JP2008150489A - Liquid crystal composition, and phase-difference plate, elliptic polarizing plate and liquid crystal display device each using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition useful for making a liquid crystal display device in such a way that an optically anisotropic layer or the like contributing to the optical compensation of the device is kept stable and the planar smoothness of the layer or the like is kept well. <P>SOLUTION: The liquid crystal composition comprises at least one liquid crystal compound and at least two polymers. In this composition, one of the at least two polymers is such a polymer (a first polymer) as to have the property to increase the surface smoothness of a film made from the composition, the other being such a polymer (a second polymer) as to have the property to adjust the average tilt angle of the molecule of the liquid crystal compound, and the following numerical relationship (1): EA<EB<EL (wherein, EA is the surface energy of the first polymer; EB is the surface energy of the second polymer; and EL is the surface energy of the liquid crystal compound) is satisfied. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  A liquid crystal display device is usually provided with a first polarizing plate and a second polarizing plate with a liquid crystal cell interposed therebetween, and the liquid crystal cell has a liquid crystal layer containing a rod-like liquid crystal between a pair of substrates. A phase difference generated in a liquid crystal cell using a rod-like liquid crystal is converted into a discotic liquid crystal compound (discotic liquid crystal compound) (for example, 2,3,6,7,10,11-hexa {4- (4-acryloyloxyhexyloxy). It has been proposed to cancel with an optical compensatory sheet having an optically anisotropic layer formed from, for example, benzoyloxy} triphenylene (for example, Patent Document 1). However, since the wavelength dispersion of the rod-like liquid crystal layer and the optically anisotropic layer is different, the phase difference cannot be canceled simultaneously for all the wavelengths of light, resulting in discoloration (not having a black color). There is a case.

  As a discotic liquid crystal compound, a trisubstituted benzene compound having a heterocyclic group has been reported (Non-patent Document 1). However, it is not easy to form an optically anisotropic layer having a desired wavelength dispersion by using this compound.

  By the way, for the optically anisotropic layer used for optical compensation of the liquid crystal cell, the retardation Re (λ) needs to be determined according to the optical properties of the liquid crystal cell to be compensated. Here, 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) of the optically anisotropic layer used for optical compensation of the liquid crystal cell is large, it is necessary to optically compensate for the birefringence of the liquid crystal cell even if the layer thickness (d) is thin. Retardation. In an optically anisotropic layer produced by fixing the alignment of liquid crystal, its Re changes depending on the alignment angle (tilt angle and average tilt angle) of the liquid crystal molecules in the layer, so that the alignment angle needs to be controlled. .

  However, it is difficult to control the orientation angle of the above-mentioned trisubstituted benzene type discotic liquid crystal substituted with a heterocyclic group, and it is particularly difficult to achieve hybrid orientation with a low average tilt angle. Although it has been proposed to add an alignment controller or alignment accelerator to the liquid crystal compound (Patent Document 2), the effect on the trisubstituted benzene type discotic liquid crystal compound is not clearly shown, and the conventional technology It was insufficient to control the orientation angle to the desired angle. Furthermore, when an alignment controller or alignment accelerator is added to the liquid crystal composition in order to control the alignment angle of the liquid crystal compound, aggregation occurs due to aging or temperature change, and the surface smoothness of the layer formed from the composition is increased. There has been a problem of reduction, and an improvement has been desired.

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

An object of the present invention is to provide a composition useful for producing an optically anisotropic layer or the like that contributes to optical compensation of a liquid crystal display device stably and with good planar smoothness. In particular, the optically anisotropic layer exhibiting optical anisotropy expressed by the hybrid orientation of the discotic liquid crystal compound is free from defects (or reduced defects) due to variations in optical property values, alignment defects, and the like, and It is an object of the present invention to provide a composition useful for producing a layer having high surface smoothness.
Another object of the present invention is to provide a retardation plate useful for optical compensation of a liquid crystal display device, an elliptically polarizing plate using the retardation plate, and a liquid crystal display device with good display characteristics.

Means for solving the above problems are as follows.
[1] A liquid crystal composition containing at least one kind of liquid crystal compound and at least two kinds of polymers, wherein one of the at least two kinds of polymers has a smooth surface of a film made of the composition. A polymer having the property of improving (first polymer), and the other type is a polymer having the property of adjusting the average tilt angle of the molecules of the liquid crystal compound (second polymer). A liquid crystal composition satisfying the formula (1):
Formula (1) EA <EB <EL
In the formula, EA is the surface energy of the first polymer, EB is the surface energy of the second polymer, and EL is the surface energy of the liquid crystal compound.

一般式（Ｉ）中、Ｒ¹は、水素原子、ハロゲン原子又はアルキル基を表し、Ｌ¹は２価の連結基を表し、ｍは１以上１２以下の整数を表し、Ｘ¹はフッ素原子又は水素原子を表す。 [2] The liquid crystal composition according to [1], wherein the first polymer is a polymer including a polymer unit derived from a monomer represented by the following general formula (I):
Formula (I)

In general formula (I), R ¹ represents a hydrogen atom, a halogen atom or an alkyl group, L ¹ represents a divalent linking group, m represents an integer of 1 to 12, and X ¹ represents a fluorine atom or Represents a hydrogen atom.

[3] The liquid crystal composition of [2], wherein L ¹ in the formula (I) is a linking group represented by the following general formula (II):
Formula (II)
^{(A) -X 10 -R 20 -} (b)
In the general formula (II), (a) represents a position bonded to the double bond side, and (b) represents a position bonded to the fluoroaliphatic group side; X ¹⁰ represents a single bond or * -COO- * *, * -COS-**, * -OCO-**, * -CON (R ²¹ )-**, or a divalent linking group represented by * -O-**, where * is a formula (I) a position bonded to the double bond side, ** represents a position bonded to R ²⁰ ; R ²¹ represents a hydrogen atom or an optionally substituted carbon atom having 1 to 8 carbon atoms. R ²⁰ represents an optionally substituted polymethylene group, an optionally substituted phenylene group, or any combination thereof. Represents a group that can be formed.

式中、Ａ¹及びＡ²はそれぞれ、−Ｏ−、−ＮＲ−（Ｒは水素原子又は置換基）、−Ｓ−、−ＣＯ−から選ばれる基を表し；Ｌ¹及びＬ²はそれぞれ、単結合又は二価の連結基を表し；Ｒ¹、Ｒ²及びＲ³はそれぞれ置換基を表し；ｎは０〜２の整数を表し、Ｘは炭素数０〜３０の直鎖状、分枝状もしく環状のアルキレン基を表す。 [4] The liquid crystal composition according to any one of [1] to [3], wherein the second polymer is a polymer including a polymer unit represented by the following general formula (III):

In the formula, A ¹ and A ² each represent a group selected from —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, —CO—; L ¹ and L ² are Represents a single bond or a divalent linking group; R ¹ , R ² and R ³ each represent a substituent; n represents an integer of 0 to 2, and X represents a linear or branched group having 0 to 30 carbon atoms. Represents a cyclic or cyclic alkylene group.

