JP2005097357A - Composition, compound, optical compensation sheet using it, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical compensation sheet excellent in optical compensation ability. <P>SOLUTION: The optical compensation sheet has an optically anisotropic layer containing a liquid crystalline compound and at least one kind of compound expressed by general formula (I): (R<SP>1</SP>-X<SP>1</SP>)<SB>m</SB>-Ar-SO<SB>3</SB>M. In the formula (I), Ar is an aromatic heterocyclic group or an aromatic hydrocarbon ring group having a valency of m+1; X<SP>1</SP>is a single bond or a divalent linking group; R<SP>1</SP>is an alkyl group or an alkyl group having a CF<SB>3</SB>group at the end or a CF<SB>2</SB>H group at the end and a plurality of R<SP>1</SP>'s may be the same or different but at least two of them are a different group from each other and at least one of them is an alkyl group having a CF<SB>3</SB>group at the end or a CF<SB>2</SB>H group at the end; M is a proton, a metallic cation or an organic cation; m is an integer of ≥2. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an optical compensation sheet having an optically anisotropic layer made of a liquid crystal compound and having an excellent optical compensation function. Furthermore, the present invention relates to a polarizing plate and a liquid crystal display device using an optical compensation sheet. The present invention also relates to a compound and a composition useful for forming an optically anisotropic layer having an excellent optical compensation function.

An optical compensation sheet having an optically anisotropic layer in which liquid crystal molecules are aligned (hybrid alignment) so that the tilt angle changes with the distance to the transparent support is a TN (Twisted Nematic) mode or OCB (Optically Compensatory). This is useful for enlarging the viewing angle of a liquid crystal display device in a Bend mode. Patent Document 1 and Patent Document 2 disclose an optical compensation sheet having an optically anisotropic layer made of a discotic liquid crystalline compound aligned at an inclination angle of 5 to 50 degrees. Patent Document 3 discloses an optical compensation sheet containing a compound having a fluorine-substituted alkyl group and a hydrophilic group (a sulfo group bonded to a benzene ring through a linking group) in an optically anisotropic layer. .
US Pat. No. 5,583,679 US Pat. No. 5,646,703 JP 2001-330725 A

  When the present inventors actually used the above optical compensation sheet in a liquid crystal display device, light leakage from an oblique direction was observed depending on the combination with the polarizing plate of the liquid crystal display device, and the viewing angle was sufficient. It was not enlarged or the optical compensation function was not enough. One reason for the insufficient optical compensation function is that the liquid crystalline molecules of the optically anisotropic layer could not be aligned with a sufficiently large tilt angle.

  The present invention has been made in view of the above problems, and provides an optical compensation sheet having an excellent optical compensation function by increasing the tilt angle of liquid crystalline molecules in the optically anisotropic layer, particularly the tilt angle on the air interface side. The task is to do. Moreover, this invention makes it a subject to provide the optical compensation sheet which contributes to the viewing angle improvement of liquid crystal display devices, such as TN mode or OCB mode. Another object of the present invention is to provide a compound that can promote the liquid crystal molecules to be hybrid-aligned, and in particular, can promote the discotic liquid crystal molecules to be hybrid-aligned at a large inclination angle on the air interface side. To do. Another object of the present invention is to provide a composition useful for stably producing an optical compensation sheet having optical compensation ability and contributing to the improvement of the viewing angle.

Means for solving the above problems are as follows.
[1] A composition comprising a liquid crystal compound and at least one compound represented by the following general formula (I).
Formula (I)
_{^{(R 1 -X 1) m -Ar}} -SO 3 M
[In the formula (I), Ar represents an (m + 1) -valent aromatic heterocyclic group or aromatic hydrocarbon ring group, X ¹ represents a single bond or a divalent linking group, and R ¹ represents a substituted or unsubstituted group. A plurality of R ^{1 s} may be the same or different, but at least two are different from each other, and at least one is a CF ₃ group at the end or CF ₂ H at the end An alkyl group having a group. M represents a proton, a metal cation or an organic cation, and m represents an integer of 2 or more. ]
[2] The composition according to [1], wherein the compound represented by the general formula (I) is represented by the following general formula (Ia).

[In the formula (Ia), X ¹¹ is an alkylene group, —O—, —S—, —CO—, —NR ^a — (wherein R ^a is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ), —SO ₂ — and a divalent linking group selected from the group consisting of at least two of these, R ¹¹ represents an unsubstituted alkyl group having 8 to 20 carbon atoms, or 60% or more of the hydrogen atoms are fluorine. Represents an alkyl group having 4 to 12 carbon atoms substituted with an atom, and a plurality of R ¹¹ may be the same or different, but at least two are different from each other, and at least one of An alkyl group having a CF ₃ group at the terminal or a CF ₂ H group at the terminal. M represents a proton, a metal cation or an organic cation, and m ¹ represents an integer of 2 or more. ]

[3] An optical compensation sheet having an optically anisotropic layer containing a liquid crystalline compound fixed in an aligned state and at least one compound represented by the general formula (I) on a support.
[4] The optical compensation sheet according to [3], wherein the liquid crystalline compound is a discotic liquid crystalline compound.
[5] The optical compensation sheet according to [4], wherein the discotic liquid crystalline compound is triphenylene liquid crystal.
[6] The optical compensation sheet according to any one of [3] to [5], wherein the compound represented by the general formula (I) is a compound represented by the general formula (Ia).
[7] A compound represented by the general formula (Ia).
[8] The liquid crystalline compound is a discotic liquid crystalline compound, the tilt angle θ1 of the liquid crystalline molecules at one interface of the optically anisotropic layer satisfies 0 ° ≦ θ1 ≦ 30 °, and The optical compensation sheet according to any one of [3] to [6], wherein the tilt angle θ2 satisfies 50 ° ≦ θ2.
[9] A liquid crystal display device having an optically anisotropic layer containing a liquid crystal compound fixed in an alignment state and at least one compound represented by the general formula (I).
[10] An elliptically polarizing plate having an optically anisotropic layer containing a liquid crystalline compound fixed in an aligned state and at least one compound represented by the general formula (I), and a linearly polarizing film.
[11] A method for producing an optically anisotropic layer, comprising a step of aligning liquid crystalline molecules in the presence of the compound represented by the general formula (I).

  In the present invention, “hybrid alignment” means the major axis direction of liquid crystal molecules (for example, the disk surface of the core in the case of discotic liquid crystal molecules) and the horizontal plane of the optically anisotropic layer (for example, optically anisotropic layer). Is formed on the support through the alignment film, the angle formed with the surface of the alignment film (hereinafter referred to as “inclination angle”) increases with the distance from the support. The orientation that changes in the thickness direction, and refers to two interfaces of the optically anisotropic layer (for example, when the optically anisotropic layer is formed on the alignment film, the interface between the alignment film and the air interface) However, when the optically anisotropic layer is once formed and then disposed on another support by transfer or the like, the two interfaces are not necessarily the alignment film interface and the air interface). Realized by liquid crystalline molecules in different alignment states. When the optically anisotropic layer is formed on the alignment film, liquid crystal having different tilt angles between the optically anisotropic layer / alignment film interface and the optically anisotropic layer / air interface that is also the outermost surface of the optical compensation sheet. Realized by sex molecules. In this specification, the aspect of the change in the inclination angle includes continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, and intermittent change including increase and decrease. Etc. shall be included. The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. “Hybrid orientation” in the present invention preferably increases or decreases as a whole even if it includes a region where the tilt angle does not change. Further, the inclination angle is preferably increased as a whole, and particularly preferably continuously changed.

  According to the present invention, by using a liquid crystal compound and a compound having a specific structure in combination, the liquid crystal molecule has an optically anisotropic layer in a hybrid alignment state in which the tilt angle of the liquid crystal molecule, particularly the tilt angle on the air interface side is large. An optical compensation sheet can be produced. As a result, an optical compensation sheet excellent in optical compensation function can be provided. In addition, according to the present invention, it is possible to provide a novel optical compensation sheet that can expand the viewing angle of the optically anisotropic layer when applied to an image display device.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail.
The optical compensation sheet of the present invention has an optically anisotropic layer containing a liquid crystalline compound fixed in an aligned state and at least one compound represented by the following general formula (I). The compound represented by the following general formula (I) contributes to increasing the tilt angle of the liquid crystal compound stably and in a hybrid alignment state having a large tilt angle, particularly the tilt angle on the air interface side. Improve. In addition, by using the compound represented by the following general formula (I), effects such as improvement in wettability between the liquid crystal layer (optically anisotropic layer) and the support (can prevent repelling) can be obtained.

