JP2009062508A - Liquid crystal composition and optically anisotropic film - Google Patents

Abstract

【選択図】なしA novel liquid crystal composition useful for producing an optically anisotropic film or the like is provided.
SOLUTION: At least one compound represented by the following general formula (1) in which Δn is reverse wavelength dispersion in the visible light region and at least one liquid crystal compound in which Δn is forward wavelength dispersion in the visible light region are contained. It is a liquid crystal composition characterized by doing. In the formula, A ¹ and A ² each independently represent —O—, —NR— or the like; Z represents a carbon atom or the like, and C—C═C—C or C═C—C described in the formula ═C forms a 5- or 6-membered ring; R ¹ , R ² and R ³ each independently represent a substituent; m is an integer of 0 to 4; L ¹ and L ² each represent a linking group. X represents a nonmetallic atom such as carbon. (However, the compound has at least one polymerizable group.)

[Selection figure] None

Description

  The present invention relates to a liquid crystal composition and an optically anisotropic film formed from the liquid crystal composition.

Liquid crystal compounds are used as important materials for performing a light shutter function in liquid crystal display devices represented by so-called liquid crystal displays. In recent years, various optical compensation materials have been developed for the purpose of improving the display characteristics of a liquid crystal display, particularly when viewed from an oblique direction. The optical compensation material is produced by stretching the polymer, aligning the polymer liquid crystal, or aligning the low molecular liquid crystal material and then fixing the alignment. The method using a low-molecular liquid crystal material has an excellent feature that the alignment speed is higher than that of the high-molecular liquid crystal material and the optical properties are hardly changed because the alignment is fixed by a polymerization reaction or the like.
By the way, most of the refractive index anisotropy materials have so-called forward wavelength dispersion, in which the wavelength dependency of the refractive index is large on the short wavelength side and small on the long wavelength side, and the long wavelength side is large and the short wavelength side is large. There are few materials that exhibit small so-called reverse wavelength dispersion (for example, Patent Document 1). On the other hand, with respect to the phase difference of the optical compensation material, there are various demands such that forward wavelength dispersion is desired in some applications and reverse wavelength dispersion is desired in other applications. Also, the degree of wavelength dispersion of the phase difference needs to be adjusted to a range suitable for optical compensation depending on the application.
JP 2005-289980 A

It is an object of the present invention to provide a novel liquid crystal composition useful for producing an optically anisotropic material such as an optically anisotropic film, and a novel optically anisotropic film formed from the liquid crystal composition. To do.
The present invention also provides a liquid crystal composition capable of easily adjusting the wavelength dispersion of refractive index anisotropy and easily producing an optically anisotropic film exhibiting a desired wavelength dispersion with a phase difference. This is the issue.

式中、Ａ¹及びＡ²は各々独立に、−Ｏ−、−ＮＲ−（Ｒは水素原子又は置換基を表す。）、−Ｓ−及び−ＣＯ−からなる群から選ばれる基を表し；Ｚは、炭素原子及び第１４〜１６族の非金属原子からなる群から選択される１つ又は２つの原子を表し、式中記載のＣ−Ｃ＝Ｃ−Ｃ又はＣ＝Ｃ−Ｃ＝Ｃと共に５又は６員環を形成し；Ｒ¹、Ｒ²及びＲ³は各々独立に置換基を表し；ｍは０〜４の整数であり；Ｌ¹及びＬ²は各々独立に単結合又は二価の連結基を表す。Ｘは第１４〜１６族の非金属原子を表し（ただし、Ｘには水素原子又は置換基Ｒ⁴が結合してもよい）；但し、Ｒ、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴の少なくとも１つは、重合性基を有する置換基である。 Means for solving the above problems are as follows.
[1] Contains at least one compound represented by the following general formula (1) in which Δn is reverse wavelength dispersion in the visible light region and at least one liquid crystal compound in which Δn is forward wavelength dispersion in the visible light region. Liquid crystal composition characterized by:

In the formula, A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S—, and —CO—; Z represents one or two atoms selected from the group consisting of a carbon atom and a non-metal atom of Groups 14 to 16, and C—C═C—C or C═C—C═C described in the formula And R ¹ , R ² and R ³ each independently represents a substituent; m is an integer of 0 to 4; L ¹ and L ² are each independently a single bond or two Represents a valent linking group. X represents a nonmetal atom of Groups 14 to 16 (provided that a hydrogen atom or a substituent R ⁴ may be bonded to X); provided that R, R ¹ , R ² , R ³ and R ⁴ At least one is a substituent having a polymerizable group.

式中、Ａ¹、Ａ²、Ｚ、Ｒ¹、Ｒ²、Ｒ³、ｍ、Ｌ¹及びＬ²は、一般式（１）中のそれぞれと同義であり、Ｒ⁵及びＲ⁶は、各々独立に置換基を表し；但し、Ｒ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵及びＲ⁶の少なくとも１つには重合性基を有する置換基である。 [2] The liquid crystal composition according to [1], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2):

In the formula, A ¹ , A ² , Z, R ¹ , R ² , R ³ , m, L ¹ and L ² have the same meanings as in general formula (1), and R ⁵ and R ⁶ are each Each independently represents a substituent; provided that at least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ is a substituent having a polymerizable group;

[3] In the formula (2), R ⁵ and R ⁶ are each a cyano group (CN), an acyl group (—COR: R represents a substituted or unsubstituted alkyl group or aryl group), substituted or unsubstituted. Or an aryloxycarbonyl group (C (═O) OR: R represents a substituted or unsubstituted alkyl group or aryl group), or a substituted or unsubstituted carbamoyl group (C (═O) NR ^11. R ¹² : R ¹¹ and R ¹² each represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group, which may be bonded to each other to form a ring] [2 ] Liquid crystal composition.
[4] Any one of [1] to [3], wherein the ring formed by Z and C—C═C—C or C═C—C═C in the formula is an aromatic ring. Liquid crystal composition.

式中、Ｌ¹¹は、単結合もしくは連結基であり、Ｒ¹¹は置換基である。 [5] The liquid crystal composition according to any one of [1] to [4], wherein R ² and R ³ are each represented by any of the following formulae.

In the formula, L ¹¹ is a single bond or a linking group, and R ¹¹ is a substituent.

[6] Any of [1] to [5], wherein the compound represented by the general formula (1) and the liquid crystal compound are contained in a mass ratio of 1:10 to 10: 1. Liquid crystal composition.
[7] An optically anisotropic film formed from the liquid crystal composition according to any one of [1] to [6].

According to the present invention, it is possible to provide a novel liquid crystal composition useful for producing an optically anisotropic film, and a novel optically anisotropic film formed from the liquid crystal composition.
Further, according to the present invention, there is provided a liquid crystal composition capable of easily adjusting the wavelength dispersion of refractive index anisotropy and easily producing an optically anisotropic film having a desired wavelength dispersion with a phase difference. Can be provided.

  Hereinafter, the present invention will be described in detail. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Definition of Re (λ) and Rth (λ)]
In this specification, Re (λ) and Rth (λ) each represent in-plane retardation (nm) and retardation in the thickness direction (nm) at wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (trade name, manufactured by Oji Scientific Instruments). In selecting the measurement wavelength λnm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.

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 the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, Rth (λ) With respect to the film normal direction (with an arbitrary direction as the rotation axis), the light of wavelength λ nm is incident from each inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side, and a total of 6 points are measured. It is calculated in KOBRA 21ADH or WR 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 in 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 by the following formulas (1) and (2).

  In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction. nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. d represents the film thickness of the film.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film without a 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 (rotary axis), and −50 ° to + 50 ° with respect to the film normal 11 points of light having a wavelength of λ nm are incident from the inclined direction in 10 degree steps until KOBRA 21ADH is measured based on the measured retardation value, the assumed average refractive index, and the input film thickness value. Or it is calculated by WR.

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

[Definition of Δn]
Δn indicates anisotropy with respect to polarized light, and is described in detail in “Liquid Crystal Handbook” (Maruzen Co., Ltd., 2000), Chapter 2, 2.3 Physical Properties. When linearly polarized light passes, the difference between the refractive index (no) when the polarization direction is perpendicular to the anisotropic axis and the refractive index (ne) when the polarization direction is parallel to the anisotropic axis is represented by Δn.

[Definition of chromatic dispersion of Δn]
Δn generally varies depending on the measurement wavelength. This is because the aforementioned no and ne differ depending on the wavelength, and the chromatic dispersion of Δn indicates the wavelength dependence of the difference in refractive index between no and ne. Details are described in “Liquid Crystal Handbook” (Maruzen Co., Ltd., 2000), Chapter 2, 2.4.13. In the present invention, Δn (450), Δn (550), and Δn (650) may be expressed, and Δn at 450 nm, 550 nm, and 650 nm, respectively. However, each measurement wavelength includes an error of ± 10 nm.

