JP4686317B2 - Liquid crystalline composition, retardation plate, and elliptically polarizing plate - Google Patents

Description

  The present invention relates to a liquid crystal composition that is very useful for producing a retardation plate and the like, and more particularly, to a liquid crystal composition that exhibits a biaxial liquid crystal phase. Moreover, it is related with the phase difference plate which has an optically anisotropic layer containing this liquid crystalline composition, and an elliptically polarizing plate.

  A biaxial film in which the refractive index in the triaxial direction is controlled is useful in the optical field using polarized light. In particular, in the field of liquid crystal displays, such a film capable of finely controlling polarization is highly important. When producing such an optical biaxial film, a method of obtaining a film obtained from a polymer by biaxial stretching is common (see, for example, Patent Document 1). In the case of obtaining a biaxial film by biaxial stretching, the refractive index in the triaxial direction can be controlled by the stretching magnification, so that the desired refractive index can be controlled relatively easily.

  A biaxial film using a biaxial liquid crystal has the merit that the film thickness can be made very thin compared with the biaxially stretched film that has been used so far. The use of liquid crystal is a useful means for making the device thinner and lighter. In addition, a film using stretching has a problem that the dimensional stability is poor and the optical performance is easily changed by wet heat or the like. However, if a polymerizable biaxial liquid crystal can be used, May also solve other problems.

  However, when a biaxial film is produced using a biaxial liquid crystal, there arises a problem that the refractive index in the triaxial direction cannot be arbitrarily controlled. This is because the refractive index in the triaxial direction of the obtained biaxial film is almost uniquely determined by the refractive index in the triaxial direction of the compound (biaxial liquid crystalline compound) that expresses the biaxial liquid crystal phase. Because it is decided. That is, there is only a method of synthesizing a biaxial liquid crystalline compound having a desired refractive index in order to set the refractive index in three directions of the biaxial film to a desired refractive index. However, since the number of biaxial liquid crystalline compounds is very small compared with a compound that exhibits a uniaxial liquid crystal phase (uniaxial liquid crystalline compound), it is not possible to arbitrarily control the refractive index in three directions. It was very difficult.

In order to avoid such a problem, a proposal has been made to develop a biaxial liquid crystal phase by mixing a rod-like liquid crystal and a disk-like liquid crystal (for example, see Non-Patent Document 1). If this method is used, the control of the refractive index in the triaxial direction is very simple because it can be performed by changing the mixing ratio of the rod-like liquid crystal and the disk-like liquid crystal. However, in response to such a proposal, attempts have been made to develop a biaxial liquid crystal phase by mixing a rod-like liquid crystal and a disc-like liquid crystal (for example, see Non-Patent Document 2). Since the compatibility of the liquid crystal is not good, there is a problem that in the mixing of these two types of liquid crystals, the liquid crystal properties are lost or the two types of liquid crystal phases cause phase separation. The biaxial liquid crystal phase could not be expressed.
JP-A-2-264905 Y. Rabin et al., Mol. Cry. Liq. Cry., 1982, 89, 67 R. Pratiba, NV Madhususana, Mol. Cry. Liq. Cry., 1985, Volume 1, p. 111

  In view of the circumstances as described above, an object of the present invention is a liquid crystalline composition obtained by mixing a plurality of liquid crystalline compositions expressing different liquid crystal phases, and a liquid crystalline composition capable of expressing a biaxial liquid crystal phase. To provide things. Another object of the present invention is to provide a retardation plate and an elliptically polarizing plate using these liquid crystalline compositions.

The above problem is solved by the following means.
(1) A liquid crystalline composition comprising a liquid crystalline composition R expressing a liquid crystal phase having a positive birefringence and a liquid crystalline composition D expressing a liquid crystal phase having a negative birefringence, The liquid crystalline composition D comprises a liquid crystalline compound represented by the following general formula (DI).
General formula (DI)

In formula (DI), Y ₁₁ , Y ₁₂ and Y ₁₃ each independently represent a methine or nitrogen atom. L ₁ , L ₂ and L ₃ each independently represents a single bond or a divalent linking group. H ₁ , H ₂ , and H ₃ each independently represent the following general formula (DI-A) or the following general formula (DI-B).
General formula (DI-A)

[In General Formula (DI-A), YA ₁ and YA ₂ each independently represent a methine group or a nitrogen atom. XA represents an oxygen atom or a sulfur atom. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
General formula (DI-B)

[In General Formula (DI-B), YB ₁ and YB ₂ each independently represent a methine group or a nitrogen atom. XB represents an oxygen atom or a sulfur atom. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
In general formula (DI), R < ₁ >, R < ₂ >, R < ₃ > represents the following general formula (DI-R) each independently.

General formula (DI-R)
*-(-L ₂₁ -divalent cyclic group) n ₁ -L ₂₂ -L ₂₃ -Q ₁

[In General Formula (DI-R), * represents a position bonded to H _{1 to} H ₃ in General Formula (DI). L ₂₁ represents a single bond or a divalent linking group. The divalent cyclic group represents a divalent linking group having at least one cyclic structure. n ₁ represents 0 to 4 integer. L ₂₂ represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —N (R ₇ ) —, * —CH ₂ —. , * —CH═CH—, * —C≡C—. (Here, * represents a position bonded to a divalent cyclic group in the general formula (DI-R), and R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.) L ₂₃ Is a divalent linking group selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—. Represents. Q ₁ each independently represents a polymerizable group or a hydrogen atom. ]
(2) The liquid crystal compound according to (1), wherein the liquid crystal compound represented by the general formula (DI) contained in the liquid crystal composition D is a liquid crystal compound represented by the following general formula (DII) Composition.
Formula (DII)

In the general formula (DII), Y ₃₁ , Y ₃₂ and Y ₃₃ each independently represents a methine or nitrogen atom. R ₃₁ , R ₃₂ and R ₃₃ are each independently represented by the following general formula (DII-R).
General formula (DII-R)

In the general formula (DII-R), A ₃₁ and A ₃₂ each independently represents a methine group or a nitrogen atom. X ₃ represents an oxygen atom or a sulfur atom. The divalent cyclic group represents a divalent linking group having a 6-membered cyclic structure. n ₃ represents 1 to 3 integer. L ₃₁ is * —O—, * —O—CO—, * —CO—O—, —O—CO—O—, * —S—, * —N (R ₇ ) —, * —CH ₂ —, * —CH═CH—, * —C≡C— is represented. (Here, * represents a position bonded to a divalent cyclic group in the general formula (DII-R). R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.) L ₃₂ Is a divalent linking group selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—. Represents. Q ₃ each independently represents a polymerizable group or a hydrogen atom.
(3) The liquid crystal phase having positive birefringence is a nematic phase, and the liquid crystal phase having negative birefringence is a discotic nematic phase. Liquid crystalline composition.
(4) Any of the above (1) to (3), wherein the liquid crystalline composition containing the liquid crystalline composition R and the liquid crystalline composition D exhibits a liquid crystal phase at 20 ° C. to 300 ° C. The liquid crystalline composition according to claim 1.
(5) The liquid crystal phase expressed by the liquid crystal composition containing the liquid crystal composition R and the liquid crystal composition D satisfies the following formula (III): The liquid crystalline composition according to any one of the above.
Formula (III) 1.1 ≦ (nx−nz) / (nx−ny) ≦ 20
In the formula (III), nx, ny, and nz represent refractive indexes in three directions orthogonal to each other in the liquid crystal phase. However, the largest refractive index is nx and the smallest refractive index is nz.

(6) A retardation plate having at least one optically anisotropic layer on a transparent support, wherein the optically anisotropic layer is described in any one of (1) to (5) above. A phase difference plate, which is an optically anisotropic layer formed from a liquid crystalline composition.
(7) An elliptically polarizing plate comprising the retardation plate according to (6) and a polarizing film.
The present invention relates to the above (1) to (7), but other matters are also described below for reference.

According to the present invention, a liquid crystal composition capable of expressing a biaxial liquid crystal phase can be provided by mixing a plurality of liquid crystal compositions expressing different liquid crystal phases. By mixing a liquid crystal composition that expresses a liquid crystal phase having positive birefringence and a liquid crystal composition that expresses a liquid crystal phase having negative birefringence as different liquid crystal phases, biaxiality is obtained. A liquid crystalline composition exhibiting a liquid crystal phase is obtained. Further, the triaxial direction of the liquid crystal phase that is expressed by the mixing ratio of the liquid crystal composition that exhibits the liquid crystal phase having positive birefringence and the liquid crystal composition that exhibits the liquid crystal phase having negative birefringence. Can be controlled.
Furthermore, according to the present invention, it is possible to provide a retardation plate having an optically anisotropic layer formed of these liquid crystal compositions and having a refractive index controlled to a desired value. With the retardation plate, it is possible to provide an elliptically polarizing plate whose polarization can be finely controlled and a liquid crystal display device having a wide viewing angle.

