JP2001081465A - Discotic liquid crystal composition, optical compensaion sheet and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease the orientation temperature of a discotic liquid crystal composition without decreasing significantly the intrinsic birefringence rate of the discotic liquid crystal composition. SOLUTION: The discotic liquid crystal composition is that comprising discotic liquid crystalline molecules and an orientation temperature decreasing agent, wherein the orientation temperature of the discotic liquid crystal composition is lower than that of the composition obtained by removing the orientation temperature decreasing agent from the discotic liquid crystal composition, the difference of the orientation temperatures being 10 deg.C or above, and the maximum intrinsic birefringence rate, measured at a wavelength of 550 nm, of the discotic liquid crystal composition is 90% or more that, measured at a wavelength of 550 nm, of the composition obtained by removing the orientation temperature decreasing agent from the discotic liquid crystal composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a discotic liquid crystal composition, an optical compensation sheet using the same, and a liquid crystal display device.

[0002]

2. Description of the Related Art A liquid crystal display device comprises a liquid crystal cell, a polarizing element, and an optical compensation sheet (retardation plate). In a transmission type liquid crystal display device, two polarizing elements are attached to both sides of a liquid crystal cell, and one or two optical compensation sheets are arranged between the liquid crystal cell and the polarizing element. In a reflection type liquid crystal display device, a reflection plate, a liquid crystal cell, one optical compensation sheet, and one polarization element are arranged in this order. The liquid crystal cell is composed of rod-like liquid crystal molecules, two substrates for enclosing the same, and an electrode layer for applying a voltage to the rod-like liquid crystal molecules. In the liquid crystal cell, the alignment state of the rod-like liquid crystal molecules is different. For the transmission type, TN (Twisted Nematic) and IPS (In-Plane Sw) are used.
itching), FLC (Ferroelectric Liquid Crysta)
l), OCB (Optically Compensatory Bend), STN
(Supper Twisted Nematic), VA (Vertically Align)
ed) and reflection type HAN (Hybrid Aligned Nem).
atic).

[0003] Optical compensatory sheets are used in various liquid crystal display devices in order to eliminate coloring of images and to increase the viewing angle. As the optical compensation sheet, a stretched birefringent film has been conventionally used. It has been proposed to use an optical compensatory sheet having an optically anisotropic layer formed of discotic liquid crystalline molecules on a transparent support, instead of the optical compensatory sheet made of a stretched birefringent film. The optically anisotropic layer is formed by applying a discotic liquid crystal composition containing discotic liquid crystal molecules on an alignment film, and heating at a temperature higher than the alignment temperature to align the discotic liquid crystal molecules. . Generally, discotic liquid crystalline molecules have a large birefringence. The discotic liquid crystal molecules have various alignment forms. By using discotic liquid crystal molecules,
It has become possible to realize optical properties that cannot be obtained with a conventional stretched birefringent film.

[0004] The optical properties of the optical compensatory sheet are determined according to the optical properties of the liquid crystal cell, specifically, the above-mentioned difference in display mode. When discotic liquid crystal molecules are used, an optical compensatory sheet having various optical properties corresponding to various display modes of a liquid crystal cell can be manufactured. As optical compensation sheets using discotic liquid crystal molecules, ones corresponding to various display modes have already been proposed. For example, an optical compensatory sheet for a TN mode liquid crystal cell is disclosed in JP-A-6-214116, US Pat.
No. 5,83,679 and 5,646,703 and German Patent Publication 391620A1. Also,
The IPS mode or FLC mode optical compensation sheet for a liquid crystal cell is described in JP-A-10-54982. Further, an optical compensatory sheet for an OCB mode or HAN mode liquid crystal cell is described in US Pat. No. 5,805,253 and International Patent Application WO 96/37804. Further, an optical compensatory sheet for a liquid crystal cell in the STN mode is described in JP-A-9-26572. An optical compensation sheet for a VA mode liquid crystal cell is described in Japanese Patent No. 2866372.

[0005] In the production of the optical compensation sheet, as described above, a treatment for aligning the discotic liquid crystal molecules by heating at a temperature higher than the orientation temperature of the discotic liquid crystal molecules (alignment treatment) is performed. However, the transparent support may be deformed at the heating temperature of the alignment treatment. For example, a triacetyl cellulose (TAC) film is often used as a transparent support. The softening point of triacetyl cellulose is about 130 ° C. Many discotic liquid crystal molecules contain a compound having an alignment temperature higher than 130 ° C. Japanese Patent Application Laid-Open No. 9-104866 discloses a method of lowering the alignment temperature of discotic liquid crystal molecules by adding an organic compound to the discotic liquid crystal molecules. The gazette states that
As an organic compound having a function of lowering the alignment temperature,
Various types of compounds have been described. In the present specification, a compound having a function of lowering the alignment temperature of discotic liquid crystal molecules is referred to as an alignment temperature lowering agent.