First, the compound of general formula (I) will be described in detail.
Formula (I)
_{^{(R 1 -X 1) m -Ar}} -SO 3 M
In formula (I), Ar represents an (m + 1) -valent aromatic heterocyclic group or aromatic hydrocarbon ring group, X ¹ represents a single bond or a divalent linking group, and R ¹ represents a substituted or unsubstituted group. Represents an alkyl group, and a plurality of R ¹ may be the same or different, but at least two are different from each other, and at least one is a CF ₃ group at the terminal or a CF ₂ H group at the terminal It is an alkyl group having M represents a proton, a metal cation or an organic cation, and m represents an integer of 2 or more.

  In the general formula (I), the (m + 1) -valent aromatic heterocyclic group represented by Ar is preferably an aromatic heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. The tello ring contains at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom as a ring constituent atom. Examples of the aromatic heterocycle include furan ring, pyrrole ring, imidazole ring, pyrazole ring, isoxazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, 1,3,5-triazine ring, indole ring, indazole A ring, a quinoline ring, and a carbazole ring are preferable. The (m + 1) -valent aromatic hydrocarbon ring group represented by Ar is preferably an aromatic hydrocarbon ring group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and a benzene ring or naphthalene ring is Particularly preferred is a benzene ring. Ar is preferably an aromatic hydrocarbon ring group.

The aromatic heterocyclic group or aromatic hydrocarbon ring group represented by Ar may have a substituent other than R ¹ —X ¹ — and —SO ₃ M, if possible. Can include the following groups.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, Particularly preferred are alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butenyl group and 3-pentenyl group), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferred). Is an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl group and 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, and a naphthyl group. A substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms. Group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group), acyloxy A group (preferably an acyloxy group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms. A silamino group, for example, an acetylamino group, a benzoylamino group, and the like, an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms). An alkoxycarbonylamino group, for example, a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms). Aryloxycarbonylamino group, for example, phenyloxycarbonylamino group and the like, sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms). 12 sulfonylamino groups such as methanesulfonyl And a sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl group). Group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably carbon number). 1 to 12 carbamoyl groups, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is C6-C12 arylthio group, for example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl group and the like), ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group , Methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms). Yes, for example, diethyl phosphoric acid amide group, phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, Carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1 to 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

The aromatic heterocycle or aromatic hydrocarbon ring represented by Ar preferably has no substituent other than R ¹ —X ¹ and SO ₃ M. When the aromatic heterocycle or aromatic hydrocarbon ring represented by Ar has a substituent, preferred substituents are an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, or An alkylthio group, particularly preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group or an acyloxy group.

The divalent linking group represented by X ¹ is an alkylene group, an alkenylene group, an arylene group, a divalent heterocyclic group, —CO—, —NR ^a — (R ^a is an alkyl having 1 to 5 carbon atoms. A divalent linking group selected from the group consisting of —O—, —S—, —SO—, —SO ₂ — and combinations thereof. The divalent linking group is a linking group selected from the group consisting of an alkylene group, —O—, —S—, —CO—, —N (R ^a ) —, and —SO ₂ —, or a group selected from the group. It is more preferable that the linking group is a combination of at least two. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms in the arylene group is preferably 6-10. An alkylene group, an alkenylene group, an arylene group and a divalent heterocyclic residue are, as possible, groups exemplified as the substituent for the aforementioned Ar (eg, alkyl group, halogen atom, cyano group, alkoxy group, acyloxy group). Etc.). X ¹ is preferably a divalent linking group, among which —O—, —S—, —OCO—, —N (R ^a ) CO—, —CO—, —COO— or —CON (R ^a )-Is particularly preferred.

The alkyl group represented by R ¹ may have a cyclic structure or a branched structure, preferably an alkyl group having 6 to 60 carbon atoms, more preferably an alkyl group having 7 to 50 carbon atoms, and 8 to 40 carbon atoms. Are more preferable, an alkyl group having 8 to 30 carbon atoms is particularly preferable, and an alkyl group having 8 to 20 carbon atoms is most preferable. If possible, the alkyl group represented by R ¹ may be substituted with a group exemplified as the substituent for the aforementioned Ar. As the substituent, a halogen atom is preferable, and a fluorine atom is more preferable. R ¹ may be the same or different, but at least two are groups different from each other, and at least one is an alkyl group having a CF ₃ group at the terminal or a CF ₂ H group at the terminal (hereinafter, “ And may be referred to as “fluorine-substituted alkyl group”. When R ¹ represents the fluorine-substituted alkyl group, the number of carbon atoms is more preferably 1-20, further preferably 4-16, and particularly preferably 4-12. The fluorine-substituted alkyl group is preferably an alkyl group in which some or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms, and 50% or more of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. It is preferable that 60% or more is substituted. Hereinafter, specific examples of R ^1.

In the general formula (I), M is preferably a proton (H ⁺ ), an alkali metal ion (eg, lithium ion, sodium ion, potassium ion, etc.), an alkaline earth metal ion (barium ion, calcium ion, etc.), An ammonium ion (for example, ammonium ion, trialkylammonium ion, tetraalkylammonium ion, pyridinium ion).

  In the general formula (I), m is preferably 2 or 3, and particularly preferably 2.

  Among the compounds represented by the general formula (I), compounds represented by the following general formula (Ia) are preferable.

In Formula (Ia), X ¹¹ is an alkylene group, —O—, —S—, —CO—, —NR ^a — (wherein R ^a is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom). , —SO ₂ — and a divalent linking group selected from the group consisting of at least two of these, R ¹¹ represents an unsubstituted alkyl group having 8 to 20 carbon atoms, or 60% or more of the hydrogen atoms are fluorine atoms. Represents an alkyl group having 4 to 12 carbon atoms, and a plurality of R ¹¹ may be the same or different, but at least two are different from each other, and at least one is a terminal Is an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal. M represents a proton, a metal cation or an organic cation, and m ¹ represents an integer of 2 or more.

In the general formula ^{(Ia), X 11, R} 11 and m ¹ are respectively the same as X ^1, R ¹ and m in the formula (I), their preferred scopes are identical. M1 substituents R ¹¹ -X ¹¹ on the benzene ring - There is no particular restriction on the substitution position of relative substitution position of -SO ₃ M, m-position and p-position (R ¹¹ -X ¹¹⁾ It is preferably substituted by-. X ₁₁ is particularly preferably a divalent linking group selected from the group consisting of an alkylene group having 1 to 12 carbon atoms, —O—, —S—, —CO—, —SO ₂ —, and combinations thereof. preferable.

  Specific examples of the compound represented by the general formula (Ia) are shown below, but the compound used in the present invention is not limited thereto.

  The compound represented by the general formula (Ia) can be easily synthesized by combining general alkyl group alkylation reaction, esterification reaction, amidation reaction, and the like.

  In the formula, Rx and Ry represent an alkyl group, Rf represents an alkyl group substituted with fluorine, and m and n represent integers.

  Step 1 is a step for producing compound (II) by reacting compound (I) with an alkylating agent in the presence of a base in a solvent. The alkylating agent is not particularly limited, but is preferably an alkyl halide or an alkyl pseudohalide. As the halogen, chlorine, bromine and iodine are preferable, and bromine is particularly preferable. As the pseudohalogen, methanesulfonyloxy, p-toluenesulfonyloxy, and trifluoromethanesulfonyloxy are preferable.

  The base to be used is not particularly limited as long as it does not affect other parts of the compound, but preferably metal alkoxides such as sodium methoxide (sodium methylate), sodium hydroxide Alkali metal hydroxides such as potassium hydroxide and lithium hydroxide, alkali metal carbonates such as potassium carbonate, lithium carbonate, sodium carbonate and cesium carbonate or metal hydrides such as sodium hydride are used. .