The liquid crystal composition of the present invention is obtained by mixing a liquid crystal composition R that exhibits a liquid crystal phase having positive birefringence and a liquid crystal composition D that exhibits a liquid crystal phase having negative birefringence. An axial liquid crystal phase is developed.
Here, the liquid crystal phase having positive birefringence is a liquid crystal phase satisfying the following formula (I), and the liquid crystal phase having negative birefringence is a liquid crystal phase satisfying the following formula (II). Point to.

Formula (I) 1.0 ≦ (nx−nz) / (nx−ny) <1.1
Formula (II) 20 <(nx−nz) / (nx−ny) ≦ ∞

In the formulas (I) and (II), nx, ny, and nz represent refractive indexes in three directions orthogonal to each liquid crystal phase that the liquid crystal composition R and the liquid crystal composition D respectively express. However, in each liquid crystal phase, the largest refractive index is nx and the smallest refractive index is nz.
As a method for obtaining the refractive index in the three directions of the liquid crystal phase, for example, a report by Sakai (“Method of analyzing birefringence of a film using an automatic birefringence meter” Plastics, Vol. 51, No. 3, 57 (2000) ) Can be helpful.

In the present invention, the liquid crystal composition R and the liquid crystal composition D are liquid crystal compositions each containing one or more liquid crystal compounds, and include the case of only one liquid crystal compound. When two or more kinds of liquid crystalline compounds are included, for example, a polymerizable liquid crystalline compound and a non-polymerizable liquid crystalline compound can be used in combination. Further, a low molecular liquid crystalline compound and a high molecular liquid crystalline compound can be used in combination.
In addition to the liquid crystalline compound, an additive (for example, an air interface alignment controller, a repellency inhibitor, a polymerization initiator, a polymerizable monomer, a solvent, etc.) that can be added in forming the optically anisotropic layer described later is included. But you can. These additives may be added when the liquid crystal composition R and the liquid crystal composition D are mixed and formed.

[Liquid Crystalline Composition R Expressing Liquid Crystal Phase that satisfies Formula (I)]
Examples of the liquid crystal phase satisfying the formula (I) include a nematic phase, a smectic A phase, and a smectic C phase in which a liquid crystalline compound having a rod-like or plate-like shape is developed. Since such a liquid crystal phase has a relationship of nx> ny = nz, it is a uniaxial liquid crystal phase having positive birefringence. Details are described in Chapter 2 of the Liquid Crystal Handbook (issued in Maruzen Co., Ltd. 2000), and in the present invention, the nematic phase is particularly preferable as the liquid crystal phase satisfying the formula (I).

On the other hand, there is also known a liquid crystal phase in which it is difficult to determine whether it is a uniaxial liquid crystal phase or a biaxial liquid crystal phase. For example, D.D. Demus, J. et al. Goodby et al. [Handbook of
Liquid Crystals Vol. 2B: Low Molecular Weight Liquid Crystals II, pp 933-943: published by WILEY-VCH] can be said to be a difficult liquid crystal phase. The liquid crystal phase satisfying the mathematical formula (I) includes such a liquid crystal phase in which it is difficult to determine uniaxiality and biaxiality (when (nx−nz) / (nx−ny) is other than 1).

  The determination of the uniaxiality of the liquid crystal phase and the positive / negative determination of birefringence can be performed by conoscopic observation using a polarizing microscope in a state where the liquid crystalline compound is homeotropically aligned. This determination can be made according to the criteria described in Chapter 3 of Seitaro Tsuboi, "Polarizing Microscope" (Iwanami Shoten, 1959).

  The liquid crystalline compound used in the liquid crystalline composition R that exhibits the liquid crystal phase satisfying the mathematical formula (I) may be a low molecular liquid crystalline compound or a high molecular liquid crystalline compound, but the liquid crystalline composition R and the mathematical formula (II From the viewpoint of compatibility with the liquid crystal composition D that exhibits a liquid crystal phase satisfying the above), a low molecular liquid crystal compound is preferred.

  As the liquid crystalline compound used in the liquid crystalline composition R that expresses the liquid crystal phase satisfying the mathematical formula (I), a liquid crystalline compound that expresses a uniaxial liquid crystal phase having positive birefringence is preferable. For example, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, Mention may be made of tolans and alkenylcyclohexylbenzonitriles.

The liquid crystal compound used in the liquid crystal composition R that exhibits the liquid crystal phase satisfying the mathematical formula (I) is in mutual contact with the liquid crystal compound that is used in the liquid crystal composition D that exhibits the liquid crystal phase satisfying the mathematical formula (II). It preferably has a substituent capable of acting (for example, a hydrogen bond or dipolar interaction) or a substituent (for example, a polymerizable group) capable of forming a covalent bond. By having such a substituent, when the liquid crystal composition R and the liquid crystal composition D are mixed, the compatibility between the compositions is improved, and each phase composed of each composition is compatible with each other. It is possible to avoid separation. For the same reason, the liquid crystal compound used for the liquid crystal composition D preferably has a similar group.

  The liquid crystalline compound used in the liquid crystalline composition R that exhibits the liquid crystal phase satisfying the formula (I) preferably has a polymerizable group, and more preferably has a polymerizable group at the end of the compound molecule. Having a polymerizable group, in addition to preventing phase separation from the liquid crystalline composition D as described above, changes in the phase difference due to heat or the like when used for a phase difference plate or the like with the liquid crystalline composition of the present invention. Can be prevented, which is preferable.

As the uniaxial liquid crystalline compound having a positive birefringence having a polymerizable group, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, JP-A-2001-328773, etc. The described compounds can be used.
Below, a preferable example is shown as a polymeric group which the liquid crystalline compound used for the liquid crystalline composition R has.

  Among the polymerizable groups, unsaturated polymerizable groups (Q1 to Q7), epoxy groups (Q8) or aziridinyl groups (Q9) are more preferable, unsaturated polymerizable groups (Q1 to Q7) are more preferable, and ethylenic properties are preferred. Unsaturated polymerizable groups (Q1 to Q6) are most preferred.

  The shape of the liquid crystal compound used in the liquid crystal composition R that exhibits the liquid crystal phase satisfying the mathematical formula (I) is not particularly limited, and may be a rod shape, a plate shape, or other shapes. Among them, the plate-like property is compatible with the liquid crystalline composition D that exhibits the liquid crystal phase satisfying the formula (II), and the liquid crystalline composition of the present invention easily develops the biaxial liquid crystal phase. From this point, it is preferable.

  The above-mentioned liquid crystal compound is “plate-like” when the compound has at least two core parts exhibiting liquid crystallinity alone, and is a planar, positive birefringence in which the core parts are connected by a covalent bond Means a uniaxial liquid crystal compound having a property. For example, in the exemplary compound (m-1) of the present invention described later, the RO-Ph-OR (Ph: benzene ring) portion corresponds to a core portion exhibiting liquid crystallinity alone. The RO-Ph-OR moiety is linked by a covalent bond to give the exemplified compound (m-1).

  More specifically, that the liquid crystal compound is “plate-like” means the following. That is, when the longest side of the rectangular parallelepiped inscribed in the stabilization structure of the liquid crystal compound and having the smallest volume is L1, the middle side is Lm, and the shortest side is Ls, the liquid crystal compound is “plate-like”. Is the case where Ll / Lm> 1.1 and Lm / Ls> 1.5. The most stabilized structure of the liquid crystal compound can be obtained by MOPAC (semi-empirical molecular orbital calculation program), and specifically, MOPAC AM1 method (Software used: WinMOPAC, distributor: Fujitsu Limited) is used. That's fine.

  In the present invention, the plate-like shape of the liquid crystal compound used in the liquid crystal composition R that exhibits the liquid crystal phase satisfying the formula (I) may further satisfy both the formula (IV) and the formula (V). preferable.

    Formula (IV) 1.2 <Ll / Lm <10

    Formula (V) 2.0 <Lm / Ls <10

As a liquid crystalline compound having a plate-like shape, Mol. Cry. Liq. Cry. , 323, 231 (1998), "Dyes and Drugs" Vol. 42, No. 4, 85 (1997), "Dyes and Drugs" Vol. 42, No. 3, p. 68 (1997) The compounds described in the above, and compounds in which a polymerizable group is introduced into the described compound can be used.
Specific examples of the liquid crystal compound having a plate-like shape and preferable for use in the liquid crystal composition R are shown below, but the present invention is not limited thereto.

The liquid crystalline compound having a plate shape is preferably a liquid crystalline compound represented by the following general formula (RI) in addition to the above specific examples.
General formula (RI)

In the formula (RI), L _A represents —≡— or —≡-≡—.
X _1A and X _2A are each independently a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, a hydroxyl group, a cyano group, a nitro group, an alkyl group, an alkyloxy group, an acyl group, or an acyloxy group. Represents an alkyloxycarbonyl group. In particular, a halogen atom, a carboxyl group, a hydroxyl group, a cyano group, an alkyl group having 1 to 10 carbon atoms, and an alkyloxy group having 1 to 10 carbon atoms are preferable, and a halogen atom and a cyano group are most preferable.
n ₁ and n ₂ each independently represents an integer of 0 to 3. n ₁ and n ₂ are each preferably 0 to 2. In particular, (n ₁ + n ₂ ) is preferably 1 to 4.
R _1A , R _2A , R _3A and R _4A each independently represent the following formula (R-IA).

