JP2010084032A - Liquid crystal compound, optically anisotropic membrane, retardation plate and polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymerizable liquid crystal compound in reverse wavelength dispersion, having both of high birefringence and steepness of the reverse wavelength dispersion, and to provide a compound capable of being controlled to any wavelength dispersion. <P>SOLUTION: The compound is represented by general formula (1) (wherein, A<SB>1</SB>and A<SB>2</SB>are each independently a group selected from the group consisting of -O-, -NR- (R is hydrogen or a substituent), -S- and -CO-; Z is an atom selected from the group consisting of group 14-16 nonmetallic atoms, and forms a 5- or 6-membered ring in combination with C-C=C-C or C=C-C=C in the formula; B and R<SB>1</SB>are each independently a substituent; R<SB>2</SB>is a divalent linking group; m is an integer of 0-4; L<SB>1</SB>and L<SB>2</SB>are each independently a divalent linking group; X is a group 14-16 nonmetallic atom (with the proviso that hydrogen or a substituent R<SB>3</SB>may bond to X); wherein when a polymerizable group is present, at least one of B, R, R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>is substituted with the polymerizable group; and n is an integer of 2-10). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid crystal compound having reverse wavelength dispersion. The present invention also relates to an optically anisotropic film formed by immobilizing the liquid crystal compound. The present invention also relates to a retardation plate having a birefringent reverse wavelength dispersion such as a broadband λ / 4 plate. Furthermore, the present invention relates to a polarizing plate and a liquid crystal display device using the retardation plate.

  Wave plates have been widely used for the purpose of improving a high contrast ratio and color shift at a wide viewing angle in color TFT liquid crystal display devices of various display modes. In order to prevent discoloration, this wave plate is required to control the wavelength dispersion of the phase difference, that is, the characteristics of the wave plate are constant regardless of the wavelength, and the wavelength dispersion of the phase difference is the phase difference on the short wave side. Is required to have a large phase difference on the long wave side, that is, reverse wavelength dispersion.

  A method for solving the above-mentioned problem is disclosed by applying a film prepared by applying and aligning an inverse wavelength dispersion polymerizable liquid crystal compound on an alignment film and then fixing the liquid crystal compound (for example, see Patent Document 1). In addition, compounds having sharper reverse wavelength dispersion and compounds and compositions that can be controlled to have arbitrary wavelength dispersion are always required in retardation plate design.

JP 2005-289980 A

  An object of the present invention is to provide a novel reverse wavelength dispersion polymerizable liquid crystal compound capable of achieving both high birefringence and a steepness of reverse wavelength dispersion. Another object of the present invention is to provide a compound or composition that can be controlled to an arbitrary wavelength dispersion by taking advantage of the steepness of the reverse wavelength dispersion. A further object of the present invention is to provide a retardation plate that does not require strict temperature control during the production of a polymer film, has a low load in the manufacturing process, and has birefringence reverse wavelength dispersion. Another object of the present invention is to provide a liquid crystal composition, a retardation plate, a polarizing plate (particularly an elliptically polarizing plate) using the above novel compound, and a liquid crystal display device using these.

The problems of the present invention have been solved by the following means.
[1] A compound represented by the following general formula (1).

(Wherein, A ₁ and A ₂ each independently represents 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 non-metallic atoms of Groups 14-16, and is 5 or together with C—C═C—C or C═C—C═C in the formula A 6-membered ring is formed, B and R ₁ each independently represent a substituent, R ₂ represents a divalent linking group, a plurality of B and R ₂ may be the same or different, and m is 0 to 0. It is an integer of 4. L ₁ and L ₂ each independently represent a divalent linking group, X represents a nonmetallic atom of Groups 14 to 16 (where X represents a hydrogen atom or a substituent R _3). may be bonded to each other.). in the case having a polymerizable group, B, R, R _1, integer der of .n 2-10 having at least one polymerizable group _{R 2} and R ₃ .)
[2] The compound according to item [1], wherein the compound represented by the general formula (1) is represented by the following general formula (2).

(Wherein, A ₁ and A ₂ each independently represents 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 non-metallic atoms of Groups 14 to 16 and forms a 5- or 6-membered ring with two carbon atoms in the formula: B, R ₁ Each independently represents a substituent, R ₂ represents a divalent linking group, a plurality of B and R ₂ may be the same or different, and m is an integer of 0 to 4. L ₁ and L ₂ Each independently represents a divalent linking group, R ₄ and R ₅ each independently represents a substituent, and when it has a polymerizable group, B, R, R ₁ , R ₂ , R ₄ , and R (At least one of ₅ is substituted with a polymerizable group. N is an integer of 2 to 10.)
[3] The compound according to item [1] or [2], wherein the polymerizable group is an addition polymerizable group.
[4] The compound according to [3], wherein the addition polymerizable group is a polymerizable group represented by any one of the following general formulas P1, P2, P3, and P4.

( _Where 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, and n ₅ represents 0 or 1.)
[5] A liquid crystal composition comprising at least one compound according to any one of [1] to [4].
[6] The liquid crystal composition according to [5], wherein the compound according to any one of [1] to [4] exhibits a nematic phase or a smectic A phase.

[7] An optically anisotropic film formed using the liquid crystal composition according to [5] or [6], wherein the compound according to any one of [1] to [4] is substantially perpendicular An optically anisotropic film formed by aligning and fixing.
[8] An optically anisotropic film formed using the liquid crystal composition according to [5] or [6], wherein the compound according to any one of [1] to [4] is substantially horizontal. An optically anisotropic film formed by aligning and fixing.
[9] An optically anisotropic film comprising the optically anisotropic film according to [7] or [8] and at least one other optically anisotropic film.
[10] The optically anisotropic film as described in [9], wherein the other optically anisotropic film is a positive A plate film.
[11] The optically anisotropic film as described in [10], wherein the other optically anisotropic film is a positive A plate film satisfying the following formulas (I) and (II):
Formula (I) Re (450 nm) / Re (550 nm) <1.0
Formula (II) Re (650 nm) / Re (550 nm)> 1.0
[Wherein, Re (450 nm), Re (550 nm), and Re (650 nm) represent retardation values at 450 nm, 550 nm, and 650 nm, respectively. However, each measurement wavelength includes an error of ± 10 nm. ]

[12] A retardation film comprising the optically anisotropic film according to any one of [9] to [11].
[13] A polarizing plate comprising the optically anisotropic film according to any one of [9] to [11].
[14] A liquid crystal display device comprising the retardation plate according to [12] or the polarizing plate according to [13].

  In the present invention, the “non-metallic atom of group 14 to 16” means a non-metallic atom belonging to group 14, 15 or 16 in the periodic table of International Pure and Applied Chemical Association (IUPAC). is there.

  ADVANTAGE OF THE INVENTION According to this invention, the novel reverse wavelength dispersion polymerizable liquid crystal compound which can make high birefringence and the steepness of reverse wavelength dispersion compatible can be provided. Further, it is possible to provide a compound that can be controlled to an arbitrary wavelength dispersion by taking advantage of the steepness of the reverse wavelength dispersion, and a liquid crystal composition containing the compound. Since the retardation plate produced using these materials does not require strict temperature control during the production of the polymer film, the load in the production process can be reduced.

  Hereinafter, the present invention will be described in detail. The following description may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. 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.

[Compound having reverse wavelength dispersion (compound represented by formula (1) or (2))]
The compound of the present invention is a compound having reverse wavelength dispersion and represented by the following general formula (1). Among these, the compound represented by the following general formula (2) is preferable.

(Wherein, A ₁ and A ₂ each independently represents 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 non-metallic atoms of Groups 14-16, and is 5 or together with C—C═C—C or C═C—C═C in the formula A 6-membered ring is formed, B and R ₁ each independently represent a substituent, R ₂ represents a divalent linking group, a plurality of B and R ₂ may be the same or different, and m is 0 to 0. It is an integer of 4. L ₁ and L ₂ each independently represent a divalent linking group, X represents a nonmetallic atom of Groups 14 to 16 (where X represents a hydrogen atom or a substituent R _3). may be bonded to each other.). in the case having a polymerizable group, B, R, R _1, .n least one of _{R 2} and R ₃ is substituted polymerizable group is 2 to 10 integer A.)

