KR20060051668A - Liquid crystalline composition, retardation film and elliptically polarizing film - Google Patents

Abstract

(assignment)

It is obtained by mixing the some liquid crystalline composition which expresses a different liquid crystal phase, and providing the liquid crystalline composition which can express a biaxial liquid crystal phase. And providing a retardation plate and an elliptical polarizing plate using these liquid crystalline compositions.

(Solution)

As a liquid crystalline composition containing the liquid crystalline composition (R) which expresses the liquid crystal phase which has positive birefringence, and the liquid crystalline composition (D) which expresses the liquid crystal phase which has negative birefringence, The liquid crystalline composition (D) contains, for example, the following liquid crystalline compound.

Description

LIQUID CRYSTALLINE COMPOSITION, RETARDATION FILM AND ELLIPTICALLY POLARIZING FILM}

Patent Document 1: Japanese Patent Application Laid-Open No. 2-264905

[Non-Patent Document 1] Y. Rabin et al., Mol. Cry. Liq. Cry., 1982, Volume 89, Page 67

Non-Patent Document 2: R. Pratiba, N. V. Madhususana, Mol. Cry. Liq. Cry., 1985, Volume 1, 111 pages

This invention relates to the liquid crystalline composition which is very useful for preparation of retardation plates, etc., especially the liquid crystalline composition which expresses a biaxial liquid crystal phase. Moreover, it is related with the retardation plate and elliptical polarizing plate which have an optically anisotropic layer containing this liquid crystalline composition.

The biaxial film which controlled the refractive index of the triaxial direction is useful in the optical field which uses polarization. Especially in the field of liquid crystal displays, the importance of such films capable of precisely controlling polarization is high. When producing such an optical biaxial film, the method of obtaining the film obtained from a polymer by biaxial stretching is common (for example, refer patent document 1). When obtaining a biaxial film by biaxial stretching, since the refractive index of a triaxial direction can be controlled by a draw ratio, it can control to a desired refractive index comparatively easily.

Since the biaxial film using the biaxial liquid crystal has the advantage of making the film thickness very thin compared to the biaxially stretched film which has been widely used so far, the use of the biaxial liquid crystal in the biaxial film is a thin layer of the device. It is a useful means to reduce weight and weight. Moreover, although the film using extending | stretching had the problem of poor dimensional stability, and optical performance tends to change with moist heat etc., the possibility that such a problem can also be solved if a polymerizable biaxial liquid crystal can be used. There is this.

However, when producing a biaxial film using a biaxial liquid crystal, the problem that the refractive index of a triaxial direction cannot be controlled arbitrarily arises. This is because the refractive index of the triaxial direction of the biaxial film obtained is almost uniquely determined by the refractive index of the triaxial direction of the compound (biaxial liquid crystalline compound) which expresses a biaxial liquid crystal phase. That is, in order to make the refractive index of three directions of a biaxial film into a desired refractive index, there was only the method of synthesize | combining the biaxial liquid crystalline compound which has a desired refractive index. However, since the number of biaxial liquid crystalline compounds is very small compared with the compound (uniaxial liquid crystalline compound) which expresses a uniaxial liquid crystalline phase, it was very difficult to arbitrarily control the refractive index of three directions.

In order to avoid such a problem, the proposal which expresses a biaxial liquid crystal phase by mixing a rod-shaped liquid crystal and a disk-shaped liquid crystal is also proposed (for example, refer nonpatent literature 1). Using this method, the control of the refractive index in the triaxial direction is very simple because it is possible by changing the mixing ratio of the rod-shaped liquid crystal and the discotic liquid crystal. However, attempts have been made to develop a biaxial liquid crystal phase by accepting such a proposal and mixing a rod-shaped liquid crystal and a discotic liquid crystal (see, for example, Non Patent Literature 2). The compatibility between the rod-shaped liquid crystal and the discotic liquid crystal is poor. Therefore, in mixing of these two types of liquid crystals, liquid crystallinity is lost, or two types of liquid crystal phases may cause phase separation, and in such a mixed system, no biaxial liquid crystal phase is expressed.

In view of the above circumstances, an object of the present invention is to provide a liquid crystal composition capable of expressing a biaxial liquid crystal phase in a liquid crystal composition obtained by mixing a plurality of liquid crystal compositions expressing another liquid crystal phase. Moreover, the objective of this invention is providing the retardation plate and elliptical polarizing plate which used these liquid crystalline compositions.

Means to solve the problem

The said subject is solved by the following means.

(1) A liquid crystal composition comprising a liquid crystal composition (R) expressing a liquid crystal phase having positive birefringence and a liquid crystal composition (D) expressing a liquid crystal phase having negative birefringence, wherein the liquid crystal composition ( D) The liquid crystalline composition containing the liquid crystalline compound represented by the following general formula (DI).

General formula (DI)

In General 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 represent 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 or nitrogen atom. XA represents an oxygen atom, a sulfur atom, methylene or imino. * Is L ₁ to L ₃ Represents a position to be combined with **, R ₁ to R ₃ And position where it is combined with.]

General formula (DI-B)

[In General Formula (DI-B), YB ₁ and YB ₂ each independently represent a methine or nitrogen atom. XB represents an oxygen atom, a sulfur atom, methylene or imino. * Indicates a position to be bonded to L ₁ to L ₃ , ** indicates R ₁ to R ₃ And position where it is combined with.]

In general formula (DI), R <_1> , R <_2> , R <_3> respectively independently represents following formula (DI-R).

General formula (DI-R)

*-(-L ₂₁ -2 pseudocyclic group) n ₁ -L ₂₂ -L ₂₃ -Q ₁

[In the general formula (DI-R), * is H ₁ H ~ ₃ of the general formula (DI) Indicates the position to be bound to. L ₂₁ represents a single bond or a divalent linking group. The divalent cyclic group represents a divalent linking group having at least one kind of cyclic structure. n ₁ represents an integer of 0-4. L ₂₂ is * -O-, * -O-CO-, * -CO-O-, * -O-CO-O-, * -S-, * -N (R ₇ )-, * -CH _2- , * -CH = CH-, * -C≡C- (wherein * represents a position bonded to a divalent cyclic group in the general formula (DI-R). In addition, R ₇ represents 1 to 7 carbon atoms). Is an alkyl group or a hydrogen atom. L ₂₃ is a divalent linking group selected from the group consisting of a combination of -O-, -S-, -C (= O)-, -NH-, -CH _2- , -CH = CH-, and -C≡C-. Indicates. Each Q ₁ independently represents a polymerizable group or a hydrogen atom.]

(2) The liquid crystal compound represented by general formula (DI) contained in a liquid crystal composition (D) is a liquid crystal compound represented by the following general formula (DII), The liquid crystal composition as described in said (1) characterized by the above-mentioned.

General formula (DII)

In General Formula (DII), Y ₃₁ , Y ₃₂ , and Y ₃₃ each independently represent 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 General Formula (DII-R), A ₃₁ and A ₃₂ each independently represent a methine or nitrogen atom. X ₃ represents an oxygen atom, a sulfur atom, methylene or imino. The divalent cyclic group represents a divalent linking group having a 6 membered cyclic structure. n <_3> represents the integer of 1-3. L ₃₁ is * -O-, * -O-CO-, * -CO-O-, -O-CO-O-, * -S-, * -N (R ₇ )-, * -CH _2- , * -CH = CH-, * -C≡C- (wherein * represents a position bonded to a divalent cyclic group in the general formula (DII-R). R ₇ is a carbon atom having 1 to 7 carbon atoms. Alkyl group or hydrogen atom). L ₃₂ is a divalent linking group selected from the group consisting of a combination of -O-, -S-, -C (= O)-, -NH-, -CH _2- , -CH = CH-, and -C≡C-. Indicates. Q ₃ each independently represents a polymerizable group or a hydrogen atom.

(3) The liquid crystal phase according to (1) or (2) above, 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 crystalline composition containing a liquid crystalline composition (R) and a liquid crystalline composition (D) expresses a liquid crystal phase at 20 degreeC-300 degreeC, any one of said (1)-(3) characterized by the above-mentioned. The liquid crystalline composition of description.

(5) The liquid crystal phase which the liquid crystalline composition containing a liquid crystalline composition (R) and a liquid crystalline composition (D) expresses satisfy | fills following formula (III), The said any one of said (1)-(4) characterized by the above-mentioned. Liquid crystal composition of Claim.

Equation (III) 1.1 ≤ (nx-nz) / (nx-ny) ≤ 20

In Formula (III), nx, ny, and nz represent the refractive index of three directions orthogonal to a 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 an optically anisotropic layer formed of the liquid crystal composition according to any one of the above (1) to (5). Retardation plate.

(7) It has a retardation plate and polarizing film as described in said (6), Elliptical polarizing plate characterized by the above-mentioned.

To practice the invention  Best form for

The liquid crystalline composition of this invention expresses a biaxial liquid crystal phase by mixing the liquid crystal composition (R) which expresses the liquid crystal phase which has positive birefringence, and the liquid crystal composition (D) which expresses the liquid crystal phase which has negative birefringence. .

Here, the liquid crystal phase which has positive birefringence is a liquid crystal phase which satisfy | fills following formula (I), and the liquid crystal phase which has negative birefringence refers to the liquid crystal phase which satisfy | fills following formula (II).

Equation (I) 1.0 ≤ (nx-nz) / (nx-ny) <1.1

Equation (II) 20 <(nx-nz) / (nx-ny) ≤ ∞

In formulas (I) and (II), nx, ny, and nz represent the refractive index of the 3 directions orthogonal to each liquid crystal phase which the said liquid crystalline composition (R) and the said liquid crystalline composition (D) express, respectively. However, in each liquid crystal phase, the largest refractive index is nx and the smallest refractive index is nz.

As a method of calculating the refractive index of the liquid crystal phase in three directions, for example, the report by Sakai (`` A method for analyzing birefringence of a film using an automatic birefringence meter '' Plastics, Vol. 51, No. 3, 57 (2000)) can do.

In this invention, a liquid crystalline composition (R) and a liquid crystalline composition (D) are respectively liquid crystalline compositions containing 1 or more types of liquid crystalline compounds, and also includes the case where it is only 1 type of liquid crystalline compounds. When containing 2 or more types of liquid crystalline compounds, combined use of a polymeric liquid crystalline compound and a nonpolymerizable liquid crystalline compound is possible, for example. Moreover, the combination of a low molecular liquid crystalline compound and a high molecular liquid crystalline compound is also possible.

Moreover, in addition to a liquid crystalline compound, you may contain the additive (for example, an air interface orientation control agent, a damping inhibitor, a polymerization initiator, a polymerizable monomer, a solvent, etc.) which can be added in formation of the optically anisotropic layer mentioned later. You may add these additives when mixing and forming a liquid crystalline composition (R) and a liquid crystalline composition (D).