  The reaction solvent is not particularly limited as long as it does not inhibit the reaction, but ethers such as tetrahydrofuran and dioxane are preferred when metal alkoxides or metal hydrides are used as the base. When an alkali metal hydroxide is used as the base, the reaction is preferably carried out in the absence of a solvent, a two-phase system of a nonpolar solvent such as toluene or hexane and water, or in water. More preferably, a phase transfer catalyst is used. When an alkali metal carbonate is used as the base, ethers such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, amides such as dimethylformamide and dimethylacetamide, and sulfoxides such as dimethyl sulfoxide are used. preferable.

The reaction temperature and reaction time vary depending on the starting materials, the solvent, the base used, and the like, and are not particularly limited, but are usually reacted in the range of 0 to 150 ° C. for 1 to 20 hours in order to suppress side reactions. .
After completion of the reaction, the compound (II) can be collected from the reaction mixture according to a conventional method.

  For example, the reaction mixture is appropriately neutralized, and if insoluble matter is present, it is removed by filtration, water and an immiscible organic solvent such as ethyl acetate are added, washed with water, and the target compound is then contained. The organic layer is separated, dried over anhydrous magnesium sulfate and the like, and then the solvent is distilled off.

  If necessary, the obtained target compound can be obtained by a conventional method such as recrystallization, reprecipitation, or a method usually used for separation and purification of organic compounds, for example, silica gel, alumina, magnesium-silica gel-type florisil. Column chromatography method using a simple carrier; Sephadex LH-20 (Pharmacia), Amberlite XAD-11 (Rohm and Haas), Diaion HP-20 (Mitsubishi Chemical) A method using a synthetic adsorbent such as partition column chromatography using a carrier, a method using ion exchange chromatography, or a normal phase / reverse phase column chromatography method using silica gel or alkylated silica gel (preferably high performance liquid Chromatography)) and combine with appropriate eluents. Separation, can be purified.

  Step 2 is a process for producing compound (IV) by reacting compound (III) with ω-halocarboxylic acid ester in the presence of a base.

  The ω-halocarboxylic acid ester is not particularly limited, but preferably an ω-bromocarboxylic acid ester. The Ry group is an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group. , N-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like are preferable, and these alkyl groups may be substituted by a substituent.

  The base to be used is not particularly limited as long as it does not affect other parts of the compound, but preferably metal alkoxides such as sodium methoxide (sodium methylate), sodium hydroxide Alkali metal hydroxides such as potassium hydroxide and lithium hydroxide or metal hydrides such as sodium hydride are used.

  The reaction solvent is not particularly limited as long as it does not inhibit the reaction, but ethers such as tetrahydrofuran and dioxane are preferred when metal alkoxides or metal hydrides are used as the base. When an alkali metal hydroxide is used as the base, the reaction is preferably carried out in the absence of a solvent, a two-phase system of a nonpolar solvent such as toluene or hexane and water, or in water. More preferably, a phase transfer catalyst is used.

The reaction temperature and reaction time vary depending on the starting materials, the solvent, the base used, and the like, and are not particularly limited, but are usually reacted in the range of 0 to 100 ° C. for 1 to 20 hours in order to suppress side reactions. .
After completion of the reaction, the target compound (IV) of this reaction can be collected from the reaction mixture according to a conventional method.

  For example, the reaction mixture is appropriately neutralized, and if insoluble matter is present, it is removed by filtration, water and an immiscible organic solvent such as ethyl acetate are added, washed with water, and the target compound is then contained. The organic layer is separated, dried over anhydrous magnesium sulfate and the like, and then the solvent is distilled off.

  If necessary, the obtained target compound can be obtained by a conventional method such as recrystallization, reprecipitation, or a method usually used for separation and purification of organic compounds, for example, silica gel, alumina, magnesium-silica gel-type florisil. Column chromatography method using a simple carrier; Sephadex LH-20 (Pharmacia), Amberlite XAD-11 (Rohm and Haas), Diaion HP-20 (Mitsubishi Chemical) A method using a synthetic adsorbent such as partition column chromatography using a carrier, a method using ion exchange chromatography, or a normal phase / reverse phase column chromatography method using silica gel or alkylated silica gel (preferably high performance liquid Chromatography)) and combine with appropriate eluents. Separation, can be purified.

  Step 3 is a process for producing the compound (V) by reducing the ester group of the compound (IV) in a solvent. For the production of the compound (V), a conventional method of ester reduction can be used. For example, the method described in “Chemical Experiment Course (4th edition)” volume 20 (1992) (Maruzen) edited by the Chemical Society of Japan is used. Can be mentioned.

  Step 4 is a step for producing compound (VI) by substituting or esterifying the hydroxyl group of compound (V) in a solvent. Moreover, the same reaction can be performed with respect to commercially available fluorinated alcohol, and it can apply to the process after Step 5.

  X is halogen or pseudohalogen. As the halogen, chlorine, bromine and iodine are preferable, and bromine is particularly preferable. As the pseudohalogen, methanesulfonyloxy, p-toluenesulfonyloxy, and trifluoromethanesulfonyloxy are preferable. When X is halogen, a conventional method for halogenation of a hydroxyl group can be used. For example, it is described in “Chemical Experiment Course (4th edition)” volume 19 (1992) (Maruzen) edited by the Chemical Society of Japan. The method is mentioned. When X is pseudohalogen, a method of reacting with a corresponding acid halide or acid anhydride in a solvent in the presence of a base is usually preferred.

  The base to be used is not particularly limited as long as it does not affect other parts of the compound, but tertiary amines such as triethylamine, diisopropylethylamine, pyridine and dimethylaminopyridine are preferable. The reaction solvent is not particularly limited as long as it does not inhibit the reaction, but halogenated hydrocarbons such as chloroform and methylene chloride are preferable. The reaction temperature and reaction time vary depending on the starting materials, the solvent, the base used, and the like, and are not particularly limited. In order to suppress side reactions, the reaction is usually carried out in the range of −10 to 10 ° C. for 1 hour to 20 hours. Let

  After completion of the reaction, the target compound VI of this reaction is collected from the reaction mixture according to a conventional method and used in the next step. Alternatively, the reaction solution is washed with water or the like according to a conventional method and then dehydrated. It can also be used as it is.

  When collected from the reaction mixture, for example, the reaction mixture is appropriately neutralized, and if insoluble matter is present, it is removed by filtration, followed by addition of an immiscible organic solvent such as water and ethyl acetate, After washing with water or the like, the organic layer containing the target compound is separated, dried over anhydrous magnesium sulfate or the like, and then the solvent is distilled off.

  If necessary, the obtained target compound can be obtained by a conventional method such as recrystallization, reprecipitation, or a method usually used for separation and purification of organic compounds, for example, silica gel, alumina, magnesium-silica gel-type florisil. Column chromatography method using a simple carrier; Sephadex LH-20 (Pharmacia), Amberlite XAD-11 (Rohm and Haas), Diaion HP-20 (Mitsubishi Chemical) A method using a synthetic adsorbent such as partition column chromatography using a carrier, a method using ion exchange chromatography, or a normal phase / reverse phase column chromatography method using silica gel or alkylated silica gel (preferably high performance liquid Chromatography)) and combine with appropriate eluents. Separation, can be purified.

  Step 5 is a step of producing compound (VII) by reacting compound (II) and compound (VI) in the presence of a base in a solvent. The target product is prepared in the same manner as in Step 1. It is possible to obtain.

Step 6 is a step for producing compound (VIII) by sulfonating compound (VII) in a solvent.
The sulfonation reagent to be used is not particularly limited as long as it is usually used for sulfonation reaction, and is preferably chlorosulfonic acid.

The reaction solvent is not particularly limited as long as it does not inhibit the reaction, but halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride are preferable. The reaction temperature and reaction time vary depending on the starting material, the solvent, the base used, etc., and are not particularly limited. In order to suppress side reactions, the reaction is usually carried out in the range of −10 to 30 ° C. for 1 hour to 3 hours. Let The product may be precipitated as crystals in the reaction system as the reaction proceeds, but the crystals can also be efficiently precipitated by cooling or adding a poor solvent such as hexane.