Examples of the method for measuring Δn of liquid crystal include a method using a wedge-shaped liquid crystal cell as described in “Liquid Crystal Handbook” 2.4.13 (Maruzen Co., Ltd., 2000). In this method, Δn of each wavelength is obtained by using three types of band-pass filters of 450 nm, 550 nm, and 650 nm.
If the material to be measured is polymerizable, a polymerization reaction may occur in a wedge-shaped liquid crystal cell, which may make measurement difficult. In such a case, it is preferable to measure by adding a polymerization inhibitor. In addition, in a state where the liquid crystal is uniformly aligned, Re is obtained at each wavelength by measuring with a device capable of measuring a phase difference such as KOBRA (trade name, manufactured by Oji Scientific Instruments Co., Ltd.). By separately measuring the thickness, Δn can also be obtained (from the equation: Δn = Re / d (film thickness)).

[Definition of order and reverse in chromatic dispersion of Δn]
In general, the refractive index of a substance increases with decreasing wavelength. The liquid crystal compound follows this, and the refractive index of no and ne increases as the measurement wavelength is shorter. However, since Δn is the difference between no and ne, when the wavelength dispersions of no and ne are different, there are cases where the wavelength dispersion of Δn is large on the short wavelength side and small on the short wavelength side. In general, the short wavelength side is often large. In this specification, the property that the short wavelength side is large for Δn is referred to as “forward dispersion” or “forward wavelength dispersion”, and the property that the short wavelength side is small for Δn is “ It is called “reverse dispersion” or “reverse wavelength dispersion”.

[Definition of wavelength dependence of retardation of optically anisotropic material]
In an optical compensation material or the like, the optical anisotropy is represented by Re or Rth (the definitions thereof are as described above). When the wavelength dependence of Re or Rth is called chromatic dispersion in Re (λ) or Rth (λ), and the short wavelength side is larger in chromatic dispersion. Is called forward chromatic dispersion, and the case where the short wavelength side is small is called reverse chromatic dispersion.

[Liquid crystal composition]
First, the liquid crystal composition of the present invention will be described.
The liquid crystal composition of the present invention includes at least one compound represented by the following general formula (1) in which Δn exhibits reverse wavelength dispersion in the visible light region, and at least one compound in which Δn exhibits forward wavelength dispersion in the visible light region. And a liquid crystal compound.
The liquid crystal compound in which Δn is reverse wavelength dispersive in the visible light region refers to a compound in which Δn is smaller as the wavelength is shorter in the visible light region. Specifically, Δn (450), Δn (550) and Δn (650) are obtained by the above-described method, and Δn (450) / Δn (550), Δn (550) / Δn (650) and Δn (450) / A compound in which at least one of Δn (650) is smaller than 1. In the present invention, a compound represented by the following general formula (1) is used as the liquid crystal compound in which Δn is reverse wavelength dispersion.

In the formula, A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S—, and —CO—. Z represents one or two atoms selected from the group consisting of a carbon atom and a non-metal atom of Groups 14 to 16, and C—C═C—C or C═C—C═C described in the formula Together with it forms a 5- or 6-membered ring. R ¹ , R ² and R ³ each independently represents a substituent. m is an integer of 0-4. L ¹ and L ² each independently represents a single bond or a divalent linking group. X represents a nonmetallic atom belonging to Groups 14 to 16 (however, a hydrogen atom or a substituent R ⁴ may be bonded to X). In addition, at least one of R, R ¹ , R ² , R ³ and R ⁴ is a substituent having a polymerizable group.

Among the compounds represented by the general formula (1), compounds represented by the following general formula (2) are preferable.

In the formula, A ¹ , A ² , Z, R ¹ , R ² , R ³ , m, L ¹ and L ² are the same as those in the general formula (1). R ⁵ and R ⁶ each independently represents a substituent. In addition, at least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ is a substituent having a polymerizable group.

In the general formula (1) or (2), the divalent linking group represented by L ¹ and L ² is not particularly limited, but preferably includes the following examples. In addition, regarding the bonding position, the bonding position between the Z and the 5- to 6-membered ring formed by C—C═C—C or C═C—C═C is on the left side of the linking group exemplified below. Shall.

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

In the general formula (1) or (2), Z represents one or two atoms selected from the group consisting of a carbon atom and a nonmetal atom of Group 14 to 16, and C—C in the formula Forms a 5- or 6-membered ring with ═C—C or C═C—C═C. Although it does not specifically limit as a 5-6 membered ring formed by Z and C-C = C-C or C = C-C = C, The following example is mentioned suitably. In the following example, the dotted line represents binding to L ¹ or L ² .

The ring formed by Z and C—C═C—C or C═C—C═C is preferably a 6-membered ring. By using a 6-membered ring, it becomes possible to align with a higher degree of alignment order. For the same reason, it is preferably an aromatic ring, more preferably an aromatic ring and a 6-membered ring.
From these viewpoints and synthetic viewpoints, the ring formed by Z and C—C═C—C or C═C—C═C is preferably a thiophene ring, a benzene ring, or a pyridine ring, and the benzene ring is most preferred. preferable.

In general formula (1) or (2), R ¹ is a substituent, and when a plurality of R ¹ are present, 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 a linear, branched or unsubstituted alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, 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), bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2 2] octan-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 , C1-C30 substitution or non-placement 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 group), alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, 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 or arylsulfinyl group (preferably substituted with 1 to 30 carbon atoms or Unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl or 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),

An aryl or heterocyclic azo group (preferably 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 a phenylazo group, a 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. Specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

R ¹ is preferably a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, cyano group or amino group, more preferably halogen. An atom, an alkyl group, a cyano group, or an alkoxy group.

When a plurality of R ¹ are present and form a ring with each other, the ring is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring. Most preferred is a 6-membered ring.

In the general formula (1) or (2), m represents the number of substitutions of R ¹ , and can be taken by a ring structure formed by Z and C—C═C—C or C═C—C═C. The number changes. When m is 0 at the minimum, Z represents two carbon atoms, and the ring formed by Z and C—C═C—C or C═C—C═C has no aromaticity The maximum is 4. m is preferably 0 or 1, more preferably 0.

In the general formula (1) or (2), R ² and R ³ each independently represent a substituent. An example of R1 is given as an example. R ² and R ³ are the longitudinal direction of the molecule in the compound represented by the general formula (1) or (2).
The compound represented by the general formula (1) or (2) preferably exhibits liquid crystallinity. As an element to develop liquid crystallinity, as described in “Liquid Crystal Handbook” (Maruzen) Chapter 3 “Molecular Structure and Liquid Crystallinity”, a rigid part called a core and a flexible part called a side chain are required. It is. Therefore, it is preferable that at least one rigid part, that is, a cyclic part exists as a substituent for R ² and R ³ . R ² and R ³ are preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclohexyl group. Preferred are a phenyl group having a substituent and a cyclohexyl group having a substituent, and more preferred are a phenyl group having a substituent at the 4-position and a cyclohexyl group having a substituent at the 4-position. More preferably, a phenyl group having a benzoyloxy group having a substituent at the 4-position at a 4-position, a phenyl group having a cyclohexyl group having a substituent at the 4-position at a 4-position, and a phenyl group having a substituent at the 4-position being at the 4-position And a cyclohexyl group having a cyclohexyl group having a substituent at the 4-position at the 4-position. That is, R ² and R ³ are each more preferably a group represented by any of the following formulae.

式中、Ｌ¹¹は、単結合もしくは連結基であり、Ｒ¹¹は置換基である。Ｌ¹¹は、単結合、又は−Ｏ−、−ＣＯＯ−もしくは−ＯＣＯ−であるのが好ましい。また、Ｒ¹¹が表す置換基の例は、Ｒ¹が表す置換基の例と同様である。中でも、置換又は無置換の炭素数１〜１０のアルキルカルボニルオキシ基（シクロアルキルカルボニルオキシ基も含む意味である）、置換又は無置換の炭素数１〜１０のアルコキシ基、及び置換又は無置換の炭素数６〜１６のアリールカルボニルオキシ基が好ましく、置換もしくは無置換の炭素数１〜８のアルキルカルボニルオキシ基、置換又は無置換の炭素数１〜１０のアルコキシ基がより好ましい。当該アルキルカルボニルオキシ基またはアルコキシ基中のアルキル部分において、隣接しない炭素原子の一方が酸素原子もしくは硫黄原子に置換されていてもよい。また、当該アルキル部分の末端が、後述する重合性基、例えば（Ｍ−１）及び（Ｍ−２）、を末端に有する基などが好ましい例として挙げられるが、これらに限定されるものではない。

In the formula, L ¹¹ is a single bond or a linking group, and R ¹¹ is a substituent. L ¹¹ is preferably a single bond, or —O—, —COO— or —OCO—. Examples of the substituent represented by R ¹¹ are the same as the examples of the substituent represented by R ¹ . Among them, a substituted or unsubstituted alkylcarbonyloxy group having 1 to 10 carbon atoms (which also includes a cycloalkylcarbonyloxy group), a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted or unsubstituted group. An arylcarbonyloxy group having 6 to 16 carbon atoms is preferable, and a substituted or unsubstituted alkylcarbonyloxy group having 1 to 8 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms are more preferable. In the alkyl moiety in the alkylcarbonyloxy group or alkoxy group, one of non-adjacent carbon atoms may be substituted with an oxygen atom or a sulfur atom. Moreover, although the group which the terminal of the said alkyl part has the polymeric group which mentions later, for example, (M-1) and (M-2), etc. is mentioned as a preferable example, it is not limited to these. .