式中、Ｘ¹、Ｘ²及びＸ³はそれぞれ、単結合、−ＮＲ−（Ｒは置換基又は水素原子）、−Ｏ−又は−Ｓ−であり；Ｒ¹、Ｒ²及びＲ³はそれぞれ、置換基を有していてもよい、アルキニル基、アルケニル基、アリーレン基又は二価の複素環基であり；Ｙ¹¹、Ｙ¹²及びＹ¹³はそれぞれ、−ＣＲ＝（Ｒは置換基又は水素原子）又は―Ｎ＝であり；Ｌ¹は単結合又は二価の連結基を表す。 [5] The liquid crystal composition according to any one of [1] to [3], wherein the second polymer is a polymer including a polymerization unit represented by the following general formula (IV).
Formula (IV)

In the formula, each of X ¹ , X ² and X ³ is a single bond, —NR— (R is a substituent or a hydrogen atom), —O— or —S—; R ¹ , R ² and R ³ are each , An alkynyl group, an alkenyl group, an arylene group or a divalent heterocyclic group which may have a substituent; Y ¹¹ , Y ¹² and Y ¹³ are each —CR═ (R is a substituent or hydrogen; Atom) or —N═; L ¹ represents a single bond or a divalent linking group.

一般式（ＤＩ）中、Ｙ¹¹、Ｙ¹²及びＹ¹³はそれぞれ、メチン又は窒素原子を表し；Ｌ¹、Ｌ²及びＬ³はそれぞれ、単結合又は二価の連結基を表し；Ｈ¹、Ｈ²及びＨ³は、それぞれ、下記一般式（ＤＩ−Ａ）又は下記一般式（ＤＩ−Ｂ）を表し；Ｒ¹、Ｒ²及びＲ³はそれぞれ、下記一般式（ＤＩ−Ｒ）を表し： [6] The liquid crystal composition according to any one of [1] to [5], wherein the liquid crystal compound is a compound represented by the following general formula (DI).
General formula (DI)

In 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); R ¹ , R ² and R ³ each represent the following general formula (DI-R) :

一般式（ＤＩ−Ａ）中、Ｙ^A1及びＹ^A2はそれぞれ、メチン又は窒素原子を表し；Ｘ^Aは酸素原子、硫黄原子、メチレン又はイミノを表し；＊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し； General formula (DI-A)

In 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 position where L ^{1 to} L ³ are bonded. ** represents a position where R ^{1 to} R ³ are bonded;

一般式（ＤＩ−Ｂ）中、Ｙ^A1及びＹ^A2はそれぞれ、メチン又は窒素原子を表し；Ｘ^Aは、酸素原子、硫黄原子、メチレン又はイミノを表し；＊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し； General formula (DI-B)

In the 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; * is bonded to L ^{1 to} L ³ Represents a position, and ** represents a position where R ^{1 to} R ³ are bonded;

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 represents a group having at least one cyclic structure. 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—, or * —C≡C— (where * represents a position bonded to the side opposite to L ^13. L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C— and these Represents a divalent linking group selected from the group consisting of a combination of the above, and when these groups are groups containing a hydrogen atom, the hydrogen atom may be substituted with a substituent; Q ¹ is a polymerizable group Or represents a hydrogen atom.

一般式（ＤII）中、Ｙ¹¹、Ｙ¹²及びＹ¹³はそれぞれ、メチン又は窒素原子を表し；Ｒ²¹、Ｒ²²及びＲ²³はそれぞれ、下記一般式（ＤII−Ｒ）を表し； [7] The liquid crystal composition according to [6], wherein the liquid crystal compound is a liquid crystal compound represented by the following general formula (DII):
General formula (DII)

In general formula (DII), Y ¹¹ , Y ¹² and Y ¹³ each represent methine or a nitrogen atom; R ²¹ , R ²² and R ²³ each represent the following general formula (DII-R);

一般式（ＤII−Ｒ）中、Ｙ^A1及びＹ^A2はそれぞれ、メチン又は窒素原子を表し；Ｘ^Aは酸素原子、硫黄原子、メチレン又はイミノを表し；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し；ｎ２は、１〜３の整数を表し；Ｌ¹²は、＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−ＮＨ−、＊−ＳＯ₂−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−又は＊−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く；Ｑ¹は重合性基又は水素原子を表す。 General formula (DII-R)

In the 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; F ¹ represents at least one cyclic 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 represented (* is bonded to the side 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 these 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.

[8] A retardation plate having an alignment film and an optically anisotropic layer formed from the composition according to any one of [1] to [7] on a support.
[9] The retardation plate according to [8], wherein the alignment film contains polyvinyl alcohols.
[10] The retardation plate according to [8] or [9], wherein the optically anisotropic layer includes a discotic liquid crystal compound in which hybrid alignment is performed.
[11] An elliptically polarizing plate having the retardation plate of any one of [8] to [10] and a polarizing film.
[12] A liquid crystal display device having the retardation plate of any one of [8] to [10].

ADVANTAGE OF THE INVENTION According to this invention, the composition useful for producing the optically anisotropic layer etc. which contribute to the optical compensation of a liquid crystal display device stably and maintaining favorable plane smoothness can be provided. In particular, the optically anisotropic layer exhibiting optical anisotropy expressed by the hybrid orientation of the discotic liquid crystal compound is free from defects (or reduced in defects) due to variations in optical characteristic values, alignment defects, and the like, and Compositions useful for making as a high surface smoothness layer can be provided.
In addition, according to the present invention, a retardation plate useful for optical compensation of a liquid crystal display device, an elliptically polarizing plate using the retardation plate, and a liquid crystal display device with good display characteristics can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
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) represent in-plane retardation and retardation in the thickness direction at a wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).
When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film The light of wavelength λ nm is incident from each of the inclined directions in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction (with the direction of the rotation axis as the rotation axis). KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (1) and (2).

式（２）
Ｒｔｈ＝｛（ｎｘ＋ｎｙ）／２−ｎｚ｝×ｄ
注記：
式中、Ｒｅ（θ）は法線方向から角度θ傾斜した方向におけるレターデーション値をあらわす。
また、式中、ｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘ及びｎｙに直交する方向の屈折率を表し、ｄは層の厚みを表す。

Formula (2)
Rth = {(nx + ny) / 2−nz} × d
Note:
In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In the formula, nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, and nz represents the refractive index in the direction orthogonal to nx and ny. , D represents the thickness of the layer.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is the above-mentioned Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) from −50 degrees to +50 degrees with respect to the film normal direction. The light of wavelength λ nm is incident from each inclined direction in 10 degree steps and measured at 11 points, and KOBRA 21ADH or WR is calculated.
In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).
The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

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

[Liquid crystal composition]
The present invention relates to a liquid crystal composition comprising at least one liquid crystal compound and at least two kinds of polymers, wherein one of the at least two kinds of polymers is a surface smoothness of a film surface comprising the composition. Is a polymer (first polymer) having the property of improving the viscosity, and the other type is a polymer (second polymer) having the property of adjusting the average tilt angle of the molecules of the liquid crystal compound, It is related with the liquid crystal composition characterized by satisfy | filling Numerical formula (1).
Formula (1) EA <EB <EL
In the formula, EA is the surface energy of the first polymer, EB is the surface energy of the second polymer, and EL is the surface energy of the liquid crystal compound.
In the present invention, the functions of the first and second polymers are made more effective by using the first and second polymers and the liquid crystal compounds, each having a surface energy satisfying the above formula (1). It is demonstrated. Therefore, by using the liquid crystal composition of the present invention, it is possible to stably produce an optically anisotropic layer having desired optical characteristics with little or no alignment defects, without impairing surface smoothness. .