  After completion of the reaction, the target compound (VIII) of this reaction is collected from the reaction mixture according to a conventional method. For example, crystals precipitated by the above method can be collected by filtration. If the product is a viscous liquid, the target solvent can also be obtained by distilling off the reaction solvent, washing the residue with a poor solvent such as hexane, and decanting the supernatant. Can do. Moreover, when isolating as a sulfonate, it can carry out in accordance with a conventional method.

In the optically anisotropic layer of the optical compensation sheet of the present invention, the addition amount of the compound represented by the general formula (I) is preferably 0.01 to 20% by mass of the amount of the liquid crystalline compound, 0.05 10 mass% is especially preferable, and 0.1-5 mass% is the most preferable.
In addition, the compound represented by the said general formula (I) may use 2 or more types together.

  The optical compensation sheet of the present invention is a liquid crystalline compound, a compound represented by the general formula (I), and a liquid crystalline composition containing various compounds to be added as necessary on the alignment film, It can be produced by a method including a step of forming an optically anisotropic layer by aligning liquid crystalline molecules. Hereinafter, materials other than the compound represented by the general formula (I) described above will be described in detail among the materials used for the optically anisotropic layer of the optical compensation sheet of the present invention.

[Liquid crystal compounds]
In the present invention, the liquid crystalline compound used in the optically anisotropic layer may be either a rod-like liquid crystalline compound or a discotic liquid crystalline compound, and may be either a polymer liquid crystal or a low molecular liquid crystal, preferably a discotic Liquid crystal, more preferably triphenylene liquid crystal. Furthermore, in the present invention, it is not necessary for the liquid crystalline compound to maintain liquid crystallinity in the optically anisotropic layer, and it is no longer necessary to exhibit liquid crystallinity after the liquid crystalline molecules are in a desired alignment state and fixed in that state. There is no. As the liquid crystalline compound used in the present invention, a discotic liquid crystalline compound is particularly preferable. In addition, the liquid crystalline compound used by this invention may be used independently, and may use 2 or more types together.

[Bar-shaped liquid crystal compound]
Preferred rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano substituted phenyl pyrimidines, alkoxy substituted phenyl pyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles. The rod-like liquid crystal compound includes a metal complex liquid crystal compound. Moreover, the liquid crystal polymer which contains a rod-shaped liquid crystalline compound in a repeating unit can also be used as a rod-shaped liquid crystalline compound. In other words, the rod-like liquid crystalline compound may be bonded to a (liquid crystal) polymer. For rod-like liquid crystalline compounds, Chapter 4, Chapter 7 and Chapter 11 of Quarterly Chemical Review Volume 22 “Chemicals of Liquid Crystals” (edited by the Chemical Society of Japan, 1994) and “Liquid Crystal Device Handbook” (Japan Science Promotion) (Chapter 3 of the 142nd Committee). The birefringence of the rod-like liquid crystalline compound is preferably in the range of 0.001 to 0.7. The rod-like liquid crystalline compound preferably has a polymerizable group in order to fix its alignment state. The rod-like liquid crystalline compound is described in WO01 / 88574A1 on page 50, line 7 to page 57, last line.

[Discotic liquid crystalline compounds]
Examples of discotic liquid crystalline compounds preferably used in the present invention include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 41 (1985), Physics lett. A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al. Am. Chem. Soc. 116, 2655 (1994), azacrown type, phenylacetylene type macrocycle, etc. can be mentioned. Further, the discotic liquid crystal compounds generally have a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain. All of these also exhibit liquid crystallinity.

  In addition, when the optically anisotropic layer is finally formed, the liquid crystal compound no longer needs to be a liquid crystal compound. For example, a low molecular weight discotic liquid crystalline compound has a group that reacts with heat, light, etc., and as a result, polymerizes or crosslinks by reaction with heat, light, etc. Also good. Preferred examples of the discotic liquid crystalline compound are described in JP-A-8-50206. The polymerization of the discotic liquid crystalline compound is described in JP-A-8-27284 and can be applied to the present invention.

  As an example of a method for fixing a discotic liquid crystalline compound by polymerization, as a discotic liquid crystalline compound, a liquid crystalline compound having a polymerizable group bonded as a substituent to a discotic core is used for hybrid alignment, and then the liquid crystalline There is a method of polymerizing and fixing a compound. However, when a polymerizable group is directly connected to the discotic core, it tends to be difficult to maintain the alignment state in the polymerization reaction. Therefore, it is preferable to introduce a linking group between the discotic core and the polymerizable group. As a preferable discotic liquid crystalline compound having a polymerizable group, a compound represented by the following general formula (II) can be mentioned.

Formula (II)
D (-L ³ -P) _n3
In formula (II), D represents a discotic core, L ³ represents a divalent linking group, P represents a polymerizable group, and n3 represents an integer of 2 to 12. Specific examples of the discotic liquid crystalline compound are described in WO01 / 88574A1 on page 58, line 6 to page 65, line 8.

  In the present invention, two or more kinds of discotic liquid crystal compounds may be used in combination. Further, for example, the polymerizable discotic liquid crystalline compound and the non-polymerizable discotic liquid crystalline compound can be used in combination. The non-polymerizable discotic liquid crystalline compound is preferably a compound in which the polymerizable group (P) of the polymerizable discotic liquid crystalline compound described above is changed to a hydrogen atom or an alkyl group. That is, the non-polymerizable discotic liquid crystalline compound is preferably a compound represented by the following general formula (III).

General formula (III)
D (-L ⁴ -Q) _n4
In general formula (III), D represents a discotic core, L ⁴ represents a divalent linking group, Q represents a hydrogen atom or an alkyl group, and n4 is an integer of 4 to 12.

[Additive for optically anisotropic layer]
In addition to the liquid crystalline compound and the compound represented by the general formula (I), any additive can be used in combination with the optically anisotropic layer. Examples of additives include an anti-repellent agent (anti-repellent agent) generated when a coating solution is applied, and a tilt angle of the alignment film (an inclination angle of the liquid crystal molecules at the optically anisotropic layer / alignment film interface). Additives for controlling the temperature, polymerization initiators, additives (plasticizers) that lower the alignment temperature, polymerizable monomers, and the like.

[Anti-repellent agent]
An anti-repellent agent is added to a composition containing a liquid crystal compound, and contributes to reducing the occurrence of repelling when the composition is applied to the surface of an object. In general, a polymer compound can be suitably used as such a repellency inhibitor. The polymer that can be used is not particularly limited as long as it is compatible with the liquid crystal compound and does not significantly inhibit the change in the tilt angle or orientation of the liquid crystal molecules. Examples of the polymer are described in JP-A-8-95030, and particularly preferred specific polymer examples include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. In order not to inhibit the alignment of the liquid crystal compound, the amount of the polymer used for the purpose of preventing repellency is generally in the range of 0.1 to 10% by mass with respect to the liquid crystal compound, and 0.1 to 8% by mass. More preferably, it is in the range of 0.1 to 5% by mass.

[Alignment film tilt angle control agent]
As an additive for controlling the tilt angle of the alignment film, a compound having both a polar group and a nonpolar group in the molecule can be added. Compounds having both polar and nonpolar groups include R—OH, R—COOH, R—O—R, R—NH ₂ , R ₂ —NH, R ₃ —N, R ₄ —N ⁺ , R _{-SH, R 2 -S, R 3} -S +, R-CO-R, R-COO-R, R-CONH-R, R-CONHCO-R, R-SO 3 H, R-SO 3 -R , R—SO ₂ NH—R, R—SO ₂ NHSO ₂ —R, R—C═N—R, HO—P (—R) ₂ , (HO—) ₂ PR, P (—R) _{3 , HO-PO (-R) 2} , (HO-) 2 PO-R, PO (-R) 3, HO-P (-OR) 2, (HO-) 2 P-OR, P (-OR) 3 _{, HO-PO (-OR) 2} , (HO-) 2 PO-OR, PO (-OR) 3, R-NO 2, R-CN, and the like as examples. Moreover, organic salts (for example, ammonium salt, pyridinium salt, carboxylate, sulfonate, phosphate) may be used. Among the above compounds, preferred compounds are R—OH, R—COOH, R—O—R, R—NH ₂ , R—SO ₃ H, HO—PO (—OR) ₂ , (HO—) ₂ PO. -OR, PO (-OR) ₃ , and organic salts.