(Wherein, A ₁ and A ₂ each independently represents 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 non-metallic atoms of Groups 14 to 16 and forms a 5- or 6-membered ring with two carbon atoms in the formula: B, R ₁ Each independently represents a substituent, R ₂ represents a divalent linking group, a plurality of B and R ₂ may be the same or different, and m is an integer of 0 to 4. L ₁ and L ₂ Each independently represents a divalent linking group, R ₄ and R ₅ each independently represents a substituent, and when it has a polymerizable group, B, R, R ₁ , R ₂ , R ₄ , and R (At least one of ₅ is substituted with a polymerizable group. N is an integer of 2 to 10.)

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. R represents a hydrogen atom or a substituent. 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.

L ₁ and L ₂ are more preferably —O—, —COO—, and —OCO—.

In the general formula (1) or (2), the divalent linking group represented by R ₂ is not particularly limited, but preferably includes the following examples. A plurality of R ₂ may be the same or may be different from one another. The dotted line represents a bond with L ₁ or L _2.

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, for example, 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. A bicyclo [2,2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group), Rukiniru 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 group A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, 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 (Preferably, 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-tetradecanoylamino group. Phenoxy 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 Or substitution of 1 to 30 carbon atoms Is an unsubstituted carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn -Octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n- Octylcarbonyloxy group), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group) , P-n-hexadecyloxycarbonyl 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 acid having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylamino Sulfonylamino 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, ethoxycarbonyl) Amino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) Carbonylamino group, for example, 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 meth Thio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), A heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 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 having 1 to 30 carbon atoms substituted 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 has 1 to 30 carbon atoms Conversion or 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 Base Preferably, the substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, 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 (preferred Is 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 carbon atoms). -30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group and dimethylaminophosphinylamino group, silyl groups (preferably substituted or unsubstituted silyl having 3 to 30 carbon atoms) Group, for example, 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, an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6), an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6), aryl Group (preferably 4-18, more preferably 6-12), heterocyclic group (preferably 1-10, more preferably 1-5), hydroxyl group, carboxyl group, alkoxy group (carbon The number is preferably 1 to 10, more preferably 1 to 6, and the aryloxy group (preferably 6 to 18, more preferably 6 to 12), the acyloxy group (preferably 1 to 20 carbons, Preferred are 1 to 10), a cyano group or an amino group, and more preferred are a halogen 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), each B independently represents a substituent. Examples of the above R ₁ may be mentioned, and preferred are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group, and an alkynyl group. Further, they may be linked to the polymerizable group according to claim 4 via L ₁ or L ₂ . B is 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 of B. B is 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.

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

  In General formula (1), n is an integer of 2-10, Preferably it is 2-5.

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, and examples thereof include the above examples of R ₁ , preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, alkenyl A alkynyl group, which may be linked to a polymerizable group via L ₁ or L ₂ ) 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 ₃ , ═C (R ₄ ) R ₅ (wherein R ₃ , R ₄ , R ₅ each independently represents a substituent, and examples of R ₁ An example is given.)

In the general formula (2), R ₄ and R ₅ each independently represent a substituent. An example of R ₁ is given as an example. Preferably, R ₄ and at least one preferably substituent constant sigma _p value of Hammett is greater than zero electron withdrawing group, sigma _p value of the electron-withdrawing 0 to 1.5 of R ₅ More preferably, it has the following substituent. Examples of such a substituent include a trifluoromethyl group, a cyano group, a carbonyl group, and a nitro group. R ₄ and R ₅ may be bonded to form a ring.
As for Hammett's substituent constants σ _p and σ _m , for example, Naoki Inamoto's “Hammett's rule-structure and reactivity-” (Maruzen), edited by the Chemical Society of Japan “New Experimental Chemistry Course 14 Synthesis of Organic Compounds” “Reaction V” 2605 (Maruzen), Tadao Nakatani “Theoretical Organic Chemistry” 217 (Tokyo Kagaku Dojin), “Chemical Review”, 91, 165-195 (1991) Yes.

The liquid crystal compound of the present invention preferably has a polymerizable group. Thereby, when it uses for a phase difference plate etc., the change of the phase difference by heat etc. can be prevented. 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 B, R, R ₁ , R ₂ and R ₃ , and in the general formula (2), at least one of B, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ One is preferably substituted with a polymerizable group. The number is preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3. The substituent that the polymerizable group preferably substitutes is B.

The polymerizable group substituted on at least one of B, R, R ₁ , R ₂ and R ₃ or B, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is an addition polymerization reaction. Or the group in which a condensation polymerization reaction is possible is preferable. 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.

( _Where 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, and n ₅ represents 0 or 1.)

R ₅₁₁ , R ₅₁₂ and R ₅₁₃ of the polymerizable group P 1 each independently represents a hydrogen atom or an alkyl group.
The alkoxy group, alkoxycarbonyl group, alkoxycarbonyloxy group residue formed by substitution of the polymerizable group P1 is an alkyleneoxy group (for example, alkyleneoxy such as ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, etc.) Oxy groups, substituted alkyleneoxy groups containing ether bonds such as ethyleneoxyethoxy), alkyleneoxycarbonyloxy groups (for example, ethyleneoxycarbonyloxy, propyleneoxycarbonyloxy, butyleneoxycarbonyloxy, pentyleneoxycarbonyloxy, hexyleneoxy) Alkyleneoxycarbonyloxy groups such as carbonyloxy and heptyleneoxycarbonyloxy, and ethers such as ethyleneoxyethoxycarbonyloxy A substituted alkyleneoxycarbonyloxy group containing a bond), an alkyleneoxycarbonyl group (for example, ethyleneoxycarbonyl group, propyleneoxycarbonyl group, butyleneoxycarbonyl group, pentyleneoxycarbonyl group, hexyleneoxycarbonyl group, heptyleneoxycarbonyl group) A substituted alkyleneoxycarbonyl group containing an ether bond such as an ethyleneoxyethoxycarbonyl group). The polymerizable group P1 may be directly bonded to the aromatic ring.

n ₅ represents an integer of 0-1, preferably n ₅ is 1, when n ₅ is 1, the polymerizable group P1 is 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 represents a hydrogen atom, a substituted or unsubstituted alkyl group (eg, 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 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 R ₅₃₁ and R ₅₃₃ are both a combination of 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 and 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 the present invention is not limited to the following specific examples. Regarding the following compounds, unless otherwise specified, the number in parentheses () indicates the exemplified compound (X). In the formula, n is an integer of 2 to 10.

  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.

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 coated on an alignment film, aligned, and then fixed, thereby having a film having reverse wavelength dispersion (optically anisotropic). A conductive film). 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 preferably satisfies the following formulas (I) and (II), and more preferably satisfies the formulas (III) and (IV). In the formula, Re (450 nm), Re (550 nm), and Re (650 nm) represent retardation values at 450 nm, 550 nm, and 650 nm. However, each measurement wavelength includes an error of ± 10 nm.

Formula (I) Re (450 nm) / Re (550 nm) <1.0
Formula (II) Re (650 nm) / Re (550 nm)> 1.0

Formula (III) 0.5 <Re (450 nm) / Re (550 nm) <1.0
Formula (IV) 1.05 <Re (650 nm) / Re (550 nm) <1.5

  In order to produce a film satisfying the above formulas (I) and (II), it is necessary to arrange the absorption wavelength and the 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 (I) and (II). 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 (inclination 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 formulas (V) and (VI Is satisfied.

Formula (V) 1> | Δn (450 nm) / Δn (550 nm) |
Formula (VI) 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 the formulas (I) and (II) 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.

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 optically anisotropic film is characterized by high steepness of reverse wavelength dispersion. The value of (Δn (450 nm) / Δn (550 nm)) is preferably 0.5 to 0.8, and more preferably 0.5 to 0.7. By having steep reverse wavelength dispersion, a high-performance optical instrument can be provided.