Formula (R-IA)
*-(L _1A -Divalent cyclic group) p-L _2A -Divalent chain group-Q _1A

  In the formula (R-IA), * represents a position bonded to the benzene ring in the formula (RI).

L _1A is a single bond or a divalent linking group. When L _1A is a divalent linking group, —O—, —S—, —C (═O) —, —NR ₇ —, —CH ₂ —, —CH═CH—, —C≡C—, and It is preferably a divalent linking group selected from the group consisting of those combinations. R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and preferably a methyl group, an ethyl group, or a hydrogen atom. More preferably, it is a hydrogen atom.

L _1A represents a single bond, and, * - O-CO -, * - CO-O -, * - CH 2 -CH 2 -, * - O-CH 2 -, * - CH 2 -O -, * - CO —CH ₂ —CH ₂ —, * —CH═CH—, * —C≡C— (wherein * represents * in the formula (R—IA)) is preferable, and in particular, a single bond, * —O— CO- is preferred.

L _2A is a single bond or a divalent linking group. When L _2A is a divalent linking group, it may be a divalent linking group selected from the group consisting of —O—, —S—, —C (═O) —, —NR ₇ —, and combinations thereof. preferable. R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and preferably a methyl group, an ethyl group, or a hydrogen atom. More preferably, it is a hydrogen atom.

L _2A represents a single bond, and * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —CO—, * —S—, * —NR ₇ —. (Where * represents a position linked to a divalent cyclic group in the general formula (R-IA)), particularly a single bond, * -O-, * -O-CO-, * -CO. -O- and * -O-CO-O- are preferable.

  A divalent cyclic group is a divalent linking group having at least one cyclic structure. The ring in the divalent cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. . The ring in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring, a pyrimidine ring, a thiophene ring, a 1,3-dioxane ring, and a 1,3-dithiane ring.

  Of the divalent cyclic groups, 1,4-phenylene is preferred as the cyclic group having a benzene ring. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl. As the cyclic group having a thiophene ring, thiophene-2,5-diyl is preferable. As the cyclic group having a 1,3-dioxane ring, 1,3-dioxylene-2,5-diyl is preferable. As the skeleton having a 1,3-dithiane ring, 1,3-dithianylene-2,5-diyl is preferable.

  The divalent cyclic group is preferably 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or 1,3-dioxylene-2,5-diyl. Further, 1,4-phenylene, 1,4-cyclohexylene and 1,3-dioxylene-2,5-diyl are preferable, and 1,4-phenylene is particularly preferable.

  The divalent cyclic group may have a substituent, and as the substituent, a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group having 1 to 8 carbon atoms, An alkyloxy group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, an acyloxy group having 2 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a nitro group, or a cyano group is preferable. In particular, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, and the number of carbon atoms A 2-4 alkoxycarbonyl group or a cyano group is preferable.

  The divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. Among these, an alkylene group, a substituted alkylene group, an alkenylene group, or a substituted alkenylene group is preferable, and an alkylene group or an alkenylene group is more preferable.

The alkylene group as the chain group may have a branch. Further, —CH ₂ — in the alkylene group may be replaced by, for example, —O— or —S—. The alkylene group preferably has 1 to 16 carbon atoms, more preferably 2 to 14 carbon atoms, and most preferably 2 to 12 carbon atoms. The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include an alkyl group and a halogen atom.

The alkenylene group as a divalent chain group may have a substituted or unsubstituted alkylene group in the main chain, or may have a branch. Also during alkenylene group -CH ₂ - when there is, -CH ₂ -, for example -O -, - may be replaced by S-. The alkenylene group preferably has 2 to 16 carbon atoms, more preferably 2 to 14 carbon atoms, and most preferably 2 to 12 carbon atoms. The alkenylene part of the substituted alkenylene group is the same as the above alkenylene group. Examples of the substituent include an alkyl group and a halogen atom.

The alkynylene group as a divalent chain group may have a substituted or unsubstituted alkylene group in the main chain, or may have a branch. Also during alkynylene group -CH ₂ - when there is, -CH ₂ -, for example -O -, - may be replaced by S-. The alkynylene group preferably has 2 to 16 carbon atoms, more preferably 2 to 14 carbon atoms, and most preferably 2 to 12 carbon atoms. The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent include an alkyl group and a halogen atom.

  Specific examples of the divalent chain group include ethylene, trimethylene, tetramethylene, 1-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-butenylene and Examples include 2-butynylene.

  The divalent chain group is preferably a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 16 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 16 carbon atoms. In particular, a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms is preferable. As the substituent of the chain group, an alkyl group having 1 to 5 carbon atoms or a halogen atom is preferable. Most preferably, it is an unsubstituted alkylene group having 1 to 12 carbon atoms.

Q _1A represents a polymerizable group. Examples of polymerizable groups are shown below.

Among the above, q1 to q10 are preferable, and q1 to q8 are more preferable.
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. R is preferably a hydrogen atom or a methyl group.
Among the above (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is most preferable.

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

  p represents an integer of 0 to 3. 1 or 2 is particularly preferable, and 1 is most preferable.

A compound in which the benzene ring methine in the general formula (RI) is replaced with a nitrogen atom can also be used.
Although the specific example of a compound represented by general formula (RI) below is shown, this invention is not limited to these.

[Liquid Crystalline Composition D Expressing Liquid Crystal Phase Satisfying Formula (II)]
Examples of the liquid crystal phase satisfying the formula (II) include a discotic nematic phase, a columnar phase, and a columnar lamellar phase in which a liquid crystalline compound having a disk shape is developed. In the present invention, the discotic nematic phase is particularly preferable as the liquid crystal phase satisfying the formula (II).
On the other hand, there is also known a liquid crystal phase in which it is difficult to determine whether it is a uniaxial liquid crystal phase or a biaxial liquid crystal phase. For example, D.D. Demus, J. et al. Goodby et al. [Handbook of
Liquid Crystals Vol. 2B: Low Molecular Weight Liquid Crystals II, pp 933-943: published by WILEY-VCH] can be said to be a difficult liquid crystal phase. The liquid crystal phase satisfying the formula (II) includes a liquid crystal phase in which it is difficult to determine such uniaxiality and biaxiality.

  The liquid crystalline compound used for the liquid crystalline composition D that exhibits the liquid crystal phase satisfying the mathematical formula (II) may be a low-molecular liquid crystalline compound or a high-molecular liquid crystalline compound, but the liquid crystalline composition D and the mathematical formula (I From the viewpoint of compatibility with the liquid crystal composition R that exhibits a liquid crystal phase satisfying the above), a low molecular liquid crystal compound is preferred.

  As the liquid crystalline composition D that exhibits a liquid crystal phase satisfying the formula (II) used in the present invention, various documents (C. Destradedeal., Mol. Crys. Liq. Crys., 71, 111 (1981)). Chemistry of the Chemical Society of Japan, Quarterly Chemical Review, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10, Section 2 (1994), B. Kohneetal., Angew. Chem. Soc. Chem. (1985), J. Zhanget et al., J. Am. Chem. Soc., 116, 2655 (1994)).

The liquid crystalline compound used for the liquid crystalline composition D that exhibits a liquid crystal phase satisfying the formula (II) preferably has a polymerizable group, and more preferably has a polymerizable group at the end of the molecule of the compound. Having a polymerizable group, in addition to preventing phase separation from the liquid crystalline composition R as described above, changes in the phase difference due to heat or the like when used for a phase difference plate or the like with the liquid crystalline composition of the present invention. Is preferable.
The liquid crystalline composition of the present invention contains a compound represented by the following general formula (DI) in the liquid crystalline composition D.
General formula (DI)

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

When Y ₁₁ , Y ₁₂ , and Y ₁₃ are methine, the methine may have a substituent. Examples of methine substituents include alkyl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, acylamino groups, alkoxycarbonylamino groups, alkylthio groups, arylthio groups, halogen atoms, and cyano groups. be able to. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number of Most preferred are 2 to 12 alkoxycarbonyl groups, 2 to 12 acyloxy groups, halogen atoms and cyano groups.

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

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

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

Of the divalent cyclic groups represented by L ₁ , L ₂ and L ₃ , 1,4-phenylene is preferred as the cyclic group having a benzene ring. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.

The divalent cyclic group represented by L ₁ , L ₂ and L ₃ may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, carbon A halogen-substituted alkyl group having 1 to 16 atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, and 2 carbon atoms And 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 an acylamino group having 2 to 16 carbon atoms.

