JP2006265283A - Liquid crystal composition, retardation plate and elliptical polarizer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal composition containing a compound having both a high Δn and a low wavelength dispersion combined and a thin film containing the compound. <P>SOLUTION: The liquid crystal composition contains at least one kind of compound expressed by general formula (DI) and the compound is oriented uniformly in the thin film (wherein, Y<SP>11</SP>, Y<SP>12</SP>and Y<SP>13</SP>are each a carbon atom or a nitrogen atom; R<SP>11</SP>, R<SP>12</SP>and R<SP>13</SP>are each a specific long chain group coupled with a 5-membered ring or a 6-membered ring). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a compound, a liquid crystal composition containing the compound, a retardation plate having an optically anisotropic layer using the compound, and an elliptically polarizing plate, and in particular, a liquid crystal that can be suitably used for an optical element such as a retardation plate. The present invention relates to a composition and its use.

  A liquid crystal display device is usually provided with a first polarizing plate and a second polarizing plate with a liquid crystal cell interposed therebetween, and the liquid crystal cell has a liquid crystal layer containing a rod-like liquid crystal between a pair of substrates. A phase difference generated in a liquid crystal cell using a rod-like liquid crystal is changed to a discotic compound (for example, 2,3,6,7,10,11-hexa {4- (4-acryloyloxyhexyloxy) benzoyloxy} triphenylene). In the case of canceling with an optical compensation sheet having an optically anisotropic layer formed from (for example, Patent Document 1), since the wavelength dispersibility of the rod-like liquid crystal and the discotic compound is different, the phase difference is simultaneously obtained for all light wavelengths. Cannot be offset and discoloration (black color does not appear) occurs.

  A trisubstituted benzene having a heterocyclic group has been reported (Non-patent Document 1). It is not easy to achieve a low wavelength dispersion by using this compound, and a compound having a smaller wavelength dispersion (Re (short wavelength (for example, 450 nm)) / Re (long wavelength (for example, 650 nm)) is small) Is desired.

  The retardation (Δnd) of the optical compensation sheet needs to be determined according to the optical properties of the liquid crystal cell to be compensated. Here, retardation (Δnd) is the product of the refractive index anisotropy (Δn) of the optically anisotropic layer and the thickness (d) of the optically anisotropic layer. If the refractive index anisotropy (Δn) of the optically anisotropic layer is large, the liquid crystal cell can be compensated even if the layer thickness (d) is small. On the other hand, when the refractive index anisotropy (Δn) becomes small, it is necessary to increase the thickness (d) of the layer, and as a result, there arises a problem that defects in the alignment of the liquid crystalline compound are likely to occur.

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

  An object of the present invention is to provide a compound having low wavelength dispersion. Another object of the present invention is to provide a compound having a low wavelength dispersion and a high Δn by a compound having a specific structure. Still another object of the present invention is to provide a liquid crystal composition containing the compound, a retardation plate and an elliptically polarizing plate using the compound.

The above object is achieved by the following invention.
1. A liquid crystal composition containing at least one compound represented by the following general formula (DI).
General formula (DI)

(In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a carbon atom or a nitrogen atom, and R ¹¹ , R ¹² and R ¹³ each independently represent the following general formula (DI- A), the following general formula (DI-B), the following general formula (DI-C), the following general formula (DI-D), the following general formula (DI-E), or the following general formula (DI-F) However, two of R ¹¹ , R ¹² and R ¹³ are the same and the other one is different.
General formula (DI-A)

(In the general formula (DI-A), A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ , A ¹⁶ each independently represents a carbon atom or a nitrogen atom, and X ¹ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ¹¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ¹² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is (It may be replaced by a substituent. Q ¹¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-B)

(In the general formula (DI-B), A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ and A ²⁶ each independently represents a carbon atom or a nitrogen atom, and X ² represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ²¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — Represents CH ₂ —, —CH═CH— or —C≡C—, and L ²² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is (It may be replaced by a substituent. Q ²¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-C)