[Liquid crystalline composition (R) expressing liquid crystal phase satisfying formula (I)]

As a liquid crystal phase which satisfy | fills Formula (I), the nematic phase, the Smectic A phase, the Smectic C phase, etc. which express a liquid crystalline compound which has a rod shape or plate shape, etc. are mentioned, for example. Since this liquid crystal phase has a relationship of nx> ny = nz, it is a uniaxial liquid crystal phase which has positive birefringence. In detail, the liquid crystal handbook (issued by Maruzen Co., Ltd.) is described in Chapter 2 and the like, and in the present invention, the nematic phase is particularly preferable as the liquid crystal phase that satisfies the formula (I).

On the other hand, the liquid crystal phase which is difficult to judge whether it is a uniaxial liquid crystal phase or a biaxial liquid crystal phase is also known. See, eg, D. Demus, J. Goodby et al. Handbook of Liquid Crystals Vol. 2B: Low Molecular Weight Liquid Crystals II, pp933-943: published by WILEY-VCH, Inc.] can be said to be a difficult liquid crystal phase. Liquid crystal phases satisfying the formula (I) also include liquid crystal phases in which such uniaxiality and biaxiality are difficult to determine (when (nx-nz) / (nx-ny) is other than 1).

The determination of the uniaxiality of the liquid crystal phase and the determination of the birefringence of the birefringence can be carried out by observing a conoscope with a polarizing microscope in a state where the liquid crystalline compound is homeotropically aligned. This judgment can be made based on the criteria described in Chapter 3 of Zibo Seitaro, "Polarizing Microscope" (Iwanami Bookstore, published in 1959).

Although the liquid crystalline compound used for the liquid crystalline composition (R) which expresses the liquid crystal phase which satisfy | fills Formula (I) may be a low molecular liquid crystalline compound, and a high molecular liquid crystalline compound may be sufficient as it, a liquid crystalline composition (R) and a formula (II) The low molecular liquid crystalline compound is preferable from the viewpoint of the compatibility of the liquid crystalline composition (D) which expresses the liquid crystalline phase which satisfies.

As a liquid crystalline compound used for the liquid crystalline composition (R) which expresses the liquid crystal phase which satisfy | fills Formula (I), the liquid crystalline compound which expresses the uniaxial liquid crystalline phase which has positive birefringence is preferable, As the compound, For example, azomethines, azoxy compounds, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano substituted phenylpyrimidines, alkoxy Substituted phenyl pyrimidines, phenyl dioxanes, tolans, and alkenylcyclohexyl benzonitriles are mentioned.

The liquid crystalline compound used for the liquid crystalline composition (R) expressing the liquid crystal phase satisfying the formula (I) is a liquid crystalline compound used for the liquid crystalline composition (D) expressing the liquid crystal phase satisfying the formula (II); Among them, it is preferable to have a substituent capable of interacting (eg, hydrogen bonding or dipole interaction) or a substituent capable of forming a covalent bond (eg, a polymerizable group). By having such a substituent, when mixing a liquid crystalline composition (R) and a liquid crystalline composition (D), the compatibility of these compositions will improve and it can avoid that phase separation for each phase which consists of each composition is carried out. It is preferable that the liquid crystalline compound used for a liquid crystalline composition (D) also has the same group for the same reason.

It is preferable that the liquid crystalline compound used for the liquid crystalline composition (R) which expresses the liquid crystal phase which satisfy | fills Formula (I) has a polymeric group, and it is more preferable to have a polymeric group at the terminal of the molecule | numerator of a compound. Having a polymerizable group is preferable in addition to preventing phase separation with the liquid crystalline composition (D) as described above, and when used in a retardation plate or the like with the liquid crystalline composition of the present invention, it is possible to prevent the change of the phase difference by heat or the like. Do.

As a uniaxial liquid crystalline compound having positive birefringence having a polymerizable group, Makromol. Chem., 190, page 2255 (1989), Advanced Materials 5, page 107 (1993), U.S. Patent No. 4683327, U.S. 5622648, U.S. 5770107, International Publication WO 95/22586, U.S. 95 / 24455, 97/00600, 98/23580, 98/52905, JP 1-272551, 6-16616, 7-110469, 11-80081 and Japan The compound described in Unexamined-Japanese-Patent No. 2001-328973 etc. can be used.

Below, the preferable example is shown as the polymeric group which the liquid crystalline compound used for a liquid crystalline composition (R) has.

Among the polymerizable groups, an unsaturated polymerizable group (Q1 to Q7), an epoxy group (Q8) or an aziridinyl group (Q9) is more preferable, an unsaturated polymerizable group (Q1 to Q7) is more preferable, and an ethylenically unsaturated polymerizable group Groups Q1 to Q6 are most preferred.

The shape of the liquid crystalline compound used for the liquid crystalline composition (R) which expresses the liquid crystal phase which satisfy | fills Formula (I) is not specifically limited, A rod shape, plate shape, or another shape may be sufficient as it. Especially, a plate shape is preferable at the point which is compatible with the liquid crystalline composition (D) which expresses the liquid crystal phase which satisfy | fills Formula (II), and the liquid crystalline composition of this invention is easy to express a biaxial liquid crystal phase.

The said liquid crystalline compound being "plate-shaped" is a uniaxial liquid crystalline compound which has at least two core parts which show the liquid crystallinity independently, and has planar positive birefringence in which core parts were connected by covalent bond. Means that. For example, in Example compound (m-1) of this invention mentioned later, the part of RO-Ph-OR (Ph: benzene ring.) Corresponds to the core part which shows liquid crystallinity independently. Portions of RO-Ph-OR are linked by covalent bonds to form exemplary compound (m-1).

More specifically, that a liquid crystalline compound "plate shape" means the following thing. That is, when the longest side of the cuboid which inscribes the stabilizing structure of the liquid crystal compound and has the smallest volume is Ll, the middle side is Lm, and the shortest side is Ls, the liquid crystal compound is Ll. / Lm> 1.1 and also Lm / Ls> 1.5. The most stabilized structure of the liquid crystal compound can be obtained by MOPAC (semi-experimental molecular orbital calculation program), and specifically, the AM1 method (use software: WinMOPAC, vendor: Fujitsu Co., Ltd.) of MOPAC may be used.

In the present invention, the plate-like shape of the liquid crystal compound used for the liquid crystal composition (R) expressing the liquid crystal phase satisfying the formula (I) further satisfies the formulas of the formulas (IV) and (V). It is preferable.

Equation (IV) 1.2 <Ll / Lm <10

Equation (Ⅴ) 2.0 <Lm / Ls <10

As a liquid crystalline compound having a plate-like shape, Mol. Cry. Liq. Cry., Vol. 323, p. 231 (1998), Dyes and Drugs, Vol. 42, No. 4, page 85 (1997), Dyes and Drugs, Vol. 42, No. 3, page 68 (1997) The compound described in the year) etc. and the compound which introduce | transduced the polymeric group in the compound described can be used.

Although the specific example of the liquid crystalline compound suitable for using for a liquid crystalline composition (R) as a liquid crystalline compound which has a plate-like shape below is shown, this invention is not limited to these.

As for the liquid crystal compound having a plate-like shape, a liquid crystal compound represented by the following general formula (R-I) in addition to the above specific examples is preferable.

General formula (R-I)

In formula (RI), L _A represents -VIII- or -VIII-VIII.

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, an acyloxy group And 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, an alkyloxy group having 1 to 10 carbon atoms is preferable, and a halogen atom and a cyano group are most preferred.

n ₁ and n ₂ each independently represent an integer of 0 to 3; As for n <_1> and n <_2> , 0-2 are preferable, respectively. In particular, the (n ₁ + n ₂₎ is from 1 to 4 are preferred.

R _1A , R _2A , R _3A and R _4A each independently represent the following formula (R-IA).

Formula (R-IA)

*-(L _1A -2 valent ring group) pL _2A -2 valent chain group -Q _1A

In formula (R-IA), * represents the position couple | bonded with the benzene ring in formula (R-I).

L _1A Is a single bond or a divalent linking group. L _1A Is a divalent linking group, -O-, -S-, -C (= O)-, -NR _7- , -CH _2- , -CH = CH-, -C≡C-, and combinations thereof It is preferred that it is a divalent linking group selected from the group. R ₇ is an alkyl group or hydrogen atom having 1 to 7 carbon atoms, preferably an alkyl group or hydrogen atom having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or a hydrogen atom, most preferably a hydrogen atom desirable.

L _1A Is 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 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. L _2A When is a bivalent coupling group, it is preferable that it is a bivalent coupling group chosen from the group which consists of -O-, -S-, -C (= O)-, -NR <_7> -, and its combination. R ₇ is an alkyl group or hydrogen atom having 1 to 7 carbon atoms, preferably an alkyl group or hydrogen atom having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or a hydrogen atom, most preferably a hydrogen atom desirable.

L _2A Is a single bond, and * -O-, * -O-CO-, * -CO-O-, * -O-CO-O-, * -CO-, * -S-, * -NR _7- (here In which * represents a position connecting to a divalent cyclic group in the general formula (R-IA). In particular, a single bond, * -O-, * -O-CO-, * -CO-O-, * -O-CO-O- is preferred.

A bivalent cyclic group is a bivalent coupling group which has at least 1 type of cyclic structure. It is preferable that the ring in a bivalent cyclic group is a 5-membered ring, a 6-membered ring, or a 7-membered ring, It is more preferable that it is a 5-membered ring or a 6-membered ring, It is most preferable that it is a 6-membered ring. The ring in the cyclic group may be a condensed ring. However, it is more preferable that it is monocyclic rather than condensed ring. In addition, the ring contained in a 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 heterocycle include pyridine ring, pyrimidine ring, thiophene ring, 1,3-dioxane ring, and 1,3-dithiane ring.

Among the divalent cyclic groups, 1,4-phenylene is preferable 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. As a cyclic group which has a cyclohexane ring, it is preferable that it is 1, 4- cyclohexylene. As a cyclic group which has a pyridine ring, pyridine-2, 5- diyl is preferable. As a cyclic group which has a pyrimidine ring, pyrimidine-2,5-diyl is preferable. As the cyclic group having a thiophene ring, thiophene-2,5-diyl is preferable. As a cyclic group which has a 1, 3- dioxane ring, 1, 3- dioxyene-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 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,3-dioxyene-2,5-diyl This is preferable, 1, 4- phenylene, 1, 4- cyclohexylene, 1, 3- dioxyene-2, 5- diyl is more preferable, and 1, 4- phenylene is especially 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, and an alkyl having 1 to 8 carbon atoms An oxy group, 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, and a halogen atom and a carbon atom number are particularly preferred. An alkyl group of 1 to 3, an alkyloxy group of 1 to 3 carbon atoms, an acyl group of 2 to 4 carbon atoms, an acyloxy group of 2 to 4 carbon atoms, an alkoxycarbonyl group of 2 to 4 carbon atoms, or a cyano group Is preferred.

A bivalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group. Especially, an alkylene group, a substituted alkylene group, an alkenylene group, or a substituted alkenylene group is preferable, and an alkylene group or alkenylene group is more preferable.

The alkylene group as a chain group may have a branch. In addition, -CH ₂ -in the alkylene group may be substituted with -O- or -S-, for example. It is preferable that carbon number of an alkylene group is 1-16, It is more preferable that it is 2-14, It is most preferable that it is 2-12. The alkylene portion of the substituted alkylene group is the same as the alkylene group. Examples of the substituent include an alkyl group or a halogen atom.