  Here, R of each said compound is a nonpolar group, The following are mentioned as this nonpolar group. Examples of the nonpolar group include an alkyl group (preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms) or an alkenyl group (preferably a linear, branched, or cyclic group having 1 to 30 carbon atoms). Substituted or unsubstituted alkenyl groups), alkynyl groups (preferably linear, branched, cyclic substituted or unsubstituted alkenyl groups having 1 to 30 carbon atoms), aryl groups (preferably substituted with 6 to 30 carbon atoms) Or an unsubstituted aryl group) and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms). The nonpolar group may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), and an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group). ), Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group , Aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino Group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, Examples include carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group and the like.

  The tilt angle at the alignment film interface can be changed by adding an alignment film tilt angle control agent, and the amount of change at that time is related to the rubbing density of the alignment film. When comparing an alignment film having a high rubbing density with an alignment film having a low rubbing density, the tilt angle of the alignment film having a low rubbing density is likely to change even if the amount of addition is the same. Accordingly, the addition amount of the alignment film tilt control agent varies depending on the rubbing density of the alignment film and the desired tilt angle, but is preferably 0.0001% by mass to 30% by mass with respect to the liquid crystal compound. 0.001% by mass to 20% by mass is preferable, and 0.005% by mass to 10% by mass is most preferable. Specific examples of the alignment film tilt angle control agent are shown below, but the compounds used in the present invention are not limited to these.

[Polymerization initiator]
In the present invention, it is preferable to fix the liquid crystalline compound in a hybrid alignment state, and therefore it is preferable to fix the liquid crystalline compound by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. In order to prevent deformation of the support and the like due to heat, the photopolymerization reaction is performed. 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) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970). The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. The light irradiation for polymerizing the liquid crystalline compound preferably uses ultraviolet rays. The irradiation energy is preferably 20 mJ / cm ^{2 to} 50 J / cm ² , and more preferably 100 mJ / cm ^{2 to} 800 mJ / cm ² . In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.

[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 cause a significant change in the tilt angle of the liquid crystal molecule or disturb the alignment. 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 addition amount of the polymerizable monomer is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the liquid crystal compound. 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.

[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, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Application method]
The optically anisotropic layer is formed by preparing a liquid crystal composition coating solution using the above-mentioned solvent, coating the liquid crystal composition on the alignment film, and aligning the liquid crystal compound. Application | coating of a coating liquid can be implemented by a well-known method (For example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method). Moreover, 1-50 mass% is preferable, as for content of the liquid crystalline compound in a coating liquid, 10-50 mass% is more preferable, and 20-40 mass% is more preferable.

[Characteristics of optically anisotropic layer]
The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and most preferably 1 to 10 μm.

  When the liquid crystalline composition of the present invention is applied on the alignment film, the liquid crystal molecules are aligned at the tilt angle of the alignment film at the interface with the alignment film and at the tilt angle of the air interface at the interface with air. After coating, the liquid crystal compound is uniformly aligned (monodomain alignment), so that the tilt angle of the liquid crystal molecules (discotic liquid crystal properties) from the air interface to the alignment film interface, that is, in the depth direction of the optically anisotropic layer In the case of molecules, it is possible to realize hybrid alignment in which the angle between the normal line of the disk surface of the liquid crystalline molecule and the normal line of the surface on which the alignment film of the transparent support is formed changes continuously. The optical compensation sheet of the present invention having an optically anisotropic layer obtained by hybrid alignment of liquid crystalline molecules expands the viewing angle and prevents contrast reduction, gradation or black-and-white reversal, hue change, and the like with respect to a change in viewing angle. be able to.

  In the presence of the compound represented by the general formula (I), the discotic liquid crystalline molecules can be aligned at a tilt angle of 50 ° or more on the air interface side. In order to realize hybrid alignment in a state where preferable performance can be exhibited as an optical compensation sheet, the tilt angle of the alignment film is preferably 3 ° to 30 °. By controlling the tilt angle of this alignment film by the above-described methods (rubbing density of alignment film, alignment film tilt angle control agent, etc.), according to the display mode of the liquid crystal display device to which the optical compensation sheet of the present invention is applied, A preferred hybrid orientation state can be realized.

[Tilt angle]
The tilt angle refers to an angle formed between the major axis direction of the liquid crystal molecule and the normal line of the interface (alignment film interface or air interface). In the present invention, the tilt angle of the alignment film is 3 ° to 30 ° and the air interface side. The tilt angle is preferably 20 to 80 °. Furthermore, the tilt angle of the preferred alignment film is 5 ° to 30 °, more preferably 7 to 20 °, and particularly preferably 9 to 20 °. The preferred tilt angle on the air interface side is 30 to 75 °, more preferably 35 to 70 °, and particularly preferably 40 to 70 °. In the case of discotic liquid crystalline molecules, if the tilt angle is too small, the time required for monodomain alignment of the discotic liquid crystalline molecules becomes long, which is preferable. However, if the tilt angle is too large, it is preferable as an optical compensation sheet. It is easy to lose optical performance. Therefore, the tilt angle in the above range is preferable from the viewpoint of both shortening the monodomain formation time and preferable optical performance as an optical compensation sheet. The tilt angle on the alignment film side can be controlled in the range of several degrees to several tens of degrees by a method of changing the rubbing density of the alignment film, which will be described later, or the addition of the alignment film tilt angle control agent described above.
As described above, when the optically anisotropic layer is once formed and then disposed between two layers by transfer or the like, the interface of the optically anisotropic layer is not necessarily the alignment film interface and the air interface. In such an embodiment, the tilt angle of the liquid crystalline molecules on one interface side and the other interface side of the two interfaces of the optically anisotropic layer is such that the alignment film side tilt angle range and the air interface side The tilt angle is preferably in the range.

[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). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. As long as the liquid crystal molecules of the optically anisotropic layer provided on the alignment film can give the desired alignment, any alignment film may be used. In the present invention, the tilt angle of the alignment film is controlled. From the viewpoint of easiness, an alignment film formed by a rubbing treatment of a polymer is particularly 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.). It is preferable to carry out by a method. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.05 to 1 μm. The polymer used for the alignment film is described in many documents, and many commercially available products can be obtained. In the alignment film for the optical compensation film of the present invention, polyvinyl alcohol and derivatives thereof are preferably used. Particularly preferred is a modified polyvinyl alcohol having a hydrophobic group bonded thereto. Regarding the alignment film, reference can be made to the description of page 43, line 24 to page 49, line 8 of WO01 / 88574A1.

[Rubbing density of alignment film]
As a method for changing the rubbing density of the alignment film, a method described in “Liquid Crystal Handbook” (Maruzen Co., Ltd.) can be used. 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). In order to increase the rubbing density, the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can reverse this. Between the rubbing density and the tilt angle of the alignment film, there is a relationship in which the tilt angle decreases as the rubbing density increases and the tilt angle increases as the rubbing density decreases.

  If the liquid crystal molecules are aligned and the state is fixed by polymerization or the like, the alignment state can be maintained without an alignment film. Therefore, after the optically anisotropic layer is formed on an alignment film (for example, an alignment film formed on a temporary support), only the optically anisotropic layer is transferred onto the transparent support. An optical compensation sheet can also be produced. That is, the present invention includes an aspect of an optical compensation sheet that does not include an alignment film.

[Support]
The support that can be used in the present invention is preferably transparent. Specifically, the light transmittance is preferably 80% or more. Optically isotropic polymer films are preferred. The description of paragraph number [0013] of JP-A No. 2002-22294 can be applied to specific examples and preferred embodiments of the polymer. In addition, even a conventionally known polymer such as polycarbonate or polysulfone, which easily develops birefringence, should have a decreased expression by modifying the molecule described in WO00 / 26705. You can also.