(In the general formula (DI-C), A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ , A ³⁶ each independently represents a carbon atom or a nitrogen atom, and X ³ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ³¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ³² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and a divalent group, and the above group is a group containing a hydrogen atom The hydrogen atom may be replaced by a substituent, and Q ³¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-D)

(In the general formula (DI-D), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ each independently represents a carbon atom or a nitrogen atom, and X ⁴ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ⁴¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ⁴² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. A divalent linking group selected from the group consisting of-, -CH = CH- and -C≡C-, and a divalent group consisting of a combination thereof, and the linking group is a group containing a hydrogen atom The hydrogen atom may be replaced with a substituent, and Q ⁴¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-E)

(In the general formula (DI-E), A ⁵¹ , A ⁵² , A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ each independently represents a carbon atom or a nitrogen atom, and X ⁵ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ⁵¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ⁵² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. -, -CH = CH- and -C≡C-, and a divalent linking group selected from the group consisting of a divalent group consisting of a combination thereof, wherein the divalent group is a group containing a hydrogen atom. In some cases, the hydrogen atom may be replaced by a substituent, and Q ⁵¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-F)

(In the general formula (DI-F), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ , A ⁶⁶ each independently represents a carbon atom or a nitrogen atom, and X ⁶ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ⁶¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ⁶² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is (It may be replaced by a substituent. Q ⁶¹ each independently represents a polymerizable group or a hydrogen atom.)
2. A retardation plate having at least one optically anisotropic layer on a transparent support, wherein the optically anisotropic layer is an optically anisotropic layer formed from the liquid crystal composition described in 1 above A retardation film characterized by that.
3. 3. An elliptically polarizing plate comprising the retardation plate according to 2 and a polarizing film.

  According to the present invention, it has become possible to provide a compound having both high Δn and low wavelength dispersibility, which could not be realized by a conventional discotic liquid crystalline compound. In addition, it has become possible to provide a liquid crystal composition, a retardation plate and an elliptically polarizing plate using the compound.

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

The compound of the present invention is represented by the following general formula (DI).
General formula (DI)

In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a carbon atom or a nitrogen atom.

When Y ¹¹ , Y ¹² and Y ¹³ are carbon atoms, the carbon atoms may have a substituent. Here, “the atom may have a substituent” means that the hydrogen atom part bonded to the atom part of the cyclic structure containing the atom may be substituted with another group (The same applies below). Examples of the substituent that the carbon atom may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, and a halogen atom. And cyano group can be mentioned as preferred examples. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom and a cyano group are most preferred.
Y ¹¹ , Y ¹² and Y ¹³ are more preferably all carbon atoms, and the carbon atoms are most preferably unsubstituted.

R ¹¹ , R ¹² and R ¹³ are each independently represented by the following general formula (DI-A), general formula (DI-B), general formula (DI-C), general formula (DI-D), The general formula (DI-E) or the following general formula (DI-F) is represented. However, two of R ¹¹ , R ¹² and R ¹³ are the same, and the other one is different.

General formula (DI-A)

In the general formula (DI-A), A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ , A ¹⁶ each independently represents a carbon atom or a nitrogen atom. At least one of A ¹¹ and A ¹² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ are preferably carbon atoms, and more preferably all are carbon atoms. When A ¹³ , A ¹⁴ , A ¹⁵ , and A ¹⁶ are carbon atoms, the carbon atoms may have a substituent. Examples of the substituent include a halogen atom (including a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, and an alkenyl having 2 to 16 carbon atoms. Group, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and the number of carbon atoms An alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and 2 to 16 carbon atoms. Acylamino groups are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable. X ¹ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, preferably an oxygen atom. * Represents a position bonded to a 6-membered ring including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (DI).

General formula (DI-B)

In the general formula (DI-B), A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ and A ²⁶ each independently represents a carbon atom or a nitrogen atom. At least one of A ²¹ and A ²² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ²³ , A ²⁴ , A ²⁵ and A ²⁶ are preferably carbon atoms, and more preferably all are carbon atoms. When A ²³ , A ²⁴ , A ²⁵ , and A ²⁶ are carbon atoms, the carbon atoms may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable. X ² represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, preferably an oxygen atom. * Represents a position bonded to a 6-membered ring including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (DI).