The alkenylene group as a divalent chain group may have a substituted or unsubstituted alkylene group in the main chain, and may have a branch. Further, -CH ₂ in the alkenylene group if it has a, -CH ₂ -, for example, or may be substituted with -O-, -S-. It is preferable that carbon number of an alkenylene group is 2-16, It is more preferable that it is 2-14, It is most preferable that it is 2-12. The alkenylene portion of the substituted alkenylene group is the same as the alkenylene group. Examples of the substituent include an alkyl group or a halogen atom.

The alkynylene group as a divalent chain group may have a substituted or unsubstituted alkylene group in the main chain, and may have a branch. Further, -CH ₂ in the alkynylene group if it has a, -CH ₂ - or may include, for example, is replaced with -O-, -S-. It is preferable that carbon number of an alkynylene group is 2-16, It is more preferable that it is 2-14, It is most preferable that it is 2-12. The alkynylene portion of the substituted alkynylene group is the same as the alkynylene group. Examples of the substituent include an alkyl group or a halogen atom.

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

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, a substituted or unsubstituted alkynylene group having 2 to 16 carbon atoms, and particularly preferably 1 to 16 carbon atoms. The substituted or unsubstituted alkylene group of 12 is preferable. As a substituent of a linear group, a C1-C5 alkyl group or a halogen atom is preferable. Most preferably, it is a C1-C12 unsubstituted alkylene group.

Q _1A represents a polymerizable group. The example of a polymeric group is shown below.

Among these, q1-q10 are preferable and q1-q8 are more preferable.

Moreover, it is especially preferable that a polymeric group is a functional group in which addition polymerization reaction is possible. As such a polymerizable group, a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group is preferable.

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 preferred, and (M-1) is most preferred.

As a ring-opening polymerizable group, a cyclic ether group is preferable, Especially, an epoxy group or an oxetanyl group is more preferable, and an epoxy group is the most preferable.

p represents the integer of 0-3. 1 or 2 is especially preferable, and 1 is the most preferable.

The compound which substituted the methine of the benzene ring in general formula (R-I) by the nitrogen atom can also be used.

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

[Liquid crystalline composition (D) which expresses liquid crystal phase satisfying formula (II)]

As a liquid crystal phase which satisfy | fills Formula (II), the discotic nematic phase in which the liquid crystalline compound which has a disk shape, the column form, the column lamellar phase, etc. are mentioned, for example. In this invention, a discotic nematic phase is especially preferable as a liquid crystal phase which satisfy | fills Formula (II).

On the other hand, the liquid crystal phase which is difficult to judge whether it is a uniaxial liquid crystal phase or a biaxial liquid crystal phase is also known. See, eg, D. Demus, J. Goodby et al. Handbook of Liquid Crystals Vol. 2B: Low Molecular Weight Liquid Crystals II, pp933-943: published by WILEY-VCH, Inc.] can be said to be a difficult liquid crystal phase. The liquid crystal phase that satisfies the formula (II) also includes a liquid crystal phase in which such uniaxiality and biaxiality determination is difficult.

Although the liquid crystalline compound used for the liquid crystalline composition (D) which expresses the liquid crystal phase which satisfy | fills Formula (II) may be a low molecular liquid crystalline compound, and a high molecular liquid crystalline compound may be sufficient as a liquid crystalline composition (D) and a formula (I) The low molecular liquid crystalline compound is preferable from the viewpoint of the compatibility of the liquid crystalline composition (R) which expresses the liquid crystalline phase which satisfies.

As a liquid crystalline composition (D) expressing a liquid crystal phase satisfying the formula (II) used in the present invention, various documents (C. Destradeetal., Mol. Crys. Liq. Crys., Vol. 71, p. 111 (1981) ), Japanese Chemical Society, Quarterly Chemistry Summary, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10, Section 2 (1994), B. Kohneetal., Angew.Chem.Soc.Chem.Comm., Pages 1794 (1985), J. Zhangetetal., J. Am. Chem. Soc., 116, 2655 pages (1994) and the like.

It is preferable that a liquid crystalline compound used for the liquid crystalline composition (D) which expresses the liquid crystal phase which satisfy | fills Formula (II) has a polymeric group, and it is more preferable to have a polymeric group in the terminal of the molecule | numerator of a compound. It is preferable to have a polymerizable group in addition to preventing phase separation with the liquid crystalline composition (R) as described above, and when used in a retardation plate or the like with the liquid crystalline composition of the present invention, it is possible to prevent the change of the phase difference by heat or the like. Do.

The liquid crystalline composition of this invention contains the compound represented by following General formula (DI) in liquid crystalline composition (D).

General formula (DI)

In General 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 the methine substituent include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom and a cyano group. Can be mentioned. In these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom, and a cyano group are more preferable, C1-C12 alkyl group, C1-C12 alkoxy group, C2-C12 alkoxycarbonyl group , C2-C12 acyloxy group, a halogen atom, and a cyano group are the most preferable.

Y _11, Y _12, Y ₁₃ is that the whole methine, and most preferably, the methine is also muchi most preferably Whanin.

In 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 is -O-, -S-, -C (= O)-, -NR _7- , -CH = CH-, -C≡C- , A divalent linking group selected from the group consisting of divalent cyclic groups and combinations thereof. R ₇ is an alkyl group or hydrogen atom having 1 to 7 carbon atoms, preferably an alkyl group or hydrogen atom having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or a hydrogen atom, most preferably a hydrogen atom desirable.

The divalent cyclic group represented by L ₁ , L ₂ , L ₃ is a divalent linking group having at least one kind of cyclic structure. It is preferable that a bivalent cyclic group is 5-membered ring, 6-membered ring, or 7-membered ring, It is more preferable that it is 5-membered ring or 6-membered ring, It is most preferable that it is 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferable that it is monocyclic rather than condensed ring. In addition, the ring contained in a cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocycle. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of heterocycles include pyridine rings and pyrimidine rings. The cyclic group is preferably an aromatic ring and a heterocycle.

Of the bivalent cyclic group represented by _{L 1, L 2, L 3} , cyclic group having a benzene ring is a 1,4-phenylene is preferred. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. As a cyclic group which has a cyclohexane ring, it is preferable that it is 1, 4- cyclohexylene. As a cyclic group which has a pyridine ring, pyridine-2, 5- diyl is preferable. As a cyclic group which has a pyrimidine ring, pyrimidine-2,5-diyl is preferable.

Divalent cyclic represented by L _1, L _2, L ₃ group 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, and a halogen having 1 to 16 carbon atoms A substituted alkyl group, 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, an acyloxy group having 2 to 16 carbon atoms, and 2 to 16 carbon atoms The alkoxycarbonyl group, carbamoyl group of 16, the alkyl substituted carbamoyl group of 2-16 carbon atoms, and the acylamino group of 2-16 carbon atoms are contained.

L ₁ , L ₂ , L ₃ are a single bond, * -O-CO-, * -CO-O-, * -CH = CH-, * -C≡C-, and * -2 valent cyclic groups-, * -O-CO-2 valent cyclic group, * -CO-O-2 valent cyclic group-, * -CH = CH-2 valent cyclic group-, * -C≡C-2 valent cyclic group-, * -2 Preferred cyclic groups -O-CO-, * -2 Prevalent cyclic groups -CO-O-, * -2 Prevalent cyclic groups -CH = CH-, * -2 Prevalent cyclic groups -C≡C- are preferable. In particular, a single bond, * -CH = CH-, * -C≡C-, * -CH = CH-2 valent cyclic group-, * -C≡C-2 valent cyclic group- are preferable, and a single bond is the most Preferred (wherein, * represents a position bonded to a 6-membered ring containing Y ₁₁ , Y ₁₂ and Y ₁₃ in General Formula (DI)).

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 , YA ₂ Each independently represents a methine or nitrogen atom. As YA ₁ and YA _2, at least one side is preferably a nitrogen atom, and most preferably both sides are nitrogen atoms. XA represents an oxygen atom, a sulfur atom, methylene or imino. As XA, it is most preferable that it is an oxygen atom. * Is L ₁ to L ₃ Represents a position to be combined with **, R ₁ to R ₃ Indicates the position to be combined with.

General formula (DI-B)

In general formula (DI-B), YB ₁ , YB ₂ Each independently represents a methine or nitrogen atom. ₁ YB, YB ₂ roneun preferably at least one nitrogen atom, and most preferable that the both sides of the nitrogen atom. XB represents an oxygen atom, a sulfur atom, methylene or imino. As XB, it is most preferable that it is an oxygen atom. * Is L ₁ to L ₃ Represents a position to be combined with **, R ₁ to R ₃ Indicates the position to be combined with.

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

General formula (DI-R)

*-(-L ₂₁ -2 pseudocyclic group) n ₁ -L ₂₂ -L ₂₃ -Q ₁

In the general formula (DI-R), * is H ₁ H ~ ₃ of the general formula (DI) Indicates the position to be bound to.

L ₂₁ is a single bond or a divalent linking group. When L ₂₁ is a divalent linking group, it is selected from the group consisting of -O-, -S-, -C (= O)-, -NR _7- , -CH = CH-, -C≡C-, and combinations thereof It is preferable that it is a bivalent coupling group used. R ₇ is an alkyl group or hydrogen atom having 1 to 7 carbon atoms, preferably an alkyl group or hydrogen atom having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or a hydrogen atom, most preferably a hydrogen atom desirable.

L ₂₁ is a single bond, and **-O-CO-, **-CO-O-, **-CH = CH-, **-C≡C- (where ** is a general formula (DI- The left side of L ₂₁ in R) is shown. In particular, a single bond is preferable.

The divalent cyclic group in General Formula (DI-R) is a divalent linking group having at least one kind of cyclic structure. It is preferable that a bivalent cyclic group is 5-membered ring, 6-membered ring, or 7-membered ring, It is more preferable that it is 5-membered ring or 6-membered ring, It is most preferable that it is 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferable that it is monocyclic rather than condensed ring. In addition, the ring contained in a 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 heterocycles include pyridine rings and pyrimidine rings.

Among the divalent cyclic groups, 1,4-phenylene is preferable 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. As a cyclic group which has a cyclohexane ring, it is preferable that it is 1, 4- cyclohexylene. As a cyclic group which has a pyridine ring, pyridine-2, 5- diyl is preferable. As a cyclic group which has a pyrimidine ring, pyrimidine-2,5-diyl is preferable. 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 the substituent include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, and 2 to carbon atoms 16 alkynyl groups, halogen-substituted alkyl groups of 1 to 16 carbon atoms, alkoxy groups of 1 to 16 carbon atoms, acyl groups of 2 to 16 carbon atoms, alkylthio groups of 1 to 16 carbon atoms, and carbon atoms 2 to 16 acyloxy groups, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, alkyl substituted carbamoyl groups having 2 to 16 carbon atoms, and acylamino groups having 2 to 16 carbon atoms. As a substituent of a bivalent cyclic group, a halogen atom, a cyano group, an alkyl group of 1 to 6 carbon atoms, a halogen substituted alkyl group of 1 to 6 carbon atoms is preferable, and a halogen atom, an alkyl group of 1 to 4 carbon atoms, carbon Halogen substituted alkyl groups having 1 to 4 atoms are more preferable, and halogen atoms, alkyl groups having 1 to 3 carbon atoms and trifluoromethyl groups are particularly preferable.

n ₁ represents an integer of 0-4. As n _1, an integer of 1 to 3 is preferable, and 1 or 2 is particularly preferable.