[Liquid crystal composition]
The liquid crystal composition of the present invention can be used in combination with any additive in addition to the polymerizable liquid crystal compound represented by the general formula (1) or (2) of the present invention. Examples of the additive include a liquid crystal compound other than the compound represented by the general formula (1) or (2), an air interface alignment controller, a repellency inhibitor, a polymerization initiator, a polymerizable monomer, and the like described later. It is done.

(Liquid crystal compound)
The liquid crystal composition of the present invention contains a compound represented by the general formula (1) or (2). When the liquid crystalline composition of the present invention is used for a retardation plate, those showing good monodomain properties are preferred for uniform alignment without defects. 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 retardation plate. In order to exhibit good monodomain properties, the liquid crystalline composition of the present invention preferably exhibits a nematic phase (N phase).

  Moreover, when using the liquid crystal composition of this invention for a phase difference plate, it is preferable that the liquid crystal temperature range exists in the range of 10-250 degreeC from surfaces, such as manufacture suitability of a phase difference plate, 10-150. More preferably, it exists in the range of ° C. When the temperature is lower than 10 ° C., a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a liquid crystal phase. When the temperature exceeds 200 ° C., a high temperature is required to make the isotropic liquid state higher than the temperature range once exhibiting a liquid crystal phase, which is disadvantageous from waste of heat energy, deformation of the substrate, and alteration.

In the liquid crystal composition of the present invention, one or more liquid crystal compounds may be used. For example, a polymerizable liquid crystal compound and a non-polymerizable liquid crystal compound can be used in combination. Also, a combination of a low-molecular liquid crystal compound and a high-molecular liquid crystal compound is possible. Furthermore, you may mix 2 types of liquid crystal compounds which satisfy | fill following numerical formula (VII).
Formula (VII) Δn (450 nm) / Δn (550 nm) <1.0

  As a liquid crystal compound other than the compound represented by the general formula (1) or (2), for example, a liquid crystal compound described in JP-A-2005-289980 can be used.

The liquid crystal compound satisfying the above formula (VII) of the present invention may be mixed with a liquid crystal compound in which the wavelength dispersion of Δn is normal dispersion. Here, the chromatic dispersion being normal dispersion means that the following formula (VIII) is satisfied.
Formula (VIII) Δn (450 nm) / Δn (550 nm)> 1.0

By mixing a liquid crystal compound satisfying the above formula (VII) of the present invention and a liquid crystal compound having a normal wavelength dispersion of Δn, a liquid crystal composition having intermediate wavelength dispersion can be created. Specifically, with the conventional liquid crystal compounds, the realization of the formula (IX) has been an extremely difficult area. However, if a liquid crystal compound satisfying the above formula (VII) of the present invention is mixed with a liquid crystal compound having a wavelength dispersion of Δn of normal dispersion, the liquid crystal composition having wavelength dispersion in the region represented by formula (IX) can be easily obtained. Can make things.
Formula (IX) 1.0 ≦ Δn (450 nm) / Δn (550 nm) <1.1

  Since the liquid crystal compound satisfying the above formula (VII) of the present invention exhibits liquid crystallinity, it can be mixed with the liquid crystal compound having a normal wavelength dispersion of Δn at any mixing ratio. Therefore, the mixing ratio may be changed according to the target wavelength dispersion.

  The content of the liquid crystal compound represented by the general formula (1) or (2) in the liquid crystal composition of the present invention is not limited as long as the composition exhibits liquid crystallinity. % By mass is preferable, and 50 to 90% by mass is more preferable.

(Air interface orientation control agent)
Liquid crystal compounds are known to have different tilt angles (tilt angles) at the air interface depending on the type of compound. It is necessary to arbitrarily control the tilt angle of the air interface according to the optical purpose of the retardation plate. For controlling the tilt angle, for example, an external field such as an electric field or a magnetic field or an additive can be used, but an additive is preferably used. As such an additive, a substituted or unsubstituted aliphatic group having 6 to 40 carbon atoms, or a substituted or unsubstituted aliphatic substituted oligosiloxanoxy group having 6 to 40 carbon atoms is incorporated in the molecule. A compound having one or more is preferable, and a compound having two or more in the molecule is more preferable. For example, as the air interface alignment control agent, those described in JP-A Nos. 11-352328 and 2002-20363 can be used. Moreover, the compound described in Unexamined-Japanese-Patent No. 2002-129162 can be used. The matters described in paragraph numbers [0072] to [0075] of Japanese Patent Application Laid-Open No. 2004-53981 can also be appropriately applied to the present invention. Also, by blending these compounds, the coating properties are improved, and the occurrence of unevenness or repellency is suppressed. As a vertical alignment agent, you may use together with the thing of Unexamined-Japanese-Patent No. 2006-106662.

  The content of the alignment control additive on the air interface side is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass with respect to the liquid crystal composition. 1% by mass to 5% by mass is most preferable.

(Anti-repellent agent)
In general, a polymer can be suitably used as a material for use together with the liquid crystal compound to prevent repellency during application of the liquid crystal composition. The polymer to be used is not particularly limited as long as the tilt angle change and orientation of the liquid crystal compound are not significantly inhibited. Examples of the polymer are described in JP-A No. 8-95030, and specific examples of particularly preferable polymers include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate.
The content of the polymer used for the purpose of preventing repellency so as not to disturb the alignment of the liquid crystal is generally preferably in the range of 0.1 to 10% by mass, preferably 0.1 to 8% by mass with respect to the liquid crystal compound. More preferably, it is in the range of 0.1 to 5% by mass.

(Polymerizable monomer)
The liquid crystal composition may contain a polymerizable monomer. The polymerizable monomer used together with the liquid crystal compound is not particularly limited as long as it has compatibility with the liquid crystal compound and does not significantly change the tilt angle or inhibit alignment of the liquid crystal compound. Among these, compounds having a polymerization active ethylenically unsaturated group such as a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloyl group are preferably used.
The content of the polymerizable monomer is generally in the range of 0.5 to 50% by mass and preferably in the range of 1 to 30% by mass with respect to the liquid crystal compound. In addition, it is particularly preferable to use a monomer having two or more reactive functional groups because an effect of improving the adhesion between the alignment film and the optically anisotropic layer can be expected.

(Polymerization initiator)
In the present invention, the liquid crystal compound is preferably fixed in a monodomain alignment, that is, in a substantially uniformly aligned state. Therefore, the polymerizable liquid crystal compound of the present invention is preferably fixed in a monodomain alignment by a polymerization reaction.

The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and a polymerization reaction by electron beam irradiation. In order to prevent the support and the like from being deformed or altered by heat. Also, a photopolymerization reaction and a polymerization reaction by electron beam irradiation are preferable.
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), oxadiazole compounds (U.S. Pat. No. 4,212,970), and the like.
The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.
Light irradiation for the polymerization of the liquid crystal compound is preferably performed using ultraviolet rays. The irradiation energy is preferably 10 to 50 J / cm ² , and more preferably 50 to 800 mJ / cm ² . In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.
Further, since the oxygen concentration in the atmosphere is related to the degree of polymerization, when the desired degree of polymerization is not reached in the air, it is preferable to reduce the oxygen concentration by a method such as nitrogen substitution. A preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and most preferably 3% or less.

(Chiral agent)
In the present invention, the cholesteric phase can be expressed by including at least one chiral agent in the liquid crystal composition. The chiral agent used in the present invention is a known chiral agent (eg, “Liquid Crystal Device Handbook” edited by Japan Society for the Promotion of Science 142nd Committee, Chapter 3-4-3, TN, chiral agent for STN, page 199, 1989. Can be used).
The chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used as the chiral agent. Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof. The chiral agent may have liquid crystallinity, and the liquid crystal compound of the present invention may also serve as the chiral agent.
The amount of the chiral agent used is preferably 0.001 to 200 mol% of the amount of the liquid crystal compound. A smaller amount of chiral agent is preferred because it often does not affect liquid crystallinity. Therefore, it is preferable that the chiral agent has a strong twisting force. As such a chiral agent having a strong twisting force, for example, a chiral agent described in JP-A-2003-287623 can be used.

(Coating solvent)
As the solvent used for preparing the liquid crystal composition, 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, toluene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides, esters and ketones are preferred. Two or more organic solvents may be used in combination.