The difference EB-EA between the surface energy EB and the first surface energy EA of the polymer of the second polymer is preferably from 10～25MNm ^-1, that is 15～25MNm ^-1 more preferable. The difference EL-EB with surface energy EB of the surface energy EL and the second polymer of the liquid crystal compound is preferably from 10～25MNm ^-1, even more preferably 15～25MNm ^-1 . As long as satisfying the above equation (1), EA, there is no particular limitation on the EB and EL, in general, EA is preferably a 15~25mNm ^-1, EB is a 25～45MNm ^-1 The EL is preferably 35 to 65 mNm ⁻¹ .

In the present invention, EA, EB, and EL refer to the surface energy of each material measured by the following method.
Surface energy measurement:
A solution prepared by dissolving a sample to be measured (polymer or liquid crystal compound) in methyl ethyl ketone is applied to the surface of the glass substrate and dried to form a film having a thickness of 1 μm. Water and methylene iodide are dropped onto the surface of the film, the contact angle at 20 ° C. is measured, and the surface energy is determined by the Owens and Wendt method. The contact angle can be measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DropMaster).

In one embodiment of the liquid crystal composition of the present invention, a discotic liquid crystal compound is contained as a liquid crystal compound, and molecules of the discotic liquid crystal compound are hybrid-aligned with a low average tilt angle to form an optically anisotropic layer. The composition used. Hereinafter, each material preferable for use in this embodiment will be described.
[Liquid Crystal Compound]
The liquid crystal compound used in this embodiment is preferably a compound showing discotic liquid crystallinity, and more preferably a compound showing a discotic nematic phase. In this embodiment, it is preferable to use a compound represented by the following general formula (DI).

In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom. When Y ¹¹ , Y ¹² and Y ¹³ are each methine, the hydrogen atom of methine may be substituted with a substituent. Examples of the substituent that methine may have include, for example, alkyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, alkylthio group, arylthio group, halogen Mention may be made of atoms and cyano groups. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and the number of carbon atoms. A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom, and a cyano group are more preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

Of F ¹ , those having a benzene ring are preferably a 1,4-phenylene group or a 1,3-phenylene group. Those having a naphthalene ring include naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6- A diylnaphthalene-2,7-diyl group is preferred. Those having a cyclohexane ring are preferably 1,4-cyclohexylene groups. Pyridine-2,5-diyl groups are preferred as those having a pyridine ring. As what has a pyrimidine ring, a pyrimidine-2,5-diyl group is preferable. F ¹ is particularly preferably a 1,4-phenylene group, a 1,3-phenylenenaphthalene-2,6-diyl group and a 1,4-cyclohexylene group.

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

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

L ²² represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH. -Or -C≡C- is represented. Preferred is —O—, —O—CO—, —CO—O—, —O—CO—O—, —CH ₂ —, —CH═CH— or —C≡C—, and more preferred. —O—, —O—CO—, —CO—O—, —O—CO—O— or —CH ₂ —.
Here, when it is a group containing a hydrogen atom among the above, the hydrogen atom may be replaced by a substituent. Examples of other substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Alkoxy group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group, carbon atom The carbamoyl group substituted by the C2-C6 alkyl group and the C2-C6 acylamino group are contained. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable.

L ²³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and two of these. A divalent linking group selected from the groups formed by linking the above. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be replaced with other substituents. Examples of other substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Alkoxy group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group, carbon atom The carbamoyl group substituted by the C2-C6 alkyl group and the C2-C6 acylamino group are contained. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable. By being substituted with these substituents, the solubility of the compound represented by the general formula (DI) in the solvent can be improved, and the composition of the present invention can be easily prepared as a coating solution. .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

L ³¹ is —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—. , -C≡C-, and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. A preferred range for L ³¹ is the same as L ^{22 in} formula (DI-R).

L ³² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, or two or more thereof. Represents a divalent linking group selected from the group formed by linking and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. A preferred range for L ³² is the same as L ^{23 in} formula (DI-R).

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

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

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

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

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

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

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

L ^{41 in} the general formula (DIII-A), L ^{51 in} the general formula (DIII-B), and L ⁶¹ in the general formula (DIII-C) are each independently —O— or —O—CO—. , —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH— or —C≡C—. Preferably, -O -, - O-CO -, - CO-O -, - O-CO-O -, - CH 2 -, - CH = CH -, - is C≡C-, more preferably, —O—, —O—CO—, —CO—O—, —O—CO—O— or —CH ₂ —. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent.
Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Group, an acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 carbon atoms Preferred examples include a carbamoyl group substituted with ~ 6 alkyl and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

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

L ⁴² , L ⁵² and L ⁶² each independently connect —O—, —C (═O) —, —CH ₂ —, —CH═CH— and —C≡C— and two or more thereof. It is preferable that it is a bivalent coupling group selected from the group formed in this way. L ⁴² , L ⁵² and L ⁶² each independently preferably contain 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. Further, L ⁴² , L ⁵² and L ⁶² each independently preferably contain 1 to 16 —CH ₂ —, and more preferably ₂ to 12 —CH ₂ —.

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

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

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

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

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

  The compound represented by the general formula (DI) used in the present invention can be synthesized by applying a known method.

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

  A discotic compound, preferably a compound represented by the above formula (DI), is used for the liquid crystal composition of this embodiment, but a rod-like liquid crystal compound may of course be used for the liquid crystal composition of the present invention. It is.

[First polymer]
The liquid crystal composition of the present invention contains at least one polymer (first polymer) having the property of improving the surface smoothness of the film made of the composition. In the present invention, as the first polymer, a polymer whose surface energy EA is lower than the surface energy of other components to be used in combination is used to cause the first polymer to be unevenly distributed on the surface side. The smoothness effect is effectively exhibited.

  The first polymer is preferably a polymer having a fluorine atom in the main chain or side chain, and is a polymer containing a polymer unit derived from a monomer represented by the following general formula (I). Is preferred.

Formula (I)

In general formula (I), R ¹ represents a hydrogen atom, a halogen atom or an alkyl group. R ¹ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. L ¹ represents a divalent linking group. m represents an integer of 1 or more and 12 or less, preferably 2 to 10, more preferably 4 to 8, and most preferably 4 or 6. X ¹ represents a fluorine atom or a hydrogen atom.

L ¹ in the formula (I) is preferably a linking group represented by the following general formula (II).
Formula (II)
^{(A) -X 10 -R 20 -} (b)
In general formula (II), (a) shows the position bonded to the double bond side, and (b) shows the position bonded to the fluoroaliphatic group side. X ¹⁰ is a single bond or 2 represented by * -COO-**, * -COS-**, * -OCO-**, * -CON (R ²¹ )-**, or * -O-**. Represents a valent linking group. Here, * represents a position bonded to the double bond side in the formula (I), and ** represents a position bonded to R ²⁰ . Among these, * -COO-**, * -COS-**, or * -CON (R ²¹ )-** is preferable, and * -COO-** or * -CON (R ²¹ )-**. Is more preferable, and * -COO-** is still more preferable.
R ²⁰ is an optionally substituted polymethylene group (for example, methylene group, ethylene group, trimethylene group, propylene group, etc.), an optionally substituted phenylene group (for example, o-phenylene group, m -Phenylene group, p-phenylene group, or the like, or a group that can be formed by any combination thereof. Among them, a polymethylene group is more preferable, and among the polymethylene groups, a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are preferable, and a methylene group and an ethylene group are more preferable.
R ²¹ represents a hydrogen atom or an alkyl group which may have a substituent having 1 to 8 carbon atoms, or an aryl group which may have a substituent having 6 to 20 carbon atoms, and represents a hydrogen atom or a carbon number A 1-6 alkyl group is more preferable, and a hydrogen atom or a C1-C4 alkyl group is still more preferable.