L ₂₂ is * -O-, * -O-CO-, * -CO-O-, * -O-CO-O-, * -S-, * -NR _7- , * -CH _2- , *- CH = CH- and * -C≡C- (wherein * 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- And, particularly preferably * -O-, * -O-CO-, * -O-CO-O-, * -CH _2- . R ₇ is an alkyl group or hydrogen atom having 1 to 7 carbon atoms, preferably an alkyl group or hydrogen atom having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or a hydrogen atom, most preferably a hydrogen atom desirable.

L ₂₃ is a divalent linking group selected from the group consisting of a combination of -O-, -S-, -C (= O)-, -NH-, -CH _2- , -CH = CH-, and -C≡C-. to be. Here, the hydrogen atoms of -NH-, -CH _2- , and -CH = CH- may be substituted 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, alkoxy groups having 1 to 6 carbon atoms, and 2 to 6 carbon atoms An acyl group, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and an alkyl substituted carbon having 2 to 6 carbon atoms Bamoyl groups and acylamino groups having 2 to 6 carbon atoms are included. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable.

L ₂₃ is -O-, -C (= O) - , -CH 2 -, preferably a preparation of -CH = CH-, -C≡C-. L ₂₃ preferably contains 1 to 20 carbon atoms, and particularly preferably 2 to 14 carbon atoms. Further, ₂₃ L is -CH ₂ - preferably contains 1 to 16 and a, -CH ₂ - is particularly preferred containing 2-12 a.

Q ₁ is each independently a polymerizable group or a hydrogen atom. When using the liquid crystalline compound of this invention in the optical film etc. where it is preferable that the magnitude | size of retardation like an optical compensation film does not change with heat, it is preferable that Q <_1> is a polymeric group. It is preferable that a polymerization reaction is addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, it is preferable that a polymeric group is a functional group in which addition polymerization reaction or condensation polymerization reaction is possible. The example of a polymeric group is shown below.

Moreover, it is especially preferable that a polymeric group is a functional group in which addition polymerization reaction is possible. As such a polymerizable group, a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group is preferable.

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 preferred, and (M-1) is most preferred.

As a ring-opening polymerizable group, a cyclic ether group is preferable, Especially, an epoxy group or an oxetanyl group is more preferable, and an epoxy group is the most preferable.

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

General formula (DII)

In general formula (DII), Y <_31> , Y <_32> , Y <_33> are the same as the definition of Y <_11> , Y <_12> , Y <_13> in general formula (DI).

In 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 General Formula (DII-R), A ₃₁ and A ₃₂ each independently represent a methine or nitrogen atom. As A ₃₁ and A _32, at least one side is preferably a nitrogen atom, and most preferably both sides are nitrogen atoms. X ₃ represents an oxygen atom, a sulfur atom, methylene or imino. As X ₃ , it is most preferable that it is an oxygen atom.

The bivalent cyclic group in general formula (DII-R) is a bivalent coupling group which has a 6-membered cyclic structure. The ring contained in the cyclic group may be a condensed ring. However, it is more preferable that it is monocyclic rather than condensed ring. In addition, the ring contained in a cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocycle. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of heterocycles include pyridine rings and pyrimidine rings.

Among the divalent cyclic groups, 1,4-phenylene is preferable 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. As a cyclic group which has a cyclohexane ring, it is preferable that it is 1, 4- cyclohexylene. As a cyclic group which has a pyridine ring, pyridine-2, 5- diyl is preferable. As a cyclic group which has a pyrimidine ring, pyrimidine-2,5-diyl is preferable. 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 the substituent include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, and 2 to carbon atoms 16 alkynyl groups, halogen-substituted alkyl groups of 1 to 16 carbon atoms, alkoxy groups of 1 to 16 carbon atoms, acyl groups of 2 to 16 carbon atoms, alkylthio groups of 1 to 16 carbon atoms, and carbon atoms 2 to 16 acyloxy groups, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, alkyl substituted carbamoyl groups having 2 to 16 carbon atoms, and acylamino groups having 2 to 16 carbon atoms. As a substituent of a bivalent cyclic group, a halogen atom, a cyano group, an alkyl group of 1 to 6 carbon atoms, a halogen substituted alkyl group of 1 to 6 carbon atoms is preferable, and a halogen atom, an alkyl group of 1 to 4 carbon atoms, carbon Halogen substituted alkyl groups having 1 to 4 atoms are more preferable, and halogen atoms, alkyl groups having 1 to 3 carbon atoms and trifluoromethyl groups are particularly preferable.

N <_3> in general formula (DII-R) represents the integer of 1-3. As n ₃ , 1 or 2 is preferable.

L ₃₁ in General Formula (DII-R) has the same definition as L ₂₂ in General Formula (DI-R).

L ₃₂ in General Formula (DII-R) has the same definition as L ₂₃ in General Formula (DI-R).

Q ₃ in General Formula (DII-R) has the same definition as Q ₁ in General Formula (DI-R).

You may use together 2 or more types of discotic liquid crystal compounds as a compound which has a disk shape. For example, you may use together the molecule which has a polymeric group (Q), and the molecule which does not have.

As a liquid crystal phase which the compound represented by general formula (DI) and the liquid crystalline composition containing this compound express, what was mentioned as a liquid crystal phase which satisfy | fills Formula (II) mentioned above is mentioned. Especially, a columner phase or a discotic nematic phase is preferable, and a discotic nematic phase is especially preferable. It is preferable to express in a range of 30-300 degreeC, and, as for a liquid crystal phase, it is more preferable to express in the range of 50-250 degreeC.

Although the specific example of a compound represented by general formula (DI) or general formula (DII) is shown below, 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 this invention contains the liquid crystalline composition (R) which expresses the liquid crystal phase which satisfy | fills Formula (I), and the liquid crystalline composition (D) which expresses the liquid crystal phase which satisfy | fills Formula (II), and is liquid crystalline It is preferable to express a liquid crystal phase in any mixing ratio in the state in which the composition (R) and the liquid crystalline composition (D) were mixed.

In the present invention, the expression of the liquid crystal phase in any mixing ratio in the 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 used in the mixing ratio. Regardless, it means that the liquid crystal phase is expressed in a mixed state without being separated from each other. Thus, for example, as reported by R. Pratiba et al. (Molecular Crystals and Liquid Crystals, 1985, Vol. 1, p. 111), the liquid crystal phase in the state where the liquid crystal composition (R) and the liquid crystal composition (D) are phase separated. When expressing is excluded from the present invention.

The liquid crystal composition of the present invention containing the liquid crystal composition (R) and the liquid crystal composition (D) is a liquid crystal in a state in which both are mixed regardless of the mixing ratio of the liquid crystal composition (R) and the liquid crystal composition (D). Proof of being able to express a phase is a contact test of a liquid crystalline composition expressing a liquid crystal phase satisfying formula (I) and a liquid crystalline composition expressing liquid crystal phase satisfying formula (II) (for example, a liquid crystal handbook). (Described in Chapter 2, page 156, etc. of Maruzen, Inc., 2000). That is, it can implement by observing the presence or absence of liquid crystalline in the area | region where two types of liquid crystalline compositions mix under a polarizing microscope. It can be said that liquid crystallinity can be expressed irrespective of a mixing ratio as long as liquid crystallinity can be observed in the whole area | region in a contact test.

The liquid crystal composition of the present invention containing the liquid crystal composition (R) and the liquid crystal composition (D) has a liquid crystal phase of 20 ° C. to 300 ° C. in a state in which the liquid crystal composition (R) and the liquid crystal composition (D) are mixed. It is preferable to express in the range. More preferably, they are 40 degreeC-280 degreeC, Most preferably, they are 60 degreeC-250 degreeC. Herein, the expression of the liquid crystal phase at 20 ° C to 300 ° C means that the liquid crystal temperature range is around 20 ° C (specifically, for example, 10 ° C to 22 ° C), or 300 ° C around (specifically, for example, 298). ° C to 310 ° C) is also included. The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.

It is preferable that the liquid crystalline composition of this invention containing a liquid crystalline composition (R) and a liquid crystalline composition (D) is a liquid crystalline composition which optically expresses a biaxial liquid crystalline phase. The biaxial liquid crystal phase is a liquid crystal phase in which the refractive indices (nx, ny, nz) in the triaxial directions are different, and satisfy the relationship of nx> ny> nz, for example.

In the liquid crystal composition of the present invention containing 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 expressing the biaxial liquid crystal phase is a liquid crystal. Since it depends on the molecular structure and molecular weight of an crystalline composition (R) and a liquid crystalline composition (D), a clear definition is not possible, but liquid crystalline composition (R) / liquid crystalline composition (D) = 10-0.02 are preferable at a mass ratio, , 5-0.05 are more preferable, and 2-0.1 are the most preferable.

The biaxial liquid crystal phase is often expressed at a lower temperature than the uniaxial liquid crystal phase. For example, it is often transferred to a biaxial nematic phase by lowering a uniaxial nematic phase (rod-shaped nematic phase or discotic nematic phase). In most cases, when the content rate of the liquid crystalline composition (R) is slightly increased on the basis of a certain mixing ratio (liquid crystalline composition (R) / liquid crystalline composition (D)), the biaxial nema is formed from the rod-like nematic phase at the time of temperature drop. Transition to tick phase occurs. In addition, when the content rate of the liquid crystalline composition (D) is slightly increased, the transition from the discotic nematic phase to the biaxial nematic phase occurs.

In the liquid crystalline composition of this invention containing a liquid crystalline composition (R) and a liquid crystalline composition (D), when there exists a uniaxial nematic phase on the high temperature side of a biaxial nematic phase, it is (nx-nz) The value of / (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 value of (nx-nz) / (nx-ny) does not change suddenly but gradually with temperature. There is a tendency to rise. Therefore, the value of (nx-nz) / (nx-ny) can be controlled by selecting the temperature which orientation fixation, such as superposition | polymerization by UV irradiation. The control range width of the (nx-nz) / (nx-ny) value when the transition from the rod-like nematic phase to the biaxial nematic phase changes depending on the molecular structure of the liquid crystal composition (R) and the liquid crystal composition (D), and the like. Therefore, although not uniformly defined, the range closer to 1.0 is easier 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 control of the (nx-nz) / (nx-ny) values becomes possible as in the case of the transition from the rod-like nematic phase, but in this case, the discotic nematic phase Since the (nx-nz) / (nx-ny) values on the ticks are ∞ (nx = ny), the range closer to ∞ is easier to control because the control range width is ∞. Specifically, 1.2 <(nx-nz) / (nx-ny) <∞ is easy to control.