[Phase difference plate]
The retardation plate of the present invention comprises an alignment film and at least one optically anisotropic layer (optically anisotropic film) containing a compound represented by the general formula (1) or (2) on a transparent support. And have. In order to fix the liquid crystal composition containing the compound represented by the general formula (1) or (2) without impairing the alignment form in the liquid crystal state, the retardation plate of the present invention is once formed at a liquid crystal phase formation temperature. And then cooling while maintaining the orientation state to form an optically anisotropic layer. Alternatively, it can be obtained by heating a liquid crystal composition obtained by adding a polymerization initiator to a liquid crystal compound having a polymerizable group to a liquid crystal phase formation temperature, followed by polymerization and cooling. Here, the state of “fixed” in the present invention is the most typical and preferred mode in which the orientation of the liquid crystal compound contained in the optically anisotropic layer is maintained, but is not limited thereto. Specifically, the optically anisotropic layer has no fluidity in a temperature range of usually 0 ° C. to 50 ° C., and under a severer condition of −30 ° C. to 70 ° C., and is oriented by an external field or an external force. This means a state in which the fixed orientation form can be kept stable without causing a change in the.

  In the retardation plate of the present invention, when the optically anisotropic layer is finally formed, the liquid crystal compound does not need to be liquid crystalline as long as the optical anisotropy is maintained. For example, a low-molecular biaxial liquid crystal compound has a group that reacts with heat, light, etc., resulting in polymerization or crosslinking by reaction with heat, light, etc., resulting in a high molecular weight and loss of liquid crystallinity. Also good.

(Optically anisotropic layer)
The optically anisotropic layer is formed by applying a liquid crystal composition coating solution prepared using the above-mentioned solvent on the alignment film and subjecting the liquid crystal compound to an alignment treatment. The coating liquid can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method).
The thickness of the optically anisotropic layer formed from the liquid crystal composition is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, and preferably 0.3 to 10 μm. Most preferred.

(Alignment treatment of liquid crystal compounds)
The alignment of liquid crystal compounds is described in Chapter 2 “Liquid crystal alignment and physical properties” in Liquid Crystal Handbook (Maruzen Co., Ltd., issued on October 30, 2000).
As a method for fixing the alignment state in the present invention, the liquid crystalline composition is once heated to the liquid crystal phase formation temperature, and then cooled while maintaining the alignment state, thereby impairing the alignment form in the liquid crystal state. It can be formed by immobilization. Moreover, after heating the composition which added the polymerization initiator to the liquid crystalline composition of this invention to liquid crystal phase formation temperature, it superposes | polymerizes and cools and can form by fixing the orientation state of a liquid crystal state. In the present invention, the alignment state is preferably fixed by the latter polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and a polymerization reaction by electron beam irradiation. In order to prevent the support and the like from being deformed or altered by heat. Also, a photopolymerization reaction or a polymerization reaction by electron beam irradiation is preferable.

(Alignment film)
The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , 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. As long as the desired orientation can be imparted to the liquid crystal compound of the optically anisotropic layer provided on the alignment film, the alignment film may be any layer, but in the present invention, it is formed by rubbing treatment or light irradiation. An alignment film is preferred. In particular, an alignment film formed by a rubbing treatment of a polymer is preferable. The rubbing treatment can be generally carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. In particular, in the present invention, it is described in “Liquid Crystal Handbook” (Maruzen Co., Ltd., 2000). It is preferable to carry out by the method described above. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.05 to 3 μm.

  The polymer used for the alignment film is described in many documents, and many commercially available products can be obtained. For the alignment film used in the retardation plate of the present invention, polyvinyl alcohol and its derivatives are preferably used. In particular, modified polyvinyl alcohol to which a hydrophobic group is bonded is preferable. As the alignment film, an alignment film used for a discotic liquid crystal can be used as an alignment film for liquid crystal. As such an alignment film, reference can be made to the description on page 43, line 24 to page 49, line 8 of the pamphlet of WO01 / 88574A1.

(Rubbing density of alignment film)
Since there is a relationship between the rubbing density of the alignment film and the tilt angle of the liquid crystal compound at the interface of the alignment film, the tilt angle decreases as the rubbing density increases, and the tilt angle increases as the rubbing density decreases. The tilt angle can be adjusted by changing the rubbing density. As a method of changing the rubbing density of the alignment film, a method described in “Liquid Crystal Handbook” (Maruzen Co., Ltd., 2000) can be used. That is, the rubbing density (L) is quantified by the following formula (A).

      Formula (A) L = Nl {1 + ((2πrn) / (60v))}

  In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of rotations (rpm) of the roller, and v is the stage moving speed (second speed).

  According to the formula (A), in order to increase the rubbing density, the number of rubbing is increased, the contact length of the rubbing roller is increased, the radius of the roller is increased, the number of rotations of the roller is increased, and the stage moving speed is decreased. On the other hand, in order to lower the rubbing density, this may be reversed.

(Vertical alignment film)
In order to align the liquid crystal compound vertically on the alignment film side, a method of reducing the surface energy of the alignment film and a method of verticalizing the liquid crystal by the excluded volume effect are effective. In order to reduce the surface energy of the alignment film, the surface energy of the alignment film is decreased by a functional group introduced into the polymer.
For this purpose, a functional group of a hydrophobic group is effective, and specifically, a fluorine atom and a hydrocarbon group having 10 or more carbon atoms are effective. In order for a fluorine atom or a hydrocarbon group to be present on the surface of the alignment film, it is preferable to introduce a fluorine atom or a hydrocarbon group into the side chain rather than the main chain of the polymer. The fluoropolymer preferably contains fluorine atoms in a proportion of 0.05 to 80% by mass, more preferably in a proportion of 0.1 to 70% by mass, and in a proportion of 0.5 to 65% by mass. More preferably, it is most preferable to contain in the ratio of 1-60 mass%. The hydrocarbon group is an aliphatic group, an aromatic group, or a combination thereof. The aliphatic group may be cyclic, branched or linear. The aliphatic group is preferably an alkyl group (which may be a cycloalkyl group) or an alkenyl group (which may be a cycloalkenyl group). The hydrocarbon group may have a substituent that does not exhibit strong hydrophilicity, such as a halogen atom. The number of carbon atoms in the hydrocarbon group is preferably 10 to 100, more preferably 10 to 60, and still more preferably 10 to 40. The main chain of the polymer preferably has a polyimide structure or a polyvinyl alcohol structure.

  Polyimide is generally synthesized by a condensation reaction of tetracarboxylic acid and diamine. A polyimide corresponding to a copolymer may be synthesized using two or more kinds of tetracarboxylic acids or two or more kinds of diamines. The fluorine atom or hydrocarbon group may be present in the repeating unit derived from tetracarboxylic acid, may be present in the repeating unit derived from diamine, or may be present in both repeating units. When introducing a hydrocarbon group into polyimide, it is particularly preferable to form a steroid structure in the main chain or side chain of the polyimide. The steroid structure present in the side chain corresponds to a hydrocarbon group having 10 or more carbon atoms, and has a function of vertically aligning the liquid crystal compound. In this specification, the steroid structure is a cyclopentanohydrophenanthrene ring structure or a ring structure in which a part of the bond of the ring is an aliphatic ring (a range in which an aromatic ring is not formed) is a double bond. means. Rigid substituents such as steroid structures and alkyl chains are more preferred because they can exhibit an excluded volume effect on the liquid crystal molecules to be aligned.

  Further, as a means for vertically aligning the liquid crystal compound, a method of mixing an organic acid with a polymer of polyvinyl alcohol, modified polyvinyl alcohol, or polyimide can be suitably used. As the acid to be mixed, carboxylic acid, sulfonic acid and amino acid are preferably used. Among the air interface alignment agents described later, those showing acidity may be used. Moreover, quaternary ammonium salts can also be used suitably. The mixing amount is preferably 0.1% by mass to 20% by mass and more preferably 0.5% by mass to 10% by mass with respect to the polymer. The saponification degree of the polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. The polymerization degree of polyvinyl alcohol is preferably 100 to 5000.