Examples of the substituent that the monomer represented by the general formula (I) may have include the following. Hydroxyl group, halogen atom, cyano group, nitro group, carboxyl group, sulfo group, linear or cyclic alkyl group having 1 to 8 carbon atoms, alkenyl group having 1 to 8 carbon atoms, alkynyl having 2 to 8 carbon atoms Groups, aralkyl groups having 7 to 12 carbon atoms, aryl groups having 6 to 10 carbon atoms, acyl groups having 1 to 10 carbon atoms, alkoxycarbonyl groups having 2 to 10 carbon atoms, and 7 to 12 carbon atoms Aryloxycarbonyl group, carbamoyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 8 carbon atoms, aryloxy group having 6 to 12 carbon atoms, acyloxy group having 2 to 12 carbon atoms, 1 to 1 carbon atom 12 sulfonyloxy groups, an amino group having 0 to 10 carbon atoms, an acylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 8 carbon atoms, and 1 to 10 carbon atoms Raid group, urethane group having 2 to 10 carbon atoms, alkylthio group having 1 to 12 carbon atoms, arylthio group having 6 to 12 carbon atoms, alkylsulfonyl group having 1 to 8 carbon atoms, 7 to 12 carbon atoms An arylsulfonyl group, a sulfamoyl group having 0 to 8 carbon atoms, a heterocyclic group, and the like.

  Although the example of the monomer represented with general formula (I) below is shown, it is not limited to these.

  The first polymer may be a homopolymer of a monomer represented by the general formula (I) or a copolymer. In the case of a copolymer, for example, it may be a copolymer with a hydroxyl group-containing monomer represented by the following general formula (I ′).

Formula (I ')

R ¹ and L ¹ in the general formula (I '), the general formula (I) in have the same meanings as R ¹ and L ¹ of, and preferred ranges are also the same.

  The molecular weight of the first polymer is preferably 2000 to 100,000, and more preferably 3000 to 80,000. The polymer containing the unit derived from the general formula (I) can be produced by a known and conventional method. For example, it can be produced by adding a general-purpose radical polymerization initiator and polymerizing the above-mentioned monomer having a fluoroaliphatic group or monomer having an amide group in an organic solvent. Or depending on the case, it can manufacture by the method similar to the above by adding another addition polymerizable unsaturated compound. Depending on the polymerizability of each monomer, a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition. Depending on the type of monomer used, methods such as anionic polymerization, cationic polymerization, and emulsion polymerization may be used.

[Second polymer]
The liquid crystal composition of the present invention contains a second polymer having the property of adjusting the average tilt angle of the molecules of the liquid crystal compound. The second polymer is a polymer having a property that the average tilt angle when aligning the molecules of the predetermined liquid crystal compound in the presence of the compound is smaller or larger than the average tilt angle in the absence. . The second polymer may be selected according to the properties of the liquid crystal compound and its structural features. When the second polymer is a polymer having an affinity for the liquid crystal compound to be combined and having a similar partial structure, when the molecules of the liquid crystal compound are aligned in the presence of the second polymer, The average tilt angle tends to decrease as compared with the case where alignment is performed in the absence. More specifically, when the molecules of the discotic liquid crystal compound are aligned in the presence of a polymer having a high polarity and a similar cyclic structure as a partial structure, the average tilt angle (the layer surface and the disc surface of the discotic liquid crystal molecule) Tends to be small). However, not all combinations show this tendency, and combinations showing other tendencies are also included in the scope of the present invention.

  In the aspect in which the liquid crystal compound is a discotic compound, the second polymer is preferably a polymer including a polymer unit represented by the following general formula (III).

In the formula, A ¹ and A ² represent groups independently selected from —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, —CO—, and L ¹ and L ² are Each represents a single bond or a divalent linking group, R ¹ , R ² and R ³ each represent a substituent, n represents an integer of 0 to 2, X represents a straight chain having 0 to 30 carbon atoms, A branched or cyclic alkylene group is represented.

A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, and —CO—. Preferred are —O—, —NR— (R represents a substituent, and examples include R ¹ described later) or —S—.

In the general formula (III), the divalent linking group represented by L ¹ and L ² preferably includes the following examples.

  More preferred are -O-, -COO-, and -OCO-.

In general formula (III), R ¹ is a substituent, and when there are a plurality of R ^{1 s} , they may be the same or different and may form a ring. The following are mentioned as an example of a substituent.
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert- Butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl) Group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. , Bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octane-3-yl group),

An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, That is, it is a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed, for example, a 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), a bicycloalkenyl group (substituted or substituted). An unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group), alkini Group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, propargyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, aromatic A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably Or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy. Group),

A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group or tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms) Ring oxy group, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6-30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably , Substituted or non-substituted with 1 to 30 carbon atoms Carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyl An oxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group. Group), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn- Hexadecyl oxy phenoxycarbonyl group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted amino having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylaminocarbonyl Mino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino Group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) Amino groups such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylamino Sulfonylamino groups), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonyl An amino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, a mercapto group, and an alkylthio group (preferably a substituent having 1 to 30 carbon atoms) Or an unsubstituted alkylthio group such as a methylthio group Ethylthio group, n-hexadecylthio group), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio A group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms substituted or An unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl and an arylsulfonyl group ( Preferably, it is substituted or substituted with 1 to 30 carbon atoms. Unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, e.g., methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p- methylphenyl sulfonyl group),

An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an acetyl group or a pivaloylbenzoyl group), Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxy Carbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl Group (preferred Is a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- ( Methylsulfonyl) carbamoyl group),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferably carbon A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted phosphinylamino group such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as , Trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

In general formula (III), R ¹ is preferably a chlorine atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, amino group, More preferably, they are a chlorine atom, an alkyl group, an aryl group, a hydroxyl group, and an amino group.

In general formula (III), R ² and R ³ each independently represent a substituent. An example of R ¹ is given as an example. Preferably, it is preferred that substituent constant sigma ^p value of Hammett is greater than zero electron withdrawing group, sigma ^p value has an electron withdrawing substituent of 0 to 1.5 Further preferred. Examples of such a substituent include a trifluoromethyl group, a cyano group, a carbonyl group, and a nitro group. R ² and R ³ may be bonded to form a ring.
Regarding σ ^p and σ ^m of Hammett's substituent constants, for example, Naoki Inamoto's “Hammett's rule-structure and reactivity-” (Maruzen), edited by the Chemical Society of Japan “New Experimental Chemistry Course 14 Synthesis of Organic Compounds” Reaction V "2605 (Maruzen), Tadao Nakatani" Theoretical Organic Chemistry "217 (Tokyo Kagaku Dojin), Chemical Review, 91, 165-195 (1991) .

  In general formula (III), X represents a linear, branched or cyclic alkylene group having 0 to 30 carbon atoms (preferably 4 to 20 carbon atoms). Examples thereof include a propylene group, a butylene group, a 2-methylbutylene group, a 1,3-cyclobutylene group, a 1,4-cyclohexylene group, and a di-1,4-cyclohexylene group. In addition, the alkylene group referred to here may be configured such that —CH 2 — is substituted with —O—, —S—, —NR— (R is a hydrogen atom or a substituent), or —CO—. For example, the following structure is mentioned.