  As the polymer film, 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 description of paragraph number [0021] of JP-A No. 2002-196146 can be applied to the degree of acetylation, the range thereof, and the chemical structure of cellulose acetate.

  The description of paragraph numbers [0018] to [0019] of JP-A-2002-139621 can be applied to the Re retardation value and the birefringence range of the cellulose acylate film used as the transparent support.

  In order to adjust the retardation of a polymer film used as a transparent support, particularly a cellulose acylate film, it is preferable to use an aromatic compound having at least two aromatic rings as a retardation increasing agent. The description of paragraph numbers [0021] to [0023] of JP-A No. 2002-139621 can be applied to the preferred range and amount of use of the aromatic compound. Such retardation increasing agents are described in WO01 / 88574A1, WO00 / 2619A1, JP-A Nos. 2000-1111914, 2000-275434, and Japanese Patent Application No. 2002-70009.

  The cellulose acylate film is preferably produced by a solvent cast method from the prepared cellulose acylate solution (dope). It is preferable to add the above-mentioned retardation increasing agent to the dope. Using the prepared cellulose acylate solution (dope), a film can be formed by casting two or more layers of the dope. For the formation of the film, paragraphs [0038] to [0040] described in JP-A No. 2002-139621 can be applied to the present invention.

  The retardation of the cellulose acylate film can be further adjusted by a stretching treatment. The draw ratio is preferably in the range of 3 to 100%. When stretching the cellulose acylate film of the present invention, tenter stretching is preferably used, and in order to control the slow axis with high accuracy, the difference between the left and right tenter clip speeds, separation timing, etc. should be as small as possible. Is preferred.

  A plasticizer can be added to the cellulose acylate film in order to improve mechanical properties or increase the drying rate. As a plasticizer, the aspect of paragraph number [0043] of JP, 2002-139621, A and a desirable range are applicable to the present invention.

  Degradation inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose acylate film. Regarding the deterioration preventing agent, the description in paragraph number [0044] of JP-A-2002-139621 can be applied to the present invention. As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. The ultraviolet ray preventing agent is described in JP-A-7-11056.

  Regarding the surface treatment of the cellulose acylate film and the surface energy of the solid, the descriptions in paragraph numbers [0051] to [0052] of JP-A No. 2002-196146 can be applied to the present invention.

  The thickness of the cellulose acylate film varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, more preferably in the range of 20 to 250 μm, and most preferably in the range of 30 to 180 μm. In addition, as an optical use, the range of 30-110 micrometers is especially preferable. About manufacturing a cellulose acylate film using a non-chlorinated solvent, it is described in detail in JIII Journal of Technical Disclosure No. 2001-1745, and the cellulose acylate film described therein is also preferably used in the present invention. it can.

[Application of optical compensation sheet]
The optical compensation sheet of the present invention can be used for an elliptically polarizing plate in combination with a polarizing film. Furthermore, by applying to a transmissive liquid crystal display device in combination with a polarizing film, it contributes to an increase in viewing angle. The elliptically polarizing plate and liquid crystal display device using the optical compensation sheet of the present invention will be described below.

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

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

[Liquid Crystal Display]
By using the optical compensation sheet of the present invention, it is possible to provide a liquid crystal display device having a wide viewing angle. Optical compensation sheets for TN mode liquid crystal cells are described in JP-A-6-214116, US Pat. No. 5,583,679, US Pat. No. 5,646,703, and German Patent Publication 3911620A1. Further, an optical compensation sheet for liquid crystal cells in IPS mode or FLC mode is described in JP-A-10-54982. Furthermore, OCB mode or HAN mode liquid crystal cell optical compensation sheets are described in US Pat. No. 5,805,253 and International Publication WO 96/37804. Furthermore, an optical compensation sheet for an STN mode liquid crystal cell is described in JP-A-9-26572. A VA mode liquid crystal cell optical compensation sheet is described in Japanese Patent No. 2866372.

  In the present invention, optical compensation sheets for liquid crystal cells of various modes can be prepared with reference to the above-mentioned publications. The optical compensation sheet of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optical Compensation Bend), STN (Super Tee VN). It can be applied to a liquid crystal display device in combination with a liquid crystal cell driven in various modes such as (Hybrid Aligned Nematic) mode. The optical compensation sheet of the present invention is particularly effective in a TN (Twisted Nematic) mode or OCB (Optically Compensatory Bend) mode liquid crystal display device.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, operations and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
[Example 1-1]
(Production of optical compensation sheet)
A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 100 μm and a size of 270 mm × 100 mm was used as a transparent support. On the transparent support, alkyl-modified polyvinyl alcohol (MP-203, manufactured by Kuraray Co., Ltd.) was applied to a thickness of 0.5 μm and dried, and the surface was rubbed to form an alignment film. On the alignment film, a coating liquid having the following composition was applied using a bar coater.

(Optically anisotropic layer coating solution)
Exemplary compound (I-1) of general formula (I) 0.4 parts by mass The following discotic liquid crystalline compound 100 parts by mass Ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9 .9 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Japan) 3.3 parts by mass sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.1 parts by mass Methyl ethyl ketone 300 parts by mass

Next, the coating layer was heated and matured at a film surface temperature of 120 ° C. for about 120 seconds, and then cooled to 80 ° C. in about 20 seconds. Subsequently, the alignment state of the optically anisotropic layer was fixed by irradiating with 0.4 J / cm ² ultraviolet rays while maintaining the same temperature. The thickness of the formed optically anisotropic layer was 1.8 μm. As described above, an optically anisotropic layer was formed to produce an optical compensation sheet.

(Evaluation of optical compensation sheet)
The tilt angle near the alignment film of the liquid crystal molecules and the tilt angle near the air interface in the optically anisotropic layer of the optical compensation sheet are changed by using an ellipsometer (APE-100, manufactured by Shimadzu Corporation). The retardation was measured, hypothesized as a refractive index ellipsoid model, and calculated by the method described in Designing Concepts of the Disco Negative Birefringence Compensation Films, SID98 DIGEST. The measurement wavelength is 632.8 nm, and the results are shown in Table 1.

[Examples 1-2 to 1-7, Comparative Examples 1-1 and 1-2]
Example compound (I-1) used in Example 1-1 was changed as shown in Table 1 (in Comparative Example 1-2, the following fluorine compound (A) was used instead of the compound of general formula (I)). Except for the above, an optical compensation sheet was prepared in the same manner as in Example 1-1, and the tilt angle was calculated in the same manner. The results are shown in Table 1.

  As can be seen from the results of Examples 1-1 to 1-6 and Comparative Examples 1-1 and 1-2 in Table 1, the optical difference containing the compound represented by the general formula (I) according to the present invention is shown. In the isotropic layer, hybrid orientation is realized in which the tilt angle of liquid crystal molecules, particularly the tilt angle on the air interface side is large. Further, as can be seen from the results of Example 1-7, the same effect can be obtained by using a combination of two or more compounds represented by the general formula (I).

Next, an application example as a liquid crystal display device will be described.
[Example 1-8]
(Preparation of transparent support)
The following components were put into a mixing tank and heated and stirred to prepare a cellulose acetate solution (dope).
(Cellulose acetate solution composition)
Cellulose acetate having an acetylation degree of 60.9% 100 parts by mass Triphenyl phosphate 6.5 parts by mass Biphenyl diphenyl phosphate 5.2 parts by mass The following retardation increasing agent (1) 0.1 part by mass The following retardation increase Agent (2) 0.2 parts by mass Methylene chloride 310.25 parts by mass Methanol 54.75 parts by mass 1-butanol 10.95 parts by mass

  The obtained dope was cast from a casting port onto a drum cooled to 0 ° C. The film is peeled off at a solvent content of 70% by mass, both ends in the width direction of the film are fixed with a pin tenter, and the stretch rate in the width direction (direction perpendicular to the machine direction) is in a region where the solvent content is 3 to 5% by mass. Was dried while maintaining an interval of 3%. Then, it is further dried by transporting between the rolls of the heat treatment apparatus, and the stretching ratio in the machine direction is substantially 0% in the region exceeding 120 ° C. (in consideration of 4% stretching in the machine direction when stripping). A cellulose acetate film having a thickness of 100 μm was prepared by adjusting the ratio of the stretching ratio in the width direction to the stretching ratio in the machine direction to be 0.75. When the retardation of the produced film was measured at a wavelength of 632.8 nm, the retardation in the thickness direction was 40 nm, and the in-plane retardation was 4 nm. The produced cellulose acetate film was used as a transparent support.