  Further, the cyclohexyl group having a substituent at the 4-position includes a cis isomer and a trans isomer, but the isomer is not limited in the present invention, and a mixture of both may be used. A trans-cyclohexyl group is preferred.

In the general formula (1) or (2), R ⁵ and R ⁶ each independently represents a substituent. An example of R ¹ is given as an example. Preferably, at least one of R ⁵ and R ^{6 is} an electron-withdrawing substituent having a Hammett's substituent constant σp value greater than 0, and an electron-withdrawing substitution having a σp value of 0 to 1.5 More preferably, it has a group. Examples of such a substituent include a trifluoromethyl group, a cyano group, a carbonyl group, and a nitro group.
As for Hammett's substituent constants σp and σm, for example, Naoki Inamoto, “Hammett's rule-structure and reactivity-” (Maruzen), edited by the Chemical Society of Japan, “New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds V” 2605 (Maruzen), Tadao Nakatani, “Explanation on Theoretical Organic Chemistry”, page 217 (Tokyo Kagaku Dojin), “Chemical Review”, 91, 165-195 (1991).

In the general formula (1) or (2), A ¹ and A ² are each independently from the group consisting of —O—, —NR— (where R is a hydrogen atom or a substituent), —S—, and —CO—. Represents a selected group. Preferably -O -, - NR- (. R represents a substituent, examples Examples of the R ¹ and the like) or -S-.

In the general formula (1), X represents a nonmetallic atom belonging to Groups 14-16. However, a hydrogen atom or a substituent may be bonded to X. X is preferably ═O, ═S, ═NR ⁴ , ═C (R ⁵ ) R ⁶ . Here, R ⁴ , R ⁵ , and R ⁶ each independently represent a substituent, and examples thereof include the examples of R ¹ described above.
Preferred examples of R ⁵ and R ⁶ include a cyano group (CN), an acyl group (—COR: R represents a substituted or unsubstituted alkyl group or aryl group), a substituted or unsubstituted alkoxycarbonyl group or aryl. Oxycarbonyl group (C (═O) OR: R represents a substituted or unsubstituted alkyl group or aryl group), or a substituted or unsubstituted carbamoyl group (C (═O) NR ¹¹ R ¹² : R ¹¹ and R ¹² represents a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group, which may be bonded to each other to form a ring. The substituted or unsubstituted alkyl group represented by R, R ¹¹ and R ¹² is preferably a C _{1 to} C ₁₀ substituted or unsubstituted alkyl group, and a C _{2 to} C ₈ substituted or unsubstituted alkyl group. and more preferably at, a still more preferably a substituted or unsubstituted alkyl group of C ₂ -C _6. Moreover, one of the carbon atoms not adjacent to each other in the alkyl group may be substituted with an oxygen atom or a sulfur atom. Examples of the substituted or unsubstituted aryl group represented by R, R ¹¹ and R ¹² include the specific examples of the aryl group exemplified as R ¹ . Examples of the substituent for the alkyl group and aryl group are the same as the examples of the substituent represented by R ¹ . It is also preferable to have a polymerizable group described later as a substituent. Examples of the ring formed by combining R ¹¹ and R ¹² with each other include a piperazine ring.
Among these, it is preferable that one of R ⁵ and R ⁶ is a cyano group and the other is a substituted or unsubstituted alkoxycarbonyl group.

The liquid crystal compound represented by the general formula (1) or (2) has a polymerizable group. Thereby, an optically anisotropic film can be formed by curing, and the retardation of the optically anisotropic film hardly changes due to heat or the like, and is excellent in durability. It is preferable to have a polymerizable group at the terminal of the molecule of the compound.
In the general formula (1), at least one of R, R ¹ , R ² , R ³ and R ⁴ or in the general formula (2), R, R ¹ , R ² , R ³ , R ⁵ and At least one of R ⁶ is a substituent having a polymerizable group. Preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3 are substituents having a polymerizable group. Among them, in the general formula (1), R ² , R ³ and R ⁴ are represented, and in the general formula (2), R ² , R ³ , R ⁵ and R ⁶ are substituents having a polymerizable group. Preferably there is.

  The polymerizable group is preferably a group capable of addition polymerization reaction or condensation polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group. 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.
The polymerizable group is preferably a group represented by any of the following general formulas P1, P2, P3, or P4.

In the formula, R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵²¹ , R ⁵²² , R ⁵²³ , R ⁵³¹ , R ⁵³² , R ⁵³³ , R ⁵⁴¹ , R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ , and R ⁵⁴⁵ are each independently Represents a hydrogen atom or an alkyl group. n represents 0 or 1.

In the polymerizable group P1, R ⁵¹¹ , R ⁵¹² and R ⁵¹³ each independently represent a hydrogen atom or an alkyl group.
The substituent having the polymerizable group P1 is preferably an alkoxy group, an alkoxycarbonyl group, or an alkoxycarbonyloxy group having the polymerizable group P1, and more specifically, an alkyleneoxy group (for example, ethyleneoxy, propyleneoxy). Alkyleneoxy groups such as butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, and substituted alkyleneoxy groups containing an ether bond such as ethyleneoxyethoxy), alkyleneoxycarbonyloxy groups (eg, ethyleneoxycarbonyloxy, propyleneoxycarbonyl) Alkyleneoxycarbonyloxy groups such as oxy, butyleneoxycarbonyloxy, pentyleneoxycarbonyloxy, hexyleneoxycarbonyloxy, heptyleneoxycarbonyloxy In addition, a substituted alkyleneoxycarbonyloxy group containing an ether bond such as ethyleneoxyethoxycarbonyloxy), an alkyleneoxycarbonyl group (for example, ethyleneoxycarbonyl group, propyleneoxycarbonyl group, butyleneoxycarbonyl group, pentyleneoxycarbonyl group, hexyleneoxy) An alkyleneoxycarbonyl group such as a carbonyl group or a heptyleneoxycarbonyl group, or a substituted alkyleneoxycarbonyl group containing an ether bond such as an ethyleneoxyethoxycarbonyl group) is preferred.
The polymerizable group P1 may be directly bonded to the aromatic ring.

n represents an integer of 0 to 1, and n is preferably 1. When n is 1, the polymerizable group P1 represents a substituted or unsubstituted vinyl ether group. R ⁵¹¹ and R ⁵¹³ are each independently a hydrogen atom or an alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, etc. An alkyl group is preferred, and methyl is more preferred), and R ⁵¹¹ is a methyl group and R ⁵¹³ is a hydrogen atom, or a combination of R ⁵¹¹ and R ⁵¹³ are both hydrogen atoms.

R ⁵¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxy And a lower alkyl group such as methyl and ethyl is preferable, and methyl is more preferable.], A hydrogen atom and a lower alkyl group are preferable, and a hydrogen atom is more preferable. Accordingly, as the polymerizable group P1, an unsubstituted vinyloxy group which is a functional group having high polymerization activity is generally preferably used.

The polymerizable group P2 represents a substituted or unsubstituted oxirane group. R ⁵²¹ and R ⁵²² are each independently a hydrogen atom or an alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, etc., and lower groups such as methyl and ethyl). An alkyl group is preferred, and methyl is more preferred), and both R ⁵²¹ and R ⁵²² are preferably hydrogen atoms.

R ⁵²³ is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxy And a lower alkyl group such as methyl or ethyl is preferable, and methyl is more preferable. A hydrogen atom or a lower alkyl group such as methyl, ethyl or n-propyl is preferable.

The polymerizable group P3 represents a substituted or unsubstituted acrylic group. Substituents R ⁵³¹ and R ⁵³³ each independently represent a hydrogen atom or an alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, methyl, ethyl, etc. R ⁵³¹ is methyl and R ⁵³³ is a hydrogen atom, or a combination of R ⁵³¹ and R ⁵³³ are both hydrogen atoms.