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

To H _1, H _2, H ₃ each independently represent the following general formula (DI-A) or the following general formula (DI-B).
General formula (DI-A)

In the general formula (DI-A), YA ₁ and YA ₂ each independently represents a methine or a nitrogen atom. As YA ₁ and YA ₂ , at least one is preferably a nitrogen atom, and most preferably both are nitrogen atoms. XA represents an oxygen atom, a sulfur atom, methylene, or imino. XA is most preferably an oxygen atom. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded.
General formula (DI-B)

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

R ₁ , R ₂ and R ₃ each independently represent the following general formula (DI-R).

General formula (DI-R)
*-(-L ₂₁ -divalent cyclic group) n ₁ -L ₂₂ -L ₂₃ -Q ₁

In the general formula (DI-R), * represents a position bonded to H _{1 to} H ₃ in the general formula (DI).

L ₂₁ is a single bond or a divalent linking group. When L ₂₁ is a divalent linking group, it consists of —O—, —S—, —C (═O) —, —NR ₇ —, —CH═CH—, —C≡C—, and combinations thereof. A divalent linking group selected from the group is preferred. R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and preferably a methyl group, an ethyl group, or a hydrogen atom. More preferably, it is a hydrogen atom.

L ₂₁ represents a single bond, and ** — O—CO—, ** — CO—O—, ** — CH═CH—, ** — C≡C— (where ** represents a general formula (DI indicates the left side of L ₂₁ in -R)) are preferred. A single bond is particularly preferable.

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

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

  The divalent cyclic group may have a substituent. Examples of substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, alkyl groups having 1 to 16 carbon atoms, and alkenyl groups having 2 to 16 carbon atoms. An alkynyl group having 2 to 16 carbon atoms, a halogen-substituted alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, the number of carbon atoms Is 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 the number of carbon atoms Includes 2 to 16 acylamino groups. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and a halogen-substituted alkyl group having 1 to 6 carbon atoms are preferable, and further, a halogen atom or a carbon atom An alkyl group having 1 to 4 carbon atoms and a halogen-substituted alkyl group having 1 to 4 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are particularly preferable.

n ₁ represents 0 to 4 integer. n ₁ is preferably an integer of 1 to 3, and particularly preferably 1 or 2.

L ₂₂ is, * - O -, * - O-CO -, * - CO-O -, * - O-CO-O -, * - S -, * - NR 7 -, * - CH 2 -, * -CH = CH-, * -C≡C-. (Here, * represents a position bonded to a divalent cyclic group in the general formula (DI-R).) Preferably, * -O-, * -O-CO-, * -CO-O-, * —O—CO—O—, * —CH ₂ —, * —CH═CH—, * —C≡C—, in particular, * —O—, * —O—CO—, * —O—CO. -O -, * - CH ₂ - is preferred. R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and preferably a methyl group, an ethyl group, or a hydrogen atom. More preferably, it is a hydrogen atom.

L ₂₃ is a divalent group selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—. The linking group of Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be replaced with other substituents. Examples of other substituents include halogen atoms, cyano groups, nitro groups, alkyl groups having 1 to 6 carbon atoms, halogen-substituted alkyl groups having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Alkoxy group, acyl group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group , An alkyl-substituted carbamoyl group having 2 to 6 carbon atoms and an acylamino group having 2 to 6 carbon atoms. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable.

L ₂₃ preferably comprises a combination of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—. L ₂₃ preferably contains 1 to 20 carbon atoms, and particularly preferably 2 to 14 carbon atoms. Further, L ₂₃ preferably contains 1 to 16 —CH ₂ —, and particularly preferably ₂ to 12 —CH ₂ —.

Q ₁ is independently a polymerizable group or a hydrogen atom. When the liquid crystalline 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 ₁ is preferably a polymerizable group. The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of 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. R is preferably a hydrogen atom or a methyl group.
Among the above (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is most preferable.

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

As the liquid crystal compound contained in the liquid crystal composition D of the present invention, a compound represented by the following general formula (DII) is preferable.
Formula (DII)

In the general formula (DII), Y ₃₁ , Y ₃₂ and Y ₃₃ are the same as the definitions of Y ₁₁ , Y ₁₂ and Y _{13 in} the general formula (DI).

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

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

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

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

  The divalent cyclic group may have a substituent. Examples of substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, alkyl groups having 1 to 16 carbon atoms, and alkenyl groups having 2 to 16 carbon atoms. An alkynyl group having 2 to 16 carbon atoms, a halogen-substituted alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, the number of carbon atoms Is 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 the number of carbon atoms Includes 2 to 16 acylamino groups. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and a halogen-substituted alkyl group having 1 to 6 carbon atoms are preferable, and further, a halogen atom or a carbon atom An alkyl group having 1 to 4 carbon atoms and a halogen-substituted alkyl group having 1 to 4 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are particularly preferable.

N < ₃ > in general formula (DII-R) represents 1-3 integers. n ₃ is preferably 1 or 2.

L ₃₁ in the general formula (DII-R) is the same as the definition of L _{22 in} the general formula (DI-R).

L ₃₂ in the general formula (DII-R) is the same as the definition of L _{23 in} the general formula (DI-R).

Q ₃ in the general formula (DII-R) is the same as defined for Q _{1 in} the general formula (DI-R).

  Two or more kinds of discotic liquid crystal compounds may be used in combination as the compound having a disk shape. For example, a molecule having a polymerizable group (Q) and a molecule not having it may be used in combination.

  Examples of the liquid crystal phase expressed by the compound represented by the general formula (DI) and the liquid crystalline composition containing the compound include those listed as the liquid crystal phase satisfying the above-described formula (II). Among these, a columnar phase or a discotic nematic phase is preferable, and a discotic nematic phase is particularly preferable. The liquid crystal phase is preferably expressed in the range of 30 to 300 ° C, and more preferably expressed in the range of 50 to 250 ° C.

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

[Liquid Crystalline Composition Containing Liquid Crystalline Composition R and Liquid Crystalline Composition D]
The liquid crystalline composition of the present invention contains a liquid crystalline composition R that exhibits a liquid crystal phase that satisfies Formula (I) and a liquid crystalline composition D that exhibits a liquid crystal phase that satisfies Formula (II). In a state where the product R and the liquid crystal composition D are mixed, it is preferable that a liquid crystal phase is exhibited at any mixing ratio.
In the present invention, the expression of a liquid crystal phase at any mixing ratio in a state where the liquid crystal composition R and the liquid crystal composition D are mixed means that the liquid crystal composition R and the liquid crystal composition D are mixed. Regardless of the ratio, it means that the phases are mixed without phase separation, and the liquid crystal phase is expressed in that state. Therefore, for example, as described in R. Pratiba et al. (Molecular Crystals and Liquid Crystals, 1985, Vol. 1, p. 111), the liquid crystal phase is separated in a state where the liquid crystal composition R and the liquid crystal composition D are phase-separated. When expressed, it is excluded from the present invention.

  The liquid crystal composition of the present invention including the liquid crystal composition R and the liquid crystal composition D is not mixed with the liquid crystal composition R and the liquid crystal composition D, and the liquid crystal phase is in a mixed state. Is proved that a liquid crystal composition that exhibits a liquid crystal phase satisfying formula (I) and a liquid crystal composition that exhibits a liquid crystal phase satisfying formula (II) (for example, liquid crystal handbook (Maruzen) (Published in 2000), described in Chapter 2, page 156, etc.). That is, it can be performed by observing the presence or absence of liquid crystallinity in a region where the two liquid crystalline compositions are mixed together under a polarizing microscope. If liquid crystallinity can be observed in the entire region in the contact test, it can be said that liquid crystallinity can be expressed regardless of the mixing ratio.

  The liquid crystal composition of the present invention including the liquid crystal composition R and the liquid crystal composition D has a liquid crystal phase in the range of 20 ° C. to 300 ° C. in a state where the liquid crystal composition R and the liquid crystal composition D are mixed. It is preferable to express in 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, for example, 298). ° C to 310 ° C). The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.

  The liquid crystalline composition of the present invention including the liquid crystalline composition R and the liquid crystalline composition D is preferably a liquid crystalline composition that exhibits an optically biaxial liquid crystal phase. The biaxial liquid crystal phase is a liquid crystal phase having different refractive indexes nx, ny, and nz in the triaxial direction and satisfying a relationship of nx> ny> nz, for example.

In the liquid crystal composition of the present invention including the liquid crystal composition R and the liquid crystal composition D, the mixing ratio of the liquid crystal composition R and the liquid crystal composition D for developing a biaxial liquid crystal phase is as follows: Although it cannot be clearly defined because it differs depending on the molecular structure and molecular weight of the liquid crystal composition R and the liquid crystal composition D, the liquid crystal composition R / liquid crystal composition D = 10 to 0.02 is preferable in terms of mass ratio. -0.05 is more preferable, and 2-0.1 is most preferable.
The biaxial liquid crystal phase often appears at a lower temperature than the uniaxial liquid crystal phase. For example, a uniaxial nematic phase (a rod-like nematic phase or a discotic nematic phase) is often transferred to a biaxial nematic phase by lowering the temperature. In many cases, the transition from the rod-like nematic phase to the biaxial nematic phase when the temperature is lowered when the content ratio of the liquid crystal composition R slightly increases with a certain mixing ratio (the liquid crystal composition R / liquid crystal composition D as a boundary. In addition, when the content of the liquid crystal composition D is slightly increased, a transition from a discotic nematic phase to a biaxial nematic phase occurs.