[0006]

Problems to be Solved by the Invention
By using the alignment temperature reducing agent described in JP-A No. 6-2006, the alignment temperature of discotic liquid crystal molecules can be easily reduced. However, when the present inventors studied an alignment temperature lowering agent, it was found that the alignment temperature lowering agent had an adverse effect on the optical properties of the discotic liquid crystal composition. According to the research by the present inventors, Japanese Patent Application Laid-Open No. 9-1
When the alignment temperature lowering agent disclosed in Japanese Patent No. 04866 is used in the method described in the same publication, the intrinsic birefringence of the discotic liquid crystal composition is significantly reduced as compared with before the addition of the alignment temperature lowering agent. The in-plane retardation (Δnd), which is an important optical property of the optical compensation sheet, is determined according to the difference in the optical properties of the liquid crystal cells to be optically compensated. For example, an optical compensation sheet suitable for an STN-type liquid crystal display device has an in-plane retardation of 880 nm (Δ
nd). In-plane retardation (Δnd)
Is the product of the intrinsic birefringence (Δn) of the optically anisotropic layer and the layer thickness (d). When the intrinsic birefringence (Δn) of the optically anisotropic layer decreases, the layer thickness (d) needs to be correspondingly increased. When the layer thickness (d) increases, it becomes difficult to control the alignment state of the discotic liquid crystalline molecules. In addition, an increase in the amount of discotic liquid crystal molecules used (an increase in cost) due to an increase in the layer thickness (d) cannot be ignored. An object of the present invention is to reduce the alignment temperature of a discotic liquid crystal composition without significantly reducing the intrinsic birefringence of the discotic liquid crystal composition.

[0007]

The object of the present invention is attained by the following discotic liquid crystal compositions (1) to (3), the following optical compensation sheet (4), and the following liquid crystal display device (5). Was. (1) A discotic liquid crystal composition comprising a discotic liquid crystal molecule and an alignment temperature lowering agent, wherein the alignment temperature of the discotic liquid crystal composition is obtained by excluding the alignment temperature lowering agent from the discotic liquid crystal composition. Lower than the alignment temperature of the composition, the difference in the alignment temperature is 10 ° C. or more, and the wavelength of the discotic liquid crystal composition is 550.
The maximum intrinsic birefringence measured at 550 nm is 90% of the maximum intrinsic birefringence measured at a wavelength of 550 nm of a composition obtained by removing the alignment temperature lowering agent from the discotic liquid crystal composition.
% Of a discotic liquid crystal composition. (2) The discotic liquid crystal composition according to (1), wherein the alignment temperature lowering agent is an aromatic compound. (3) The discotic liquid crystal composition according to (1), wherein the discotic liquid crystal composition contains an alignment temperature lowering agent in an amount of 1 to 50% by weight based on the amount of the discotic liquid crystal compound.

(4) An optical compensation sheet in which a transparent support, an alignment film, and an optically anisotropic layer formed of discotic liquid crystalline molecules are laminated in this order, wherein the optically anisotropic layer comprises: Including a discotic liquid crystal molecule and an alignment temperature lowering agent, the alignment temperature of the discotic liquid crystal composition is lower than the alignment temperature of the composition obtained by excluding the alignment temperature lowering agent from the discotic liquid crystal composition, the alignment temperature Is greater than or equal to 10 ° C., and the maximum intrinsic birefringence measured at the wavelength of 550 nm of the discotic liquid crystal composition is 550 nm of the composition obtained by excluding the alignment temperature lowering agent from the discotic liquid crystal composition. A discotic liquid crystal composition having a maximum intrinsic birefringence of 90% or more measured in the step is coated on the alignment film, and heated at a temperature higher than the alignment temperature. The optical compensation sheet, wherein the Kotikku a liquid crystal molecule layer formed by orienting.

(5) a liquid crystal cell, two polarizing elements disposed on both sides of the liquid crystal cell, and one or two optical compensation sheets disposed between the liquid crystal cell and one or both polarizing elements; A transmission type liquid crystal display device in which an optical compensation sheet is laminated with a transparent support, an alignment film and an optically anisotropic layer formed from discotic liquid crystal molecules in order from the polarizing element side, The non-conductive layer contains a discotic liquid crystal molecule and an alignment temperature lowering agent, and the alignment temperature of the discotic liquid crystal composition is higher than the alignment temperature of the composition obtained by removing the alignment temperature lowering agent from the discotic liquid crystal composition. Low, the difference in alignment temperature is 10 ° C. or more, and the wavelength of the discotic liquid crystal composition is 550 n.
The maximum intrinsic birefringence measured at m is 90% of the maximum intrinsic birefringence measured at a wavelength of 550 nm of a composition obtained by removing the alignment temperature lowering agent from the discotic liquid crystal composition.
A liquid crystal display device comprising a layer formed by coating the above-mentioned discotic liquid crystal composition on an alignment film and heating the film at a temperature higher than the alignment temperature to align the discotic liquid crystal molecules.

[0010]

As a result of the research by the present inventors, it has been found that when an alignment temperature lowering agent is used, it is necessary to suppress the decrease in the intrinsic birefringence of the discotic liquid crystal composition to 10% or less. In the invention described in JP-A-9-104866, the problem that the intrinsic birefringence of the discotic liquid crystal composition is lowered is not recognized, and an alignment temperature reducing agent is used by focusing only on the effect of lowering the alignment temperature. It had been. Furthermore, as a result of the present inventor's research, by adjusting the type and amount of the compound used as the orientation temperature lowering agent,
It has also been found that a decrease in the intrinsic birefringence can be suppressed. Thus, the alignment temperature of the discotic liquid crystal composition was successfully reduced without significantly lowering the intrinsic birefringence of the discotic liquid crystal composition. That is,
The discotic liquid crystal composition of the present invention is characterized by having a high intrinsic birefringence and a low alignment temperature. Because the discotic liquid crystal composition of the present invention has a high intrinsic birefringence,
An optical compensatory sheet having a relatively thin optically anisotropic layer can be produced. In addition, since the discotic liquid crystal composition of the present invention has a low alignment temperature, an optical compensation sheet can be manufactured without deforming the transparent support.