When the liquid crystalline composition of the present invention containing the liquid crystalline composition (R) and the liquid crystalline composition (D) expresses a biaxial liquid crystal phase optically, the refractive indexes in the three directions of the biaxial liquid crystal phase are nx, ny, nz (nx > ny> nz), each value preferably satisfies the following formula (III), and more preferably satisfies the following formula (VI). By satisfy | filling the value of this range, the angle dependence of retardation can be controlled according to a liquid crystal display device.

Equation (III) 1.1 ≤ (nx-nz) / (nx-ny) ≤ 20

Equation (VI) 1.2 ≤ (nx-nz) / (nx-ny) ≤ 10

Moreover, it is preferable that the liquid crystalline composition of this invention containing a liquid crystalline composition (R) and a liquid crystalline composition (D) has the said optical property, takes uniform, defect-free orientation, and shows favorable monodomain property. Do. In the case where the monodomain property is poor, the structure obtained becomes a polydomain, and orientation defects occur at the boundary between domains, resulting in light scattering. When good monodomain property is shown, when used for a retardation plate, it becomes easy to have a high light transmittance.

As a biaxial liquid crystal phase which the liquid crystal composition of this invention containing a liquid crystal composition (R) and a liquid crystal composition (D) expresses, a biaxial nematic phase, a biaxial smectic A phase, and a biaxial smectic C phase are mentioned. have. In these liquid crystal phases, the biaxial nematic phase (Nb phase) which shows favorable monodomain property is preferable. A biaxial nematic phase is one kind of liquid crystal phase which a nematic liquid crystalline compound can take, and when the space of a liquid crystal phase is defined by the x-axis, the y-axis, and the z-axis, the liquid crystalline compound xz centered on the y-axis The free rotation of the plane and the free rotation of the xy plane about the z axis are also prohibited.

[Phase plate]

The retardation plate of the present invention has at least one optically anisotropic layer formed of the liquid crystal composition of the present invention on the transparent support. It is preferable to form an alignment film between the transparent support and the optically anisotropic layer. An optically anisotropic layer is obtained by adding another additive as needed to the liquid crystal composition of this invention, apply | coating this composition on an oriented film, and fixing it by fixing the orientation of a liquid crystal state.

It is preferable that the thickness of the optically anisotropic layer in the retardation plate of this invention is 0.1-20 micrometers, It is more preferable that it is 0.2-15 micrometers, It is most preferable that it is 0.5-10 micrometers.

The phase difference plate of this invention can be used for the use of an elliptical polarizing plate in combination with a polarizing film. In addition, by applying in combination with a polarizing film to a transmissive, reflective and transflective liquid crystal display device, it is possible to contribute to the expansion of the viewing angle of the device.

[Optical anisotropic layer]

By forming the optically anisotropic layer using the liquid crystal composition of the present invention, the optical anisotropy of the optically anisotropic layer can be adjusted so that the refractive index main values in three directions perpendicular to each other are different optical biaxiality. It is preferable that the refractive index main value in the three directions of the optically anisotropic layer also satisfies the following formula (III), and more preferably satisfies the following formula (VI).

Equation (III) 1.1 ≤ (nx-nz) / (nx-ny) ≤ 20

Equation (VI) 1.2 ≤ (nx-nz) / (nx-ny) ≤ 10

The angle dependence of retardation differs in the biaxial retardation plate which provided the biaxial liquid crystalline composition on the transparent support body, and the uniaxial retardation plate which provided the uniaxial liquid crystalline composition. For example, in a retardation plate using a uniaxial liquid crystalline composition, retardation in the normal direction of the plate surface and retardation in the angular direction of several tens of degrees from the normal line are significantly different (retardation becomes smaller when tilted in the slow axis direction, Tilt in direction to increase). On the other hand, in the case of a biaxial liquid crystalline composition, it differs from the retardation change rate in a uniaxial liquid crystalline composition. When manufacturing the retardation plate used for various liquid crystal display devices, it is necessary to control the angle dependence of retardation according to the liquid crystal display device, When using a biaxial liquid crystalline composition, the refractive index difference of nx, ny, nz is used. It is very useful because the angle dependence of the retardation can be arbitrarily controlled by changing the direction of orientation of each axis.

An optically anisotropic layer can be formed by fixing the liquid crystalline composition of this invention to a liquid crystal phase formation temperature once, and then cooling it, maintaining the orientation state, without impairing the orientation form in the liquid crystal state. 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 can superpose | polymerize and cool, 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 immobilized is a state in which the orientation is maintained, which is the most typical and preferred embodiment. However, the state is not limited thereto. Under harsh conditions, the immobilized liquid crystal composition does not have fluidity in the temperature range of −30 ° C. to 70 ° C., and does not change the alignment form due to the exterior or external force, and can stably maintain the fixed alignment form. It's a state of presence. Moreover, when the orientation state is finally fixed and the optically anisotropic layer is formed, the liquid crystalline composition of the present invention does not need to exhibit liquid crystal anymore. For example, since the compound which has a polymeric group is used as a liquid crystalline compound, superposition | polymerization or crosslinking reaction advances by reaction with heat, light, etc. as a result, it may make high molecular weight and lose liquid crystalline.

Examples of the additive which can be added to the liquid crystalline composition of the present invention in the formation of the optically anisotropic layer include an air interface alignment control agent, a antifogging agent, a polymerization initiator, a polymerizable monomer and the like.

[Air Interface Orientation Control Agent]

The liquid crystal composition is oriented at the tilt angle of the air interface at the air interface. For example, in the case of a biaxial liquid crystalline composition, this tilt angle has three types of tilt angles formed by the nx refractive index direction and the air interface, tilt angles formed by the ny refractive index direction, and the air interface, and tilt angles formed by the nz refractive index direction and the air interface. There is.

When this tilt angle contains the kind and two or more types of liquid crystalline compounds contained in a liquid crystalline composition, since the grade changes with the mixing ratio, it is necessary to arbitrarily control the tilt angle of an air interface according to the objective.

For the control of the tilt angle, for example, an sheath such as an electric field or a magnetic field can be used or an additive can be used, but an additive is preferably used. As such an additive, a compound having 6 or 40 substituted or unsubstituted aliphatic groups having 6 to 40 carbon atoms, or one or more substituted or unsubstituted aliphatic substituted oligosiloxaneoxy groups having 6 to 40 carbon atoms in the molecule, is preferable. The compound which has two or more is more preferable. For example, the hydrophobic exclusion volume effect compound of Unexamined-Japanese-Patent No. 2002-20363 can be used as an air interface orientation control agent.

As addition amount of the orientation control additive on an air interface side, 0.001 mass%-20 mass% are preferable with respect to the liquid crystalline composition of this invention, 0.01 mass%-10 mass% are more preferable, 0.1 mass%-5 mass% Most preferred.

[Prevention agent]

As a material for adding to the liquid crystalline composition of the present invention and preventing splashing during coating of the composition, a high molecular compound can be preferably used.

As a polymer to be used, there is no restriction | limiting in particular, unless the inclination-angle change and orientation of the liquid crystalline composition of this invention are remarkably inhibited.

Examples of the polymer are described in Japanese Patent Application Laid-open No. Hei 8-95030, and examples of particularly preferred specific polymers include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose and cellulose acetate butyrate.

The addition amount of the polymer used for the purpose of anti-fogging so as not to inhibit the orientation of the liquid crystalline composition of the present invention is generally in the range of 0.1 to 10% by mass and in the range of 0.1 to 8% by mass relative to the liquid crystalline composition of the present invention. It is more preferable to exist, and it is still more preferable to exist in the range of 0.1-5 mass%.

[Polymerization Initiator]

In this invention, it is preferable that the liquid crystalline composition is fixed in the state in which the monodomain orientation, ie, it is substantially uniformly oriented. Therefore, when the compound contained in a liquid crystalline composition (R) and / or a liquid crystalline composition (D) has a polymeric group, it is preferable to superpose | polymerize and fix it 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 deformation or deterioration of a support or the like by heat, Polymerization reaction is preferred.

Examples of photopolymerization initiators include α-carbonyl compounds (described in the specifications of US Pat. No. 23,684,1, 2367670), acyloinether (described in the specification of US Pat. No. 2448828), α-hydrocarbon substituted aromatic acylin compounds (US Patent No. 2722512), multinuclear quinone compounds (see US Pat. No. 3046127, each specification in US Pat. No. 2951758), combination of triarylimidazole dimers and p-aminophenylketone (described in US Pat. No. 3549367), Acridine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, described in US Pat. No. 4,239,850 specifications), and oxadiazole compounds (described in US Pat. No. 4,212,970 specifications).

It is preferable that it is 0.01-20 mass% of the coating liquid solid content of an optically anisotropic layer, and, as for the usage-amount of a photoinitiator, it is more preferable that it is 0.5-5 mass%.

It is preferable to use ultraviolet rays for light irradiation for polymerization. It is preferable that it is 10mJ-50J / cm <2>, and, as for irradiation energy, it is more preferable that it is 50mJ-800mJ / cm <2>. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. In addition, since the oxygen concentration in the atmosphere is involved in the degree of polymerization, when the desired degree of polymerization is not reached in air, it is preferable to lower the oxygen concentration by a method such as nitrogen substitution. As a preferable oxygen concentration, 10% or less is preferable, 7% or less is more preferable, and 3% or less is the most preferable.

[Polymerizable Monomer]

You may add a polymerizable monomer to the liquid crystalline composition of this invention. As a polymerizable monomer which can be used by this invention, it has compatibility with the compound contained in the liquid crystalline composition (R) and liquid crystalline composition (D) of this invention, and does not cause the inclination angle change and orientation inhibition of a liquid crystal composition remarkably. There is no limitation in particular. In these, the compound which has a polymerization activity ethylenically unsaturated group, for example, a vinyl group, a vinyloxy group, acryloyl group, a methacryloyl group, etc. is used preferably. It is preferable that the addition amount of the said polymerizable monomer exists in the range of 0.5-50 mass% with respect to a liquid crystalline compound generally, and exists in the range of 1-30 mass%. Moreover, since the effect of improving the adhesiveness between an oriented film and an optically anisotropic layer can be anticipated when using the monomer with 2 or more reactive functional groups, it is especially preferable.

Coating solvent

As a solvent used for preparation of the liquid crystalline composition of this invention, an organic solvent is used preferably. 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 (e.g. methyl acetate, butyl acetate), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (e.g. tetrahydrofuran, 1,2- Dimethoxyethane). Alkyl halides, esters and ketones are preferred. You may use together 2 or more types of organic solvents.

[Application method]

An optically anisotropic layer is formed by preparing the coating liquid of the liquid crystalline composition of the present invention using the above solvent, applying it on an alignment film, and orientation treatment of the liquid crystalline composition of the present invention. Application | coating of a coating liquid can be performed by a well-known method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).