In the liquid crystal composition of the present invention including the liquid crystal composition R and the liquid crystal composition D, when a uniaxial nematic phase is present on the high temperature side of the biaxial nematic phase, the biaxial liquid crystal phase (nx -Nz) / (nx-ny) can be controlled.
For example, when the temperature is lowered from the rod-like nematic phase ((nx−nz) / (nx−ny) = 1.0), the (nx−nz) / (nx−ny) value does not change suddenly, It tends to increase gradually according to the temperature. Therefore, the (nx−nz) / (nx−ny) value can be controlled by selecting the temperature at which the orientation is fixed such as polymerization by UV irradiation. When the rod-like nematic phase is changed to the biaxial nematic phase, the control range width of the (nx-nz) / (nx-ny) value depends on the molecular structure of the liquid crystal composition R and the liquid crystal composition D. Since it changes, it cannot be defined unconditionally, but a range closer to 1.0 is easy to control. Specifically, 1.0 <(nx−nz) / (nx−ny) <10 is easy to control.
In addition, when the transition from the discotic nematic phase to the biaxial nematic phase is performed, the value of (nx−nz) / (nx−ny) can be controlled in the same manner as the transition from the rod-like nematic phase. In this case, since the (nx−nz) / (nx−ny) value of the discotic nematic phase is ∞ (nx = ny), the control range width is easily controlled in a range closer to ∞. Specifically, 1.2 <(nx−nz) / (nx−ny) <∞ is easy to control.

  When the liquid crystalline composition of the present invention including the liquid crystalline composition R and the liquid crystalline composition D expresses an optically biaxial liquid crystal phase, the refractive index in the three directions of the biaxial liquid crystal phase is nx, Assuming ny and nz (nx> ny> nz), each value preferably satisfies the following mathematical formula (III), and more preferably satisfies the following mathematical formula (VI). By satisfying a value in this range, the angle dependency of retardation can be controlled in accordance with the liquid crystal display device.

    Formula (III) 1.1 ≦ (nx−nz) / (nx−ny) ≦ 20

    Formula (VI) 1.2 ≦ (nx−nz) / (nx−ny) ≦ 10

  Furthermore, the liquid crystalline composition of the present invention including the liquid crystalline composition R and the liquid crystalline composition D has the above optical properties, and at the same time, has a uniform and defect-free orientation and has a good monodomain property. What is shown 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, the retardation plate tends to have a high light transmittance when used in a retardation plate.

  Examples of the biaxial liquid crystal phase expressed by the liquid crystal composition of the present invention including the liquid crystal composition R and the liquid crystal composition D include a biaxial nematic phase, a biaxial smectic A phase, and a biaxial smectic C. Phases can be mentioned. Among these liquid crystal phases, a biaxial nematic phase (Nb phase) exhibiting good monodomain properties is preferable. The biaxial nematic phase is a kind of liquid crystal phase that a nematic liquid crystal compound can take, but when the liquid crystal phase space is defined by the x, y, and z axes, the liquid crystal compound is centered on the y axis. The free rotation of the xz plane and the free rotation of the xy plane around the z axis are also prohibited.

[Phase difference plate]
The retardation plate of the present invention has at least one optically anisotropic layer formed from the liquid crystalline 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.

[Optically anisotropic layer]
By forming an optically anisotropic layer using the liquid crystal composition of the present invention, the optical anisotropy of the optically anisotropic layer is different from the optical biaxiality in which the principal refractive index values in three directions orthogonal to each other are different. Can be adjusted. The principal value of the refractive index in the three directions of the optically anisotropic layer preferably satisfies the following formula (III), and more preferably satisfies the following formula (VI), similarly to the refractive index ratio of the biaxial liquid crystal phase.

    Formula (III) 1.1 ≦ (nx−nz) / (nx−ny) ≦ 20

    Formula (VI) 1.2 ≦ (nx−nz) / (nx−ny) ≦ 10

  A biaxial retardation plate provided with a biaxial liquid crystalline composition on a transparent support and a uniaxial retardation plate provided with a uniaxial liquid crystalline composition have different retardation angle dependency. For example, in a retardation plate using a uniaxial liquid crystalline composition, the retardation in the normal direction of the plate surface and the retardation in the direction of an angle of several tens of degrees from the normal line are greatly different (the retardation is in the direction of the slow axis). If it is tilted, it will become smaller, and if it is tilted in the fast axis direction, it will become larger). On the other hand, in the case of a biaxial liquid crystalline composition, the retardation change rate differs from that of a uniaxial liquid crystalline composition. When producing retardation plates for use in various liquid crystal display devices, it is necessary to control the angle dependency of retardation in accordance with the liquid crystal display device. When a biaxial liquid crystalline composition is used, nx, This is very useful because the angle dependency of retardation can be arbitrarily controlled by changing the refractive index difference between ny and nz and the orientation direction of each axis.

  The optically anisotropic layer fixes the liquid crystal composition of the present invention to the liquid crystal phase formation temperature once, and then cools 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 crystalline composition of this invention to liquid crystal phase formation temperature, it superposes | polymerizes and cools and can form by fixing the orientation state of a liquid crystal state.

In the present invention, the 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. Specifically, the state is usually 0 ° C. to 50 ° C. Under more severe conditions, the immobilized liquid crystal composition has no fluidity in a temperature range of −30 ° C. to 70 ° C., and it does not change the alignment form due to an external field or an external force. This indicates a state in which the oriented orientation can be kept stable. When the alignment state is finally fixed and the optically anisotropic layer is formed, the liquid crystalline composition of the present invention no longer needs 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 crystalline composition of the present invention in forming the optically anisotropic layer include an air interface alignment controller, a repellency inhibitor, a polymerization initiator, and a polymerizable monomer.

[Air interface alignment control agent]
The liquid crystal composition is aligned at the tilt angle of the air interface at the air interface. For example, in the case of a biaxial liquid crystalline composition, the tilt angle is determined by the tilt angle formed by the nx refractive index direction and the air interface, the tilt angle formed by the ny refractive index direction and the air interface, the nz refractive index direction, and the air. There are three types of tilt angles formed by the interface.
This tilt angle varies depending on the type of liquid crystalline compound contained in the liquid crystalline composition or the mixing ratio of the two types of liquid crystalline compounds. Therefore, the tilt angle of the air interface is arbitrarily controlled according to the purpose. There is a need.

  For controlling the tilt angle, for example, an external field such as an electric field or a magnetic field or an additive can be used, but an additive is preferably used. Such additives include substituted or unsubstituted aliphatic groups having 6 to 40 carbon atoms, or substituted or unsubstituted aliphatic substituted oligosiloxanoxy groups 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, and more preferably 0.01% by mass to 10% by mass with respect to the liquid crystalline composition of the present invention. 0.1 mass% to 5 mass% is 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.
There is no restriction | limiting in particular as a polymer to be used, unless the inclination-angle change and orientation of the liquid crystalline composition of this invention are inhibited significantly.
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 disturb the alignment of the liquid crystalline 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 crystalline composition of the present invention. More preferably, it is in the range of 0.1 to 8% by mass, and further preferably in the range of 0.1 to 5% by mass.

[Polymerization initiator]
In the present invention, the liquid crystalline composition is preferably fixed in a monodomain orientation, that is, in a substantially uniform orientation. Therefore, when the compound contained in the liquid crystalline composition R and / or the liquid crystalline composition D has a polymerizable group, it is preferably polymerized and fixed by a polymerization reaction.
The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and a polymerization reaction by electron beam irradiation. In order to prevent the support and the like from being deformed or altered by heat. Also, a photopolymerization reaction 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 compatible with the compounds contained in the liquid crystal composition R and the liquid crystal composition D of the present invention, and does not cause a significant change in the tilt angle or alignment inhibition of the liquid crystal composition. As long as there is no particular limitation. 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 the preparation of the liquid crystalline 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 optically anisotropic layer is formed by preparing a coating solution of the liquid crystalline composition of the present invention using the above solvent, coating the alignment liquid on the alignment film, and subjecting the liquid crystalline 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).

[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.
Any layer can be used as the alignment film as long as the liquid crystal composition of the present invention of the optically anisotropic layer provided on the alignment film can provide a desired alignment. An alignment film formed by light irradiation is preferred. An alignment film formed by a 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 having 2 (cellulose acetate), 3 (cellulose propionate) or 4 carbon atoms.
(Cellulose butyrate) is preferred. 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, Synthetic Example 2 described in Paragraph Nos. 0048 to 0049, and Paragraph Nos. 0051 to 0052. It can be synthesized with reference to the method of Synthesis Example 3 described.