[0011]

FIG. 1 is a schematic diagram showing the basic structure of a transmission type liquid crystal display device. In the transmission type liquid crystal display device shown in FIG. 1A, the polarizing element (1a), the transparent support (2a) of the optical compensation sheet, and the optical anisotropy of the optical compensation sheet are arranged in this order from the backlight (BL) side. Layer (3a),
Lower substrate of liquid crystal cell (4a), rod-like liquid crystalline molecules (5), upper substrate of liquid crystal cell (4b), optically anisotropic layer of optical compensation sheet (3b), transparent support of optical compensation sheet (2b) ,
And it consists of a polarizing element (1b). In the transmission type liquid crystal display device shown in FIG. 1B, the polarizing element (1a), the transparent support of the optical compensation sheet (2), and the optical anisotropy of the optical compensation sheet are arranged in this order from the backlight (BL) side. It comprises a layer (3), a lower substrate (4a) of a liquid crystal cell, rod-like liquid crystal molecules (5), an upper substrate (4b) of a liquid crystal cell, and a polarizing element (1b). The transmission type liquid crystal display device shown in FIG. 1C has a polarizing element (1a), a lower substrate (4a) of a liquid crystal cell, a rod-shaped liquid crystal molecule (5), and a liquid crystal cell in order from the backlight (BL) side. It comprises an upper substrate (4b), an optically anisotropic layer (3) of an optical compensation sheet, a transparent support (2) of an optical compensation sheet, and a polarizing element (1b). FIG. 2 is a schematic diagram showing a basic configuration of a reflection type liquid crystal display device. The reflection type liquid crystal display device shown in FIG. 2 includes, in order from the reflection plate (RP) side, a lower substrate (4a) of a liquid crystal cell, rod-like liquid crystal molecules (5), an upper substrate (4b) of a liquid crystal cell, and an optical compensation sheet. It comprises an optically anisotropic layer (3), a transparent support of an optical compensation sheet (2), and a polarizing element (1).

[Alignment Temperature Reducing Agent] The alignment temperature lowering agent is used to lower the alignment temperature of the discotic liquid crystal composition by 10 ° C. or more. Specifically, the alignment temperature of the discotic liquid crystal composition including the discotic liquid crystal molecules and the alignment temperature lowering agent is higher than the alignment temperature of the composition obtained by removing the alignment temperature lowering agent from the discotic liquid crystal composition. The type and amount of the alignment temperature lowering agent are adjusted so that the temperature is low and the difference in the alignment temperature is 10 ° C. or more. The orientation temperature is preferably lowered by 15 ° C. or more, more preferably by 20 ° C. or more. It is preferable that the orientation temperature is greatly reduced, but a decrease of about 100 ° C. is a technical limit. The orientation temperature of the liquid crystal composition can be measured by heating the liquid crystal composition while observing it with a polarizing microscope.

Further, the alignment temperature lowering agent greatly increases the intrinsic birefringence (10% or more) of the discotic liquid crystal composition.
Use without lowering. Specifically, the maximum intrinsic birefringence measured at a wavelength of 550 nm of a discotic liquid crystal composition containing a discotic liquid crystal molecule and an alignment temperature lowering agent is obtained by excluding the alignment temperature lowering agent from the discotic liquid crystal composition. The composition to be 90% or more of the maximum intrinsic birefringence measured at a wavelength of 550 nm,
Adjust the kind and amount of the orientation temperature lowering agent. The maximum intrinsic birefringence of the discotic liquid crystal composition is preferably 91% or more, more preferably 92% or more, of the maximum intrinsic birefringence of the composition obtained by excluding the alignment temperature lowering agent. . Although the maximum intrinsic birefringence of the discotic liquid crystal composition can be set to a value (100% or more) larger than the maximum intrinsic birefringence of the composition obtained by excluding the alignment temperature lowering agent, it is usually used. The maximum intrinsic birefringence is reduced (below 100%) by adding an orientation temperature lowering agent. The maximum intrinsic birefringence can be measured by placing the liquid crystal composition in a wedge cell, uniformly aligning the liquid crystal composition, applying light having passed through an interference filter of 550 nm, and observing with a polarizing microscope.

The orientation temperature lowering agent is preferably an aromatic compound. The aromatic compound has at least one aromatic ring or aromatic heterocyclic ring. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a biphenylene ring, a naphthacene ring, a pyrene ring, a pentalene ring, a heptalene ring, and an as- Indacene ring, s-indacene ring, phenalene ring, fluoranthene ring, acephenanthrylene ring, aceanthrylene ring, triphenylene ring, chrysene ring, preyaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring, tetraphenylene ring , A hexaphene ring, a hexacene ring, a rubicene ring, a coronene ring, a trinaphthylene ring, a heptaphen ring, a heptacene ring, a pyranthrene ring and an ovalene ring. The aromatic heterocycle is generally a 5- or 6-membered unsaturated heterocycle. The heterocycle preferably contains the most double bonds. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring,
It includes imidazole, pyrazole, furazane, pyran, pyridine, pyridazine, pyrimidine and pyrazine rings. The aromatic hetero ring and the aromatic ring may form a condensed ring. An aromatic ring is more preferable than an aromatic heterocyclic ring, and a benzene ring is particularly preferable.

The number of aromatic rings or aromatic heterocycles contained in the orientation temperature lowering agent is preferably from 1 to 20, more preferably from 2 to 10. It is particularly preferable that the alignment temperature lowering agent is an aromatic compound having 2 to 10 aromatic rings. It is preferable that a plurality of aromatic rings or aromatic heterocycles be bonded via a single bond or a divalent linking group. More preferably, a plurality of aromatic rings are bonded via a single bond or a divalent linking group, and most preferably, a plurality of aromatic rings are bonded via a divalent linking group. . The divalent linking group is -C≡C
-, -CH = CH-, -CH = N-, -CO-, -O
-, -NH- or a combination thereof is preferred. Examples of the divalent linking group obtained by the combination include -C≡CC−C-, -C≡C-CH = CH-C≡
C-, -CO-O-, -CO-NH-, -O-CO-C
H = CH- and -NH-CO-CH = CH- are included.