General formula (DI-C)

In formula ^{(DI-C), A 31} , A 32, A 33, A 34, A 35, A 36 each independently represents a carbon atom or a nitrogen atom. At least one of A ³¹ and A ³² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ³³ , A ³⁴ , A ³⁵ and A ³⁶ are preferably carbon atoms, and more preferably all are carbon atoms. When ^A33 , ^A34 , ^A35 , ^A36 is a carbon atom, the carbon atom may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkyl group substituted with a trifluoromethyl group is more preferable. X ³ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, preferably an oxygen atom. * Represents a position bonded to a 6-membered ring including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (DI).

General formula (DI-D)

In the general formula (DI-D), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ each independently represents a carbon atom or a nitrogen atom. At least one of A ⁴¹ and A ⁴² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ are preferably carbon atoms, and more preferably all are carbon atoms. When A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ are carbon atoms, the carbon atoms may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable. X ⁴ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, preferably an oxygen atom. * Represents a position bonded to a 6-membered ring including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (DI).

General formula (DI-E)

In the general formula (DI-E), A ⁵¹ , A ⁵² , A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ each independently represents a carbon atom or a nitrogen atom. At least one of A ⁵¹ and A ⁵² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ are preferably carbon atoms, and more preferably all are carbon atoms. When A ⁵³ , A ⁵⁴ , A ⁵⁵ , A ⁵⁶ are carbon atoms, the carbon atoms may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable. X ⁵ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, preferably an oxygen atom. * Represents a position bonded to a 6-membered ring including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (DI).

General formula (DI-F)

In the general formula (DI-F), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ each independently represent a carbon atom or a nitrogen atom. It is preferable that at least one of A ⁶¹ and A ⁶² is a nitrogen atom, and it is more preferable that both are nitrogen atoms. At least three of A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ are preferably carbon atoms, and more preferably all are carbon atoms. When A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ are carbon atoms, the carbon atoms may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable. X ⁶ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, preferably an oxygen atom. * Represents a position bonded to a 6-membered ring including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (DI).

L ¹¹ in formula (DI-A), L ²¹ in formula (DI-B), L ³¹ in formula (DI-C), L ⁴¹ in formula (DI-D), formula L ⁵¹ in (DI-E) and L ^{61 in} formula (DI-F) are each independently —O—, —O—CO—, —CO—O—, —O—CO—O—. , —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH— or —C≡C—. Preferably, -O -, - O-CO -, - CO-O -, - O-CO-O -, - CH 2 -, - CH = CH -, - is C≡C-, more preferably, —O—, —O—CO—, —O—CO—O—, —CH ₂ —. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

Formula (DI-A) L ¹² in the general formula (DI-B) in L ^22, formula (DI-C) in the L ^32, the general formula (DI-D) in the L ^42, formula L ⁵² in (DI-E) and L ^{62 in} formula (DI-F) are each independently —O—, —S—, —C (═O) —, —SO ₂ —, — It represents a divalent linking group selected from the group consisting of NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ¹² , L ²² , L ³² , L ⁴² , L ⁵² and L ⁶² are each independently —O—, —C (═O) —, —CH ₂ —, —CH═CH— and —C≡. It is preferably selected from the group consisting of C- and combinations thereof. L ¹² , L ²² , L ³² , L ⁴² , L ⁵² and L ⁶² each independently preferably contain 1 to 20 carbon atoms, and more preferably contain 2 to 14 carbon atoms. . Further ^{L 12, L 22, L 32} , L 42, L 52, L 62 are each independently, -CH ₂ - preferably contains 1 to 16 a, -CH ₂ - 2 to 12 pieces containing More preferably.