  The alignment film is formed using a polymer having a side chain having a crosslinkable functional group bonded to the main chain or a polymer having a crosslinkable functional group on a side chain having a function of aligning liquid crystal molecules, and a position on the polymer. When the retardation film is formed using a composition containing a polyfunctional monomer, the polymer in the alignment film and the polyfunctional monomer in the retardation film formed thereon can be copolymerized. As a result, a covalent bond is formed not only between the polyfunctional monomers but also between the alignment film polymers and between the polyfunctional monomer and the alignment film polymer, and the alignment film and the retardation film are firmly bonded. Therefore, the strength of the optical compensation sheet can be remarkably improved by forming the alignment film using a polymer having a crosslinkable functional group. The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specific examples include those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216.

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

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

The alignment film is basically formed by applying a composition containing the above-mentioned polymer that is an alignment film forming material and a crosslinking agent onto a transparent support, followed by drying by heating (crosslinking) and rubbing treatment as necessary. Can be formed.
It is preferable not to perform rubbing treatment for the vertical alignment of the rod-like liquid crystal compound. As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating liquid is preferably a mixed solvent of an organic solvent (for example, methanol) having a defoaming action and water. The ratio of water: methanol is preferably 0: 100 to 99: 1, and more preferably 0: 100 to 91: 9. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the alignment film and also the phase difference layer surface reduces significantly.

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

  The retardation film of the present invention is sufficiently adhered to a glass substrate, a color filter provided on the glass substrate, an alignment film, an overcoat (OC) layer, and a reflector by coating and heating itself. However, depending on the purpose, the following method can be used to adjust the adhesion. Specifically, surface activation, surface modification, and a method of mixing an adhesion promoter in the retardation film coating solution.

Surface activation methods include chemical treatment with acid or alkali, mechanical treatment, corona discharge treatment, flame treatment, UV treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and ozone oxidation treatment. it can. The glow discharge treatment here may be low-temperature plasma that occurs in a low-pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable. A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail on pages 30 to 32 in the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention), and are preferably used in the present invention. be able to. In the plasma treatment at atmospheric pressure, which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 kGy is used under 10 to 1000 keV, and more preferably irradiation energy of 20 to 300 kGy is used under 30 to 500 keV.

Examples of the method by surface modification include undercoat layer formation, silane coupling treatment using a silane coupling agent described later, and anchor coat layer formation. Details of the undercoat layer are described on page 32 of the Japan Institute of Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention).
As a method for mixing the adhesion promoter with the retardation film coating solution, examples of suitable methods include those disclosed in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. Preferable examples include adhesion promoters described in Japanese Patent Publication No. Gazette. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole , Amino group-containing benzotriazole, polymerizable organometallic compound having a hydrolyzable group or radical polymerizable group, α, β-ethylenically unsaturated carboxylic acid ester, silane coupling agent, titanium coupling And the like.

  Examples of the silane coupling agent include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltri Ethoxysilane, vinyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ- Aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysila , Γ-aminobutyltributoxysilane and the like, and examples of the titanium coupling agent include γ-aminopropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopropyltripropoxytitanium, γ- Aminopropyl tributoxy titanium, γ-aminoethyl triethoxy titanium, γ-aminoethyl trimethoxy titanium, γ-aminoethyl tripropoxy titanium, γ-aminoethyl tributoxy titanium, γ-aminobutyl triethoxy titanium, γ-aminobutyl Examples include trimethoxy titanium, γ-aminobutyl tripropoxy titanium, and γ-aminobutyl tributoxy titanium. Two or more of these may be used in combination.

  As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to all the components of the said phase difference layer, 0.01-10 mass% is more preferable, 0.1 mass%-5 Mass% is particularly preferred.

  The adhesion can also be controlled by the polymerization initiator. Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds. , Acylphosphine oxide compounds, aromatic onium salts, metallocenes and the like. Among these, a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, a ketone compound, and a hexaarylbiimidazole compound are preferable from the viewpoints of sensitivity, storage stability, adhesion, and the like.

(Transparent support)
The transparent support of the retardation plate of the present invention is not particularly limited as long as it is mainly optically isotropic and has a light transmittance of 80% or more, but a polymer film is preferred. Specific examples of the polymer include cellulose esters (eg, cellulose diacetate, cellulose triacetate), norbornene polymers, poly (meth) acrylate esters, and the like, and many commercially available polymers are preferably used. Is possible. Of these, cellulose esters are preferable from the viewpoint of optical performance, and lower fatty acid esters of cellulose are more preferable. The lower fatty acid is a fatty acid having 6 or less carbon atoms, and the number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose triacetate is particularly preferred. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used. Moreover, even if it is a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence, it is possible to modify the molecule described in International Publication No. 00/26705 to reduce the expression. It can also be used.
In the present invention, the transparent support and the alignment film are indispensable at the stage of forming the retardation film, but after the retardation film is formed, it is transferred to a different substrate, and the transparent support and / or the alignment film is peeled off. May be removed.

  Hereinafter, the cellulose ester (especially cellulose triacetate) preferably used as the transparent support will be described in detail. As the cellulose ester, it is preferable to use cellulose acetate having an acetylation degree of 55.0 to 62.5%. In particular, the acetylation degree is preferably 57.0 to 62.0%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). The viscosity average polymerization degree (DP) of the cellulose ester is preferably 250 or more, and more preferably 290 or more. The cellulose ester used in the present invention preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably 1.0 to 4.0, more preferably 1.3 to 3.5, and most preferably 1.4 to 3.0. preferable.

  In cellulose triacetate, the hydroxyl groups at the 2nd, 3rd and 6th positions of cellulose are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6th hydroxyl group tends to be small. It is preferable that the substitution degree of the 6-position hydroxyl group of cellulose is larger than the 2-position and 3-position. The ratio in which the hydroxyl group at the 6-position is substituted with an acyl group with respect to the total degree of substitution is preferably 30% or more and 40% or less, more preferably 31% or more, and particularly preferably 32% or more. The substitution degree at the 6-position is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with an acyl group having 3 or more carbon atoms (eg, propionyl, butyryl, valeroyl, benzoyl, acryloyl) in addition to the acetyl group. The degree of substitution at each position can be determined by NMR. Cellulose esters having a high degree of substitution at the 6-position hydroxyl group are described in Synthesis Example 1 described in Paragraph Nos. 0043 to 0044 of JP-A No. 11-5851, Synthetic Example 2 described in Paragraph Nos. 0048 to 0049, and Paragraph Nos. 0051 to 0052. It can be synthesized with reference to the method of Synthesis Example 3 described.

  In order to adjust the retardation of a polymer film used as a transparent support, particularly a cellulose acetate film, an aromatic compound having at least two aromatic rings can be used as a retardation increasing agent. When using such a retardation increasing agent, a retardation increasing agent is used in 0.01-20 mass parts with respect to 100 mass parts of cellulose acetate. The retardation increasing agent is preferably used in a range of 0.05 to 15 parts by mass, and more preferably in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. Two or more aromatic compounds may be used in combination. Here, the aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to the aromatic hydrocarbon ring.

  The aromatic hydrocarbon ring of the aromatic compound as the retardation increasing agent is particularly preferably a 6-membered ring (that is, a benzene ring). In addition, the aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring. As the aromatic ring, benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring are preferable, More preferred are a benzene ring and a 1,3,5-triazine ring. It is particularly preferred that the aromatic compound has at least one 1,3,5-triazine ring. The number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 8, and most preferably 2 to 6. .

  In addition, the bonding relationship between the two aromatic rings of the aromatic compound as the retardation increasing agent is as follows: (a) when a condensed ring is formed, (b) when directly bonded by a single bond, and (c) via a linking group. (Spiro bonds cannot be formed because of the aromatic ring). The connection relationship may be any of (a) to (c). Such retardation increasing agents are described in WO01 / 88574A1 pamphlet, WO00 / 2619A1 pamphlet, JP-A Nos. 2000-1111914, 2000-275434, 2002-363343 and the like.