In order to adjust the retardation of a polymer film used as a transparent support, particularly a cellulose 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 by high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

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 preventing agent is hardly recognized. When the addition amount exceeds 1% by mass, bleed-out (bleeding) of the deterioration preventing agent to the film surface may be observed.
As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. The ultraviolet ray preventing agent is described in JP-A-7-11056.

The cellulose 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 on which 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 (Hybrid Aligned Nematic) modes can be used for liquid crystal display devices in various display modes.
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.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these specific examples.

Example 1
[Production of retardation plate]
(Formation of alignment film)
The following modified polyvinyl alcohol and glutaraldehyde (5% by mass of the modified polyvinyl alcohol) were dissolved in a methanol / water mixed solvent (volume ratio = 20/80) to prepare a 5% by mass solution.

  This solution was applied on a glass substrate and dried with hot air at 100 ° C. for 120 seconds, followed by rubbing to form an alignment film. The thickness of the obtained alignment film was 0.5 μm.

(Formation of optically anisotropic layer)
On the rubbed alignment film prepared above, an optically anisotropic layer coating solution having the following composition was applied using a spin coater.

(Optical anisotropic layer coating solution)
-70.0 parts by mass of the liquid crystalline compound D-109-30.0 parts by mass of the liquid crystalline compound TO-3-0.2 parts by mass of the air interface alignment control agent V- (1)-Irgacure 907 (Ciba Specialty) Chemicals Corporation)
1.0 part by mass / 700 parts by mass of chloroform

When the glass substrate coated with the above optically anisotropic layer was placed in a thermostatic bath at 130 ° C. and cooled while observing with a polarizing microscope, it transitioned to a nematic phase at 80 ° C. Then, it cooled to 70 degreeC and hold | maintained at the temperature for 2 minutes. Next, it was placed in a constant temperature bath of 80 ° C. with an oxygen concentration of 2%, and after 5 minutes, 600 mJ ultraviolet rays were irradiated to fix the orientation state of the optically anisotropic layer. The film was allowed to cool to room temperature to prepare a retardation plate. The thickness of the optically anisotropic layer was 0.8 μm.
The retardation of the obtained retardation plate was measured for the angle dependency, and (nx-nz) / (nx-ny) was determined to be 4.0, confirming that it was a biaxial liquid crystal phase. .

(Example 2)
[Synthesis of D-101]
Synthesized according to the following scheme.

100 ml of tetrahydrofuran and 11.7 ml of hexanol were added to 5.18 g of sodium hydride. After stirring at room temperature for 20 minutes, a solution of 10 g of 3,4-difluorobenzonitrile dissolved in 80 ml of tetrahydrofuran was added dropwise under ice cooling. After stirring at room temperature for 5 hours, water was added dropwise to the reaction solution, extracted with ethyl acetate, the organic layer was concentrated and purified using column chromatography to obtain 15.5 g of D-101A crystals. It was. Thereafter, 15.5 g of D-101A was dissolved in 50 ml of ethanol, 12.0 ml of 50% hydroxylamine solution was added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling, methanol was added to the reaction solution, and the precipitated crystals were separated by filtration and dried to obtain 17.0 g of D-101B crystals.
17.0 g of the obtained D-101B was dissolved in 100 ml of 1,4-dioxane, 5.0 g of trimesic acid chloride and 5.4 ml of pyridine were added, and the mixture was stirred at 90 ° C. for 7 hours. After cooling, methanol was added and the precipitated crystals were collected by filtration. Purification by column chromatography gave D-101. The NMR spectrum of D-101 obtained is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
0.95 (9H, t)
1.30-1.40 (12H, m)
1.40-1.50 (6H, m)
1.85-1.95 (6H, m)
4.20 (6H, t)
7.10 (3H, dd)
7.90-8.00 (6H, m)
9.20 (3H, s)

  When the phase transition temperature of the obtained D-101 was measured by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase around 135 ° C. It turned into a phase. That is, it was found that D-101 exhibits a discotic nematic liquid crystal phase between 135 ° C. and 162 ° C.

  D-101 (containing 0.1 wt% hydroquinone monomethyl ether) was injected into a horizontal alignment cell (manufactured by EHC; KSRP-10 / A107M1NSS (ZZ)) having a cell gap of 10 μm at 180 ° C., and homeo at 150 ° C. Tropic orientation was used. In this state, (nx−nz) / (nx−ny) is ∞ (that is, nx = ny) from the measurement of the angle dependency of retardation and conoscopic observation, and D−101 is expressed by formula (II). It was found that the liquid crystal phase to be satisfied was developed.

(Example 3)
[Synthesis of D-109]
Synthesized according to the following scheme.

11.0 g of D-109A (the same compound as D-101) was dissolved in 50 ml of CH ₂ Cl _{2, and} 135 ml of boron tribromide (1.0 M CH ₂ Cl ₂ solution) was added. After stirring at 40 ° C. for 8 hours, water was added to the reaction solution, and the precipitated crystals were collected by filtration. This crystal was dried to obtain 7.8 g of D-109B.
After dissolving 0.34 g of 6-bromohexanol in 5 ml of dimethylacetamide, 0.26 ml of acrylic acid chloride was added dropwise, and after stirring for 1 hour at room temperature, 20 ml of water and 20 ml of hexane were added to wash the organic layer. After liquid separation, the hexane layer was distilled off, 0.3 g of D-109B, 0.43 g of potassium carbonate and dimethylformamide were added, and the mixture was stirred at 100 ° C. for 5 hours. Water was added to the reaction mixture, and the mixture was extracted with CH ₂ Cl _{2. The} organic layer was concentrated and purified using column chromatography to obtain 0.37 g of D-109 crystals. The NMR spectrum of D-109 obtained is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
1.40-1.60 (12H, m)
1.65-1.75 (6H, m)
1.75-1.85 (6H, m)
4.15 (6H, t)
4.25 (6H, t)
5.80 (3H, dd)
6.15 (3H, dd)
6.45 (3H, dd)
7.10 (3H, dd)
7.90-8.00 (6H, m)
9.25 (3H, s)

  When the phase transition temperature of the obtained D-109 was observed by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase around 79 ° C. It turned into a phase. That is, it was found that D-109 exhibits a discotic nematic liquid crystal phase between 79 ° C. and 120 ° C.

  D-109 (containing 0.1 wt% hydroquinone monomethyl ether) was injected at 150 ° C. into a horizontal alignment cell (manufactured by EHC; KSRP-10 / A107M1NSS (ZZ)) having a cell gap of 10 μm, and homeo at 100 ° C. Tropic orientation was used. In this state, (nx−nz) / (nx−ny) is ∞ (that is, nx = ny), and D-109 is expressed by formula (II) from the measurement of the angle dependency of retardation and conoscopic observation. It was found that the liquid crystal phase to be satisfied was developed.

Example 4
[Synthesis of m-4]
M-4 was synthesized according to the following scheme.

(Synthesis of m-4A)
25.0 g of bromohydroquinone was dissolved in 70 ml of pyridine (Py), and 37 ml of acetic anhydride (Ac ₂ O) was added dropwise at a reaction temperature of 50 ° C. or lower. After stirring for 3 hours, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate, diluted hydrochloric acid, water and saturated brine, and the solvent was evaporated under reduced pressure. Crystallization with hexane gave 32.2 g of m-4A crystals.

(Synthesis of m-4B)
32.2 g of m-4A, 17.4 g of trimethylsilyl (TMS) acetylene, 0.5 g of triphenylphosphine, 0.25 g of bis (triphenylphosphine) palladium (II) dichloride and 80 mg of copper (I) iodide are dissolved in 200 ml of triethylamine. And refluxed for 10 hours under a nitrogen atmosphere. After cooling, the precipitated triethylamine hydrochloride was filtered off, and the organic layer was distilled off under reduced pressure. The obtained residue was purified by column chromatography to obtain 32.0 g of m-4B crystals.

(Synthesis of m-4C)
32.0 g of m-4B was dissolved in 200 ml of tetrahydrofuran, 120 ml of a tetrahydrofuran solution (1.0 M solution) of tetrabutylammonium fluoride (TBAF) was added, and the mixture was stirred at room temperature for 30 minutes. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and washed with saturated brine. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 20.5 g of m-4C crystals.

(Synthesis of m-4D)
m-4C 3.0 g, 1,3-dibromobenzene 1.38 g, triphenylphosphine 58 mg, bis (triphenylphosphine) palladium (II) dichloride 29 mg and copper (I) iodide 10 mg were dissolved in triethylamine 23 ml, and nitrogen was added. Refluxed for 10 hours under atmosphere. After cooling, 100 ml of methanol was added, and the precipitated crystals were collected by filtration. Purification was performed by column chromatography to obtain 2.1 g of m-4D crystals.