R ⁵³² is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxy Ethyl, and lower alkyl groups such as methyl and ethyl are preferred, and methyl is more preferred), and a hydrogen atom is preferred. Accordingly, as the polymerizable group P3, generally, a functional group having high polymerization activity such as an unsubstituted acryloxy group, methacryloxy group, crotonyloxy is preferably used.

The polymerizable group P4 represents a substituted or unsubstituted oxetane group. R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ are each independently a hydrogen atom or an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, methyl And lower alkyl groups such as ethyl are preferable, and methyl is more preferable.), And R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ are all preferably hydrogen atoms.

R ⁵⁴¹ is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxy And a lower alkyl group such as methyl or ethyl is preferable, and methyl is more preferable. A hydrogen atom or a lower alkyl group such as methyl, ethyl or n-propyl is preferable.

  Specific examples of the compound represented by the general formula (1) or (2) are shown below, but are not limited to the following specific examples. Regarding the following compounds, unless otherwise specified, the number in parentheses () indicates the exemplified compound (X).

  The compound represented by the general formula (1) or (2) can be synthesized with reference to a known method. For example, exemplary compound (2) can be synthesized according to the following scheme.

In the scheme, the synthesis from the compound (2-1) to the compound (2-3) is described in “Journal of Chemical Crystallography” (1997), 27 (9), p.515-526. It can be performed with reference to the method described in 1.
Furthermore, as shown in the above-mentioned scheme, compound (2-6) is obtained from compound (2-4) and compound (2-5) by standard esterification using dicyclohexylcarbodiimide (DCC). . A small amount of a polymerization inhibitor (Irganox 1010, trade name, manufactured by Ciba Specialty Chemicals) is added to a suspension of compound (2-3) and compound (2-6) in N-methyl-2-pyrrolidone (NMP). The compound (2-7) is obtained by heating. Compound (2-9) obtained by adding pyridine (Py) as a base to a solution of compound (2-7) in tetrahydrofuran (THF) and synthesizing acid chloride from compound (2-8) using thionyl chloride. Exemplified compound (2) can be obtained by adding.

(Birefringence)
The polymerizable liquid crystal compound represented by the general formula (1) or (2) according to the present invention has an intrinsic birefringence Δn having reverse wavelength dispersion, that is, wavelength dispersion satisfying the following formula (3). preferable.
Formula (3) Δn (450 nm) / Δn (550 nm) <1.0

  If the liquid crystal compound of the present invention is the same liquid crystal phase, the wavelength dispersibility hardly depends on the temperature, but in order to clarify the present invention more, the value in the equation (3) is the temperature at which the phase changes. The value measured at 20 ° C. from the upper limit temperature shall be indicated. Further, when the liquid crystal temperature range is 20 ° C. or less, the value measured at 10 ° C. from the upper limit temperature of the liquid crystal phase, and when the liquid crystal temperature range is 10 ° C. or less, the value measured at 5 ° C. from the upper limit temperature, the liquid crystal temperature range When the temperature is 5 ° C. or lower, the value measured at 2 ° C.

  The preferable range of the wavelength dispersion of Δn cannot be uniquely limited because the preferable range varies depending on the use of the liquid crystal compound. However, more preferable ranges of the wavelength dispersion of Δn include the following formulas (4) and (5). ) Is preferably satisfied.

Formula (4) 0.60 <Δn (450 nm) / Δn (550 nm) <0.99
Formula (5) 1.01 <Δn (650 nm) / Δn (550 nm) <1.35

  Furthermore, considering the case where the liquid crystal compound of the present invention is used as a λ / 4 plate, it is preferable to satisfy the following formulas (6) and (7).

Formula (6) 0.60 <Δn (450 nm) / Δn (550 nm) <0.95
Formula (7) 1.04 <Δn (650 nm) / Δn (550 nm) <1.35

  In the formulas (3) to (7), Δn (450), Δn (550), and Δn (650) represent Δn at 450 nm, 550 nm, and 650 nm, respectively. However, each measurement wavelength includes an error of ± 10 nm.

Examples of the method for measuring Δn of liquid crystal include a method using a wedge-shaped liquid crystal cell as described in “Liquid Crystal Handbook” 2.4.13 (Maruzen Co., Ltd., 2000). In this method, Δn of each wavelength is obtained by using three types of band-pass filters of 450 nm, 550 nm, and 650 nm.
When the liquid crystal compound has a polymerizable group as in the compound of the present invention, a polymerization reaction may occur in a wedge-shaped liquid crystal cell, which is likely to be difficult to measure. In such a case, it is preferable to measure by adding a polymerization inhibitor. In addition, in a state where the liquid crystal is uniformly oriented, Re at each wavelength is obtained by measuring with a device capable of measuring a phase difference such as KOBRA (trade name, manufactured by Oji Scientific Instruments Co., Ltd.). By separately measuring the thickness, Δn can be obtained (from the formula of Δn = Re / d (film thickness)).

The liquid crystal compound of the present invention may have either positive or negative birefringence, but preferably has positive birefringence.
The liquid crystal phase having positive birefringence is described in detail in Chapter 2 of “Liquid Crystal Handbook” (Maruzen Co., Ltd., 2000), for example. For example, nematic phase, cholesteric phase, smectic phase (for example, (Smectic A phase, smectic C phase).

When the liquid crystal compound of the present invention is used for an optically anisotropic layer, those showing good monodomain properties are preferred for uniform defect-free alignment. When the monodomain property is poor, the resulting structure becomes a polydomain, an orientation defect occurs at the boundary between domains, and light is scattered. This is not preferable because it leads to a decrease in the transmittance of the optically anisotropic layer. To a good monodomain property, the liquid crystal compounds of the present invention, it is preferable to express the nematic phase (N phase) or smectic A phase (S _A phase). In particular, it is preferable to develop a nematic phase.

  The liquid crystal compound may be a low-molecular liquid crystal compound or a high-molecular liquid crystal compound, but the low-molecular liquid crystal compound is preferred in consideration of the ease of alignment of the liquid crystal.

(Preparation of film having reverse wavelength dispersion)
The polymerizable liquid crystal compound represented by the general formula (1) or (2) of the present invention is applied on an alignment film, aligned, and then fixed to prepare a film having reverse wavelength dispersibility. Can do. For example, when the liquid crystal compound of the present invention is substantially horizontally aligned on the alignment film (so-called A plate), the alignment direction (hereinafter referred to as TD direction) and the direction orthogonal to the alignment direction (hereinafter referred to as MD direction) The phase difference Re (550 nm) is positive, and the phase difference Re at a specific wavelength satisfies the following formulas (8) and (9).

Formula (8) 0.5 <Re (450 nm) / Re (550 nm) <1.0
Formula (9) 1.05 <Re (650 nm) / Re (550 nm) <1.5

  In order to produce a film satisfying the above formulas (8) and (9), it is necessary to arrange the absorption wavelength and the direction of transition moment in the TD direction and the MD direction well as the film. Here, they are blue (450 nm), green (550 nm), and red (650 nm), and it is necessary to match the optimum retardation at each wavelength in order to improve viewing angle characteristics. In the present invention, the preferred range of blue (450 nm) and red (650 nm) when giving positive birefringence to the most important green (550 nm) is the range of the above formulas (8) and (9). It becomes.

  Re is a phase difference between the TD direction and the MD direction, that is, a proportional relationship of a value (Δn) obtained by subtracting the refractive index in the MD direction from the refractive index in the TD direction. If the chromatic dispersion in the direction is more downward (slope of Δn when the left is the short wavelength side and the right is the long wavelength side), the subtracted value is expressed by the following equations (10) and (11 Is satisfied.

Formula (10) 1> | Δn (450 nm) / Δn (550 nm) |
Formula (11) 1 <| Δn (650 nm) / Δn (550 nm) |

  Since the wavelength dispersion of the refractive index is closely related to the absorption of the substance as represented by the Lorentz-Lorenz equation, in order to make the wavelength dispersion in the MD direction more downward, TD If the absorption transition wavelength in the MD direction can be made longer than that in the direction, a film satisfying equations (8) and (9) can be designed. For example, in a polymer material that has been stretched, the MD direction is perpendicular to the molecular chain. It is very difficult for a polymer material to lengthen the absorption transition wavelength in the polymer width direction.

  When the liquid crystal compound of the present invention is substantially vertically aligned (so-called C plate), the retardation Rth (550 nm) in the thickness direction is negative and the retardation Rth at a specific wavelength is expressed by the following formula (12) and (13) is satisfied.