Q ¹¹ in formula (DI-A), Q ²¹ in formula (DI-B), Q ³¹ in formula (DI-C), Q ⁴¹ in formula (DI-D), formula Q ⁵¹ in (DI-E) and Q ^{61 in} general formula (DI-F) each independently represent a polymerizable group or a hydrogen atom. When the compound of the present invention is used for an optical film or the like that preferably has a phase difference that does not change due to heat, such as an optical compensation film, Q ¹¹ , Q ²¹ , Q ³¹ , Q ⁴¹ , Q ⁵¹ , Q ⁶¹ Is preferably a polymerizable group. The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

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

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

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

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

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

  The uniformly oriented state of the present invention refers to a monodomain oriented state that is uniform and free of defects. In order to realize such an alignment state, a liquid crystal phase exhibiting good monodomain properties is desirable. 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. When good monodomain properties are exhibited, for example, when used for a phase difference plate, the phase difference plate tends to have a high light transmittance.

The liquid crystal phase liquid crystal compound of the present invention is expressed, it can be given a columnar phase and a discotic nematic phase (N _D phase). Among these liquid crystal phases, a discotic nematic phase having a good monodomain property (N _D phase) is preferable.

  When using the compound of this invention as a liquid crystal compound, it is preferable to express a liquid crystal phase in the range of 20 degreeC-300 degreeC. More preferably, it is 40 degreeC-280 degreeC, Most preferably, it is 60 degreeC-250 degreeC. Here, the expression of the liquid crystal phase at 20 ° C. to 300 ° C. means that the liquid crystal temperature range crosses 20 ° C. (specifically, for example, 10 ° C. to 22 ° C.) or 300 ° C. (specifically, eg, 298 (° C. to 310 ° C.). The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.

  In order to obtain the thin film (optically anisotropic layer) of the present invention as a uniformly oriented thin film, another additive was added as required for the liquid crystalline compound to form a liquid crystal composition, and the liquid crystal composition was applied. Thereafter, it is obtained by uniform alignment in a liquid crystal state. Examples of the additive that can be added to the liquid crystal compound include an air interface alignment controller, a repellency inhibitor, a polymerization initiator, and a polymerizable monomer described later.

In order to realize a uniformly aligned state, it is preferable to provide an alignment film. However, in the case where the optical axis direction of the discotic liquid crystalline compound coincides with the normal direction of the thin film surface (homeotropic alignment), the alignment film is not necessarily required.
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 liquid crystal composition of the present invention can be provided with a desired alignment, the alignment film may be any layer. In the present invention, an alignment film formed by rubbing treatment or light irradiation is preferable. An alignment film formed by polymer rubbing treatment 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 the present invention, in particular, the method described in the liquid crystal manual (Maruzen Co., Ltd.) is used. Preferably it is done. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.05 to 3 μm.

In the present invention, the state in which the orientation state is fixed is a state in which the orientation is maintained, which is the most typical and preferred embodiment, but is not limited thereto, and is 0 ° C. to 50 ° C. under normal conditions. The conditions of −30 ° C. to 70 ° C. are preferable under more severe conditions. In such a temperature range, the fixed liquid crystal composition has no fluidity, and the fixed alignment form can be kept stable without causing a change in the alignment form due to an external field or an external force. It refers to the state. When the alignment state is finally fixed and the optically anisotropic layer is formed, the liquid crystal composition of the present invention does not need to exhibit liquid crystallinity. For example, since a compound having a polymerizable group is used as the liquid crystal compound, as a result, the polymerization or the cross-linking reaction proceeds by reaction with heat, light, etc., and the liquid crystallinity may be lost by increasing the molecular weight.
Examples of additives that can be added to the liquid crystal composition of the present invention in forming the optically anisotropic layer include air interface alignment control agents, repellency inhibitors, polymerization initiators, polymerizable monomers, and the like.

[Air interface alignment control agent]
The liquid crystal composition is aligned at the tilt angle of the air interface at the air interface. The tilt angle varies depending on the type of liquid crystal compound contained in the liquid crystal composition, the type of additive, and the like. Therefore, it is necessary to arbitrarily control the tilt angle of the air interface according to the purpose.

  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, and an additive is preferably used. Examples of such an additive include 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 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, a hydrophobic excluded volume effect compound described in JP-A No. 2002-20363 can be used as the air interface alignment control agent.