(Synthesis of m-4E)
0.6 g of m-4D was dissolved in 30 ml of methanol, and 2 ml of sodium methoxide (28% methanol solution) was added under nitrogen bubbling. After stirring at room temperature for 1 hour, dilute hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The obtained organic layer was distilled off under reduced pressure to obtain 0.4 g of m-4E crystals.

(Synthesis of m-4)
4-Octyloxybenzoic acid chloride (5.0 g) and m-4E (0.4 g) obtained by a conventional method were dissolved in tetrahydrofuran (20 ml), and diisopropylethylamine (3.0 ml) and dimethylaminopyridine (0.1 g) were added. After stirring at room temperature for 6 hours, water was added to the reaction mixture, and the mixture was extracted with CH ₂ Cl ₂ . After concentration under reduced pressure, purification was performed using column chromatography to obtain 1.1 g of m-4 crystals. The NMR spectrum of the obtained m-4 is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
0.85-0.95 (12H, m)
1.20-1.60 (40H, m)
1.70-1.90 (8H, m)
3.95-4.10 (8H, m)
6.90-7.00 (8H, m)
7.05-7.15 (4H, m)
7.27 (2H)
7.43 (2H, d)
7.46 (2H, d)
8.10-8.20 (8H, m)

  Further, when the phase transition temperature of the obtained m-4 was measured by texture observation with a polarizing microscope, the temperature was increased and the crystal phase was changed to a nematic liquid crystal phase at around 105 ° C. It turned into a phase. That is, m-4 was found to exhibit a nematic liquid crystal phase between 105 ° C and 156 ° C.

  m-4 (containing 0.1 wt% hydroquinone monomethyl ether) was injected at 170 ° C. into a horizontal alignment cell (manufactured by EHC; KSRP-05 / A107M1NSS (ZZ)) having a cell gap of 5 μm, and homogeneous at 140 ° C. Oriented. In this state, the angle dependency of the retardation was measured and (nx−nz) / (nx−ny) was determined to be 1.0 or more and less than 1.1, and m−4 represents the formula (I). It was found that the liquid crystal phase to be satisfied was developed.

(Example 5)
[Synthesis of m-22]
M-22 was synthesized according to the following scheme.

(Synthesis of m-22A)
3.0 g of m-4C obtained according to Example 4, 10 g of 1,4-dibromobenzene, 58 mg of triphenylphosphine, 29 mg of bis (triphenylphosphine) palladium (II) dichloride and 10 mg of copper (I) iodide were mixed with 50 ml of triethylamine. And refluxed for 10 hours under a nitrogen atmosphere. After cooling, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and washed with saturated brine. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 2.9 g of m-22A.

(Synthesis of m-22B)
2.1 g of m-22A, 0.83 g of trimethylsilylacetylene, 24 mg of triphenylphosphine, 12 mg of bis (triphenylphosphine) palladium (II) dichloride and 4 mg of copper (I) iodide are dissolved in 20 ml of triethylamine, and 10 under nitrogen atmosphere. Reflux for hours. After cooling, water was added to the reaction mixture, extracted with ethyl acetate, and washed with saturated brine. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 1.5 g of m-22B.

(Synthesis of m-22C)
1.5 g of m-22B was dissolved in 200 ml of tetrahydrofuran, 5 ml of a tetrahydrofuran solution (1.0 M solution) of tetrabutylammonium fluoride was added, and the mixture was stirred at room temperature for 30 minutes. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and washed with saturated brine. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 0.9 g of m-22C.

(Synthesis of m-22D)
200 ml of water and 54.3 ml of 1M aqueous sodium hydroxide solution are added to 15.2 g of 3,5-dibromo-4-hydroxybenzaldehyde, heated to 50 ° C., and then 6.2 ml of hydrogen peroxide solution.
A solution diluted with 20 ml of (31%) water was added dropwise. After reaction at 50 ° C. for 5 hours, hydrochloric acid was added and the precipitated crystals were collected by filtration. After drying the crystals, 100 ml of toluene, 7.0 g of cyanoacetic acid octyl ester, 1 ml of acetic acid and 0.5 g of ammonium chloride were added, and the mixture was refluxed for 3 hours while removing water. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and washed with saturated brine. After the organic layer was concentrated under reduced pressure, hexane was added to the obtained crystals and washed with heating for 30 minutes. Filtration was performed in a heated state to obtain 7.4 g of m-22D crystals.

(Synthesis of m-22E)
7.35 g of m-22D was dissolved in 20 ml of pyridine, and 7.8 ml of acetic anhydride was added dropwise at a reaction temperature of 50 ° C. or lower. After stirring at 50 ° C. for 3 hours, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate, diluted hydrochloric acid, water and saturated brine, and the solvent was evaporated under reduced pressure. Crystallization with hexane gave 9.3 g of m-22E crystals.

(Synthesis of m-22F)
m-22C 0.7 g, m-22E 0.37 g, triphenylphosphine 10 mg, bis (triphenylphosphine) palladium (II) dichloride 5 mg and copper (I) iodide 2 mg were dissolved in 20 ml of triethylamine, and under nitrogen atmosphere. Refluxed for 10 hours. After cooling, water was added to the reaction mixture, extracted with ethyl acetate, and washed with saturated brine. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 0.15 g of m-22F.

(Synthesis of m-22G)
0.15 g of m-22F was dissolved in a mixed solution of 20 ml of tetrahydrofuran and 5 ml of methanol, and 0.4 ml of sodium methoxide (28% methanol solution) was added under nitrogen bubbling. After stirring at room temperature for 1 hour, dilute hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The obtained organic layer was distilled off under reduced pressure to obtain 0.10 g of m-22G crystals.

(Synthesis of m-22)
0.05 g of m-22G and 0.4 g of 4-octyloxybenzoic acid chloride were dissolved in 10 ml of tetrahydrofuran, and 0.2 g of diisopropylethylamine and 0.01 g of 4-dimethylaminopyridine were added. After stirring at room temperature for 12 hours, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. After concentration under reduced pressure, the residue was purified using column chromatography to obtain 0.2 g of m-22 crystals. The NMR spectrum of the obtained m-22 is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
0.85-0.95 (18H, m)
1.20-1.60 (60H, m)
1.70-1.90 (12H, m)
3.95-4.10 (12H, m)
6.90-7.00 (12H, m)
7.00-7.50 (16H, m)
8.10-8.25 (12H, m)

  When the phase transition temperature of the obtained m-22 was measured by texture observation with a polarizing microscope, the temperature was increased and the crystal phase was changed to a nematic liquid crystal phase around 110 ° C, and when it exceeded 156 ° C, it became an isotropic liquid phase. It has changed. That is, it was found that m-22 exhibits a nematic liquid crystal phase between 110 ° C. and 156 ° C.

  m-22 (containing 0.1 wt% hydroquinone monomethyl ether) was injected at 170 ° C. into a horizontal alignment cell (manufactured by EHC; KSRP-05 / A107M1NSS (ZZ)) having a cell gap of 5 μm, and homogeneous at 140 ° C. Oriented. In this state, the angle dependence of the retardation was measured and (nx−nz) / (nx−ny) was determined to be 1.0 or more and less than 1.1, and m−22 represents the formula (I). It was found that the liquid crystal phase to be satisfied was developed.

(Example 6)
[Synthesis of m-23]
M-23 was synthesized according to the following scheme.

  0.43 g of methanesulfonyl chloride was dissolved in 10 ml of tetrahydrofuran and cooled to 0 ° C. To this solution was added dropwise a solution of 1.0 g of 4- (4-acryloyloxybutyloxy) benzoic acid and 0.51 g of diisopropylethylamine in 10 ml of tetrahydrofuran. After stirring at 0 ° C. for 1 hour, 0.51 g of diisopropylethylamine and 0.02 g of 4-dimethylaminopyridine were added, and then a solution of 0.05 g of m-22G obtained according to Example 5 in 10 ml of tetrahydrofuran was added. After stirring at room temperature for 12 hours, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. After concentration under reduced pressure, purification was performed using column chromatography to obtain 0.15 g of m-23 crystals. The NMR spectrum of the obtained m-23 is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
1.70-1.90 (12H, m)
1.90-2.00 (12H, m)
3.95-4.30 (24H, m)
5.75-5.80 (6H, m)
6.05-6.20 (6H, m)
6.35-6.50 (6H, m)
6.90-7.00 (12H, m)
7.00-7.50 (16H, m)
8.10-8.25 (12H, m)

  The phase transition temperature of the obtained m-23 was measured by texture observation using a polarizing microscope. When the temperature was first raised, the crystal phase changed to an isotropic liquid phase around 100 ° C. Next, when the temperature was gradually lowered from 110 ° C., it changed to a nematic phase around 95 ° C., and when it was lowered to room temperature, it changed to a crystalline phase again. That is, it was found that m-23 exhibited a nematic phase between 95 ° C. and room temperature when the temperature was lowered.

  m-23 (containing 0.1 wt% hydroquinone monomethyl ether) was injected at 120 ° C. into a horizontal alignment cell (HC) manufactured by EHC having a cell gap of 5 μm; KSRP-05 / A107M1NSS (ZZ) and homogeneously oriented at 80 ° C. I let you. In this state, the angle dependency of retardation was measured, and (nx−nz) / (nx−ny) was determined to be 1.0 or more and less than 1.1, and m−23 satisfies the formula (I). It was found that a liquid crystal phase was developed.