The aromatic ring or aromatic heterocyclic ring may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), cyano, nitro, an aliphatic group,
-OR, -CO-R, -O-CO-R, -CO-O-
R, -NH-CO-R, -CO-NH-R, -SO 3 -
R and -SiR ₄ contains. R is a hydrogen atom or an aliphatic group. The aliphatic group includes an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group. As the alkyl group, a chain alkyl group is more preferable than a cyclic alkyl group. The chain alkyl group may have a branch. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 12, and most preferably 1 to 10. The alkyl part of the substituted alkyl group is the same as the above-mentioned alkyl group. Examples of the substituent of the substituted alkyl group include a halogen atom (F, Cl, Br, I), cyano, nitro, and-.
OR, -CO-R, -O-CO-R, -CO-O-
R, -NH-R, -NH-CO-R, -CO-NH-
R, include -SO ₃ -R, and -SiR _4. R is
It is a hydrogen atom or an aliphatic group.

The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. The chain alkenyl group may have a branch. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably has 2 to 15 carbon atoms, further preferably has 2 to 12 carbon atoms, and most preferably has 2 to 10 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. Examples of the substituent of the substituted alkenyl group are the same as the examples of the substituent of the substituted alkyl group. The alkynyl group is more preferably a chain alkynyl group than a cyclic alkynyl group. The chain alkynyl group may have a branch. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms,
It is more preferably from 2 to 12, and most preferably from 2 to 10. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. Examples of the substituent of the substituted alkynyl group are the same as the examples of the substituent of the substituted alkyl group.

The alignment temperature lowering agent is selected from the aromatic compounds described above in consideration of the effects on the alignment temperature and the intrinsic birefringence of the discotic liquid crystal composition. Examples of the aromatic compound which can be preferably used as the alignment temperature lowering agent are shown below.

[0019]

Embedded image

(1) R ¹ : -H, R ² : -H (2) R ¹ : -H, R ² :-(CH ₂ ) ₄ -O-CO-
CH = CH ₂ (3) R ¹ : -H, R ² :-( CH ₂ ) ₂ CH ₃ (4) R ¹ : -H, R ² : -O-CO-CH = CH ₂ (5) R ^{1 : -H, R 2: -O- (} CH 2) 2 -O-C
_{O-CH = CH 2 (6} ) R 1: -H, R 2: -O-CO-C (CH 3) =
CH ₂ (7) R ¹ : —H, R ² : —O— (CH ₂ ) ₂ —O—C
_{O-C (CH 3) =} CH 2 (8) R 1: -H, R 2: -NH-CO-CH = CH 2 (9) R 1: -CN, R 2: -H (10) R 1 : -CN, R ² :-(CH ₂ ) ₂ CH ₃ (11) R ¹ : -CN, R ² : -O-CO-CH = CH
^{_{2 (12) R 1: -CN}} , R 2: -O- (CH 2) 2 -O
_{-CO-CH = CH 2 (13} ) R 1: -CN, R 2: -O-CO-C (C
_{H 3) = CH 2 (14} ) R 1: -CN, R 2: -O- (CH 2) 2 -O
_{-CO-C (CH 3) =} CH 2 (15) R 1: -CN, R 2: -NH-CO-CH = C
H ₂

(16) R ¹ : -F, R ² : -H (17) R ¹ : -F, R ² :-(CH ₂ ) ₂ CH ₃ (18) R ¹ : -F, R ² :- _{O-CO-CH = CH 2} (19) R 1: -F, R 2: -O- (CH 2) 2 -O-
_{CO-CH = CH 2 (20} ) R 1: -F, R 2: -O-CO-C (CH 3)
ＣＨCH ₂ (21) R ¹ : —F, R ² : —O— (CH ₂ ) ₂ —O—
CO-C (CH ₃ ) = CH ₂ (22) R ¹ : -F, R ² : -NH-CO-CH = CH
₂ (23) R ¹ :-(CH ₂ ) ₂ CH ₃ , R ² :-(CH
₂ ) ₂ CH ₃ (24) R ¹ : —O—CH ₃ , R ² : —O—CH ₃ (25) R ¹ : —O—CH ₂ —O—CH ₃ , R ² : —O
_{-CH 2 -O-CH 3 (26} ) R 1: -O-CO-CH = CH 2, R 2: -O
_{-CO-CH = CH 2 (27} ) R 1: -O- (CH 2) 2 -O-CO-CH =
^{_{CH 2, R 2: -O- (}} CH 2) 2 -O-CO-CH =
CH ₂ (28) R ¹ : —O—CO—C (CH ₃ ) = CH ₂ , R
² : —O—CO—C (CH ₃ ) ＝ CH ₂ (29) R ¹ : —O— (CH ₂ ) ₂ —O—CO—C (C
H ₃ ) = CH ₂ , R ² : —O— (CH ₂ ) ₂ —O—CO
_{-C (CH 3) = CH 2} (30) R 1: -NH-CO-CH = CH 2, R 2: -
NH-CO-CH = CH ₂

[0022]

Embedded image

(31) R ¹ : —O— (CH ₂ ) ₄ —O—
CO—CH ＝ CH ₂ , R ² : —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0024]

Embedded image

(32) R ¹ : —O— (CH ₂ ) ₄ —O—
CO—CH ＝ CH ₂ , R ² : —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0026]