  The addition amount 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 of the present invention. 0.1 mass%-5 mass% are the most preferable.

[Anti-repellent agent]
As a material for adding to the liquid crystal composition of the present invention and preventing repelling at the time of application of the composition, generally, a polymer compound can be suitably used.
The polymer to be used is not particularly limited as long as the tilt angle change and orientation of the liquid crystal composition of the present invention are not significantly inhibited.
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 composition of the present invention, 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 composition of the present invention. More preferably, it is in the range of 1 to 8% by mass, and more preferably in the range of 0.1 to 5% by mass.

[Polymerization initiator]
The alignment state in the present invention is fixed, for example, by heating the liquid crystal composition once to the liquid crystal phase formation temperature and then cooling it while maintaining the alignment state without impairing the alignment form in the liquid crystal state. Can be formed. Moreover, after heating the composition which added the polymerization initiator to the liquid-crystal 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.

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 liquid for the optically anisotropic layer.

It is preferable to use ultraviolet rays for light irradiation for polymerization. The irradiation energy is preferably 10mJ~50J / cm ^2, further preferably 50mJ~800mJ / 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.

[Polymerizable monomer]
A polymerizable monomer may be added to the liquid crystal composition of the present invention. The polymerizable monomer that can be used in the present invention is not particularly limited as long as it is compatible with the compound of the present invention and does not cause significant alignment inhibition of the liquid crystal composition. 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 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.

[Coating solvent]
As the solvent used for preparing the liquid crystal composition of the present invention, 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.

[Application method]
The thin film of the present invention can be formed by preparing a coating liquid for the liquid crystal composition of the present invention using the above solvent, applying the coating liquid on the alignment film, and subjecting the liquid crystal composition of the present invention 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).

[Phase difference plate]
The retardation plate of the present invention has an optically anisotropic layer formed from the liquid crystal composition of the present invention on a transparent support. An alignment film is preferably provided between the transparent support and the optically anisotropic layer. The optically anisotropic layer is obtained by adding other additives as necessary to the liquid crystal composition of the present invention, coating the composition on the alignment film, and then fixing the alignment in the liquid crystal state.

  The thickness of the optically anisotropic layer in the retardation plate of the present invention is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, and preferably 0.5 to 10 μm. Most preferred.

  The retardation plate of the present invention can be used for an elliptically polarizing plate in combination with a polarizing film. Furthermore, application to a transmissive, reflective, and transflective liquid crystal display device in combination with a polarizing film can contribute to an increase in the viewing angle of the device.

[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 liquid crystal composition of the present invention of the optically anisotropic layer provided on the alignment film can give a desired alignment, any layer may be used as the alignment film, but in the present invention, rubbing treatment or An alignment film formed by light irradiation is preferred. An alignment film formed by polymer rubbing treatment 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 the present invention, in particular, the method described in the liquid crystal manual (Maruzen Co., Ltd.) is used. Preferably it is done. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.05 to 3 μm.

(Rubbing density of alignment film)
Since there is a relationship between the rubbing density of the alignment film and the pretilt angle of the liquid crystal compound at the interface of the alignment film, increasing the rubbing density decreases the pretilt angle, and decreasing the rubbing density increases the pretilt angle. By changing the rubbing density of the film, the pretilt angle can be adjusted.
As a method for changing the rubbing density of the alignment film, a method described in “Liquid Crystal Handbook” edited by the Liquid Crystal Handbook Editorial Committee (Maruzen Co., Ltd., 2000) can be used. The rubbing density (L) is quantified by the 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.

[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 acylates (eg, cellulose diacetate, cellulose triacetate), norbornene-based polymers, poly (meth) acrylate ester films, etc., and many commercially available polymers are preferably used. It is possible. Among these, cellulose esters are preferable from the viewpoint of optical performance, and lower fatty acid esters of cellulose are more preferable. The lower fatty acid is a fatty acid having 6 or less carbon atoms, and the number of carbon atoms is preferably 2 (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, a polymer whose expression is lowered by modification of molecules described in WO 00/26705 can be used.