[Alignment Film]

The alignment film is an organic compound (e.g., ω) by rubbing treatment of an organic compound (preferably a polymer), evaporation of an inorganic compound, formation of a layer having a microgroove, or a Langmuir blob method (LB film). -Trichoic acid, methyl stearyl acid), and the like. Moreover, the orientation film which an orientation function produces by provision of an electric field, provision of a magnetic field, or light irradiation is also known.

Although what kind of layer may be sufficient as an orientation film as long as it can provide a desired orientation to the liquid crystalline composition of this invention of the optically anisotropic layer formed on an orientation film, in this invention, the orientation film formed by a rubbing process or light irradiation is preferable. Do. The alignment film formed by the rubbing process of a polymer is especially preferable. In general, the rubbing treatment can be carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. Particularly, in the present invention, the rubbing treatment is preferably carried out by the method described in the liquid crystal handbook (Maruzen Co., Ltd.). Do. It is preferable that it is 0.01-10 micrometers, and, as for the thickness of an oriented film, it is more preferable that it is 0.05-3 micrometers.

(Rubber Density of Alignment Film)

Between the rubbing density of the alignment film and the pretilt angle of the liquid crystal compound at the alignment film interface, if the rubbing density is increased, the pretilt angle becomes smaller, and if the rubbing density is lowered, the pretilt angle increases, so the rubbing density of the alignment film You can adjust the pretilt angle by changing.

As a method of changing the rubbing density of an oriented film, the method described in the "liquid crystal handbook" liquid crystal handbook editing committee edition (Maruzen Co., 2000) can be used. The rubbing density (L) is quantified by the formula (A).

Formula (A) L = Nl {1+ (2πrn / 60v)}

In 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 rotation speed (rpm) of the roller, and v is the stage moving speed (second speed). In order to increase the rubbing density, the number of rubbings may be increased, the contact length of the rubbing rollers may be increased, the radius of the rollers may be increased, the number of rotations of the rollers may be increased, or the stage moving speed may be slowed. This can be done in reverse.

[Transparent support]

The transparent support of the retardation plate of the present invention is mainly optically isotropic, and if the light transmittance is 80% or more, the material is not particularly limited, but a polymer film is preferable.

Specific examples of the polymer include cellulose acylates (eg, cellulose diacetate, cellulose triacetate), norbornene-based polymers, films of poly (meth) acrylate esters, and the like. It is possible to do Among these, cellulose esters are preferable from a viewpoint of optical performance, and the lower fatty acid ester of cellulose is more preferable. Lower fatty acids are fatty acids having 6 or less carbon atoms, and the carbon atoms are preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose triacetate is particularly preferred. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used. Moreover, the polymer which is easy to express birefringence, such as a polycarbonate and polysulfone conventionally known, may be used, or the thing which reduced the expressability by the modification of the molecule | numerator of WO00 / 26705 specification can also be used.

Hereinafter, the cellulose acylate (especially cellulose triacetate) used preferably as a transparent support body is described in detail.

As cellulose acylate, it is preferable to use the cellulose acetate whose acelation degree is 55.0-62.5%. It is preferable that especially the degree of acetonitrile is 57.0-62.0%. Acetization degree means the amount of bound acetic acid per cellulose unit mass. Acetization degree is based on the measurement and calculation of the acetylation degree in ASTM: D-817-91 (test methods, such as a cellulose acetate). It is preferable that it is 250 or more, and, as for the viscosity average polymerization degree (DP) of a cellulose ester, it is more preferable that it is 290 or more. Moreover, it is preferable that the cellulose ester used for this invention has a narrow molecular weight distribution of Mw / Mn (Mw is mass mean molecular weight, Mn is number average molecular weight) by gel permeation chromatography. As a specific value of Mw / Mn, it is preferable that it is 1.0-1.7, It is more preferable that it is 1.3-1.65, It is most preferable that it is 1.4-1.6.

In cellulose acylate, hydroxyl groups in the second, third and sixth positions of cellulose are not evenly distributed by 1/3 of the total degree of substitution, but tend to decrease the degree of substitution of the sixth position hydroxyl groups. It is preferable that the substitution degree of the 6th-position hydroxyl group of cellulose is large compared with 2nd and 3rd positions. It is preferable that the hydroxyl group at the 6th position is substituted with an acyl group at 30% or more and 40% or less with respect to the total degree of substitution, more preferably 31% or more, particularly 32% or more. It is preferable that the substitution degree of 6 is 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 measurement of the substitution degree of each position can be calculated | required by NMR. The cellulose ester with a high degree of substitution of a 6-position hydroxyl group is the synthesis example 1 of Paragraph No. 0043-0044 of Unexamined-Japanese-Patent No. 11-5851, the synthesis example 2 of Paragraph No. 0048-0049, and the synthesis of Paragraph No. 0051-0052. Synthesis can be carried out with reference to the method of Example 3.

In order to adjust retardation, the polymer film used as a transparent support body, especially a cellulose acylate film, can also use the aromatic compound which has an at least 2 aromatic ring as a retardation increasing agent. When using such a retardation increasing agent, it uses in the range of 0.01-20 mass parts with respect to 100 mass parts of cellulose acylates. It is preferable to use a retardation increasing agent in 0.05-15 mass parts with respect to 100 mass parts of cellulose acylates, and it is more preferable to use in 0.1-10 mass parts. You may use together 2 or more types of aromatic compounds.

The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to the aromatic hydrocarbon ring.

It is particularly preferable that the aromatic hydrocarbon ring is a 6-membered ring (that is, a benzene ring).

Aromatic heterocycles are generally unsaturated heterocycles. It is preferable that an aromatic heterocyclic ring is a 5-membered ring, a 6-membered ring, or a 7-membered ring, and it is more preferable that it is a 5-membered ring or a 6-membered ring. Aromatic heterocycles generally have the largest number of double bonds. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, and a nitrogen atom is especially preferable.

As 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. And a benzene ring and a 1,3,5-triazine ring are more preferable. It is particularly preferable that the aromatic compound has at least one 1,3,5-triazine ring.

Examples of the aromatic hetero ring include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring, Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.

It is preferable that the number of the aromatic rings which an aromatic compound has is 2-20, It is more preferable that it is 2-12, It is further more preferable that it is 2-8, It is most preferable that it is 2-6. The bond relationship between two aromatic rings can be classified into (a) forming a condensed ring, (b) directly connecting into a single bond, and (c) bonding through a linking group. Can't). The coupling relationship may be any of (a) to (c). Such retardation synergists are described in WO 01/88574 A1, WO 00/2619 A1, Japanese Patent Laid-Open Nos. 2000-111914, 2000-275434, Japanese Patent Application No. 2002-70009, and the like.

It is preferable to manufacture a cellulose acylate film by the solvent cast method from the prepared cellulose acylate solution (dope). You may add the said retardation increasing agent to dope.

The dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust density | concentration so that dope before casting may be 18 to 35% of solid content. It is preferable to finish the surface of a drum or a band in a mirror state. For the casting and drying method in the solvent cast method, U.S. Pat.Nos.2336310, 2367603, 2492078, 2492977, 2492978, 2607704, 2739069, 2739070, and British Patent No. 640731 Japanese Patent Publication Nos. 45-4554, 49-5614, 60-176834, 60-203430, 62-115035, and the like. have.

It is preferable that the said dope be cast on the drum or band whose surface temperature is 10 degrees C or less. It is preferable to let air dry for 2 seconds or more after being soft. The obtained film may be peeled off from the drum or the band, and further dried by hot air at which the temperature is sequentially changed to 100 to 160 ° C to evaporate the residual solvent. The above method is described in Japanese Patent Application Laid-open No. Hei 5-17844. According to this method, it is possible to shorten the time from casting to peeling. In order to carry out this method, it is necessary to gel dope at the surface temperature of the drum or band at the time of 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 flexible on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust density | concentration so that dope before casting may be 10 to 40% of solid content. It is preferable to finish the surface of a drum or a band in a mirror surface state.

When a some cellulose acylate solution is cast, the film containing the cellulose acylate may be cast by laminating them from a plurality of oil studies formed at intervals in the advancing direction of the support. For example, the method described in each of Unexamined-Japanese-Patent No. 61-158414, Unexamined-Japanese-Patent No. 1-22419, and Unexamined-Japanese-Patent No. 11-198285 can be used. Moreover, you may shape into a film by casting a cellulose acylate solution from two oil studies. For example, Japanese Patent Application Laid-Open No. 60-27562, Japanese Patent Application Laid-Open No. 61-94724, Japanese Patent Application Laid-Open No. 61-104813, Japanese Patent Application Laid-Open No. 61-158413, and Japanese Patent Application Laid-Open No. 6 The method described in each publication of -134933 can be used. In addition, the flow of the high viscosity cellulose acetate solution described in Japanese Patent Application Laid-open No. 56-162617 is wrapped with a low viscosity cellulose acetate solution, and the softness of the cellulose acetate film which simultaneously extrudes the high viscosity and low viscosity cellulose acetate solution. You can also use the method.

A cellulose acylate film can further adjust retardation by an extending | stretching process. It is preferable that a draw ratio exists in 0 to 100% of range. In extending | stretching the cellulose acylate film used for this invention, tenter extending | stretching is used preferably, and in order to control a slow axis highly precisely, it is preferable to make the difference of left and right tenter clip speeds, departure timing, etc. as small as possible.

Plasticizer may be added to the cellulose acylate film in order to improve mechanical properties or to improve the drying speed. Phosphoric acid ester or carboxylic acid ester is used as a plasticizer. Examples of phosphoric acid esters include triphenylphosphate (TPP), diphenylbiphenylphosphate and tricresylphosphate (TCP). Representative carboxylic acid esters are phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and di-2-ethylhexyl phthalate (DEHP). It is contained. Examples of citric acid esters include O-acetylcitrate triethyl (OACTE) and O-acetylcitrate tributyl (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalic acid ester plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred. It is preferable that the addition amount of a plasticizer is 0.1-25 mass% of the quantity of a cellulose ester, It is more preferable that it is 1-20 mass%, It is most preferable that it is 3-15 mass%.

You may add a deterioration inhibitor (for example, antioxidant, a peroxide decomposer, a radical inhibitor, a metal deactivator, an acid trapping agent, an amine), and an ultraviolet-ray to a cellulose acylate film. The deterioration inhibitor is described in Japanese Unexamined Patent Publications No. 3-199201, 5-197073, 5-194789, 5-271471, and 6-107854. It is preferable that it is 0.01-1 mass% of the solution (dope) to prepare, and, as for the addition amount of a deterioration inhibitor, it is more preferable that it is 0.01-0.2 mass%. If the amount added is less than 0.01% by mass, the effect of the deterioration inhibitor is hardly observed. When addition amount exceeds 1 mass%, the bleed out (flow) of the anti-deterioration agent to a film surface may be observed.

Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT). The ultraviolet-ray inhibitor is described in Unexamined-Japanese-Patent No. 7-11056.

It is preferable to perform surface treatment of a cellulose acylate film. Specific methods include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment or ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is also preferably used to form the undercoat layer.

It is preferable to make temperature of a cellulose acylate film below Tg (glass transition temperature), specifically 150 degrees C or less in these processes from a viewpoint of maintaining planarity of a film.