Embedded image

(33) R ¹ : -H, R ² : -H (34) R ¹ : -H, R ² :-(CH ₂ ) ₄ -O-CO
-CH = CH ₂ (35) R ¹ : -H, R ² :-( CH ₂ ) ₂ CH ₃ (36) R ¹ : -H, R ² : -O-CO-CH = CH ₂ (37) R ¹ : —H, R ² : —O— (CH ₂ ) ₂ —O—
_{CO-CH = CH 2 (38} ) R 1: -H, R 2: -O-CO-C (CH 3)
= CH ₂ (39) R ¹ : -H, R ² : -O- (CH ₂ ) ₂ -O-
_{CO-C (CH 3) =} CH 2 (40) R 1: -H, R 2: -NH-CO-CH = CH
^{_{2 (41) R 1: -CN}} , R 2: -H (42) R 1: -CN, R 2 :-( CH 2) 2 CH 3 (43) R 1: -CN, R 2: -O- CO-CH = CH
₂ (44) R ¹ : -CN, R ² : -O- (CH ₂ ) ₂ -O
_{-CO-CH = CH 2 (45} ) R 1: -CN, R 2: -O-CO-C (C
_{H 3) = CH 2 (46} ) R 1: -CN, R 2: -O- (CH 2) 2 -O
_{-CO-C (CH 3) =} CH 2 (47) R 1: -CN, R 2: -NH-CO-CH = C
H ₂

(48) R ¹ : -F, R ² : -H (49) R ¹ : -F, R ² :-(CH ₂ ) ₂ CH ₃ (50) R ¹ : -F, R ² :- _{O-CO-CH = CH 2} (51) R 1: -F, R 2: -O- (CH 2) 2 -O-
_{CO-CH = CH 2 (52} ) R 1: -F, R 2: -O-CO-C (CH 3)
= CH ₂ (53) R ¹ : -F, R ² : -O- (CH ₂ ) ₂ -O-
_{CO-C (CH 3) =} CH 2 (54) R 1: -F, R 2: -NH-CO-CH = CH
₂ (55) R ¹ :-(CH ₂ ) ₂ CH ₃ , R ² :-(CH
₂ ) ₂ CH ₃ (56) R ¹ : —O—CH ₃ , R ² : —O—CH ₃ (57) R ¹ : —O—CH ₂ —O—CH ₃ , R ² : —O
_{-CH 2 -O-CH 3 (58} ) R 1: -O-CO-CH = CH 2, R 2: -O
_{-CO-CH = CH 2 (59} ) R 1: -O- (CH 2) 2 -O-CO-CH =
^{_{CH 2, R 2: -O- (}} CH 2) 2 -O-CO-CH =
CH ₂ (60) R ¹ : —O—CO—C (CH ₃ ) = CH ₂ , R
² : —O—CO—C (CH ₃ ) ＝ CH ₂ (61) R ¹ : —O— (CH ₂ ) ₂ —O—CO—C (C
H ₃ ) = CH ₂ , R ² : —O— (CH ₂ ) ₂ —O—CO
_{-C (CH 3) = CH 2} (62) R 1: -NH-CO-CH = CH 2, R 2: -
NH-CO-CH = CH ₂

[0029]

Embedded image

(63) R ¹ : —O— (CH ₂ ) ₄ —O—
CO—CH ＝ CH ₂ , R ² : —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0031]

Embedded image

(64) R ¹ : —O— (CH ₂ ) ₄ —O—
CO—CH ＝ CH ₂ , R ² : —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0033]

Embedded image

(65) R ¹ : -H, R ² : -H (66) R ¹ : -H, R ² :-(CH ₂ ) ₄ -O-CO
_{-CH = CH 2 (67) R} 1: -H, R 2 :-( CH 2) 2 CH 3 (68) R 1: -H, R 2: -O-CO-CH = CH 2 (69) R ¹ : —H, R ² : —O— (CH ₂ ) ₂ —O—
_{CO-CH = CH 2 (70} ) R 1: -H, R 2: -O-CO-C (CH 3)
= CH ₂ (71) R ¹ : -H, R ² : -O- (CH ₂ ) ₂ -O-
_{CO-C (CH 3) =} CH 2 (72) R 1: -H, R 2: -NH-CO-CH = CH
₂ (73) R ¹ : -CN, R ² : -H (74) R ¹ : -CN, R ² :-(CH ₂ ) ₂ CH ₃ (75) R ¹ : -CN, R ² : -O- CO-CH = CH
^{_{2 (76) R 1: -CN}} , R 2: -O- (CH 2) 2 -O
_{-CO-CH = CH 2 (77} ) R 1: -CN, R 2: -O-CO-C (C
_{H 3) = CH 2 (78} ) R 1: -CN, R 2: -O- (CH 2) 2 -O
_{-CO-C (CH 3) =} CH 2 (79) R 1: -CN, R 2: -NH-CO-CH = C
H ₂