Hereinafter, cellulose acylate (particularly, cellulose triacetate) that is preferably used as the transparent support will be described in detail.
As the cellulose acylate, it is preferable to use cellulose acetate having an acetylation degree of 55.0 to 62.5%. In particular, the acetylation degree is preferably 57.0 to 62.0%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). The viscosity average polymerization degree (DP) of the cellulose ester is preferably 250 or more, and more preferably 290 or more. The cellulose ester used in the present invention preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

  In cellulose acylate, the hydroxyl groups at the 2nd, 3rd and 6th positions of cellulose are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6th hydroxyl group tends to be small. It is preferable that the substitution degree of the 6-position hydroxyl group of cellulose is larger than the 2-position and 3-position. The hydroxyl group at the 6-position with respect to the total substitution degree is preferably 30% or more and 40% or less and is preferably substituted with an acyl group, 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, Synthesis Example 2 described in paragraph Nos. 0048 to 0049, and paragraph numbers 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 acylate 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 acylates. The retardation increasing agent is preferably used in the range of 0.05 to 15 parts by mass, more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the cellulose acylate. Two or more aromatic compounds may be used in combination.
The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to the aromatic hydrocarbon ring.

The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring).
The aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable.

  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.

  Examples of the aromatic heterocycle 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 Rings, pyridazine rings, pyrimidine rings, pyrazine rings and 1,3,5-triazine rings are included.

  The number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, further preferably 2 to 8, and most preferably 2 to 6. . The bonding relationship between two aromatic rings can be classified into (a) when a condensed ring is formed, (b) when directly linked by a single bond, and (c) when linked via a linking group (for aromatic rings). , Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c). Such retardation increasing agents are 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). The above-mentioned retardation increasing agent may be added to the dope.
The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. The surface of the drum or band is preferably finished in a mirror state. As for casting and drying methods in the solvent casting method, U.S. Pat. No. 736892, JP-B Nos. 45-4554, 49-5614, JP-A-60-176834, No. 60-203430, and No. 62-1115035.

  The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 ° C. to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

It is also possible to form a film by casting two or more layers of dope using the prepared cellulose acylate solution (dope). The dope is cast on a drum or band and the solvent is evaporated to form a film. The dope before casting is preferably adjusted in concentration so that the solid content is 10 to 40%. The surface of the drum or band is preferably finished in a mirror state.
When casting a plurality of cellulose acylate solutions, a solution containing cellulose acylate is cast from a plurality of casting openings provided at intervals in the traveling direction of the support, and the film is laminated while laminating them. It may be produced. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. Alternatively, the cellulose acylate solution may be cast from two casting ports to form a film. For example, the methods described in JP-B-60-27562, JP-A-61-94724, JP-A-61-104813, JP-A-61-158413, and JP-A-6-134933 are used. Can do. Further, a cellulose acetate film casting method in which a flow of a high-viscosity cellulose acetate solution is wrapped with a low-viscosity cellulose acetate solution and the high-viscosity and low-viscosity cellulose acetate solutions are simultaneously extruded as described in JP-A-56-162617. A method may be used.

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

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

Degradation inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose acylate film. The deterioration inhibitors are described in JP-A-3-199201, JP-A-597073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared, and more preferably 0.01 to 0.2% by mass. When the addition amount is less than 0.01% by mass, the effect of the deterioration inhibitor is hardly recognized. When the addition amount exceeds 1% by mass, bleed-out (bleeding) of the deterioration preventing agent to the film surface may be observed.
As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. The ultraviolet ray preventing agent is described in JP-A-7-11056.

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

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

The surface energy of the cellulose acylate film is preferably 55 mN / m or more, and more preferably in the range of 60 to 75 mN / m.
The surface energy 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 acylate film used in the present invention, it is preferable to use a contact angle method. Specifically, two kinds of solutions having known surface energies are dropped on a cellulose acylate film, and at the intersection of the surface of the droplet and the surface of the film, the angle formed between 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 acylate 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.