  Cellulose acetate as a transparent support is composed of a single layer or a plurality of layers. For example, in the case of cellulose triacetate, a single layer of cellulose triacetate can be produced by drum casting or band casting disclosed in JP-A-7-11055, etc. It can be prepared by the so-called co-casting method disclosed in JP-A-61-94725 and JP-B-62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose ester dope, and the film is dried to some extent on the support to release the rigid film, and then peeled off from the support. A process comprising passed through a drying section by species of the conveying means to remove the solvent.

  A typical solvent for dissolving cellulose triacetate as described above is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass). When preparing a cellulose triacetate dope using a solvent substantially free of dichloromethane or the like, a special dissolution method as described below is essential. These are called a cooling dissolution method and a high temperature dissolution method. A cellulose acetate film substantially free of halogenated hydrocarbons such as dichloromethane and a process for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, hereinafter Published Technical Report 2001-1745). (Abbreviated as No.).

  As additives to be added for improving various physical properties of cellulose acetate, those described in the published technical report 2001-1745 can be preferably used.

  When the transparent support is cellulose acetate, it is preferable to carry out a saponification treatment in order to sufficiently adhere the adhesive to other functional layers or substrates by providing an adhesive layer on one side. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkali solution, it is preferable to sufficiently wash with water or neutralize the alkali component by immersing in a dilute acid so that the alkali component does not remain in the film. By saponification treatment, the surface of the transparent support is hydrophilized. The hydrophilized surface is particularly effective for improving the adhesion with a deflection film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so that it is difficult for dust to enter between the deflecting film and the transparent support when bonded to the deflecting film, thereby preventing point defects due to dust. It is effective for.

  The saponification treatment is preferably carried out so that the contact angle with water on the surface of the transparent support is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two. The following (1) is excellent in that it can be processed in the same process as a general-purpose cellulose acetate film, but since the saponification treatment is performed up to the surface of the optically anisotropic layer, the surface is alkali-hydrolyzed and the film deteriorates. If the saponification solution remains, it may become a problem. In that case, although it becomes a special process, the following (2) is excellent.
(1) After forming the optically anisotropic layer on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after forming the optically anisotropic layer on the transparent support, an alkaline liquid is applied to the surface of the transparent support opposite to the surface on which the optically anisotropic layer is formed, and heating, washing and By neutralizing, only the back surface of the transparent support is saponified.

  The surface energy of the cellulose acetate film is preferably 55 mN / m or more, and more preferably in the range of 60 to 75 mN / m. The surface energy of a solid can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” (issued by Realize 1989.12.10). In the case of the cellulose acetate film of the present invention, it is preferable to use a contact angle method. Specifically, two types of solutions having known surface energies are dropped on a cellulose acetate film, and at the intersection between the surface of the droplet and the surface of the film, the angle formed by the tangent line drawn on the droplet and the film surface The surface angle of the film can be calculated by defining the angle containing the droplet as the contact angle.

  The thickness of the cellulose acetate film is usually preferably in the range of 5 to 500 μm, preferably in the range of 20 to 250 μm, more preferably in the range of 30 to 180 μm, and particularly preferably in the range of 30 to 110 μm.

(Wavelength dispersion)
The wavelength dispersion of the retardation plate of the present invention more preferably satisfies the following formulas (A-1) and (A-2).

Formula (A-1) 0.60 <Re (450 nm) / Re (550 nm) <0.99
Formula (A-2) 1.01 <Re (650 nm) / Re (550 nm) <1.35
[Wherein, Re (450 nm), Re (550 nm), and Re (650 nm) represent retardation values at 450 nm, 550 nm, and 650 nm, respectively. However, each measurement wavelength includes an error of ± 10 nm. ]

  When it is out of these ranges, for example, when it is used as a λ / 4 plate, when linearly polarized light of 400 to 700 nm is incident on this phase difference plate, the polarization state obtained is a perfect circle at a specific wavelength. Although polarized light can be obtained, there may be a problem that it is greatly deviated from circularly polarized light at other wavelengths. Therefore, it is more preferable to satisfy the following expressions (A-3) and (A-4).

Formula (A-3) 0.60 <Re (450 nm) / Re (550 nm) <0.95
Formula (A-4) 1.04 <Re (650 nm) / Re (550 nm) <1.35
[Wherein, Re (450 nm), Re (550 nm), and Re (650 nm) represent retardation values at 450 nm, 550 nm, and 650 nm, respectively. However, each measurement wavelength includes an error of ± 10 nm. ]

[Polarizer]
The retardation plate of the present invention is particularly useful for a polarizing plate protective film. When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There is a method in which the obtained cellulose film is subjected to alkali treatment, and a polyvinyl alcohol film is dipped in an iodine solution and bonded to both surfaces of the polarizing film using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.
Examples of the adhesive used to bond the protective film-treated surface and the polarizing film include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like.
The polarizing plate is composed of a polarizing film and protective films that protect both surfaces thereof, and may further be configured by bonding a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.
In a liquid crystal display device, a substrate containing liquid crystal is usually disposed between two polarizing plates. However, a polarizing plate protective film to which the cellulose film of the present invention is applied can provide excellent display properties regardless of the location. . In particular, the polarizing plate protective film on the display side outermost surface of the liquid crystal display device is provided with a transparent hard coat layer, an antiglare layer, an antireflection layer, and the like.

In the case of using an optical film containing the liquid crystal compound of the present invention as a protective film for polarizing plate, the value of the photoelasticity ^{0.5 × 10 -13 ~9.0 × 10 -13} [cm 2 / dyn It is preferable that the value of moisture permeability (however, converted to a film thickness of 80 μm) is 180 to 435 [g / cm ² · 24 h]. The value of photoelasticity is more preferably 0.5 × 10 ^{−13 to} 7.0 × 10 ⁻¹³ [cm ² / dyn], and 0.5 × 10 ^{−13 to} 5.0 × 10 ⁻¹³ [ More preferably, it is cm ² / dyn]. Further, the value of moisture permeability (however, the film thickness converted to 80 μm) is more preferably 180 to 400 [g / cm ² · 24 h], and 180 to 350 [g / cm ² · 24 h]. More preferably. When the film of the present invention has the above-described properties, when it is used as a protective film for a polarizing plate, it is possible to reduce a decrease in performance due to the influence of humidity.

[Optically anisotropic film]
The optically anisotropic film (optically anisotropic film (A)) in which the liquid crystal compound of the present invention is substantially vertically aligned and fixed can be used as a brightness enhancement film and an optical compensation film for IPS.

  The optically anisotropic film (A) of the present invention can be used for an elliptically polarizing plate in combination with a polarizing film. Furthermore, application to a transmissive liquid crystal display device in combination with a polarizing film can contribute to an increase in the viewing angle of the liquid crystal display device.

The optically anisotropic film (A) of the present invention can be provided with an adhesive layer. The pressure-sensitive adhesive layer can be used for adhering to a liquid crystal cell, and can be used for laminating other optically anisotropic films (optically anisotropic films (B)) and the like.
The pressure-sensitive adhesive layer can also be provided on one side or both sides of a polarizing plate or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as the adhesion layers of a different composition, a kind, thickness, etc. in the front and back of a polarizing plate or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is preferably 1 to 500 μm, more preferably 5 to 200 μm, and still more preferably 10 to 100 μm.

  On the exposed surface of the adhesive layer, a separator is temporarily attached and covered for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, laminate thereof, or the like, if necessary In addition, an appropriate one according to the prior art, such as those coated with an appropriate release agent such as a long mirror alkyl type, a fluorine type or molybdenum sulfide, can be used.

[Liquid Crystal Display]
<Configuration of general liquid crystal display device>
The optical film containing the liquid crystal compound of the present invention can be applied to a liquid crystal display device. The liquid crystal display device includes a liquid crystal cell having a liquid crystal supported between two electrode substrates, two polarizing films disposed on both sides thereof, and at least one sheet between the liquid crystal cell and the polarizing film. The optical compensation film is arranged.
The liquid crystal layer of the liquid crystal cell is usually formed by sealing liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive substance. The liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer (undercoat layer) (used for adhesion of the transparent electrode layer). These layers are usually provided on the substrate. The substrate of the liquid crystal cell preferably has a thickness of 50 μm to 2 mm.