(80) R ¹ : -F, R ² : -H (81) R ¹ : -F, R ² :-(CH ₂ ) ₂ CH ₃ (82) R ¹ : -F, R ² :- _{O-CO-CH = CH 2} (83) R 1: -F, R 2: -O- (CH 2) 2 -O-
CO-CH = CH ₂ (84) R ¹ : -F, R ² : -O-CO-C (CH ₃ )
= CH ₂ (85) R ¹ : -F, R ² : -O- (CH ₂ ) ₂ -O-
CO—C (CH ₃ ) = CH ₂ (86) R ¹ : —F, R ² : —NH—CO—CH ＝ CH
₂ (87) R ¹ :-(CH ₂ ) ₂ CH ₃ , R ² :-(CH
₂ ) ₂ CH ₃ (88) R ¹ : —O—CH ₃ , R ² : —O—CH ₃ (89) R ¹ : —O—CH ₂ —O—CH ₃ , R ² : —O
_{-CH 2 -O-CH 3 (90} ) R 1: -O-CO-CH = CH 2, R 2: -O
-CO-CH = CH ₂ (91) R ¹ : -O- (CH ₂ ) ₂ -O-CO-CH =
^{_{CH 2, R 2: -O- (}} CH 2) 2 -O-CO-CH =
CH ₂ (92) R ¹ : —O—CO—C (CH ₃ ) = CH ₂ , R
² : —O—CO—C (CH ₃ ) ＝ CH ₂ (93) R ¹ : —O— (CH ₂ ) ₂ —O—CO—C (C
H ₃ ) = CH ₂ , R ² : —O— (CH ₂ ) ₂ —O—CO
_{-C (CH 3) = CH 2} (94) R 1: -NH-CO-CH = CH 2, R 2: -
NH-CO-CH = CH ₂

[0036]

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(95) R ¹ : —O— (CH ₂ ) ₄ —O—
CO—CH ＝ CH ₂ , R ² : —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0038]

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(96) R ¹ : —O— (CH ₂ ) ₄ —O—
CO—CH ＝ CH ₂ , R ² : —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0040]

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(97) R ¹ : -H, R ² : -H (98) R ¹ : -H, R ² :-(CH ₂ ) ₄ -O-CO
-CH = CH ₂ (99) R ¹ : -H, R ² :-( CH ₂ ) ₂ CH ₃ (100) R ¹ : -H, R ² : -O-CO-CH = CH
₂ (101) R ¹ : -H, R ² : -O- (CH ₂ ) ₂ -O
_{-CO-CH = CH 2 (102} ) R 1: -H, R 2: -O-CO-C (C
_{H 3) = CH 2 (103} ) R 1: -H, R 2: -O- (CH 2) 2 -O
-CO-C (CH ₃ ) = CH ₂ (104) R ¹ : -H, R ² : -NH-CO-CH = C
^{_{H 2 (105) R 1:}} -CN, R 2: -H (106) R 1: -CN, R 2 :-( CH 2) 2 CH 3 (107) R 1: -CN, R 2: -O -CO-CH = C
^{_{H 2 (108) R 1:}} -CN, R 2: -O- (CH 2) 2 -
_{O-CO-CH = CH 2} (109) R 1: -CN, R 2: -O-CO-C (CH
₃ ) = CH ₂ (110) R ¹ : -CN, R ² : -O- (CH ₂ ) _2-
O-CO-C (CH ₃ ) = CH ₂ (111) R ¹ : -CN, R ² : -NH-CO-CH =
CH ₂

(112) R¹: -F, R^Two: -H (113) R¹: -F, R^Two:-( CH_Two)_TwoCH_Three (114) R¹: -F, R^Two: -O-CO-CH = CH
_Two (115) R¹: -F, R^Two: -O- (CH_Two)_Two-O
-CO-CH = CH_Two (116) R¹: -F, R^Two: -O-CO-C (C
H_Three) = CH_Two (117) R¹: -F, R^Two: -O- (CH_Two)_Two-O
-CO-C (CH_Three) = CH_Two (118) R¹: -F, R^Two: -NH-CO-CH = C
H_Two (119) R¹:-( CH_Two)_TwoCH_Three, R^Two:-( C
H_Two)_TwoCH_Three (120) R¹: -O-CH_Three, R^Two: -O-CH_Three (121) R¹: -O-CH_Two-O-CH_Three, R^Two:-
O-CH_Two-O-CH _Three (122) R¹: -O-CO-CH = CH_Two, R^Two:-
O-CO-CH = CH_Two (123) R¹: -O- (CH_Two)_Two-O-CO-CH
= CH_Two, R^Two: -O- (CH_Two)_Two-O-CO-CH
= CH_Two (124) R¹: -O-CO-C (CH_Three) = CH_Two,
R^Two: -O-CO-C (CH_Three) = CH_Two (125) R¹: -O- (CH_Two)_Two-O-CO-C
(CH_Three) = CH_Two, R^Two: -O- (CH_Two)_Two-O-
CO-C (CH_Three) = CH_Two (126) R¹: -NH-CO-CH = CH_Two, R^Two:
-NH-CO-CH = CH_Two

[0043]

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(127) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0045]

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(128) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0047]

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(129) R ¹ : -H, R ² : -H (130) R ¹ : -H, R ² :-(CH ₂ ) ₄ -OC
_{O-CH = CH 2 (131} ) R 1: -H, R 2 :-( CH 2) 2 CH 3 (132) R 1: -H, R 2: -O-CO-CH = CH
₂ (133) R ¹ : -H, R ² : -O- (CH ₂ ) ₂ -O
_{-CO-CH = CH 2 (134} ) R 1: -H, R 2: -O-CO-C (C
_{H 3) = CH 2 (135} ) R 1: -H, R 2: -O- (CH 2) 2 -O
-CO-C (CH ₃ ) = CH ₂ (136) R ¹ : -H, R ² : -NH-CO-CH = C
^{_{H 2 (137) R 1:}} -CN, R 2: -H (138) R 1: -CN, R 2 :-( CH 2) 2 CH 3 (139) R 1: -CN, R 2: -O -CO-CH = C
^{_{H 2 (140) R 1:}} -CN, R 2: -O- (CH 2) 2 -
_{O-CO-CH = CH 2} (141) R 1: -CN, R 2: -O-CO-C (CH
₃ ) = CH ₂ (142) R ¹ : -CN, R ² : -O- (CH ₂ ) _2-
O-CO-C (CH ₃ ) = CH ₂ (143) R ¹ : -CN, R ² : -NH-CO-CH =
CH ₂