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

  The polarizing film is laminated on the optically anisotropic layer side of the retardation plate. It is preferable to form a transparent protective film on the surface opposite to the side where the retardation film 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 retardation plate of the present invention, a liquid crystal display device with an enlarged viewing angle can be provided. TN mode liquid crystal cell retardation plates (optical compensation sheets) are described in JP-A-6-214116, US Pat. Nos. 5,583,679, 5,646,703, and German Patent 3,911,620A1. 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, liquid crystal cell retardation plates (optical compensation sheets) of various modes can be prepared with reference to the above-mentioned publications. The retardation plate of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Super Twisted Nematic), VA (Vertically Aligned), and HAN. It can be used for liquid crystal display devices of various display modes such as (Hybrid Aligned Nematic) mode.
The liquid crystal display device includes a liquid crystal cell, a polarizing element, and a phase difference plate (optical compensation sheet). A polarizing element generally comprises a polarizing film and a protective film. As the polarizing film and the protective film, those described for the elliptically polarized light can be used.

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

[Example 1]
[Preparation of thin film in which D-97 is uniformly oriented]
An aqueous solution of PVA-203 (manufactured by Kuraray Co., Ltd.) is applied on a glass substrate and dried at 100 ° C. for 3 minutes. The thickness of PVA-203 is 0.5 μm. The following coating solution is spin-coated on the substrate provided with the thin film of PVA-203, put in a thermostat at 80 ° C., and irradiated with 600 mJ ultraviolet rays after 5 minutes to fix the alignment state. When the alignment state is observed with a polarizing microscope after cooling to room temperature, it can be seen that the discotic liquid crystalline compound is homeotropically aligned without defects. The thickness of the liquid crystal compound layer is 3.2 μm.

(Coating solution)
-50 parts by mass of the liquid crystalline compound D-97-50 parts by mass of JD-5-0.2 parts by mass of the air interface alignment controller V- (1) below-Irgacure 907 (Nagase Sangyo Co., Ltd.) 3.0 parts by mass・ Diethyl thioxanthone 1.0 mass part ・ Methyl ethyl ketone 250 mass parts

[Comparative Example 1]
[Preparation of thin films in which conventional discotic liquid crystalline compounds are uniformly aligned]
The following coating solution was spin-coated on the substrate provided with the thin film of PVA-203, put in a thermostatic bath at 190 ° C., and irradiated with 600 mJ ultraviolet rays after 5 minutes to fix the alignment state. After cooling to room temperature and observing the alignment state with a polarizing microscope, it was found that the discotic liquid crystalline compound was homeotropically aligned without defects.
The thickness of the liquid crystal compound layer was 3.0 μm.

(Coating solution)
-The following liquid crystalline compound JD-1 100 parts by mass-Air interface alignment control agent V- (1) 0.2 parts by mass-Irgacure 907 (Nagase Sangyo Co., Ltd.) 3.0 parts by mass-Diethylthioxanthone 1.0 mass / Methyl ethyl ketone 250 parts by mass

[Comparison of Δn and wavelength dispersion]
The chromatic dispersion values (Re (478 nm) / Re (748 nm) of the thin films obtained in Examples and Comparative Example 1 were measured using KOBRA (manufactured by Oji Scientific Instruments Co., Ltd.) at an angle of 40 ° to 478 nm and 748 nm. It is obtained by measuring the foundation.
In addition, Δn is measured by using KOBRA (manufactured by Oji Scientific Instruments Co., Ltd.), changing the observation angle using a wavelength of 589 nm, measuring the retardation, assuming a refractive index ellipsoid model, and Designing Concepts of the It calculates | requires by calculating (DELTA) n * d by the method described in Discotic Negative Compensation Films SID98 DIGEST, and dividing by the film thickness (d) calculated | required separately. The results are shown in Table 1.

  From the results shown in Table 1 above, it was confirmed that the liquid crystal compound of the present invention had high Δn and low wavelength dispersion as compared with the conventional liquid crystal compound.