<Types of liquid crystal display devices>
The optical film containing the liquid crystal compound of the present invention can be used for liquid crystal cells in various display modes. Specifically, TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Super Twisted Nematic), VA (Vertically Aligned), ECB (Electrically Controlled Birefringence), and HAN (Hybrid Aligned Nematic) display modes. The display mode can also be used in a display mode in which the orientation is divided.

(TN type liquid crystal display device)
The optical film containing the liquid crystal compound of the present invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. TN mode liquid crystal cells and TN type liquid crystal display devices have been well known for a long time. The optical compensation sheet used in the TN type liquid crystal display device can be produced according to the descriptions in JP-A-3-9325, JP-A-6-148429, JP-A-8-50206, and JP-A-9-26572. it can. Also, Mori et al. (Jpn. J. Appl. Phys. Vol. 36, (1997), p. 143 and Jpn. J. Appl. Phys. Vol. 36, (1997), p. 1068). ).

(STN type liquid crystal display device)
The optical film containing the liquid crystal compound of the present invention may be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell. In general, in a STN type liquid crystal display device, rod-like liquid crystalline molecules in a liquid crystal cell are twisted in the range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d) of the rod-like liquid crystalline molecules. Product (Δnd) is in the range of 300 to 1500 nm. The optical compensation sheet used in the STN type liquid crystal display device can be manufactured according to the description in JP-A-2000-105316.

(VA type liquid crystal display device)
The optical film containing the liquid crystal compound of the present invention is particularly advantageously used as a support for an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell. The Re value of the optical compensation sheet used in the VA liquid crystal display device is preferably 0 to 150 nm and the Rth value is preferably 70 to 400 nm. When two optically anisotropic polymer films are used for the VA liquid crystal display device, the Rth value of the film is preferably 70 to 250 nm. When one optically anisotropic polymer film is used for the VA liquid crystal display device, the Rth value of the film is preferably 150 to 400 nm. The VA-type liquid crystal display device may be an alignment-divided system as described in, for example, JP-A-10-123576.

(IPS liquid crystal display device and ECB liquid crystal display device)
The optical film containing the liquid crystal compound of the present invention is a support for an optical compensation sheet of an IPS liquid crystal display device and an ECB liquid crystal display device having IPS mode and ECB mode liquid crystal cells, or a protective film for a polarizing plate. Are also advantageously used. In these modes, the liquid crystal material is aligned substantially in parallel during black display, and black is displayed by aligning liquid crystal molecules in parallel with the substrate surface in the absence of applied voltage. In these embodiments, the polarizing plate using the cellulose film of the present invention contributes to the improvement of the color tone, the expansion of the viewing angle, and the improvement of the contrast. In this aspect, among the protective films of the polarizing plates above and below the liquid crystal cell, at least one side of the polarizing plate of the present invention is applied to the protective film (the protective film on the cell side) disposed between the liquid crystal cell and the polarizing plate. It is preferable to use for. More preferably, an optically anisotropic layer is disposed between the protective film of the polarizing plate and the liquid crystal cell, and the retardation value of the disposed optically anisotropic layer is not more than twice the value of Δn · d of the liquid crystal layer. It is preferable to set to.

(OCB type liquid crystal display device and HAN type liquid crystal display device)
The optical film comprising the liquid crystal compound of the present invention is also advantageous as a support for an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell. Used. In the optical compensation sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of the retardation value is minimum does not exist in the plane of the optical compensation sheet or in the normal direction. The optical properties of the optical compensation sheet used in the OCB type liquid crystal display device or the HAN type liquid crystal display device are also the optical properties of the optical anisotropic layer, the optical properties of the support, and the optical anisotropic layer and the support. Is determined by the arrangement of An optical compensation sheet used for an OCB type liquid crystal display device or a HAN type liquid crystal display device can be produced according to the description in JP-A-9-197397. It can also be prepared according to the description of Mori et al. (Jpn. J. Appl. Phys. Vol. 38, (1999), p. 2837).

(Reflective liquid crystal display)
The optical film containing the liquid crystal compound of the present invention is also advantageously used as an optical compensation sheet for a reflective liquid crystal display device of TN type, STN type, HAN type, and GH (Guest-Host) type. These display modes have been well known since ancient times. The TN-type reflective liquid crystal display device can be manufactured according to the descriptions in JP-A-10-123478, International Publication WO98 / 48320, and Japanese Patent No. 3022477. The optical compensation sheet used in the reflective liquid crystal display device can be produced according to the description in International Publication WO00 / 65384.

(Other liquid crystal display devices)
The optical film containing the liquid crystal compound of the present invention is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having a liquid crystal cell in an ASM (axially aligned microcell) mode. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted. Other properties are the same as those of the TN mode liquid crystal cell. The ASM mode liquid crystal cell and the ASM type liquid crystal display device can be manufactured according to the description of Kume et al. (Kume et al., SID 98 Digest, (1998), p. 1089).

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Example 1
[Synthesis of Compound A]

Compound A: Compound (oligomer) wherein n is 2 to 5 in the above formula
Compound B: Compound in which n is 1 in the above formula Compound C: Compound (polymer) in which n is 18 in the above formula

  Compound I (3.7 g, 10 mmol) and Compound II (5.1 g, 20 mmol) were dissolved in 200 mL of THF and cooled to −7 ° C. in a methanol-ice bath. A solution of pyridine (2.4 mL, 30 mmol) in THF (20 mL) was slowly added dropwise thereto. After stirring at −7 ° C. for 1 hour and at room temperature for 1 hour, a solution of 4HBA (5.4 mL, 40 mmol) and pyridine (2.4 mL, 30 mmol) in THF (20 mL) was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated to 1/3 by evaporation, crystallized in methanol, and filtered to obtain a crude product. This was subjected to column chromatography purification to obtain 5 g of compound A and 1 g of compound B which is a comparative example compound. As a result of confirmation by GPC using polystyrene as a standard substance, n of compound A was 2-5. In the same manner, it was confirmed that n of Compound B was 1.

[Synthesis of Compound C]
Compound I (3.7 g, 10 mmol) and compound II (2.6 g, 10 mmol) were dissolved in 50 mL of THF and cooled to 7 ° C. in an ice bath. A solution of pyridine (2.4 mL, 30 mmol) in THF (20 mL) was slowly added dropwise thereto. After stirring at 7 ° C. for 1 hour and at room temperature for 1 hour, a solution of 4HBA (5.4 mL, 40 mmol) and pyridine (2.4 mL, 30 mmol) in THF (20 mL) was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated to 1/3 by evaporation, crystallized in methanol, and filtered to obtain 2 g of Compound C as a comparative compound. When confirmed by GPC using polystyrene as a standard substance, the weight average molecular weight of Compound C was 12000, and n was equivalent to 18.

Example 2
[Preparation of Polymeric Film (A Plate) Aligned in Horizontal Horizontal Using Compound A]
A polyimide alignment film formed by homogeneously aligning a solution prepared by dissolving 100 parts by mass of Compound A and 3 parts by mass of a polymerization initiator (Irgacure 819, trade name, manufactured by Ciba Specialty Chemicals) in 700 parts by mass of chloroform is formed. A thin film was produced by spin-coating on the glass plate. When the liquid crystal compound was aligned at a substrate temperature of 180 ° C., it was aligned uniformly. Thereafter, ultraviolet rays of 100 mW / cm ² were irradiated at an arbitrary temperature to polymerize the liquid crystal compound, and this was cooled to form a polymerizable film in which the alignment state of the liquid crystal compound was fixed. As a result, a film a (polymerization temperature 140 ° C., film thickness 5.21 μm), a film b (polymerization temperature 160 ° C., film thickness 5.85 μm), and a film c (polymerization temperature 180 ° C., film thickness 6.07 μm) were obtained.