(Example 7)
[Synthesis of TO-3]
TO-3 was synthesized according to the following scheme.

(Synthesis of TO-3A)
20.4 g of 2,3-dicyanohydroquinone was dissolved in 150 ml of t-butanol, and 22.6 g of NBS (N-bromosuccinimide) was added, followed by stirring at room temperature for 4 hours. The reaction mixture was added to 1 L of water, and the precipitated crystals were filtered. Concentrated hydrochloric acid was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 8.5 g of TO-3A.

(Synthesis of TO-3B)
8.0 g of TO-3A was dissolved in 50 ml of tetrahydrofuran, and 25 ml of pyridine (Py) and 20 ml of acetic anhydride (Ac ₂ O) were added dropwise. After stirring for 12 hours, the reaction solution was added to 1 L of water, and the precipitated crystals were separated by filtration and dried. The obtained crystals were purified by column chromatography to obtain 9.7 g of TO-3B.

(Synthesis of TO-3C)
3.0 g of TO-3B, 2.43 g of m-4C obtained according to Example 4, 60 mg of triphenylphosphine, 30 mg of bis (triphenylphosphine) palladium (II) dichloride and 10 mg of copper (I) iodide are dissolved in 100 ml of triethylamine. And heated at 60 ° C. for 5 hours under a nitrogen atmosphere. After cooling, methanol was added to the reaction solution, and the precipitated crystals were separated by filtration and dried. The obtained crystals were purified by column chromatography to obtain 1.7 g of TO-3C.

(Synthesis of TO-3D)
1.7 g of TO-3C was dissolved in 40 ml of tetrahydrofuran, and 5 ml of sodium methoxide (28% methanol solution) and 20 ml of methanol were added under nitrogen bubbling. After stirring at room temperature for 30 minutes, dilute hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The obtained organic layer was distilled off under reduced pressure to obtain 1.0 g of TO-3D.

(Synthesis of TO-3)
0.43 g of methanesulfonyl chloride was dissolved in 10 ml of tetrahydrofuran and cooled to 0 ° C. To this solution was added dropwise a solution of 1.0 g of 4- (4-acryloyloxybutyloxy) benzoic acid and 0.51 g of diisopropylethylamine in 10 ml of tetrahydrofuran. After stirring at 0 ° C. for 1 hour, 0.51 g of diisopropylethylamine and 0.02 g of 4-dimethylaminopyridine were added, and then a solution of 0.14 g of TO-3D in 10 ml of tetrahydrofuran was added. After stirring at room temperature for 12 hours, water was added to the reaction mixture, and the mixture was extracted with CH ₂ Cl ₂ . After concentration under reduced pressure, the residue was purified using column chromatography to obtain 0.32 g of TO-3 crystals. The NMR spectrum of the obtained TO-3 is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm):
1.70-1.90 (8H, m)
1.90-2.00 (8H, m)
3.90-4.00 (4H, m)
4.08-4.18 (4H, m)
4.19-4.30 (8H, m)
5.80-5.90 (4H, m)
6.07-6.20 (4H, m)
6.36-6.48 (4H, m)
6.90-7.05 (9H, m)
7.25 (1H, dd)
7.32 (1H, d)
7.47 (1H, d)
8.06-8.20 (8H, m)

  When the phase transition temperature of the obtained TO-3 was measured by texture observation with a polarizing microscope, the temperature was raised and the crystal phase was changed to a nematic liquid crystal phase at around 122 ° C, and when it exceeded 195 ° C, it became an isotropic liquid phase. It has changed. That is, it was found that TO-3 exhibits a nematic liquid crystal phase between 122 ° C. and 195 ° C.

  TO-3 (containing 0.1 wt% hydroquinone monomethyl ether) was injected at 130 ° C. into a horizontal alignment cell (HC) manufactured by EHC having a cell gap of 5 μm; KSRP-05 / A107M1NSS (ZZ) and homogeneously oriented at 130 ° C. I let you. In this state, the angle dependency of the retardation was measured, and (nx−nz) / (nx−ny) was determined to be 1.0 or more and less than 1.1, and TO-3 satisfies the formula (I). It was found that a liquid crystal phase was developed.

Claims (7)

A liquid crystal composition comprising a liquid crystal composition R expressing a liquid crystal phase having a positive birefringence and a liquid crystal composition D expressing a liquid crystal phase having a negative birefringence, wherein the liquid crystal composition A liquid crystal composition, wherein the composition D contains a liquid crystal compound represented by the following general formula (DI).
General formula (DI)
In formula (DI), Y ₁₁ , Y ₁₂ and Y ₁₃ each independently represent a methine or nitrogen atom. L ₁ , L ₂ and L ₃ each independently represents a single bond or a divalent linking group. H ₁ , H ₂ , and H ₃ each independently represent the following general formula (DI-A) or the following general formula (DI-B).
General formula (DI-A)
[In General Formula (DI-A), YA ₁ and YA ₂ each independently represent a methine group or a nitrogen atom. XA represents an oxygen atom or a sulfur atom. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
General formula (DI-B)
[In General Formula (DI-B), YB ₁ and YB ₂ each independently represent a methine group or a nitrogen atom. XB represents an oxygen atom or a sulfur atom. * Represents a position where L _{1 to} L ₃ are bonded, and ** represents a position where R _{1 to} R ₃ are bonded. ]
In general formula (DI), R < ₁ >, R < ₂ >, R < ₃ > represents the following general formula (DI-R) each independently.
General formula (DI-R)
*-(-L ₂₁ -divalent cyclic group) n ₁ -L ₂₂ -L ₂₃ -Q ₁
[In General Formula (DI-R), * represents a position bonded to H _{1 to} H ₃ in General Formula (DI). L ₂₁ represents a single bond or a divalent linking group. The divalent cyclic group represents a divalent linking group having at least one cyclic structure. n ₁ represents 0 to 4 integer. L ₂₂ represents * —O—, * —O—CO—, * —CO—O—, * —O—CO—O—, * —S—, * —N (R ₇ ) —, * —CH ₂ —. , * —CH═CH—, * —C≡C—. (Here, * represents a position bonded to a divalent cyclic group in the general formula (DI-R), and R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.) L ₂₃ Is a divalent linking group selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—. Represents. Q ₁ each independently represents a polymerizable group or a hydrogen atom. ] 2. The liquid crystal composition according to claim 1, wherein the liquid crystal compound represented by the general formula (DI) contained in the liquid crystal composition D is a liquid crystal compound represented by the following general formula (DII).
Formula (DII)
In the general formula (DII), Y ₃₁ , Y ₃₂ and Y ₃₃ each independently represents a methine or nitrogen atom. R ₃₁ , R ₃₂ and R ₃₃ are each independently represented by the following general formula (DII-R).
General formula (DII-R)
In the general formula (DII-R), A ₃₁ and A ₃₂ each independently represents a methine group or a nitrogen atom. X ₃ represents an oxygen atom or a sulfur atom. The divalent cyclic group represents a divalent linking group having a 6-membered cyclic structure. n ₃ represents 1 to 3 integer. L ₃₁ is * —O—, * —O—CO—, * —CO—O—, —O—CO—O—, * —S—, * —N (R ₇ ) —, * —CH ₂ —, * —CH═CH—, * —C≡C— is represented. (Here, * represents a position bonded to a divalent cyclic group in the general formula (DII-R). R ₇ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.) L ₃₂ Is a divalent linking group selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—. Represents. Q ₃ each independently represents a polymerizable group or a hydrogen atom.   3. The liquid crystalline composition according to claim 1, wherein the liquid crystal phase having positive birefringence is a nematic phase, and the liquid crystal phase having negative birefringence is a discotic nematic phase.   4. The liquid crystal composition containing the liquid crystal composition R and the liquid crystal composition D exhibits a liquid crystal phase at 20 ° C. to 300 ° C. 4. Liquid crystalline composition. The liquid crystal phase expressed by the liquid crystal composition containing the liquid crystal composition R and the liquid crystal composition D satisfies the following mathematical formula (III). Liquid crystalline composition.
Formula (III) 1.1 ≦ (nx−nz) / (nx−ny) ≦ 20
In the formula (III), nx, ny, and nz represent refractive indexes in three directions orthogonal to each other in the liquid crystal phase. However, the largest refractive index is nx and the smallest refractive index is nz.   A retardation plate having at least one optically anisotropic layer on a transparent support, wherein the optically anisotropic layer is formed from the liquid crystalline composition according to any one of claims 1 to 5. A phase difference plate, which is an optically anisotropic layer.   An elliptically polarizing plate comprising the retardation plate according to claim 6 and a polarizing film.