  In the general formula (III), n represents an integer of 0 to 2, preferably 0 or 1.

  The repeating unit represented by the general formula (III) is preferably a repeating unit represented by the following general formula (III ').

General formula (III ')

In the general formula (III ′), A ¹ and A ² each represent a group selected from —O—, —NR— (where R is a hydrogen atom or a substituent), —S—, and —CO—; ¹ and L ² each represent a single bond or a divalent linking group, R ¹ , R ² and R ³ each represent a substituent, and n represents an integer of 0 to 2.
In general formula (III ′), A ¹ , A ² , L ¹ , L ² , R ¹ , R ² , R ³ , and n are respectively A ¹ , A ² , L ¹ , in general formula (III), ^{L 2, R 1, R 2} , R 3, and have the same meanings as n, preferred ranges are also the same.

  Specific examples of the repeating unit represented by the general formula (III) or (III ′) are shown below, but the present invention is not limited thereto.

  The second polymer may be a polymer composed only of polymerized units represented by the general formula (III), or may contain other polymerized units. The molecular weight is preferably 1000 to 1000000, more preferably 1000 to 500000. The polymer containing the polymer unit represented by the general formula (III) can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  In the embodiment in which the liquid crystal composition of the present invention contains a discotic compound, it is preferable to use a polymer containing a polymer unit represented by the following general formula (IV) as the second polymer.

Formula (IV)

In the formula (IV), X ¹ , X ² and X ³ are each independently a single bond, —NR— (where R is a substituent or a hydrogen atom), —O— or —S—; R ¹ , R ² and R ³ are each independently an alkynyl group, alkenyl group, arylene group or divalent heterocyclic group which may have a substituent; Y ¹¹ , Y ¹² and Y ¹³ are each -CR = (R is a substituted group or a hydrogen atom) is or -N =, L ¹ represents a single bond or a divalent linking group.

In the formula (IV), Y ¹¹ , Y ¹² and Y ¹³ are preferably —N═, that is, a polymer containing a repeating unit represented by the following formula (V) is preferred.

Formula (V)

In the formula (V), X ¹ , X ² , X ³ , R ¹ , R ² , R ³ and L ¹ have the same meanings as in the formula (IV).

In the formulas (IV) and (V), X ¹ , X ² and X ³ are each preferably —NR—. R is a substituent or a hydrogen atom, and is preferably a substituted or unsubstituted alkyl group. Among these, an alkyl group substituted with an unsubstituted alkyl group is preferable. R ^{1 to} R ³ are each preferably an alkylene group, and preferably a C _{1 to} C ₁₀ alkylene group. L ¹ is preferably —NH—, —O—, or —S—, and preferably —NH or —O—.
Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, Isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4 -N-dodecylcyclohexyl group), a bicycloalkyl group (preferably a mono- or di-substituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octane- -Yl group), an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms). That is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), bicyclo Alkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. For example, bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl ), An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or a propargyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, For example, a phenyl group, p-tolyl group, naphthyl group), a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group. ), Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy group, ethoxy Group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy group 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy Group, tert-butyldimethylsilyloxy group), heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyl Oxy group), acyloxy group (preferably formyloxy group, carbon number 2-3) Substituted or unsubstituted alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p- Methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholino A carbonyloxy group, an N, N-di-n-octylaminocarbonyloxy group, an Nn-octylcarbamoyloxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms) For example, methoxyca A bonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, , Phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms) A substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formyl Amino group, 1-30 carbon atoms Substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonyl An amino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino; Group), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, and an n-octadeci group. An oxycarbonylamino group, an N-methyl-methoxycarbonylamino group), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as a phenoxycarbonylamino group, p- Chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino Group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, carbon number) 6-30 substituted or unsubstituted Reelsulfonylamino group, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably Is a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group or an n-hexadecylthio group, an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, Phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulf Famoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms substituted or An unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl and an arylsulfonyl group ( Preferably, a C1-C30 substituted or unsubstituted Substituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group) A substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an acetyl group and a pivaloylbenzoyl group, and an aryloxycarbonyl group (preferably A substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group), an alkoxycarbonyl group (Preferably 2-30 carbon atoms A substituted or unsubstituted alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms) Groups such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group), aryl and heterocyclic azo groups ( Preferably, it is a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3 , 4-thiadiazol-2-ylazo group), imide group (preferably , N-succinimide group, N-phthalimide group), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group) A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group), a phosphinyloxy group (preferably A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having 2 to 30 carbon atoms) Substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group, Tilaminophosphinylamino group) and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as a trimethylsilyl group, a tert-butyldimethylsilyl group, and a phenyldimethylsilyl group).

  Specific examples of the repeating unit represented by the general formula (IV) or (V) are shown below, but are not limited thereto.

  The second polymer may be a polymer composed only of polymerized units represented by the general formula (IV), or may contain other polymerized units. The molecular weight is preferably 2000 to 100,000, and more preferably 3000 to 80,000. In addition, the polymer containing the polymer unit represented by the general formula (IV) can be produced by a known and commonly used method. For example, it can be produced by adding a general-purpose radical polymerization initiator in an organic solvent and polymerizing it. Or depending on the case, it can manufacture by the method similar to the above by adding another addition polymerizable unsaturated compound. Depending on the polymerizability of each monomer, a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition. Depending on the type of monomer used, methods such as anionic polymerization, cationic polymerization, and emulsion polymerization may be used.

  When using the liquid-crystal composition of this invention for formation of an optically anisotropic layer, it is preferable that content of the said liquid-crystal compound is 20-100 mass%, and it is more preferable that it is 50-100 mass%. The content of the first polymer is preferably 0.01 to 50% by mass and more preferably 0.05 to 20% by mass with respect to the liquid crystal compound. In addition, the content of the second polymer is preferably 0.01 to 50% by mass and more preferably 0.05 to 20% by mass with respect to the liquid crystal compound.

[Phase difference plate]
The retardation plate of the present invention is characterized by having an optically anisotropic layer made of the composition of the present invention. One aspect of the retardation plate of the present invention 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 said optically anisotropic layer consists of the liquid-crystal composition of this invention. The composition is preferably curable, and the liquid crystal compound preferably has a polymerizable group or contains a polymerizable monomer separately. Further, the composition may contain a polymerization initiator and other additives as desired. For example, the composition of the present invention is prepared as a coating solution, the coating solution is applied to the surface of an alignment film formed on a support, and the molecules of the liquid crystal compound are aligned and then cured by polymerization. An optically anisotropic layer can be formed by fixing molecules in that state. After forming the optically anisotropic layer, the support may be peeled off.

The optically anisotropic layer is formed on a support by applying a coating solution prepared by dissolving a liquid crystal compound and the first and second polymers in a solvent capable of dissolving the alignment, and is provided 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., simultaneously aligning the molecules of the liquid crystal 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 20 mJ / cm ^{2 to} 50 J / cm ² , and more preferably 100 mJ / cm ^{2 to} 800 mJ / cm ² . In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the optically anisotropic layer formed in this manner varies depending on the optimum retardation value depending on the application such as optical compensation, but is generally preferably 0.1 to 10 μm, More preferably, it is 0.5-5 micrometers.