(Formation of first undercoat layer)
On the transparent support, a coating solution having the following composition was applied at 28 ml / m ² and dried to form a first undercoat layer.

(First undercoat layer coating solution composition)
Gelatin 5.42 parts by mass Formaldehyde 1.36 parts by mass Salicylic acid 1.60 parts by mass Acetone 391 parts by mass Methanol 158 parts by mass Methylene chloride 406 parts by mass Water 12 parts by mass

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

(Second undercoat layer coating solution composition)
The following anionic polymer 0.79 parts by mass Citric acid monoethyl ester 10.1 parts by mass Acetone 200 parts by mass Methanol 877 parts by mass Water 40.5 parts by mass

(Formation of back layer)
On the opposite side of the transparent support, a coating solution having the following composition was applied at 25 ml / m ² and dried to form a back layer.

(Back layer coating solution composition)
Cellulose diacetate having an acetylation degree of 55% 6.56 parts by mass Silica matting agent (average particle size: 1 μm) 0.65 parts by mass Acetone 679 parts by mass Methanol 104 parts by mass

(Formation of alignment film)
On the second undercoat layer, an aqueous solution of the alkyl-modified polyvinyl alcohol (MP-203, manufactured by Kuraray Co., Ltd.) used in Example 1-1 was applied, dried with hot air at 60 ° C. for 90 seconds, and then rubbed. The alignment film was formed by processing. The thickness of the obtained alignment film layer was 0.5 μm. The rubbing direction of the alignment film was parallel to the casting direction of the transparent support.

(Formation of optically anisotropic layer)
On the alignment film, the optically anisotropic layer coating solution shown in Example 1 was applied using a # 4 wire bar. The thickness of the formed optically anisotropic layer was 1.74 μm.

The film coated with the above optically anisotropic layer is placed in a thermostatic bath at 130 ° C., heated to a film surface temperature of 120 ° C. over about 20 seconds, held as it is for about 120 seconds, and then 80 seconds in about 20 seconds. Cooled to ° C. While maintaining the same temperature, 0.4 J / cm ² of ultraviolet light was irradiated to fix the alignment state of the optically anisotropic layer. After cooling to room temperature, an optical compensation sheet was produced.

(Production of liquid crystal display device)
A polyimide alignment film was provided on a glass substrate provided with an ITO transparent electrode, and a rubbing treatment was performed. The two substrates were stacked with the alignment film facing each other through a 5 μm spacer. The two substrates were arranged so that the rubbing directions of the alignment films were orthogonal. A rod-like liquid crystal molecule (ZL4792, manufactured by Merck & Co., Inc.) was injected into the gap between the substrates to form a rod-like liquid crystal layer. The birefringence Δn of the rod-like liquid crystal molecule was 0.0969. On both sides of the TN liquid crystal cell produced as described above, two produced optical compensation sheets were attached so that the optical anisotropic layer faced the substrate of the liquid crystal cell. Furthermore, two polarizing plates were affixed to the outside of them to produce a liquid crystal display device. The rubbing direction of the alignment film of the optical compensation sheet and the rubbing direction of the alignment film of the liquid crystal cell adjacent thereto were arranged to be antiparallel. Moreover, it arrange | positioned so that the absorption axis of a polarizing plate and the rubbing direction of a liquid crystal cell may become parallel. A voltage is applied to the liquid crystal cell of the liquid crystal display device, and the transmittance ratio between white display and black display in white display 2 V and black display 5 V is used as a contrast ratio, and a region with a contrast ratio of 10 in the vertical and horizontal directions and no gradation inversion is viewed. Measured as a corner. The results are shown in Table 2.

[Examples 1-9 to 1-14, Comparative Example 1-3]
A liquid crystal display device was produced and evaluated in the same manner as in Example 1-8 except that the exemplified compound (I-1) used in Example 1-8 was changed as shown in Table 2. The results are shown in Table 2.

  As can be seen from the results of Examples 1-8 to 1-14 and Comparative Example 1-3 shown in Table 2, the optical anisotropy containing the compound represented by the general formula (I) according to the present invention. The optical compensation sheet having a layer greatly contributes to the expansion of the viewing angle of the liquid crystal display device. This is presumably because the tilt angle of the liquid crystal molecules is increased in the optically anisotropic layer in the optical compensation sheet of the example.

[Example 2]
(Synthesis example of exemplary compound (I-1))
Synthesis of 2- (2-dodecyloxyphenoxy) ethanol:
7.7 g (50 mmol) of 2- (2-hydroxyethoxy) phenol, 15.0 g (60 mol) of lauryl bromide, and 27.6 g (200 mmol) of potassium carbonate were dissolved in 100 ml of dimethylacetamide, and 1 at 120 ° C. in a nitrogen atmosphere. Stir for hours. After cooling to room temperature, 1 L of water was added, the precipitated solid was filtered off, and washed several times with water. This white solid was dried to obtain 16.1 g (yield 100%) of the desired product.
¹ H NMR (CDCl ₃ ): δ 0.9 (t, 3H), 1.2-1.4 (br, 16H), 1.5 (quint, 2H), 1.8 (quint, 2H), 2. 7 (br, 1H), 3.9 (br, 2H), 4.0 (t, 2H), 4.1 (t, 2H), 6.9-7.0 (m, 4H).

Synthesis of methanesulfonic acid 2- (2-dodecyloxyphenoxy) ethyl ester:
16.1 g (50 mmol) of 2- (2-dodecyloxyphenoxy) ethanol and 6.7 g (66 mmol) of triethylamine were dissolved in 300 ml of ethyl acetate, cooled in an ice bath, and 6.9 g (60 mmol) of methanesulfonyl chloride was added dropwise. . After completion of dropping, the mixture was stirred at room temperature for 30 minutes. Thereafter, the organic layer was washed with water and a saturated aqueous sodium chloride solution, and then the organic layer was recovered. The solid obtained by distilling the organic solvent under reduced pressure was recrystallized with methanol to obtain 19.3 g of the desired product (yield 96%).
¹ H NMR (CDCl ₃ ): δ 0.9 (t, 3H), 1.2-1.4 (br, 16H), 1.5 (m, 2H), 1.8 (quint, 2H), 3. 1 (s, 3H), 4.0 (t, 2H), 4.3 (t, 2H), 4.6 (t, 2H), 6.9-7.0 (m, 4H).

Synthesis of 1-dodecyloxy-2- [2- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) ethoxy] benzene:
3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-ol 6.6 g (18 mmol), tetrabutylammonium hydrogen sulfate 0.5 g (1.5 mmol) was dissolved in 30 ml of toluene, 15 ml of 50% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 30 minutes. After 30 minutes, 6.0 g (15 mmol) of methanesulfonic acid 2- (2-dodecyloxyphenoxy) ethyl ester was added, and the mixture was stirred at 80 ° C. for 1 hour. After cooling to room temperature, the mixture was neutralized with 2M hydrochloric acid, 200 ml of ethyl acetate was added, the organic layer was washed with water and a saturated aqueous sodium chloride solution, and then the organic layer was recovered. The organic solvent was distilled under reduced pressure and purified by silica gel column chromatography (hexane / ethyl acetate: 4/1 (volume ratio)) to obtain 8.0 g (yield 80%) of the desired product as a pale yellow liquid. .
¹ H NMR (CDCl ₃ ): δ 0.9 (t, 3H), 1.2-1.4 (br, 16H), 1.5 (quint, 2H), 1.8 (quint, 2H), 2. 4 (tt, 2H), 3.8-3.9 (m, 4H), 4.0 (t, 2H), 4.2 (t, 2H), 6.8-7.0 (m, 4H) .