As for the surface treatment of a cellulose acylate film, it is especially preferable to perform acid treatment or alkali treatment, ie, saponification treatment with respect to a cellulose acylate, from an adhesive viewpoint with an oriented film. Hereinafter, it demonstrates concretely, taking an alkali saponification process as an example. The alkali saponification treatment is preferably performed in a cycle in which the film surface is immersed in an alkaline 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. It is preferable to exist in the range of room temperature-90 degreeC, and, as for alkaline solution temperature, it is more preferable to exist in the range which is 40-70 degreeC.

Moreover, it is preferable that it is 55 mN / m or more, and, as for the surface energy of a cellulose acylate film, it is more preferable to exist in the range of 60-75 mN / m.

Surface energy can be calculated | required by the contact angle method, the wet heat method, and the adsorption method, as described in "The basis and application of wetness" (Issue 1989.12.10). In the case of the cellulose acylate film used for this invention, it is preferable to use a contact angle method. Specifically, two kinds of solutions in which the surface energy is known are added dropwise to the cellulose acylate film, and at the intersection of the surface of the droplet and the film surface, the angle of the side containing the droplet at the angle formed by the tangent drawn on the droplet and the film surface. Is defined as the contact angle, and the surface energy of the film can be calculated by calculation.

The range of 5-500 micrometers is preferable normally, as for the thickness of a cellulose acylate film, the range of 20-250 micrometers is preferable, The range of 30-180 micrometers is more preferable, The range of 30-110 micrometers is especially preferable.

[Elliptical Polarizer]

An elliptical polarizing plate can be produced by laminating the retardation plate and the polarizing film of the present invention. By using the phase difference plate of this invention, the elliptical polarizing plate which can enlarge the viewing angle of a liquid crystal display device can be provided.

The polarizing film includes an iodine polarizing film and a dye polarizing film or a polyene polarizing film using a dichroic dye. 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 on the opposite side to the side which laminated | stacked the phase difference plate of a polarizing film. It is preferable that a transparent protective film is 80% or more in light transmittance. Generally as a transparent protective film, a cellulose ester film, Preferably a triacetyl cellulose film is used. It is preferable to form a cellulose-ester film by the solvent cast method. It is preferable that it is 20-500 micrometers, and, as for the thickness of a transparent protective film, it is more preferable that it is 50-200 micrometers.

[Liquid crystal display device]

The use of the retardation plate of the present invention can provide a liquid crystal display device having an enlarged viewing angle. Retardation plates (optical compensation sheets) for liquid crystal cells in TN mode are described in the specifications of JP-A-6-214116, US Pat. No. 5,538,379, 5646703, and German Patent No. 3911620 A1. In addition, the optical compensation sheet for liquid crystal cells of IPS mode or FLC mode is described in Unexamined-Japanese-Patent No. 10-54982. Further, optical compensation sheets for liquid crystal cells in OCB mode or HAN mode are described in US Pat. No. 5,525,525 and International Publication WO 96/37804. In addition, the optical compensation sheet for liquid crystal cells of STN mode is described in Unexamined-Japanese-Patent No. 9-26572. And the optical compensation sheet for liquid crystal cells of VA mode is described in Unexamined-Japanese-Patent No. 2866372.

In the present invention, a retardation plate (optical compensation sheet) for liquid crystal cells of various modes can be produced with reference to the above-described publication. The retarder of the present invention is twisted nematic (TN), In-Plane Switching (IPS), ferroelectric liquid crystal (FLC), optically Compensatory Bend (OCB), super twisted nematic (STN), vertically aligned (VA) and hybrid (HAN) hybrid It can be used for the liquid crystal display device of various display modes, such as Aligned Nematic mode.

The liquid crystal display device consists of a liquid crystal cell, a polarizing element, and a retardation plate (optical compensation sheet). A polarizing element generally consists of a polarizing film and a protective film. As the polarizing film and the protective film, those described for the elliptical polarization can be used.

(Example)

Although an Example is given to the following and this invention is demonstrated, this invention is not limited to these specific examples.

(Example 1)

[Production of phase difference board]

(Formation of alignment film)

The following modified polyvinyl alcohol and glutaraldehyde (5 mass% of modified polyvinyl alcohol) were dissolved in a mixed solvent of methanol / water (volume ratio = 20/80) to prepare a 5 mass% solution.

This solution was applied onto a glass base, dried for 120 seconds with warm air at 100 ° C., and then subjected to a rubbing treatment to form an alignment film. The film thickness of the obtained alignment film was 0.5 micrometer.

(Formation of optically anisotropic layer)

The optically anisotropic layer coating liquid which has the following composition was apply | coated on the rubbed alignment film produced above using the spin coater.

(Optical anisotropic layer coating liquid)

ㆍ 70.0 parts by mass of liquid crystal compound D-109

ㆍ 30.0 parts by mass of the liquid crystalline compound TO-3

ㆍ 0.2 parts by mass of air interface alignment control agent V- (1)

ㆍ Solucure 907 (Chiba Specialty Chemicals, Inc.) 1.0 parts by mass

ㆍ 700 parts by mass of chloroform

Air Interface Orientation Control Agent V- (1)

The glass base coated with the optically anisotropic layer was placed in a thermostat at 130 ° C. and cooled while observing with a polarization microscope, and then transitioned to a nematic phase at 80 ° C. Then, it cooled to 70 degreeC and hold | maintained at that temperature for 2 minutes. Next, it put into the 80 degreeC thermostat of 2% of oxygen concentration, and after 5 minutes, irradiated with 600mJ ultraviolet-ray, and fixed the orientation state of the optically anisotropic layer. It cooled to room temperature and the retardation plate was produced. The thickness of the optically anisotropic layer was 0.8 mu m.

The angle dependence of the retardation of the obtained retardation plate was measured, and when (nx-nz) / (nx-ny) was calculated | required, it was 4.0 and confirmed that it was a biaxial liquid crystal phase.

(Example 2)

Synthesis of D-101

It synthesized according to the following scheme.

To 5.18 g of sodium hydride, 100 ml of tetrahydrofuran and 11.7 ml of hexanol were added. After 20 minutes of stirring at room temperature, a solution in which 10 g of 3,4-difluorobenzonitrile was 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, followed by extraction with ethyl acetate, and then the organic layer was concentrated and purified using column chromatography to obtain 15.5 g of D-101A crystals. Then, 15.5 g of D-101A was dissolved in 50 ml of ethanol, and 12.0 ml of 50% hydroxylamine solution was added, followed by stirring 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, followed by stirring at 90 ° C. for 7 hours. After cooling, methanol was added to precipitate precipitated crystals. Purification by column chromatography gave D-101. The NMR spectrum of obtained D-101 is as follows.

As a result of performing the phase transition temperature of the obtained D-101 by the texture observation by a polarization microscope, the temperature was raised, it changed into a discotic nematic liquid crystal phase from 135 degreeC vicinity, and when it exceeded 162 degreeC, it turned into an isotropic liquid 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% of hydroquinone monomethyl ether) was injected into a horizontally aligned cell (manufactured by EHC Co., Ltd .; KSPR-10 / A107M1NSS (ZZ)) having a cell gap of 10 μm at 180 ° C., at 150 ° C. Homeotropic orientation. In this state, (nx-nz) / (nx-ny) is ∞ (that is, nx = ny) from the angle dependence measurement of the retardation and the observation of the conoscope, and D-101 is a liquid crystal phase satisfying the formula (II). It was found to express.

(Example 3)

Synthesis of D-109

It synthesized according to the following scheme.

11.0 g of D-109A (the same compound as D-101) is replaced with CH ₂ Cl ₂ Dissolved in 50 ml boron tribromide (1.0 M CH ₂ Cl ₂ Solution) 135 ml was added. After stirring at 40 degreeC for 8 hours, water was added to the reaction liquid, and the precipitated crystal | crystallization was obtained by filtration. By drying this crystal, 7.8g of D-109B was obtained.

After dissolving 0.34 g of 6-bromohexanol in 5 ml of dimethylacetamide, 0.26 ml of acrylic acid chloride was added dropwise, stirred at room temperature for 1 hour, and then 20 ml of water and 20 ml of hexane were added to wash the organic layer. . After 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 solution, the mixture was extracted with CH ₂ Cl ₂ , and the organic layer was concentrated and purified by column chromatography to obtain 0.37 g of D-109 crystals. The NMR spectrum of D-109 obtained is as follows.

As a result of performing the phase transition temperature of D-109 obtained by the texture observation by a polarization microscope, temperature was raised, it changed into a discotic nematic liquid crystal phase from 79 degreeC vicinity, and turned into an isotropic liquid phase when it exceeded 120 degreeC. 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% of hydroquinone monomethyl ether) was injected into a horizontally aligned cell (manufactured by EHC Co., Ltd .; KSRP-10 / A107M1NSS (ZZ)) having a cell gap of 10 μm at 150 ° C., and at 110 ° C. Homeotropic orientation. In this state, (nx-nz) / (nx-ny) is ∞ (that is, nx = ny) from the angle dependence measurement of the retardation and the observation of the conscope, and D-109 is a liquid crystal phase satisfying formula (II). It was found to express.

(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 solution, followed by extraction with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, dilute hydrochloric acid, water and saturated brine, and then the solvent was evaporated under reduced pressure. Crystallized with hexane, 32.2 g of m-4A crystals were obtained.

(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 iodide (triethylamine) It was dissolved in 200 ml and refluxed under nitrogen atmosphere for 10 hours. After cooling, the precipitated triethylamine hydrochloride was separated by filtration, 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 (1.0M solution) of tetrabutylammonium fluoride (TBAF) was added, and the mixture was stirred at room temperature for 30 minutes. Water was added to the reaction solution, followed by extraction with ethyl acetate and washing with saturated brine. The organic layer was concentrated under reduced pressure, and then purified by column chromatography to obtain 20.5 g of m-4C crystals.

(synthesis of m-4D)

Trimethyl phosphate 3.0 g, 1,3-dibromobenzene 1.38 g, triphenylphosphine 58 mg, bis (triphenylphosphine) palladium (II) dichloride and 29 mg of copper iodide (I) It was dissolved in 23 ml of ethylamine and refluxed under nitrogen atmosphere for 10 hours. After cooling, 100 ml of methanol was added, and the precipitated crystals were filtered out. Purification by column chromatography gave 2.1 g of crystals of m-4D.

(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 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)

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

Moreover, when the phase transition temperature of m-4 obtained was performed by the texture observation by a polarization microscope, temperature was raised, it changed into a nematic liquid crystal phase from 105 degreeC vicinity, and turned into an isotropic liquid phase when it exceeded 156 degreeC. That is, it was found that m-4 exhibits a nematic liquid crystal phase between 105 ° C and 156 ° C.

m-4 (containing 0.1 wt% of hydroquinone monomethyl ether) was injected into a horizontally aligned cell (manufactured by EHC Co., Ltd .; KSPR-10 / A107M1NSS (ZZ)) having a cell gap of 5 μm at 170 ° C., and at 140 ° C. Homogeneous orientation. In this state, the angle dependence of the retardation was measured and (nx-nz) / (nx-ny) was determined, and as a result, it was found that m-4 represents a liquid crystal phase satisfying the formula (I). okay.