  The molecules of the liquid crystal compound are preferably substantially uniformly oriented in the optically anisotropic layer, more preferably fixed in a substantially uniformly oriented state, and polymerization reaction. It is more preferable that the liquid crystal compound is fixed by the above.

  Ratio of the liquid crystal compound (preferably a compound represented by the general formula (DI) or a polymer obtained from the compound represented by the general formula (DI)) in the composition for forming the optically anisotropic layer Is preferably 10 to 100% by mass, more preferably 30 to 99% by mass, and still more preferably 50 to 99% by mass.

  The composition of the present invention used for forming the optically anisotropic layer preferably contains a polymerization initiator. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and EB curing using an electron beam. Among these, photopolymerization reaction (photocuring) and EB curing are preferable. Examples of polymerization initiators that generate radicals by the action of light include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (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), triarylimidazole dimer and p-aminophenyl Combinations with ketones (described in U.S. Pat. No. 3,549,367), acridine and phenazine compounds (described in JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,221,970) Acetophenone) Compounds, benzoin ether compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, and the like are preferable. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy -2-methyl-propiophenone, p-dimethylaminoacetone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like. Examples of the benzyl compound include benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, 1-hydroxycyclohexyl phenyl ketone and the like. Examples of the benzoin ether compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, and benzoin isobutyl ether. Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and the like. Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. Among such photosensitive radical polymerization initiators composed of aromatic ketones, acetophenone compounds and benzyl compounds are particularly preferable in terms of curing characteristics, storage stability, odor, and the like. The photosensitive radical polymerization initiators composed of these aromatic ketones can be used alone or in combination of two or more according to the desired performance. In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like.

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

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

  When the composition of the present invention is prepared as a coating solution, the solid content concentration in the coating solution is preferably 0.1% by mass to 60% by mass, more preferably 0.5% by mass to 50% by mass. More preferably, 40% by mass. The viscosity of the coating solution is preferably 0.01 cp to 100 cp, more preferably 0.1 cp to 50 cp.

  The optically anisotropic layer formed by the composition of the present invention fixes the state in which the discotic nematic phase is hybrid-aligned when used as a phase difference plate in a liquid crystal display mode such as TN (Twisted Nematic). Is preferable. Here, the hybrid alignment represents a state in which the tilt angle of the liquid crystal compound continuously changes in the film thickness direction.

After the liquid crystal compound is applied on the support (more preferably on the alignment film), the liquid crystal phase is expressed by, for example, heating, so that the liquid crystal compound has a support surface or a coating film interface (alignment film provided on the support side interface). In the case of using a discotic liquid crystal compound, the orientation is made at the support surface and the disc surface direction of the liquid crystal compound, and the air interface is tilted at the interface with air. It will be oriented at the corners.
In the present invention, the average tilt angle of the liquid crystal molecules in the optically anisotropic layer (for example, the angle formed between the layer surface and the disc surface direction of the molecules of the discotic liquid crystal compound) is preferably 10 to 70 °, and 15 to 50 °. Is more preferable, and 20 to 35 ° is even more preferable.
Further, the tilt angle at each interface is a combination of the tilt angle at the air interface of 0 to 50 ° and the tilt angle of the support side interface of 20 to 90 °, or the tilt angle of the support side interface of 0 to 50 °. A combination in which the tilt angle of the air interface is 20 to 90 ° is preferable. In particular, a combination in which the tilt angle of the air interface is 0 to 40 ° and the tilt angle of the support side interface is 40 to 80 °, or the tilt angle of the support side interface is 0 to 40 ° and the tilt angle of the air interface is 40 to 40 °. A combination of 80 ° is preferred.

(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, rubbing treatment of a compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a micro groove, 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 crystal compound, a crosslinkable function having a function of bonding a side chain having a crosslinkable functional group (for example, a double bond) to the main chain or aligning the liquid crystal compound. It is preferred to introduce the 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, methacrylate polymer, styrene polymer, polyolefin, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), polyester described in paragraph No. [0022] of JP-A-8-338913. , Polyimide, vinyl acetate polymer, carboxymethyl cellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are more preferable. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization.

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

A side chain having a function of aligning a 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 Atom-substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy groups, dialkoxy groups, monoalkoxy groups) and the like can be mentioned. Specific examples of these modified polyvinyl alcohol compounds include, for example, paragraphs [0022] to [0145] of JP-A No. 2000-155216 and paragraphs [0018] to [0022] of JP-A No. 2002-62426. And the like.

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

Apart from the crosslinkable functional group, the alignment film polymer can also be crosslinked using a crosslinking agent.
Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraph numbers [0023] to [0024] of JP-A 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 when the alignment film is used for a long time in a liquid crystal display device or left in a high-temperature and high-humidity atmosphere for a long time, sufficient durability without occurrence of reticulation can be obtained.

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

  The coating method used for forming the alignment film is preferably a spin coating method, a dip coating method, a curtain coating method, an extrusion coating method, a rod coating method or a roll coating method. A rod coating method is particularly preferable. The film thickness after drying is preferably 0.1 to 10 μm. The heat drying can be performed at 20 ° C. to 110 ° C., for example. In order to form sufficient cross-linking, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is more preferable. The drying time can be, for example, 1 minute to 36 hours, and preferably 1 minute to 30 minutes. The pH is also preferably set to an optimum value for the crosslinking agent to be used. When glutaraldehyde is used, pH 4.5 to 5.5 is preferable, and 5 is more preferable.

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

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

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

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

In addition to the alignment film polymer, an additive may be appropriately added to the coating solution. For example, when the alignment film polymer is difficult to dissolve in a water-soluble solvent, a basic compound (for example, sodium hydroxide, lithium hydroxide, triethylamine, etc.), 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 of the present invention may have a support, and the support is preferably a transparent support. The support is not particularly limited as long as it is optically isotropic and has a light transmittance of 80% or more, but a polymer film is preferable. Specific examples of the polymer include cellulose esters (for example, cellulose diacetate, cellulose triacetate), norbornene-based polymers, poly (meth) acrylate esters, and the like, and many commercially available polymers are preferably used. Is possible. Among these, cellulose esters are preferable from the viewpoint of optical performance, and lower fatty acid esters of cellulose are more preferable. The lower fatty acid is a fatty acid having 6 or less carbon atoms, and preferably having 2, 3, or 4 carbon atoms. Specific examples include cellulose acetate, cellulose propionate, and cellulose butyrate. Among these, cellulose triacetate is particularly preferable. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used. Further, even a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence is used by reducing the expression by modifying the molecule described in International Publication WO00 / 26705. You can also.

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

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

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

  The number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 8, and particularly preferably 2 to 6. . The bonding relationship between two aromatic rings can be classified into (a) when forming a condensed ring, (b) when directly connecting with a single bond, and (c) when connecting via a linking group (for aromatic rings). , Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c). Such retardation increasing agents are disclosed in International Publication WO01 / 88574, International Publication WO00 / 2619, JP2000-1111914, JP2000-275434, JP2002-363343, and the like. Are listed.