Formula (12) 0.6 <Rth (450 nm) / Rth (550 nm) <0.99
Formula (13) 1.01 <Rth (650 nm) / Rth (550 nm) <1.35

  In order to produce a film satisfying the above equations (12) and (13), it is necessary to arrange the absorption wavelength and the direction of transition moment in the in-plane direction and the thickness direction well as the film. Here, they are blue (450 nm), green (550 nm), and red (650 nm), and it is necessary to match the optimum retardation at each wavelength in order to improve viewing angle characteristics. In the present invention, the preferred range of blue (450 nm) and red (650 nm) when giving positive birefringence to the most important green (550 nm) is the range of the above formulas (12) and (13). It becomes.

  In order to produce a film that has a negative retardation Rth (550 nm) in the thickness direction and satisfies the above formulas (12) and (13), the refractive index in the thickness direction is larger than the refractive index in the in-plane direction. In addition, this can be achieved by making the absorption transition wavelength in the in-plane direction longer than that in the thickness direction. However, for example, when a polymer material is used, since the molecular chains are aligned in the in-plane direction, it is relatively easy to make the absorption transition wavelength in the in-plane direction longer than that in the thickness direction. It is very difficult to increase the refractive index of the material relative to the refractive index in the in-plane direction, and it is even more difficult to satisfy both of these conditions simultaneously.

  In addition, when the liquid crystal compound of the present invention is substantially spirally aligned and the helical axis is substantially perpendicular to the substrate, the thickness direction retardation Rth (550 nm) is positive and the retardation Rth at a specific wavelength is Expressions (14) and (15) are satisfied.

Formula (14) 0.6 <Rth (450 nm) / Rth (550 nm) <0.99
Formula (15) 1.01 <Rth (650 nm) / Rth (550 nm) <1.35

  In order to produce a film satisfying the above formulas (14) and (15), it is necessary to arrange the absorption wavelength and the direction of transition moment in the in-plane direction and the thickness direction well as the film.

  In order to produce a film having a positive retardation Rth (550 nm) in the thickness direction and satisfying the above formulas (14) and (15), the refractive index in the in-plane direction is larger than the refractive index in the thickness direction. In addition, this can be achieved by making the absorption transition wavelength in the thickness direction longer than that in the in-plane direction. However, for example, when a polymer material is used, since the molecular chains are aligned in the in-plane direction, it is relatively easy to increase the refractive index in the in-plane direction relative to the refractive index in the thickness direction. In comparison, it is very difficult to make the absorption transition wavelength in the thickness direction longer, and it is further difficult to satisfy both of these conditions simultaneously.

As described above, after aligning the liquid crystal compound of the present invention and fixing it, a film that is very difficult when using a polymer material, that is,
1) A film having a positive phase difference in the in-plane direction of the film and a dispersion thereof having a reverse wavelength dispersion
2) A film whose retardation is negative in the film thickness direction and whose dispersion is reverse wavelength dispersion, or 3) A film whose retardation is positive in the film thickness direction and whose dispersion is reverse wavelength dispersion. Can do.

  The preferable range of the wavelength dispersion of Δn cannot be uniquely limited because the preferable range varies depending on the use of the liquid crystal compound. However, more preferable ranges of the wavelength dispersion of Δn include the following formulas (4) and (5). ) Is preferably satisfied.

Formula (4) 0.60 <Δn (450 nm) / Δn (550 nm) <0.99
Formula (5) 1.01 <Δn (650 nm) / Δn (550 nm) <1.35

The compound represented by the general formula (1) may have either positive or negative birefringence, but preferably has positive birefringence.
The liquid crystal phase having positive birefringence is described in detail in Chapter 2 of “Liquid Crystal Handbook” (Maruzen Co., Ltd., 2000). For example, a nematic phase, a cholesteric phase, a smectic phase (for example, (Smectic A phase, smectic C phase).

  When the liquid crystal composition of the present invention is used for forming an optically anisotropic film, the molecules of the compound represented by the general formula (1) are preferably in a uniform defect-free alignment state. Those exhibiting good monodomain properties are preferred. When the monodomain property is poor, the resulting structure becomes a polydomain, an orientation defect occurs at the boundary between domains, and light is scattered. This is not preferable because it leads to a decrease in transmittance of the optically anisotropic film. In order to exhibit good monodomain properties, the compound represented by the general formula (1) preferably exhibits a nematic phase (N phase) or a smectic A phase (SA phase). In particular, it is preferable to develop a nematic phase.

  The compound represented by the general formula (1) may be a low-molecular liquid crystal compound or a high-molecular liquid crystal compound, but a low-molecular liquid crystal compound is more preferable in consideration of the ease of alignment of liquid crystals.

The liquid crystal composition of the present invention further contains a liquid crystal compound in which the wavelength dispersion of Δn is forward dispersion in the visible light region.
The liquid crystal compound in which Δn is forward wavelength dispersive in the visible light region refers to a compound having a larger Δn as the wavelength is shorter in the visible light region. Specifically, Δn (450), Δn (550) and Δn (650) are obtained by the above-described method, and Δn (450) / Δn (550), Δn (550) / Δn (650) and Δn (450) / A compound in which all of Δn (650) is 1 or more is represented. The liquid crystal compound in which Δn is forward wavelength dispersive is preferably a rod-like liquid crystal compound, and specifically, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoates, cyclohexanecarboxyl Acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.

  As the liquid crystal compound having a forward wavelength dispersion of Δn, a compound having a partial structure capable of causing polymerization or a crosslinking reaction by actinic rays, electron beams, heat, or the like is preferable. That is, a compound having one or more polymerizable groups is preferable, a compound having 1 to 6 is more preferable, a compound having 1 to 3 is more preferable, and a compound having 2 or 3 is more preferable. The polymerizable group is preferably a radically polymerizable unsaturated group. Specifically, for example, the polymerizable group described in JP 2000-514202 A or JP 2002-62427 A can be mentioned, and also described in the gazette. The polymerizable liquid crystal compound is also preferable.

  Examples of liquid crystal compounds having a forward wavelength dispersion of Δn used in the present invention include Japanese Patent Laid-Open Nos. 11-80081, 2000-281628, 2002-128742, 2002-145830, JP 2002-265475 A, JP 2002-308831 A, JP 2003-12762 A, JP 2003-192645 A, JP 2007-191442 A, JP 2004-182678 A, Special Table. No. 2005-502730, No. 2005-542219, No. 2002-539182, No. 2002-522410, No. 2002-521354, No. 2001-527570, Registered Patent 3901238. Publication, registered patent No. 3973707, registration No. 3866307, JP 2002-30042, JP 11-116538, JP 11-513029, JP 2003-238491, JP 2004-175728, 2004. No. 231638, JP-A No. 2005-15473, JP-A No. 2005-112850, JP-A No. 2005-179557, JP-A No. 2005-206579, JP-A No. 2005-320317, JP-A No. 2005-35985 JP, JP 2005-60373, JP 2006-111571, JP 2006-225463, JP 2006-241116, JP 2006-225607, JP 2006-232809, JP 2006-241116 A, JP 20 JP 06-348022, JP 2007-70285, JP 2007-70302, JP 2001-270848, JP 2001-199938, JP 2004-91380, JP 2006. 219533, JP-A 2006-219524, JP-A 2007-119415, JP-A 2005-309255, JP 2000-507932 A, and the like.

  The liquid crystal compound having a forward wavelength dispersion of Δn may be polymerizable or non-polymerizable, or may be used in combination. The liquid crystal compound may form a nematic liquid crystal phase, a smectic liquid crystal phase, or a cholesteric liquid crystal phase, but more preferably forms a nematic phase or a smectic phase.

As a liquid crystal compound in which Δn is forward wavelength dispersible, a compound represented by the following general formula (3) is preferable.
Formula ^{(3): Q 1 -SP 1} -X 1 -MG-X 2 -SP 2 -Q 2
In the general formula (3), Q ¹ and Q ² each represent a reactive group, SP ¹ and SP ² each represent a spacer group, X ¹ and X ² each represent a linking group, and MG represents a mesogenic group. .
Q ¹ and Q ² are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of the polymerizable group are shown below.

The polymerizable group (Q ¹ and Q ² ) is preferably an unsaturated polymerizable group (Q-1 to Q-7), an epoxy group (Q-8) or an aziridinyl group (Q-9). It is further preferably a polymerizable group, more preferably an ethylenically unsaturated polymerizable group (Q-1 to Q-6).

In Formula (3), SP ¹ and SP ² are each independently a divalent spacer group. SP ¹ and SP ² are each independently a divalent linking group selected from the group consisting of —O—, —S—, —CO—, —NR ² —, a divalent chain group, and combinations thereof. Preferably there is. R ² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. The example of the bivalent coupling group which consists of a combination is shown below.
The left side is bonded to Q (Q ¹ or Q ² ), and the right side is bonded to X (X ¹ or X ² ).

