 3 to 5 cases were compared as B, 6 to 10 cases as C, 11 to 20 as D, and 21 or more as E. The evaluation of the alignment defect of each retardation plate evaluated in this manner is shown in Table 4 below.

  From the results shown in Table 4, it was confirmed that even when a rod-like liquid crystalline compound was used, a retardation plate with few alignment defects could be produced by using the general formula (A) of the present invention.

Claims (10)

A composition comprising at least one liquid crystal compound and at least one compound represented by the following general formula (A).
Formula (A)

(In the general formula (A), R ^1A represents a substituent containing a hetero atom, and R ^2A represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group or a hetero atom. R ^3A and R ^4A each represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, —OR ^31A , —NR ^32A R ^33A or —C ( ^═X ) R ^34A , wherein R ^31A , R ^32A and R ^33A are each a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aryl group. R ^34A represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group or —NR ^35A R ^36A , X represents an oxygen atom, a sulfur atom or NR ^37A , R ^35A , R ^{3 6A} and R ^37A each represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aryl group. In the general formula (A), R ^1A represents —OR ^11A , —NR ^12A R ^13A or —SR ^14A , and R ^11A , R ^12A , R ^13A, and R ^14A are each a hydrogen atom, substituted or unsubstituted. The composition according to claim 1, which represents an aliphatic hydrocarbon group or a substituted or unsubstituted aryl group. The composition according to claim 1 or 2, wherein in the general formula (A), R ^2A is a hydrogen atom. The composition according to any one of claims 1 to 3, wherein the liquid crystal compound is represented by the following general formula (DI).
General formula (DI)

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

(In the general formula (DI-A), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene or imino. * Represents a bond to L ^{1 to} L ³ . ** represents a position where R ^{1 to} R ³ are bonded.)
General formula (DI-B)

(In General Formula (DI-B), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene or imino, and * represents L ^{1 to} L ³ . (The bond position is represented, and ** represents the bond position with R ^{1 to} R ^3. )
General formula (DI-R)
*-(-L ¹¹ -F ¹ ) _n1 -L ¹² -L ¹³ -Q ¹
(In the general formula (DI-R), * represents a position bonded to H ^{1 to} H ^3. L ¹¹ represents a single bond or a divalent linking group. F ¹ has at least one kind of cyclic structure. Represents a divalent cyclic linking group, n1 represents an integer of 0 to 4. L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —NH—, * —SO ₂ —, * —CH ₂ —, * —CH═CH—, * —C≡C— (* represents the position on the opposite side of L ¹³⁾ L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C— and When the divalent linking group selected from the group consisting of these combinations is a group containing a hydrogen atom, the hydrogen atom may be substituted with a substituent, and Q ¹ is polymerizable. Group or hydrogen atom Represent.)) The composition according to claim 4, wherein the liquid crystal compound represented by the general formula (DI) is a liquid crystal compound represented by the following general formula (DII).
Formula (DII)

(In general formula (DII), Y ¹¹ , Y ¹² and Y ¹³ each represent a methine or nitrogen atom. R ²¹ , R ²² and R ²³ are each represented by the following general formula (DII-R). The
General formula (DII-R)

(In General Formula (DII-R), Y ^A1 and Y ^A2 each represent a methine or nitrogen atom, X ^A represents an oxygen atom, a sulfur atom, methylene or imino, and F ¹ represents at least one kind of cyclic group. Represents a divalent cyclic linking group having a structure, n2 represents an integer of 1 to 3. L ¹² represents * —O—, * —O—CO—, * —CO—O—, * —O—. CO—O—, * —S—, * —NH—, * —SO ₂ —, * —CH ₂ —, * —CH═CH— or * —C≡C— (* is opposite to L ¹³⁾ L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —. C≡C— represents a divalent linking group selected from the group consisting of a combination thereof, and when these groups are groups containing a hydrogen atom, the hydrogen atom is substituted with a substituent. Q ¹ represents a polymerizable group or a hydrogen atom.)) A phase difference plate having an alignment film and an optically anisotropic layer formed from the composition according to claim 1 on a support. The retardation film according to claim 6, wherein the alignment film contains polyvinyl alcohols. The phase difference plate according to claim 6 or 7, wherein the optically anisotropic layer contains a discotic liquid crystalline compound in which hybrid alignment is performed. An elliptically polarizing plate comprising the retardation plate according to claim 6 and a polarizing film. A liquid crystal display device comprising the retardation plate according to claim 6.