  The cellulose acetate film is preferably produced from the prepared cellulose acetate solution (dope) by a solvent cast method. The above-mentioned retardation increasing agent may be added to the dope. The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. The surface of the drum or band is preferably finished in a mirror state. The casting and drying methods in the solvent casting method are described in U.S. Pat. Nos. 2,336,310, 2,367,603, 2,429,2078, 2,429,297, 2,429,978, 2,607,704, 2,273,069, and 2,739,070, British Patent 6,407,331. No. 736892, JP-B 45-4554, JP-B 49-5614, JP-A-60-176834, JP-A-60-203430, JP-A-62-115035 There are descriptions in each publication. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

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

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

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

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

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

  The cellulose acetate film is preferably subjected to a surface treatment. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is preferable to provide an undercoat layer. From the viewpoint of maintaining the flatness of the film, the temperature of the cellulose acetate film in these treatments is preferably Tg (glass transition temperature) or less, specifically 150 ° C. or less.

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

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

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

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

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

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

  In the present invention, liquid crystal cell retardation plates (optical compensation sheets) of various modes can be prepared with reference to the above-mentioned publications. The phase difference plate is composed of TN (Twisted Nematic), IPS (In-PDane Switching), FDC (Ferroelectric Diid Liquid CrystaD), OCB (OpticaDyDenHyDV, STN (SupidDV). 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 (MeOH), and 2.8 ml of 50% hydroxylamine solution was added, followed by stirring at 40 ° C. for 1 hour. After cooling, water was added to the reaction solution, and the precipitated crystals were separated by filtration and dried to obtain 3.4 g of D3-10A.

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

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

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

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

[Synthesis Example 2: Synthesis of Polymer (1)]
A polymer (1) was synthesized according to the following scheme.

Synthesis from compound (1-A) to compound (1-D) was performed by Journal of Chemical Crystallography (1997); 27 (9); 515-526. It carried out by the method of description.
20.7 g of compound (1-D), 2.0 g of p-sec-butylphenol, 1.8 g of tetrabutylammonium chloride, 200 ml of dichloromethane, 64 ml of 2 mol / L sodium hydroxide aqueous solution, 86 ml of water, equipped with a stirrer The reaction vessel was put into a reaction vessel and stirred at room temperature (25 ° C.) 300 rpm under a nitrogen stream. After 30 minutes, a solution of 11.2 g of adipic acid chloride dissolved in 100 ml of dichloromethane was added. Thereafter, stirring was continued for 3 hours, and then 100 mL of dichloromethane was added to separate the organic phase. Further, a solution obtained by diluting 0.52 ml of 12 mol / L hydrochloric acid water with 250 ml of water was added to wash the organic layer. After further washing with 250 ml of water twice, 100 ml of dichloromethane was added to the separated organic layer, diluted, and then poured into 2.5 liters of vigorously stirred methanol over 1 hour. The milky white precipitate obtained was collected by filtration in methanol, heat-dried at 40 ° C. for 12 hours, and then dried at 70 ° C. for 3 hours under reduced pressure to obtain 36.9 g of polymer (1).
As a result of measuring the molecular weight of the obtained polymer (1) with GPC (THF solvent), the weight average molecular weight was 10,900.
In addition, regarding the solution absorption of the compound (1-D), it is determined that λ _max : 338 nm and λ _max : 349 nm are Journal of Chemical Crystallography (1997); 27 (9); 515-526. It is described in. Adipic acid was also measured in the same manner as in the above document, but no absorption was observed at λ> 300 nm.

[Synthesis Example 3: Synthesis of Polymer (2)]
First, compound (2-B) was synthesized according to the following scheme. The synthesis from compound (2-A) to compound (2-B) was performed by a known method.

20.7 g of the compound (1-D) produced above, 2.0 g of p-sec-butylphenol, 1.8 g of tetrabutylammonium chloride, 200 ml of dichloromethane, 64 ml of 2 mol / L sodium hydroxide aqueous solution, 86 ml of water, stirring The mixture was put into a reaction vessel equipped with an apparatus, and stirred at room temperature (25 ° C.) 300 rpm under a nitrogen stream. After 30 minutes, a solution of 8.96 g of adipic acid chloride and 2.56 g of compound (2-B) dissolved in 110 ml of dichloromethane was added. Thereafter, stirring was continued for 3 hours, and then 100 mL of dichloromethane was added to separate the organic phase. Further, a solution obtained by diluting 0.52 ml of 12 mol / L hydrochloric acid water with 250 ml of water was added to wash the organic layer. After further washing with 250 ml of water twice, 100 ml of dichloromethane was added to the separated organic layer, diluted, and then poured into 2.5 liters of vigorously stirred methanol over 1 hour. The milky white precipitate obtained was collected by filtration in methanol, dried by heating at 40 ° C. for 12 hours, and then dried at 70 ° C. for 3 hours under reduced pressure to obtain 37.0 g of the polymer (2).
As a result of measuring the molecular weight of the obtained polymer (2) with GPC (THF solvent), the weight average molecular weight was 10,500.
For Compound (2-A), Journal of Chemical Crystallography (1997); 27 (9); 515-526. As a result, the absorption was not observed at λ> 300 nm.

[Example 1: Preparation of liquid crystal compositions (LM-1 to LM-6)]
A composition (LM-1) having the following composition was prepared.
Composition of composition (LM-1) Liquid crystal compound: D3-10 100 parts by mass Additive A (F-1): 0.4 parts by mass Additive B (1) 1.0 part by mass Irgacure 907 ( Ciba Specialty Chemicals Co., Ltd.) 3.0 parts by mass, diethylthioxanthone 1.0 parts by mass, methyl ethyl ketone 250 parts by mass

In the preparation of the composition LM-1, the polymer (F-1) used as the additive A (first polymer) and the polymer (1) used as the additive B (second polymer) are shown in the following table. The compositions (LM-2) to (LM-6) of the present invention were prepared in the same manner except that they were changed to the polymers described in 1.
In any of the polymers used as additive A in the following table, the composition to which the polymer is added improves the smoothness of the surface of the film made of the composition compared to the composition to which the polymer is not added. And the polymer used as the additive B in the above table changes the average tilt angle of the molecules of the liquid crystal compound D3-10 in the presence and absence thereof, thereby adjusting the average tilt angle. It was confirmed to have properties.

[Comparative Example 1: Preparation of comparative compositions (LH-1, LH-2, LH-3)]
A comparative composition (LH-1) was prepared in the same manner as the composition (LM-1) of Example 1 except that additive A (F-1) and additive B (1) were not added. Prepared. Further, a comparative composition (LH-2) was prepared in the same manner as the composition (LM-1) of Example 2 except that the polymer (1) having the ability to adjust the average tilt angle was not added. .
Further, a composition for comparison was made in the same manner as the composition (LM-1) of Example 2 except that the following polymer W-1 having the same ability to adjust the average tilt angle was used instead of the polymer (1). (LH-3) was prepared.

  In addition, according to the said method, the surface energy of the liquid crystal compound in the table | surface, additive A, and additive B was measured. The measured values are shown in Table 2 below.