L-1: —CO—O—divalent chain group—
L-2: —CO—O—divalent chain group—O—divalent chain group—
L-3: —CO—O—divalent chain group—S—divalent chain group—

  The divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group or a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group and an alkenylene group are more preferred. The alkylene group may have a branch. The number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 2 to 10, and still more preferably 2 to 8. The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent of the substituted alkylene group include an alkoxy group and a halogen primitive. The alkenylene group may have a branch. The alkenylene group has preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 8 carbon atoms. The alkenylene part of the substituted alkenylene group is the same as the above alkenylene group. Examples of the substituent of the substituted alkenylene group include an alkoxy group and a rogen atom. The alkynylene group may have a branch. The number of carbon atoms in the alkynylene group is preferably 2 to 12, more preferably 2 to 10, and still more preferably 2 to 8. The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent of the substituted alkynylene group include an alkoxy group and a halogen atom.

In the general formula (3), X ¹ and X ² are each independently a divalent linking group. X ¹ and X ² are each independently preferably a divalent linking group selected from the group consisting of a single bond, —O—, —S—, —CO—, —NR ² — and combinations thereof. . More preferably, they are a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, or -O-CO-O-.

In the general formula (3), MG represents a mesogenic group. A group represented by the following formula (MG-I) is preferable.
MG-I:-(A ¹ -Z ¹ ) _m -A ² -Z ² -A ^3-
In the formula, A ¹ , A ^2, and A ³ are each independently a 1,4-phenylene group, or a heterocyclic ring in which one or more CH groups in the 1,4-phenylene group are replaced by N 1, 1-cyclohexylene group, 1-cyclohexylene group 1 CH ₂ group or ₂ non-adjacent CH ₂ groups may be replaced by O and / or S It is a cyclic group, or a 1,4-cyclohexenylene group or a naphthalene-2,6-diyl group, and these groups may have a substituent. Z ¹ and Z ² are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, — CH = CH—COO—, —OCO—CH═CH— or a single bond, and m is 0, 1 or 2.
Bicyclic or tricyclic mesogenic groups are preferred, Z ¹ and ^{Z 2, -COO -, - OCO} -, - CH 2 -CH 2 -, - CH = CH-COO -, - OCO-CH = CH- or A compound that is a single bond is particularly preferred.

  Examples of preferred mesogenic groups represented by MG-I are shown below. Abbreviations were used for brevity, where Phe is 1,4-phenylene, PheL is substituted with at least one substituent L, and Cyc is 1,4-cyclohex. Shiren.

In these, preferably, Z ¹ and Z ^2, -COO -, - OCO -, - CH 2 CH 2 -, - is a CH = CH-COO- or a single bond.
A particularly preferred mesogenic group is a group represented by the following formula.

r represents an integer of 0 to 4, and r is preferably 0, 1 or 2. When r is 2, two Ls may be the same or different.
Next, the substituent L will be described. Examples of the substituent include a halogen atom, cyano, nitro, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, carbon An alkylthio group having 1 to 5 atoms, an acyl group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl, and the number of carbon atoms 2-6 alkyl-substituted carbamoyl groups and amide groups having 2-6 carbon atoms are included. More preferably, a halogen atom, cyano, an alkyl group having 1 to 3 carbon atoms, a halogen-substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or 2 to 4 carbon atoms. Of the acyloxy group.
L is preferably F, Cl, Br, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , especially F, Br, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ and OCF ₃ , still more preferably F, Br, CH ₃ , OCH ₃ and COCH ₃ .

  Although the specific example of a compound represented by General formula (3) below is shown, it is not limited to these.

  In the liquid crystal composition of the present invention, Δn is a compound represented by the general formula (1) having a reverse wavelength dispersion (hereinafter referred to as “reverse dispersion compound”), and Δn is a liquid crystal compound having a forward wavelength dispersion (hereinafter, referred to as “reverse dispersion compound”). The ratio to the “orderly dispersible compound” is not particularly limited, and the preferred range varies depending on the application, etc., but in general, the reversely dispersible compound represented by the formula (1) and the order The ratio with the dispersible compound is preferably contained in a mass ratio of 1:10 to 10: 1.

The liquid crystal composition of the present invention preferably exhibits a nematic phase, a smectic phase, or a cholesteric phase. The liquid crystal composition of the present invention may contain other additives together with the compound of the general formula (1) and the forward-dispersing liquid crystal compound.
-Alignment Accelerator In the liquid crystal composition of the present invention, an additive that promotes molecular alignment of the reverse-dispersing compound and / or the forward-dispersing compound may be added. The content of the additive for promoting the orientation in the composition is preferably 0.01 to 10% by mass, and 0.05 to 5% by mass with respect to the reverse dispersibility and forward dispersibility compound. More preferably, it is 0.05-4 mass%. The additive that promotes alignment contributes to aligning the molecules of the liquid crystal compound by the excluded volume effect or electrostatic effect at the air interface or alignment film interface. The compounds described in JP 2002-20363 A and JP 2002-129162 A can be used. Also, paragraph numbers [0072] to [0075] of Japanese Patent Application Laid-Open No. 2004-53981, paragraph numbers [0071] to [0078] of Japanese Patent Application Laid-Open No. 2004-4688, and paragraphs of Japanese Patent Application Laid-Open No. 2004-139015. The matters described in the numbers [0052] to [0054], [0065] to [0066], and [0092] to [0094] can be appropriately applied to the present invention.

Chain transfer agent A chain transfer agent may be used in the liquid crystal composition of the present invention. The content in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the reverse-dispersible and forward-dispersible compound. More preferably, it is -4 mass%. As the specific chain transfer agent, generally known ones can be used, but preferably a compound having a mercapto group (thiol compound such as dodecyl mercaptan, octyl mercaptan, trimethylolpropane tris (3-mercaptopropionate). ), Pentaerythritol tetrakis (3-mercaptopropionate, etc.) and disulfide compounds (for example, diphenyl disulfide, etc.). Compatibility with reverse dispersibility and forward dispersibility is also necessary, and thiol compounds exhibiting liquid crystallinity are more preferred from the viewpoint of compatibility. Examples of the thiol compound exhibiting liquid crystallinity include compounds described in US Pat. No. 6,096,241.

Other additives The liquid crystal composition of the present invention contains a polymerization initiator, a plasticizer, a surfactant, a polymerizable monomer and the like in addition to the alignment accelerator and the chain transfer agent that are optionally added. May be. These materials are added for various purposes, for example, for the purpose of fixing the orientation, improving the uniformity of the coating film, the strength of the film, and the orientation of the liquid crystal compound. These materials are preferably compatible with the liquid crystal compound used in combination and do not inhibit the alignment.

  As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator may be used. Photoinitiators are preferred. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Description), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970). The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the solid content of the coating solution.

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

  Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specific examples include compounds described in paragraph numbers [0028] to [0056] in JP-A-2001-330725.

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

[Optically anisotropic film]
Next, an optical anisotropic film formed from the liquid crystal composition of the present invention will be described.
The optically anisotropic film of the present invention can be formed by applying the liquid crystal composition of the present invention to the surface of an alignment film or the like to obtain a certain alignment state and then fixing the film. The liquid crystal composition of the present invention preferably exhibits a nematic phase or a smectic phase.
The liquid crystal composition of the present invention may be prepared as a coating solution. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides, esters and ketones are preferred, and esters and ketones are particularly preferred. Two or more organic solvents may be used in combination.

  The coating solution can be applied by a known method (eg, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).

  The coating film formed by coating is brought into a desired orientation state. After applying the liquid crystal composition, it is preferable that the liquid crystal composition is kept in a nematic phase or an isotropic phase and then cooled to a smectic phase. The temperature above the transition temperature to the smectic phase is preferably 0.1 ° or higher, more preferably 1 ° or higher, and further preferably 5 ° to 20 °. The heat treatment time in the nematic phase or isotropic phase is preferably maintained for 10 seconds or more, more preferably 20 seconds or more, and further preferably 30 seconds or more and 3 minutes or less.

After obtaining a desired alignment state, the alignment state is fixed. Immobilization can be performed by a polymerization reaction of a polymerizable compound. For the polymerization reaction carried out for immobilization, it is preferable to use a photopolymerization reaction using a photopolymerization initiator. It is preferable to use ultraviolet rays for light irradiation for polymerization. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. Further, the polymerization may be carried out by reducing the oxygen concentration.

  The thickness of the optically anisotropic film is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and still more preferably 0.5 to 5 μm.

  An alignment film may be used for producing the optically anisotropic film of the present invention. The alignment film has a function of regulating the alignment direction of the liquid crystalline molecules. Furthermore, the alignment film is used for the purpose of improving the uniformity of alignment and improving the adhesion between the polymer substrate used as a support and the optically anisotropic film. Note that if the alignment state of the liquid crystalline compound is fixed after the alignment, the alignment film plays the role and can be removed.