[Comparative Example 2]
The following compound JD-2 synthesized according to the method described in the literature (Kim, Bong Gi et al., Molecular Crystals and Liquid Crystals, 2001, Vol. 370, page 391) was converted into a 10 μm cell gap horizontal alignment cell (EHC) Manufactured by KSRP-10 / A107M1NSS (ZZ)) at 150 ° C. and homeotropically oriented at 130 ° C. Thereafter, the chromatic dispersion value obtained by the above method was 1.19.

[Comparative Example 3]
The following compound JD-3 was injected into a 10 μm cell gap horizontal alignment cell (manufactured by EHC; KSRP-10 / A107M1NSS (ZZ)) at 200 ° C. and homeotropically aligned at 190 ° C. Thereafter, the chromatic dispersion value obtained by the above method was 1.18.

  From the comparison of Comparative Example 2 and Comparative Example 3, the compound of the present invention has a smaller wavelength dispersion than JD-2, which has a skeleton close to that of the present invention, as well as JD-3, which is a non-polymerizable type of a conventional liquid crystalline compound. It was found to have a value.

Claims (3)

A liquid crystal composition containing at least one compound represented by the following general formula (DI).
General formula (DI)

(In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a carbon atom or a nitrogen atom, and R ¹¹ , R ¹² and R ¹³ each independently represent the following general formula (DI- A), the following general formula (DI-B), the following general formula (DI-C), the following general formula (DI-D), the following general formula (DI-E), or the following general formula (DI-F) However, two of R ¹¹ , R ¹² and R ¹³ are the same and the other one is different.
General formula (DI-A)

(In the general formula (DI-A), A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ , A ¹⁶ each independently represents a carbon atom or a nitrogen atom, and X ¹ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ¹¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ¹² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is (It may be replaced by a substituent. Q ¹¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-B)

(In the general formula (DI-B), A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ and A ²⁶ each independently represents a carbon atom or a nitrogen atom, and X ² represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ²¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — Represents CH ₂ —, —CH═CH— or —C≡C—, and L ²² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is (It may be replaced by a substituent. Q ²¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-C)

(In the general formula (DI-C), A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ , A ³⁶ each independently represents a carbon atom or a nitrogen atom, and X ³ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ³¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ³² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and a divalent group, and the above group is a group containing a hydrogen atom The hydrogen atom may be replaced by a substituent, and Q ³¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-D)

(In the general formula (DI-D), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ each independently represents a carbon atom or a nitrogen atom, and X ⁴ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ⁴¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ⁴² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. A divalent linking group selected from the group consisting of-, -CH = CH- and -C≡C-, and a divalent group consisting of a combination thereof, and the linking group is a group containing a hydrogen atom The hydrogen atom may be replaced with a substituent, and Q ⁴¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-E)

(In the general formula (DI-E), A ⁵¹ , A ⁵² , A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ each independently represents a carbon atom or a nitrogen atom, and X ⁵ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ⁵¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ⁵² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. -, -CH = CH- and -C≡C-, and a divalent linking group selected from the group consisting of a divalent group consisting of a combination thereof, wherein the divalent group is a group containing a hydrogen atom. In some cases, the hydrogen atom may be replaced by a substituent, and Q ⁵¹ each independently represents a polymerizable group or a hydrogen atom.)
General formula (DI-F)

(In the general formula (DI-F), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ , A ⁶⁶ each independently represents a carbon atom or a nitrogen atom, and X ⁶ represents an oxygen atom or a sulfur atom. Represents a carbon atom or a nitrogen atom, and L ⁶¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, — CH ₂ —, —CH═CH— or —C≡C— is represented, and L ⁶² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH _2. Represents a divalent linking group selected from the group consisting of —, —CH═CH— and —C≡C—, and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom is (It may be replaced by a substituent. Q ⁶¹ each independently represents a polymerizable group or a hydrogen atom.)   A retardation plate having at least one optically anisotropic layer on a transparent support, wherein the optically anisotropic layer is an optically anisotropic layer formed from the liquid crystal composition according to claim 1. A retardation plate characterized by being.   An elliptically polarizing plate comprising the retardation plate according to claim 2 and a polarizing film.