(144) R ¹ : -F, R ² : -H (145) R ¹ : -F, R ² :-(CH ₂ ) ₂ CH ₃ (146) R ¹ : -F, R ² :- O-CO-CH = CH
₂ (147) R ¹ : -F, R ² : -O- (CH ₂ ) ₂ -O
-CO-CH = CH ₂ (148) R ¹ : -F, R ² : -O-CO-C (C
_{H 3) = CH 2 (149} ) R 1: -F, R 2: -O- (CH 2) 2 -O
-CO-C (CH ₃ ) = CH ₂ (150) R ¹ : -F, R ² : -NH-CO-CH = C
H ₂ (151) R ¹ :-( CH ₂ ) ₂ CH ₃ , R ² :-( C
_{H 2) 2 CH 3 (152} ) R 1: -O-CH 3, R 2: -O-CH 3 (153) R 1: -O-CH 2 -O-CH 3, R 2: -
_{O-CH 2 -O-CH 3} (154) R 1: -O-CO-CH = CH 2, R 2: -
_{O-CO-CH = CH 2} (155) R 1: -O- (CH 2) 2 -O-CO-CH
ＣＨCH ₂ , R ² : —O— (CH ₂ ) ₂ —O—CO—CH
ＣＨCH ₂ (156) R ¹ : —O—CO—C (CH ₃ ) ＝ CH ₂ ,
R ² : —O—CO—C (CH ₃ ) ＝ CH ₂ (157) R ¹ : —O— (CH ₂ ) ₂ —O—CO—C
(CH ₃ ) = CH ₂ , R ² : —O— (CH ₂ ) ₂ —O—
CO—C (CH ₃ ) ＣＨCH ₂ (158) R ¹ : —NH—CO—CH ＝ CH ₂ , R ² :
-NH-CO-CH = CH ₂

[0050]

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(159) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0052]

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(160) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0054]

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(161) R ¹ : -H, R ² : -H (162) R ¹ : -H, R ² :-(CH ₂ ) ₄ -OC
O-CH = CH ₂ (163) R ¹ : -H, R ² :-( CH ₂ ) ₂ CH ₃ (164) R ¹ : -H, R ² : -O-CO-CH = CH
^{_{2 (165) R 1: -H}} , R 2: -O- (CH 2) 2 -O
_{-CO-CH = CH 2 (166} ) R 1: -H, R 2: -O-CO-C (C
_{H 3) = CH 2 (167} ) R 1: -H, R 2: -O- (CH 2) 2 -O
-CO-C (CH ₃ ) = CH ₂ (168) R ¹ : -H, R ² : -NH-CO-CH = C
^{_{H 2 (169) R 1:}} -CN, R 2: -H (170) R 1: -CN, R 2 :-( CH 2) 2 CH 3 (171) R 1: -CN, R 2: -O -CO-CH = C
^{_{H 2 (172) R 1:}} -CN, R 2: -O- (CH 2) 2 -
_{O-CO-CH = CH 2} (173) R 1: -CN, R 2: -O-CO-C (CH
₃ ) = CH ₂ (174) R ¹ : —CN, R ² : —O— (CH ₂ ) ₂ —
O-CO-C (CH ₃ ) = CH ₂ (175) R ¹ : -CN, R ² : -NH-CO-CH =
CH ₂

(176) R ¹ : -F, R ² : -H (177) R ¹ : -F, R ² :-(CH ₂ ) ₂ CH ₃ (178) R ¹ : -F, R ² :- O-CO-CH = CH
₂ (179) R ¹ : -F, R ² : -O- (CH ₂ ) ₂ -O
_{-CO-CH = CH 2 (180} ) R 1: -F, R 2: -O-CO-C (C
_{H 3) = CH 2 (181} ) R 1: -F, R 2: -O- (CH 2) 2 -O
-CO-C (CH ₃ ) = CH ₂ (182) R ¹ : -F, R ² : -NH-CO-CH = C
^{_{H 2 (183) R 1 :-(}} CH 2) 2 CH 3, R 2 :-( C
_{H 2) 2 CH 3 (184} ) R 1: -O-CH 3, R 2: -O-CH 3 (185) R 1: -O-CH 2 -O-CH 3, R 2: -
_{O-CH 2 -O-CH 3} (186) R 1: -O-CO-CH = CH 2, R 2: -
_{O-CO-CH = CH 2} (187) R 1: -O- (CH 2) 2 -O-CO-CH
ＣＨCH ₂ , R ² : —O— (CH ₂ ) ₂ —O—CO—CH
ＣＨCH ₂ (188) R ¹ : —O—CO—C (CH ₃ ) ＝ CH ₂ ,
R ² : —O—CO—C (CH ₃ ) ＝ CH ₂ (189) R ¹ : —O— (CH ₂ ) ₂ —O—CO—C
(CH ₃ ) = CH ₂ , R ² : —O— (CH ₂ ) ₂ —O—
CO—C (CH ₃ ) ＝ CH ₂ (190) R ¹ : —NH—CO—CH ＝ CH ₂ , R ² :
-NH-CO-CH = CH ₂

[0057]

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(191) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0059]

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(192) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0061]