  The alignment film is an organic compound (eg, ω-) by rubbing treatment of an organic compound (preferably polymer) film, oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). Tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.

  In the present invention, it is preferable to use an alignment film formed by rubbing the surface of the polymer film. Examples of the alignment film forming polymer include, for example, a methacrylate polymer, a styrene polymer, a polyolefin, a polyvinyl alcohol, a modified polyvinyl alcohol, and a poly (N) described in paragraph No. [0022] of JP-A-8-338913. -Methylolacrylamide), polyester, polyimide, vinyl acetate polymer, carboxymethylcellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (eg, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol) are preferred, gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred, and polyvinyl alcohol and modified polyvinyl alcohol are most preferred. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization.

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

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

The alignment film-forming polymer preferably has a crosslinkable functional group (eg, a double bond) in the side chain, and the crosslinkable functional group also has a function of aligning liquid crystal molecules. Also good. In addition, 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.
When the alignment film-forming polymer has a crosslinkable functional group in the side chain, the alignment film polymer and the polyfunctional monomer contained in the optically anisotropic film formed thereon 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 can be firmly bonded by a covalent bond. it can.
The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specific examples include those described in paragraphs [0080] to [0100] in JP-A-2000-155216.

As described above, the alignment film polymer can be cross-linked using a cross-linking agent separately from the cross-linkable functional group.
Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraphs [0023] to [024] in JP-A-2002-62426. Aldehydes having high reaction activity, particularly glutaraldehyde are preferred.

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

  In general, the alignment film is formed by applying the above-mentioned polymer, which is an alignment film forming material, and, optionally, a composition containing a crosslinking agent to the surface of a transparent support such as a polymer film, followed by heat drying (crosslinking). If necessary, it can be formed by rubbing. As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating solution is preferably a mixed solvent of an organic solvent (eg, 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 surface of the alignment film and also the optically anisotropic film formed on it is remarkably reduced.

  The coating method for forming the alignment film is preferably a spin coating method, a dip coating method, a curtain coating method, an extrusion coating method, a rod coating method or a roll coating method. A rod coating method is particularly preferable. The film thickness after drying is preferably 0.1 to 10 μm. Heat drying can be performed at 20-110 degreeC. In order to form sufficient crosslinking, 60 to 100 ° C. is preferable, and 80 to 100 ° C. is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is also preferably set to an optimum value for the cross-linking agent to be used. When glutaraldehyde is used, the pH is 4.5 to 5.5, and 4.8 to 5.2 is particularly preferable.

  The rubbing treatment performed as desired is generally performed by rubbing the surface of the polymer film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber, or the like. In general, a cloth in which fibers having a uniform length and thickness are flocked on average is used.

[Support]
The optically anisotropic film of the present invention may be formed on a support. The support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.
Examples of the polymer film as the support include cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyacrylate and polymethacrylate films. A cellulose ester film is preferred, an acetyl cellulose film is more preferred, and a triacetyl cellulose film is most preferred. The polymer film is preferably formed by a solvent cast method. The thickness of the transparent support is preferably 20 to 500 μm, and more preferably 40 to 200 μm. In order to improve adhesion between the transparent support and the layer (adhesive layer, vertical alignment film or retardation layer) provided thereon, surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet light (UV) ) Treatment, flame treatment, saponification treatment). An adhesive layer (undercoat layer) may be provided on the transparent support. Moreover, the average particle diameter is 10 to 100 nm in order to give the transparent support or the long transparent support a slip property in the transport process or to prevent the back surface and the surface from sticking after winding. It is preferable to use what formed the polymer layer which mixed the inorganic particle of about 5%-40% by solid content mass ratio on the one side of the support body by application | coating or co-casting with a support body.

  The optically anisotropic film of the present invention can be used for various applications. The optically anisotropic film of the present invention is a mixture of a compound represented by the general formula (1) in which Δn is reverse wavelength dispersion in the visible light region and a liquid crystal compound in which Δn is forward wavelength dispersion in the visible light region. Depending on the ratio, the wavelength dispersion of the in-plane retardation Re with respect to light in the visible light region can achieve any characteristic of forward dispersion, reverse dispersion, or constant regardless of wavelength.

The features of the present invention will be described more specifically with reference to examples and comparative 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 should not be construed as being limited by the specific examples shown below.
[Example 1]
Compound (78) was synthesized by the following route.

Synthesis of compound (78) -B benzoquinone (compound (78) -A) was used as a starting material. Org. Chem. 69, 2164-2177 (2004) to give compound (78) -B.

-Synthesis of Compound (78) -C 16.4 g (50 mmol) of Compound (78) -B and 8.5 g (60 mmol) of butyl cyanoacetate were added to 50 ml of N-methyl-pyrrolidinone and stirred at 90 ° C for 2 hours. . After cooling to room temperature, 300 ml of methanol was added to the contents and the precipitate was filtered off to obtain 15.2 g of the desired compound (78) -C. The ¹ H-NMR spectrum of the obtained compound was as follows.
¹ H-NMR (300 MHz, d ⁶ -DMSO): 0.93 ppm (3H, t), 1.40 ppm (2H, m), 1.65 ppm (2H, m), 4.23 ppm (2H, t), 6 .79 ppm (2H, s), 10.32 ppm (1 H, s), 10.37 ppm (1 H, s),
It was confirmed to be the target product from ¹ H-NMR and other spectra.

Synthesis of Compound (78) -K 7.2 g (50 mmol) of trans-4-hydroxy-cyclohexanecarboxylic acid and 10.2 g (60 mmol) of benzyl bromide were added to 90 ml of N-methyl-pyrrolidinone and stirred, and sodium hydrogen carbonate 8 .2 g (100 mmol) was added and stirred at 90 ° C. for 3 hours. After cooling to room temperature, the contents were extracted by adding 400 ml of ethyl acetate and 300 ml of water. The organic layer was washed with dilute hydrochloric acid and water, dried over sodium sulfate, and concentrated. The concentrate was purified by silica gel column chromatography to obtain 9.2 g of compound (78) -K. ^{From 1} H-NMR, it was confirmed to be the target product.

-Synthesis of compound (78) -D Compound (78) -D was prepared as described in Recl. Trav. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).

Synthesis of Compound (78) -E 24.4 g (0.1 mol) of Compound (78) -D was added to 200 ml of N-methyl-pyrrolidinone and stirred, and 54.8 g of tert-butyldiphenylchlorosilane (0. 22 mol) and 27.2 g of imidazole were added. After stirring at room temperature for 3 hours, 500 ml of ethyl acetate and 500 ml of diluted hydrochloric acid were added for extraction, and the organic layer was washed with water, dried over sodium sulfate, and concentrated. The concentrate was dissolved in 300 ml of methanol and 200 ml of tetrahydrofuran, and a solution of 28 g of potassium carbonate in 200 ml of water was added and stirred at room temperature for 8 hours. After the solution was concentrated, 500 ml of ethyl acetate and 300 ml of water were added for extraction, and the organic layer was washed with water, dried over sodium sulfate, and concentrated. The concentrate was purified by silica gel column chromatography to obtain 28.5 g (61 mmol) of compound (78) -E. ^{From 1} H-NMR, it was confirmed to be the target product.

-Synthesis of Compound (78) -F Compound (78) -E (9.5 g, 20.4 mmol) was dissolved in toluene (30 ml), N, N-dimethylformamide (0.1 ml) and thionyl chloride (2 ml) were added, and the mixture was heated at 70 ° C. Stir for 3 hours. After distilling off the solvent under reduced pressure, the residue was added to 30 ml of N-methyl-pyrrolidinone and stirred, and 4.7 g (20 mol) of compound (78) -K was added and cooled to 5 ° C. or lower. After cooling, 3 ml of triethylamine and then 100 mg of 4-N, N-dimethylaminopyridine were sequentially added, followed by stirring at 5 ° C. or lower for 30 minutes, and then stirring at room temperature for 2 hours. The reaction solution was extracted by adding 200 ml of acetic acid and 200 ml of dilute hydrochloric acid, and the organic layer was washed with water, dried over sodium sulfate, and concentrated. The concentrate was purified by silica gel column chromatography to obtain 10.0 g (14.3 mmol) of compound (78) -F. ^{From 1} H-NMR, it was confirmed to be the target product.