3-dodecyloxy-4- [2- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) ethoxy] benzenesulfonic acid (illustrated Synthesis of Compound (I-1)):
1-dodecyloxy-2- [2- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) ethoxy] benzene (3.0 g) 4.5 mmol) was dissolved in 10 ml of methylene chloride and ice-cooled to 0 ° C. To this solution, 0.36 ml (5.4 mmol) of chlorosulfonic acid was slowly added dropwise and stirred at room temperature for 10 minutes. After 10 minutes, 0.1 ml of water was added, the solvent was distilled under reduced pressure, and purification was performed by silica gel column chromatography (methylene chloride / methanol: 9/1 (volume ratio)). 7 g (yield 50%) was obtained.
¹ H NMR (acetone-d6): δ 0.9 (t, 3H), 1.2-1.4 (br, 16H), 1.5 (br, 2H), 1.8 (quint, 2H), 2 .4 (tt, 2H), 3.8-3.9 (m, 4H), 4.1 (t, 2H), 4.2 (t, 2H), 7.1 (d, 1H) 7.4 -7.5 (m, 2H).

(Synthesis Example of Exemplary Compound (I-37))
2- [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, -hexadecafluorononyloxy) -phenoxy] ethanol Synthesis:
1.54 g (10 mmol) of 2- (2-hydroxyethoxy) phenol, trifluoromethanesulfonic acid 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9, 6.2 g (11 mol) of 9, -hexadecafluorononyl ester and 2.8 g (20 mmol) of potassium carbonate were dissolved in 20 ml of dimethylacetamide and stirred at 120 ° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature, 100 ml of ethyl acetate was added, the organic layer was washed with water and a saturated aqueous sodium chloride solution, the organic layer was recovered, and the organic solvent was distilled under reduced pressure. Purification operation was performed by silica gel column chromatography (hexane / ethyl acetate: 1/1 (volume ratio)) to obtain 3.2 g (yield 56%) of the desired product as a white solid.
¹ H NMR (CDCl ₃ ): δ1.9 (br, 1H), 3.9 (t, 2H), 4.1 (t, 2H), 4.5 (t, 2H), 6.1 (tt, 1H), 6.9-7.1 (m, 4H).

Methanesulfonic acid 2- [2- (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9, -hexadecafluorononyloxy) -phenoxy Synthesis of ethyl ester:
2- [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, -hexadecafluorononyloxy) -phenoxy] ethanol 3 0.2 g (5.6 mmol) and triethylamine 0.69 g (6.8 mmol) were dissolved in 50 ml of ethyl acetate, cooled in an ice bath, and 0.71 g (6.2 mmol) of methanesulfonyl chloride was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 30 minutes. Thereafter, the organic layer was washed with water and a saturated aqueous sodium chloride solution, and then the organic layer was recovered. The organic solvent was distilled under reduced pressure to obtain 3.4 g (yield 94%) of the desired product as a white solid.
¹ H NMR (CDCl ₃ ): δ 3.1 (s, 3H), 4.3 (t, 2H), 4.5 (t, 2H), 4.6 (t, 2H), 6.1 (tt, 1H), 6.9-7.0 (m, 4H).

1- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, -hexadecafluorononyloxy) -2- [2- (3 , 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) ethoxy] benzene:
3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-ol 2.1 g (5.8 mmol), tetrabutylammonium hydrogensulfate 0 0.2 g (0.6 mmol) was dissolved in 10 ml of toluene, 5 ml of 50% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 30 minutes. After 30 minutes, methanesulfonic acid 2- [2- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, -hexadecafluorononyl) Oxy) -phenoxy] ethyl ester (3.4 g, 5.3 mmol) was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, the mixture was neutralized with 2M hydrochloric acid, 100 ml of ethyl acetate was added, the organic layer was washed with water and a saturated aqueous sodium chloride solution, and then the organic layer was recovered. The organic solvent was distilled under reduced pressure and purified by silica gel column chromatography (hexane / ethyl acetate: 10/1 (volume ratio)) to obtain 2.4 g (yield 50%) of the desired product as a pale yellow solid. .
¹ H NMR (CDCl ₃ ): δ 2.4 (tt, 2H), 3.8-3.9 (m, 4H), 4.1 (t, 2H), 4.5 (t, 2H), 6. 1 (tt, 1H), 6.8-7.0 (m, 4H).

3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, -hexadecafluorononyloxy) -4- [2- (3 , 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) ethoxy] benzenesulfonic acid (Exemplary Compound (I-37)):
1- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, -hexadecafluorononyloxy) -2- [2- (3 , 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) ethoxy] benzene 2.4 g (2.6 mmol) is dissolved in 10 ml of methylene chloride, Ice-cooled to 0 ° C. To this solution, 0.21 ml (3.1 mmol) of chlorosulfonic acid was slowly added dropwise and stirred at room temperature for 10 minutes. Ten minutes later, 0.1 ml of water was added, and the solvent was distilled under reduced pressure. Purification operation was performed by silica gel column chromatography (methylene chloride / methanol: 9/1 (volume ratio)) to obtain 1.3 g (yield 50%) of the desired product as a white solid.
¹ H NMR (acetone-d6): δ 2.5 (tt, 2H), 3.8-3.9 (m, 4H), 4.3 (t, 2H), 4.9 (t, 2H), 6 .8 (tt, 1H), 7.2 (d, 1H) 7.5 (s, 1H), 7.6 (d, 1H).

Claims (8)

A composition comprising a liquid crystal compound and at least one compound represented by the following general formula (I).
Formula (I)
_{^{(R 1 -X 1) m -Ar}} -SO 3 M
[In the formula (I), Ar represents an (m + 1) -valent aromatic heterocyclic group or aromatic hydrocarbon ring group, X ¹ represents a single bond or a divalent linking group, and R ¹ represents a substituted or unsubstituted group. A plurality of R ^{1 s} may be the same or different, but at least two are different from each other, and at least one is a CF ₃ group at the end or CF ₂ H at the end An alkyl group having a group. M represents a proton, a metal cation or an organic cation, and m represents an integer of 2 or more. ] The composition according to claim 1, wherein the compound represented by the general formula (I) is represented by the following general formula (Ia).

[In the formula (Ia), X ¹¹ is an alkylene group, —O—, —S—, —CO—, —NR ^a — (wherein R ^a is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ), —SO ₂ — and a divalent linking group selected from the group consisting of at least two of these, R ¹¹ represents an unsubstituted alkyl group having 8 to 20 carbon atoms, or 60% or more of the hydrogen atoms are fluorine. Represents an alkyl group having 4 to 12 carbon atoms substituted with an atom, and a plurality of R ¹¹ may be the same or different, but at least two are different from each other, and at least one of An alkyl group having a CF ₃ group at the terminal or a CF ₂ H group at the terminal. M represents a proton, a metal cation or an organic cation, and m ¹ represents an integer of 2 or more. ] An optical compensation sheet having an optically anisotropic layer containing a liquid crystalline compound fixed in an aligned state and at least one compound represented by formula (I) in claim 1 on a support. The optical compensation sheet according to claim 3, wherein the liquid crystalline compound is a discotic liquid crystalline compound. The optical compensation sheet according to claim 4, wherein the discotic liquid crystalline compound is triphenylene liquid crystal. The optical compensation sheet according to any one of claims 3 to 5, wherein the compound represented by the general formula (I) is represented by the general formula (Ia) according to claim 2. The compound represented by the following general formula (Ia).

[In the formula (Ia), X ¹¹ is an alkylene group, —O—, —S—, —CO—, —NR ^a — (wherein R ^a is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. ), —SO ₂ — and a divalent linking group selected from the group consisting of at least two of these, R ¹¹ represents an unsubstituted alkyl group having 8 to 20 carbon atoms, or 60% or more of the hydrogen atoms are fluorine. Represents an alkyl group having 4 to 12 carbon atoms substituted with an atom, and a plurality of R ¹¹ may be the same or different, but at least two are different from each other, and at least one of An alkyl group having a CF ₃ group at the terminal or a CF ₂ H group at the terminal. M represents a proton, a metal cation or an organic cation, and m ¹ represents an integer of 2 or more. ] The liquid crystal display device which has an optically anisotropic layer containing the liquid crystalline compound fixed to the orientation state, and at least 1 type of the compound represented by general formula (I) in Claim 1.