Comparative Example 1
[Preparation of Polymerization Film (A Plate) Aligned in Horizontal Horizontal Using Compound B]
A polyimide alignment film formed by homogeneously aligning a solution obtained by dissolving 100 parts by mass of Compound B and 3 parts by mass of a polymerization initiator (Irgacure 819, trade name, manufactured by Ciba Specialty Chemicals) in 1400 parts by mass of chloroform is formed. A thin film was produced by spin-coating on the glass plate. When the liquid crystal compound was aligned at a substrate temperature of 180 ° C., it was aligned uniformly. Thereafter, ultraviolet rays of 400 mJ / cm ² were irradiated at an arbitrary temperature to polymerize the liquid crystal compound, and this was cooled to form a polymerizable film in which the alignment state of the liquid crystal compound was fixed. As a result, a film d (polymerization temperature 140 ° C., film thickness 2.12 μm), film e (polymerization temperature 160 ° C., film thickness 2.45 μm), and film f (polymerization temperature 180 ° C., film thickness 2.66 μm) were obtained.

Comparative Example 2
[Preparation of Polymeric Film (A Plate) Aligned in Horizontal Horizontal Using Compound C]
A polyimide alignment film formed by homogeneously aligning a solution obtained by dissolving 100 parts by mass of Compound C and 3 parts by mass of a polymerization initiator (Irgacure 819, trade name, manufactured by Ciba Specialty Chemicals) in 1400 parts by mass of chloroform is formed. A thin film was produced by spin-coating on the glass plate. An attempt was made to align the liquid crystal compound at a substrate temperature of 180 ° C., but it could not be uniformly aligned because of the high phase transition temperature.

  The result of having measured the birefringence with respect to the wavelength of the produced film | membrane a-f using the Mueller matrix polarimeter (made by AXOMETRICS) is shown in FIG. Table 1 shows the polymerization temperature, birefringence, and steepness of the films a to f.

As is apparent from FIG. 1 and Table 1, in the retardation films (films a to c) of the examples of the present invention, the birefringence Δn (450 nm) at a wavelength of 450 nm and the birefringence Δn (550 nm) at a wavelength of 550 nm Ratio (Δn (450 nm) / (Δn (550 nm)) is smaller than that of the retardation film (films df) of the comparative example. Therefore, the retardation film of the example has sharp wavelength dispersion. Also, the birefringence Δn (550 nm) at a wavelength of 550 nm was higher in the retardation film of the example than the retardation film of the comparative example, and thus the compound of the present invention. It can be seen that in the retardation film, both the improvement of the steepness of the wavelength dispersion and the improvement of the birefringence at the wavelength of 550 nm can be achieved in the retardation film.
Further, when the retardation films (films df) of the comparative example are viewed, the retardation data (films) of the examples are shown in spite of variations in these chromatic dispersion graph data (birefringence values). a to c) show almost the same wavelength dispersion data, and the dependence of the birefringence on the polymerization temperature was not substantially observed. Therefore, it can also be seen that when the compound of the present invention is used, an excellent retardation film can be easily produced without requiring strict temperature control during the polymerization of the retardation film.

  Compared with the films d to f, the films a to c had a steeper slope of chromatic dispersion (Dn (450 nm) / Dn (550 nm)) and a high birefringence index Dn. In addition, the dependence of the birefringence index Dn on the polymerization temperature was hardly observed in the films ac.

Example 3
[Preparation of polymerizable film (A plate) in which composition of compound A and forward-dispersion polymerized liquid crystal (compound D) is substantially horizontally aligned]
100 parts by mass of a composition obtained by mixing compound A and the following forward-dispersion polymerized liquid crystal (compound D), and 3 parts by mass of a polymerization initiator (Irgacure 819, trade name, manufactured by Ciba Specialty Chemicals) into 700 parts by mass of chloroform The dissolved solution was spin-coated on a glass plate on which a polyimide alignment film subjected to a homogeneous alignment process was formed, to prepare a thin film. When the liquid crystal compound was aligned at a substrate temperature of 100 ° C. to 120 ° C., it was aligned uniformly. Thereafter, the liquid crystal compound was polymerized by irradiating 100 mW / cm ² of ultraviolet rays at 100 ° C. to 120 ° C., and cooled to form a polymerizable film in which the alignment state of the liquid crystal compound was fixed. Thereby, membrane g (compound A / compound D = 0/100 (mass ratio, the same applies hereinafter)), membrane h (compound A / compound D = 20/80), membrane i (compound A / compound D = 40/60) ), Membrane j (compound A / compound D = 60/40), membrane k (compound A / compound D = 20/80), membrane 1 (compound A / compound D = 100/0).

The result of measuring the birefringence with respect to the wavelength of the produced films g to l using a Mueller matrix polarimeter (manufactured by AXOMETRICS) is shown in FIG.
It was shown that the wavelength dispersion (Dn (450 nm) / Dn (550 nm)) can be controlled from 1.12 to 0.62 by mixing Compound A and Compound D at an arbitrary mass ratio.

It is a graph which shows the result of having measured the birefringence with respect to the wavelength of retardation film af produced in Example 2 and Comparative Example 1. FIG. It is a graph which shows the result of having measured the birefringence with respect to the wavelength of retardation film gl produced in Example 3. FIG.

Claims (14)

A compound represented by the following general formula (1).

(Wherein, A ₁ and A ₂ each independently represents 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 non-metallic atoms of Groups 14-16, and is 5 or together with C—C═C—C or C═C—C═C in the formula A 6-membered ring is formed, B and R ₁ each independently represent a substituent, R ₂ represents a divalent substituent, a plurality of B and R ₂ may be the same or different, and m is 0 to 0. It is an integer of 4. L ₁ and L ₂ each independently represent a divalent linking group, X represents a nonmetallic atom of Groups 14 to 16 (where X represents a hydrogen atom or a substituent R _3). may be bonded to each other.). in the case having a polymerizable group, B, R, R _1, integer der of .n 2-10 having at least one polymerizable group _{R 2} and R ₃ .) The compound according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (2).

(Wherein, A ₁ and A ₂ each independently represents 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 non-metallic atoms of Groups 14-16, and is 5 or together with C—C═C—C or C═C—C═C in the formula A 6-membered ring is formed, B and R ₁ each independently represent a substituent, R ₂ represents a divalent substituent, a plurality of B and R ₂ may be the same or different, and m is 0 to 0. It is an integer of 4. L ₁ and L ₂ each independently represent a divalent linking group, R ₄ and R ₅ each independently represent a substituent, and when having a polymerizable group, B, R, (At least one of R ₁ , R ₂ , R ₄ , and R ₅ is substituted with a polymerizable group. N is an integer of 2 to 10.)   The compound according to claim 1 or 2, wherein the polymerizable group is an addition polymerizable group. The compound according to claim 3, wherein the addition polymerizable group is a polymerizable group represented by any one of the following general formulas P1, P2, P3, and P4.

( _Where 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, and n ₅ represents 0 or 1.)   A liquid crystal composition comprising at least one compound according to any one of claims 1 to 4.   The liquid crystal composition according to claim 5, wherein the compound according to any one of claims 1 to 4 exhibits a nematic phase or a smectic A phase.   An optically anisotropic film formed using the liquid crystal composition according to claim 5 or 6, wherein the compound according to any one of claims 1 to 4 is substantially vertically aligned and fixed. An optically anisotropic film formed by   An optically anisotropic film formed using the liquid crystal composition according to claim 5 or 6, wherein the compound according to any one of claims 1 to 4 is substantially horizontally aligned and fixed. An optically anisotropic film formed by   9. An optically anisotropic film comprising the optically anisotropic film according to claim 7 and 8 and at least one other optically anisotropic film.   The optically anisotropic film according to claim 9, wherein the other optically anisotropic film is a positive A plate film. The optically anisotropic film according to claim 10, wherein the other optically anisotropic film is a positive A plate film satisfying the following mathematical formulas (I) and (II).
Formula (I) Re (450 nm) / Re (550 nm) <1.0
Formula (II) Re (650 nm) / Re (550 nm)> 1.0
[Wherein, Re (450 nm), Re (550 nm), and Re (650 nm) represent retardation values at 450 nm, 550 nm, and 650 nm, respectively. However, each measurement wavelength includes an error of ± 10 nm. ]   The phase difference plate which consists of an optically anisotropic film of any one of Claims 7-11.   The polarizing plate containing the optically anisotropic film of any one of Claims 7-11.   A liquid crystal display device comprising the retardation plate according to claim 12 or the polarizing plate according to claim 13.

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