Synthesis of Compound (78) -G Compound (78) -F 20 g (28.6 mmol) was dissolved in 100 ml of tetrahydrofuran, 5 ml of acetic acid was added, and then 30 ml of tetrabutylammonium fluoride (tetrahydrofuran solution, concentration 1 mol / l) was added. In addition, the mixture was stirred at room temperature for 3 hours. The reaction solution was extracted by adding 200 ml of acetic acid and 200 ml of diluted hydrochloric acid, and the organic layer was washed with water, dried over sodium sulfate, and concentrated. The concentrate was purified by silica gel column chromatography to obtain 13.0 g (28.2 mmol) of compound (78) -G. The ¹ H-NMR spectrum of the obtained compound was as follows.
¹ H-NMR (300 MHz, CDCl ₃ ): 1.16 to 2.12 ppm (24 H, m), 2.21 ppm (1 H, m), 2.34 ppm (1 H, m), 3.47 ppm (2 H, t) 3.65 ppm (2H, s), 4.70 ppm (1 H, m), 5.11 ppm (2 H, s), 7.37 ppm (5 H, m).
^{From 1} H-NMR, it was confirmed to be the target product.

-Synthesis | combination of compound (78) -H Compound (78) -G 13g (28.2mmol) was melt | dissolved in ethanol 130ml, 1.3g of 10% palladium carbon was added, and hydrogenated under normal pressure. The catalyst was filtered through Celite, and the filtrate was concentrated to obtain 9.3 g (25 mmol) of Compound (78) -H. ^{From 1} H-NMR, it was confirmed to be the target product.

Synthesis of Compound (78) -I 7.2 g (19 mmol) of Compound (78) -H was added to 40 ml of N-methyl-pyrrolidinone and stirred, and 5 ml of acryloyl chloride was added at 5 ° C. or lower. After stirring at room temperature for 3 hours, the mixture was again cooled to 5 ° C. or lower, and a mixed solution of 6 ml of pyridine and 6 ml of water was added dropwise. The reaction solution was extracted by adding 200 ml of ethyl acetate and 200 ml of dilute hydrochloric acid, and the organic layer was washed with water, dried over sodium sulfate, and concentrated. The target compound (78) -I (7.3 g, 17 l) was obtained. ^{From 1} H-NMR, it was confirmed to be the target product.

-Synthesis of Compound (78) 4.5 g (10.6 mmol) of Compound (78) -I was dissolved in 20 ml of toluene, 0.1 ml of N, N-dimethylformamide and 1.1 ml of thionyl chloride were added, and at 70 ° C. Stir for 3 hours. After distilling off the solvent under reduced pressure, the residue was added to 20 ml of N-methyl-pyrrolidinone and stirred, 1.61 g (5 mol) of Compound (78) -C was added, and the mixture was cooled to 5 ° C. or lower. Under cooling, 2 ml of triethylamine and then 100 mg of 4-N, N-dimethylaminopyridine were sequentially added, followed by stirring at 5 ° C. or lower for 30 minutes and then stirring at room temperature for 2 hours. The reaction solution was extracted by adding 200 ml of ethyl acetate and 200 ml of dilute hydrochloric acid, and the organic layer was washed with water, dried over sodium sulfate, and concentrated. The concentrate was purified by silica gel column chromatography to obtain 2.5 g (2.2 mmol) of the desired compound (78). The ¹ H-NMR spectrum of the obtained compound was as follows.
¹ H-NMR (300 MHz, CDCl ₃ ): 0.93 ppm (3H, t), 1.20 to 1.86 ppm (36 H, m), 1.98 to 2.32 ppm (18 H, m), 2.65 ppm ( 2H, m), 3.21 ppm (2H, m), 3.46 ppm (4H, m), 4.19 ppm (4H, m), 4.30 ppm (2H, t), 4.79 (2H, m), 5.65 ppm (2H, d), 6.14 ppm (2H, dd), 6.42 ppm (2H, d), 7.23 ppm (2H, d), 7.27 (2H, d).
^{From 1} H-NMR and other spectral data, it was confirmed to be the target product.
In addition, the phase transition temperature of compound (78) was as follows.
Crystal-147 ° C → Nematic phase-163 ° C → Isotropic phase

(Example 2: Preparation of composition)
A liquid crystal composition was prepared using the compound (V-1) as the forward-dispersed liquid crystal compound and the compound (78) as the reverse wavelength-dispersed liquid crystal compound. 3 parts by weight of Irgacure 819 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 part by weight of the additive having the following structure are added to 1,100 parts by weight of the mixture of compound (V-1) and compound (78) , 2-trichloroethane was dissolved in 430 parts by mass to obtain a solution. The mixing ratio of the compound (78) to the liquid crystal compound mixture is 25% for solution a, 50% for solution b, 75% for solution c, 80% for solution d, and 90% for solution e. It was adjusted. As a comparative example, a solution x prepared by compound (V-1) alone and a solution y prepared by compound (78) alone were prepared.

(Example 3: Preparation of optically anisotropic film and evaluation of optical characteristics)
The solution (a to e, x and y) prepared in Example 2 was applied to a glass substrate subjected to rubbing treatment by spin coating. After drying at 100 ° C. for 1 minute, the mixture was aged at 115 ° C. for 1 minute and irradiated with a high-pressure mercury lamp in a nitrogen atmosphere. The retardation values of the obtained samples a to e and x and y in the front (normal direction with respect to the film surface) were measured by changing the measurement wavelength, and Re (450 nm) / Re (550 nm) were measured as wavelength dispersion characteristics. ) The results are shown in the table.

  From the results shown in the above table, it can be understood that the wavelength dispersion characteristics of the optically anisotropic film can be easily controlled by changing the mixing ratio.

(Comparative Example 1: Evaluation of zeonore and polycarbonate)
An optically anisotropic film composed of ZEONOR and polycarbonate manufactured by ZEON CORPORATION was prepared, and the anisotropy of the birefringence was examined, and Re (450 nm) / Re (550 nm) was obtained as wavelength dispersion characteristics. Zeonore was 1.01 and polycarbonate was 1.07.
According to the present invention, an optically anisotropic film exhibiting the same wavelength dependency as various commercially available optically anisotropic films is mixed with a predetermined reverse wavelength dispersive compound and a forward-dispersed liquid crystal. Can be easily manufactured.

(Example 4: Preparation of optically anisotropic film and evaluation of optical properties)
A solution sample (a2 to e2, x2) was prepared in the same manner as in Example 2 except that Compound V-71 was used instead of Compound V-1 used in Example 2, and Example 3 In the same manner, optically anisotropic film samples a2 to e2 and x2 were respectively produced. The retardation value in the front (normal direction to the film surface) of each sample was measured by changing the measurement wavelength, and Re (450 nm) / Re (550 nm) was obtained as the wavelength dispersion characteristic. The results are shown in the table below.

  From the results shown in the above table, it can be understood that the wavelength dispersion characteristics of the optically anisotropic film can be easily controlled by changing the mixing ratio.

Claims (7)

It contains at least one compound represented by the following general formula (1) in which Δn is reverse wavelength dispersion in the visible light region and at least one liquid crystal compound in which Δn is forward wavelength dispersion in the visible light region. Liquid crystal composition:

In the formula, A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S—, and —CO—; Z represents one or two atoms selected from the group consisting of a carbon atom and a non-metal atom of Groups 14 to 16, and C—C═C—C or C═C—C═C described in the formula And R ¹ , R ² and R ³ each independently represents a substituent; m is an integer of 0 to 4; L ¹ and L ² are each independently a single bond or two Represents a valent linking group. X represents a nonmetal atom of Groups 14 to 16 (provided that a hydrogen atom or a substituent R ⁴ may be bonded to X); provided that R, R ¹ , R ² , R ³ and R ⁴ At least one is a substituent having a polymerizable group. The liquid crystal composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2):

In the formula, A ¹ , A ² , Z, R ¹ , R ² , R ³ , m, L ¹ and L ² have the same meanings as in general formula (1), and R ⁵ and R ⁶ are each Each independently represents a substituent; provided that at least one of R, R ¹ , R ² , R ³ , R ⁵ and R ⁶ is a substituent having a polymerizable group; In the formula (2), R ⁵ and R ⁶ are each a cyano group (CN), an acyl group (—COR: R represents a substituted or unsubstituted alkyl group or aryl group), a substituted or unsubstituted alkoxy group. Carbonyl group or aryloxycarbonyl group (C (═O) OR: R represents a substituted or unsubstituted alkyl group or aryl group), or a substituted or unsubstituted carbamoyl group (C (═O) NR ¹¹ R ¹² : R ¹¹ and R ¹² each represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group, which may be bonded to each other to form a ring. Liquid crystal composition.   The ring formed by Z and C—C═C—C or C═C—C═C in the formula is an aromatic ring, according to claim 1. Liquid crystal composition. 5. The liquid crystal composition according to claim 1, wherein R ² and R ³ are each represented by any of the following formulae.

In the formula, L ¹¹ is a single bond or a linking group, and R ¹¹ is a substituent. The compound represented by the general formula (1) and the liquid crystal compound are contained in a mass ratio of 1:10 to 10: 1. Liquid crystal composition. An optically anisotropic film formed from the liquid crystal composition according to claim 1.