(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 copper iodide (I 10 mg) was dissolved in 50 ml of triethylamine, and the mixture was refluxed under a nitrogen atmosphere for 10 hours. After cooling, water was added to the reaction solution, the mixture was extracted with ethyl acetate, and then washed with saturated brine. The organic layer was concentrated under reduced pressure, and then 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 iodide in 20 ml of triethylamine It was dissolved and refluxed under nitrogen atmosphere for 10 hours. After cooling, water was added to the reaction solution, followed by extraction with ethyl acetate and washing with saturated brine. The organic layer was concentrated under reduced pressure, and then 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 (1.0M solution) of tetrabutylammonium fluoride was added, and stirred at room temperature for 30 minutes. Water was added to the reaction solution, followed by extraction with ethyl acetate and washing with saturated brine. The organic layer was concentrated under reduced pressure, and then 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 were added to 15.2 g of 3,5-dibromo-4-hydroxybenzaldehyde, and heated to 50 ° C, followed by 20 ml of 6.2 ml (31%) of hydrogen peroxide water. The diluted solution was added dropwise. After reacting at 50 degreeC for 5 hours, hydrochloric acid was added and the precipitated crystal | crystallization was obtained by filtration. After the crystals were dried, 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 with water removed. Water was added to the reaction solution, followed by extraction with ethyl acetate and washing with saturated brine. The organic layer was concentrated under reduced pressure, and then hexane was added to the obtained crystals, followed by heating and washing for 30 minutes. Filtration in the heating state gave 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 solution, followed by extraction with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, dilute hydrochloric acid, water and saturated brine, and then the solvent was evaporated under reduced pressure. Crystallization with hexane gave 9.3 g of crystals of m-22E.

(synthesis of m-22F)

0.7 g of m-22C, 0.37 g of m-22E, 10 mg of triphenylphosphine, 5 mg of bis (triphenylphosphine) palladium (II) dichloride and 2 mg of copper iodide in 20 ml of triethylamine It was dissolved and refluxed under nitrogen atmosphere for 10 hours. After cooling, water was added to the reaction solution, followed by extraction with ethyl acetate and washing with saturated brine. The organic layer was concentrated under reduced pressure, and then 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 extracted with ethyl acetate. The obtained organic layer was distilled off under reduced pressure to obtain 0.10 g of m-22G crystal.

(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 solution, 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 crystal of m-22. The NMR spectrum of obtained m-22 is as follows.

As a result of performing the phase transition temperature of m-22 obtained by the texture observation by a polarization microscope, temperature was raised, it turned into a nematic liquid crystal phase from 110 degreeC vicinity, and turned into an isotropic liquid phase when it exceeded 156 degreeC. That is, it turned out that m-22 shows the nematic liquid crystal phase between 110 degreeC and 156 degreeC.

m-22 (containing 0.1 wt% of hydroquinone monomethyl ether) was injected into a horizontally aligned cell (manufactured by EHC Co., Ltd .; KSPR-10 / A107M1NSS (ZZ)) having a cell gap of 5 μm at 170 ° C., and at 140 ° C. Homogeneous orientation. In this state, the angle dependence of the retardation was measured, and (nx-nz) / (nx-ny) was determined, and as a result, it was found that m-22 expressed a liquid crystal phase satisfying the formula (I). okay.

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

The phase transition temperature of obtained m-23 was performed by texture observation with a polarization microscope. First, when temperature was raised, it changed from a crystal phase to an isotropic liquid phase in the vicinity of 100 degreeC. Subsequently, when the temperature was gradually lowered at 110 ° C, it was changed into a nematic phase near 95 ° C, and when it was lowered to room temperature, it was changed to a crystalline phase again. That is, it was found that m-23 exhibits a nematic phase between 95 ° C and room temperature at the time of temperature drop.

m-23 (containing 0.1 wt% of hydroquinone monomethyl ether) was injected into a horizontally aligned cell (manufactured by EHC Co., Ltd .; KSRP-05 / A107M1NSS (ZZ)) having a cell gap of 5 μm at 120 ° C., and at 80 ° C. Homogeneous orientation. In this state, the angle dependence of the retardation was measured, and (nx-nz) / (nx-ny) was determined, and as a result, it was found that m-23 expressed a liquid crystal phase satisfying the formula (I). okay.

(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 solution was added to 1 L of water, and the precipitated crystals were filtered, and then concentrated hydrochloric acid was added to the filtrate, and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure, and then 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 iodide (I) It dissolved in 100 ml of triethylamine, and heated at 60 degreeC for 5 hours in 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 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 at 0 ° C. A 10 ml solution of tetrahydrofuran of 1.0 g of 4- (4-acryloyloxybutyloxy) benzoic acid and 0.51 g of diisopropylethylamine was added dropwise to this solution. After stirring at 0 ° C. for 1 hour, 0.51 g of diisopropylethylamine and 0.02 g of 4-dimethylaminopyridine were added, followed by a 10 mL solution of 0.14 g of TO-3D tetrahydrofuran. After stirring at room temperature for 12 hours, water was added to the reaction solution, and the mixture was extracted with CH ₂ Cl ₂ . After concentration under reduced pressure, the residue was purified by column chromatography to obtain 0.32 g of TO-3 crystals. The NMR spectrum of obtained TO-3 is as follows.

As a result of performing the phase transition temperature of TO-3 obtained by the texture observation by a polarization microscope, temperature was raised, it changed into a nematic liquid crystal phase from a crystalline phase in the vicinity of 122 degreeC, and turned into an isotropic liquid phase when it exceeded 195 degreeC. That is, it was found that TO-3 exhibited a nematic liquid crystal phase between 122 ° C and 195 ° C.

TO-3 (containing 0.1 wt% of hydroquinone monomethyl ether) was injected into a horizontally aligned cell (manufactured by EHC; KSRP-05 / A107M1NSS (ZZ)) having a cell gap of 5 μm at 130 ° C., and at 130 ° C. Homogeneous orientation. In this state, the angle dependence of the retardation was measured and (nx-nz) / (nx-ny) was determined, and as a result, it was found that the liquid crystal phase satisfying the formula (I) was found to be at least 1.0 and less than 1.1. okay.

According to this invention, the liquid crystal composition which can express a biaxial liquid crystal phase by mixing several liquid crystalline composition which expresses another liquid crystal phase can be provided. A liquid crystalline composition expressing a biaxial liquid crystal phase is obtained by mixing a liquid crystalline composition expressing a liquid crystal phase having positive birefringence as a liquid crystal phase different from each other and a liquid crystalline composition expressing a liquid crystal phase having negative birefringence. Lose. Moreover, the refractive index of the triaxial direction of the liquid crystal phase expressed can be controlled by the mixing ratio of the liquid crystalline composition which expresses the liquid crystal phase which has positive birefringence, and the liquid crystalline composition which expresses the liquid crystal phase which has negative birefringence.

Moreover, according to this invention, the retardation plate formed by these liquid crystalline compositions and having the optically anisotropic layer in which the refractive index was controlled to the desired value can be provided. The retardation plate can provide an elliptically polarizing plate which can precisely control polarization and a liquid crystal display device having a wide viewing angle.

Claims (7)

As a liquid crystalline composition containing the liquid crystalline composition (R) which expresses the liquid crystal phase which has positive birefringence, and the liquid crystalline composition (D) which expresses the liquid crystal phase which has negative birefringence, The liquid crystal composition (D) contains a liquid crystal compound represented by the following General Formula (DI). General formula (DI)

In General 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 represent 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 or nitrogen atom. XA represents an oxygen atom, a sulfur atom, methylene or imino. * Is L ₁ to L ₃ Represents a position to be combined with **, R ₁ to R ₃ And position where it is combined with.] General formula (DI-B)

[In General Formula (DI-B), YB ₁ and YB ₂ each independently represent a methine or nitrogen atom. XB represents an oxygen atom, a sulfur atom, methylene or imino. * Indicates a position to be bonded to L ₁ to L ₃ , ** indicates R ₁ to R ₃ And position where it is combined with.] In general formula (DI), R <_1> , R <_2> , R <_3> respectively independently represents following formula (DI-R). General formula (DI-R) *-(-L ₂₁ -2 pseudocyclic group) n ₁ -L ₂₂ -L ₂₃ -Q ₁ [In the general formula (DI-R), * is H ₁ H ~ ₃ of the general formula (DI) Indicates the position to be bound to. L ₂₁ represents a single bond or a divalent linking group. The divalent cyclic group represents a divalent linking group having at least one kind of cyclic structure. ₁ n represents an integer of 0-4. L ₂₂ is * -O-, * -O-CO-, * -CO-O-, * -O-CO-O-, * -S-, * -N (R ₇ )-, * -CH _2- , * -CH = CH-, * -C≡C- (wherein * represents a position bonded to a divalent cyclic group in the general formula (DI-R). In addition, R ₇ represents 1 to 7 carbon atoms). Is an alkyl group or a hydrogen atom. L ₂₃ is a divalent linking group selected from the group consisting of a combination of -O-, -S-, -C (= O)-, -NH-, -CH _2- , -CH = CH-, and -C≡C-. Indicates. Each Q ₁ independently represents a polymerizable group or a hydrogen atom.] 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). General formula (DII)

In General Formula (DII), Y ₃₁ , Y ₃₂ , and Y ₃₃ each independently represent 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 General Formula (DII-R), A ₃₁ and A ₃₂ each independently represent a methine or nitrogen atom. X ₃ represents an oxygen atom, a sulfur atom, methylene or imino. The divalent cyclic group represents a divalent linking group having a 6 membered cyclic structure. n <_3> represents the integer of 1-3. L ₃₁ is * -O-, * -O-CO-, * -CO-O-, -O-CO-O-, * -S-, * -N (R ₇ )-, * -CH _2- , * -CH = CH-, * -C≡C- (wherein * represents a position bonded to a divalent cyclic group in the general formula (DII-R). R ₇ is a carbon atom having 1 to 7 carbon atoms. Alkyl group or hydrogen atom). L ₃₂ is a divalent linking group selected from the group consisting of a combination of -O-, -S-, -C (= O)-, -NH-, -CH _2- , -CH = CH-, and -C≡C-. Indicates. Q ₃ each independently represents a polymerizable group or a hydrogen atom. The liquid crystal 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. The liquid crystal composition according to claim 1, wherein the liquid crystal composition containing the liquid crystal composition (R) and the liquid crystal composition (D) expresses a liquid crystal phase at 20 ° C to 300 ° C. The liquid crystal phase according to claim 1, wherein 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). Equation (III) 1.1 ≤ (nx-nz) / (nx-ny) ≤ 20 In Formula (III), nx, ny, and nz represent the refractive index of three directions orthogonal to a 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 an optically anisotropic layer formed of the liquid crystal composition according to claim 1. It has the retardation film of Claim 6, and a polarizing film, The elliptical polarizing plate characterized by the above-mentioned.