[Example 2: Production of retardation plates (RM-1 to RM-6) of the present invention]
(Preparation of transparent support)
The following components were put into a mixing tank and heated and stirred to prepare a cellulose acetate solution (hereinafter sometimes referred to as a dope).
――――――――――――――――――――――――――――――――――――
Cellulose acetate solution composition ――――――――――――――――――――――――――――――――――――
Cellulose acetate having an acetylation degree of 60.9% 100 parts by mass Triphenyl phosphate 6.5 parts by mass Biphenyl diphenyl phosphate 5.2 parts by mass The following retardation increasing agent (1) 0.1 part by mass The following retardation increasing agent ( 2) 0.2 parts by mass Methylene chloride 310.25 parts by mass Methanol 54.75 parts by mass 1-butanol 10.95 parts by mass ―――――――――――――――――――――― ――――――――――――――

Retardation raising agent (1)

Retardation increasing agent (2)

  The obtained dope was cast from a casting port onto a drum cooled to 0 ° C. The film is peeled off at a solvent content of 70% by mass, both ends in the width direction of the film are fixed with a pin tenter, and the stretch rate in the width direction (direction perpendicular to the machine direction) is in a region where the solvent content is 3 to 5% by mass. Was dried while maintaining an interval of 3%. Thereafter, the film is further dried by being conveyed between rolls of a heat treatment apparatus. In a region exceeding 120 ° C., the stretching ratio in the machine direction is substantially 0%, and the ratio between the stretching ratio in the width direction and the stretching ratio in the machine direction is 0.00. A cellulose acetate film having a thickness of 100 μm was prepared by adjusting to 75. When the retardation value of the produced film was measured at a wavelength of 632.8 nm, the retardation value in the thickness direction was 40 nm, and the in-plane retardation value was 4 nm. The produced cellulose acetate film was used as a support.

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

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

――――――――――――――――――――――――――――――――――――
Composition of the second undercoat coating solution ―――――――――――――――――――――――――――――――――――
The following anionic polymers 0.77 parts by mass Citric acid monoethyl ester 10.1 parts by mass Acetone 200 parts by mass Methanol 877 parts by mass Water 40.5 parts by mass ――――――――――――――― ――――――――――――――――――――

Anionic polymer

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

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

This solution was applied onto the second undercoat layer and dried with hot air at 100 ° C. for 120 seconds, followed by a rubbing treatment to form an alignment film. The thickness of the obtained alignment film was 0.5 μm. The rubbing direction of the alignment film was parallel to the casting direction of the transparent support.
(Formation of optically anisotropic layer)
The coating liquid of the composition (LM-1) of the present invention prepared above was applied onto the rubbing treated surface of the alignment film prepared above using a wire bar. The film coated with the optically anisotropic layer was oriented in a constant temperature bath at 120 ° C., and irradiated with 200 mJ / cm ² of ultraviolet rays at the same temperature to fix the orientation state of the optically anisotropic layer. The solution was allowed to cool to room temperature to produce a retardation plate (RM-1) of the present invention. The thickness of the formed optically anisotropic layer was about 0.7 μm.

  In the production of the phase difference plate RM-1, everything was the same except that the composition (LM-1) was changed to the compositions (LM-2) to (LM-6), and the phase difference plate (RM-2). ) To (RM-6).

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

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

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

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

From the results of Table 3, the retardation plates (RM-1) to (RM-7) of the present invention are optically anisotropic compared to the retardation plates (RH-1) to (RH-3) of the comparative examples. It can be understood that the average tilt angle of the conductive layer is low and the planar smoothness is good.
From these results, it is understood that when the composition of the example of the present invention is used, an optically anisotropic layer having a hybrid orientation with a low average tilt angle can be stably formed, and the surface smoothness thereof is also improved. it can.

Claims (12)

A liquid crystal composition comprising at least one liquid crystal compound and at least two kinds of polymers, wherein one of the at least two kinds of polymers improves the smoothness of the surface of the film made of the composition. Is a polymer having the property (first polymer), and the other type is a polymer (second polymer) having the property of adjusting the average tilt angle of the molecules of the liquid crystal compound. A liquid crystal composition satisfying 1):
Formula (1) EA <EB <EL
In the formula, EA is the surface energy of the first polymer, EB is the surface energy of the second polymer, and EL is the surface energy of the liquid crystal compound. The liquid crystal composition according to claim 1, wherein the first polymer is a polymer containing a polymer unit derived from a monomer represented by the following general formula (I):
Formula (I)

In general formula (I), R ¹ represents a hydrogen atom, a halogen atom or an alkyl group, L ¹ represents a divalent linking group, m represents an integer of 1 to 12, and X ¹ represents a fluorine atom or Represents a hydrogen atom. The liquid crystal composition according to claim 2, wherein L ¹ in the formula (I) is a linking group represented by the following general formula (II):
Formula (II)
^{(A) -X 10 -R 20 -} (b)
In the general formula (II), (a) represents a position bonded to the double bond side, and (b) represents a position bonded to the fluoroaliphatic group side; X ¹⁰ represents a single bond or * -COO- * *, * -COS-**, * -OCO-**, * -CON (R ²¹ )-**, or a divalent linking group represented by * -O-**, where * is a formula (I) a position bonded to the double bond side, ** represents a position bonded to R ²⁰ ; R ²¹ represents a hydrogen atom or an optionally substituted carbon atom having 1 to 8 carbon atoms. R ²⁰ represents an optionally substituted polymethylene group, an optionally substituted phenylene group, or any combination thereof. Represents a group that can be formed. The liquid crystal composition according to any one of claims 1 to 3, wherein the second polymer is a polymer containing a polymer unit represented by the following general formula (III).

In the formula, A ¹ and A ² each represent a group selected from —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, —CO—; L ¹ and L ² are each Represents a single bond or a divalent linking group; R ¹ , R ² and R ³ each represents a substituent; n represents an integer of 0 to 2; X represents a straight chain having 0 to 30 carbon atoms, A branched or cyclic alkylene group is represented. The liquid crystal composition according to any one of claims 1 to 3, wherein the second polymer is a polymer including a polymer unit represented by the following general formula (IV).
Formula (IV)

In the formula, X ¹ , X ² and X ³ are each independently a single bond, —NR— (R is a substituent or a hydrogen atom), —O— or —S—; R ¹ , R ² and R ³ is each independently an alkynyl group, alkenyl group, arylene group or divalent heterocyclic group which may have a substituent; Y ¹¹ , Y ¹² and Y ¹³ each represent —CR═ ( R represents a substituent or a hydrogen atom) or —N═; L ¹ represents a single bond or a divalent linking group. The liquid crystal composition according to claim 1, wherein the liquid crystal compound is a compound represented by the following general formula (DI).
General formula (DI)

In 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 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 position where L ^{1 to} L ³ are bonded. ** represents a position where R ^{1 to} R ³ are bonded;
General formula (DI-B)

In the 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; * is bonded to L ^{1 to} L ³ Represents a position, and ** represents a position where R ^{1 to} R ³ are bonded;
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 represents a group having at least one cyclic structure. 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—, or * —C≡C— (where * represents a position bonded to the side opposite to L ^13. L ¹³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C— and Represents a divalent linking group selected from the group consisting of these combinations, and when these groups are groups containing hydrogen atoms, the hydrogen atoms may be substituted with substituents; Q ¹ is polymerizable Group or hydrogen atom It is. The liquid crystal composition according to claim 6, wherein the liquid crystal compound is a liquid crystal compound represented by the following general formula (DII):
General formula (DII)

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

In the 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; F ¹ represents at least one cyclic 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 represented (* is bonded to the side 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 these 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. 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 phase difference plate according to claim 8, wherein the alignment film contains polyvinyl alcohols. The phase difference plate according to claim 8 or 9, wherein the optically anisotropic layer contains a discotic liquid crystal compound with hybrid alignment. An elliptically polarizing plate comprising the phase difference plate according to claim 8 and a polarizing film. The liquid crystal display device which has a phase difference plate of any one of Claims 8-10.