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(193) R ¹ : -H, R ² : -H (194) R ¹ : -H, R ² :-(CH ₂ ) ₄ -OC
O-CH = CH ₂ (195) R ¹ : -H, R ² :-( CH ₂ ) ₂ CH ₃ (196) R ¹ : -H, R ² : -O-CO-CH = CH
₂ (197) R ¹ : -H, R ² : -O- (CH ₂ ) ₂ -O
_{-CO-CH = CH 2 (198} ) R 1: -H, R 2: -O-CO-C (C
_{H 3) = CH 2 (199} ) R 1: -H, R 2: -O- (CH 2) 2 -O
_{-CO-C (CH 3) =} CH 2 (200) R 1: -H, R 2: -NH-CO-CH = C
^{_{H 2 (201) R 1:}} -CN, R 2: -H (202) R 1: -CN, R 2 :-( CH 2) 2 CH 3 (203) R 1: -CN, R 2: -O -CO-CH = C
^{_{H 2 (204) R 1:}} -CN, R 2: -O- (CH 2) 2 -
O-CO-CH = CH ₂ (205) R ¹ : -CN, R ² : -O-CO-C (CH
₃ ) = CH ₂ (206) R ¹ : —CN, R ² : —O— (CH ₂ ) ₂ —
O-CO-C (CH ₃ ) = CH ₂ (207) R ¹ : -CN, R ² : -NH-CO-CH =
CH ₂

(208) R ¹ : -F, R ² : -H (209) R ¹ : -F, R ² :-(CH ₂ ) ₂ CH ₃ (210) R ¹ : -F, R ² :- O-CO-CH = CH
₂ (211) R ¹ : -F, R ² : -O- (CH ₂ ) ₂ -O
_{-CO-CH = CH 2 (212} ) R 1: -F, R 2: -O-CO-C (C
_{H 3) = CH 2 (213} ) R 1: -F, R 2: -O- (CH 2) 2 -O
-CO-C (CH ₃ ) = CH ₂ (214) R ¹ : -F, R ² : -NH-CO-CH = C
^{_{H 2 (215) R 1 :-(}} CH 2) 2 CH 3, R 2 :-( C
_{H 2) 2 CH 3 (216} ) R 1: -O-CH 3, R 2: -O-CH 3 (217) R 1: -O-CH 2 -O-CH 3, R 2: -
_{O-CH 2 -O-CH 3} (218) R 1: -O-CO-CH = CH 2, R 2: -
_{O-CO-CH = CH 2} (219) R 1: -O- (CH 2) 2 -O-CO-CH
ＣＨCH ₂ , R ² : —O— (CH ₂ ) ₂ —O—CO—CH
ＣＨCH ₂ (220) R ¹ : —O—CO—C (CH ₃ ) ＝ CH ₂ ,
R ² : —O—CO—C (CH ₃ ) ＝ CH ₂ (221) R ¹ : —O— (CH ₂ ) ₂ —O—CO—C
(CH ₃ ) = CH ₂ , R ² : —O— (CH ₂ ) ₂ —O—
CO—C (CH ₃ ) ＝ CH ₂ (222) R ¹ : —NH—CO—CH ＝ CH ₂ , R ² :
-NH-CO-CH = CH ₂

[0064]

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(223) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0066]

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(224) R ¹ : —O— (CH ₂ ) ₄ —O
_{-CO-CH = CH 2, R} 2: -O- (CH 2) 4 -O
-CO-CH = CH ₂

[0068]

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[0069] (225) R: -H (226 ) R: -CH 3 (227) R :-( CH 2) 2 -CH 3 (228) R :-( CH 2) 5 -CH 3 (229) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (230) R :-( CH 2} ) 2 -O-CO-C (C
_{H 3) = CH 2 (231} ) R :-( CH 2) 4 -O-CO-CH = CH
_{2 (232) R: -OH (} 233) R: -O- (CH 2) 2 -CH 3 (234) R: -O- (CH 2) 3 -CH 3 (235) R: -O- (CH ₂ -O-CH _{2) 2} -CH
_{3 (236) R: -O-} CO-CH = CH 2 (237) R: -O- (CH 2) 2 -O-CO-CH =
_{CH 2 (238) R: -O} -CO-C (CH 3) = CH 2 (239) R: -O- (CH 2) 2 -O-CO-C (C
_{H 3) = CH 2 (240} ) R: -O-CO- (CH 2) 2 -O-CO-
CH = CH ₂ (241) R: —O—CO— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂

[0070]

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(242) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0072]

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(243) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0074]

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[0075] (244) R: -H (245 ) R: -CH 3 (246) R :-( CH 2) 2 -CH 3 (247) R :-( CH 2) 5 -CH 3 (248) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (249) R :-( CH 2} ) 2 -O-CO-C (C
_{H 3) = CH 2 (250} ) R :-( CH 2) 4 -O-CO-CH = CH
_{2 (251) R: -OH (} 252) R: -O- (CH 2) 2 -CH 3 (253) R: -O- (CH 2) 3 -CH 3 (254) R: -O- (CH ₂ -O-CH _{2) 2} -CH
_{3 (255) R: -O-} CO-CH = CH 2 (256) R: -O- (CH 2) 2 -O-CO-CH =
_{CH 2 (257) R: -O} -CO-C (CH 3) = CH 2 (258) R: -O- (CH 2) 2 -O-CO-C (C
H ₃ ) = CH ₂ (259) R: —O—CO— (CH ₂ ) ₂ —O—CO—
CH = CH ₂ (260) R: —O—CO— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂

[0076]

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(261) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0078]

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(262) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0080]

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[0081] (263) R: -H (264 ) R: -CH 3 (265) R :-( CH 2) 2 -CH 3 (266) R :-( CH 2) 5 -CH 3 (267) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (268) R :-( CH 2} ) 2 -O-CO-C (C
_{H 3) = CH 2 (269} ) R :-( CH 2) 4 -O-CO-CH = CH
_{2 (270) R: -OH (} 271) R: -O- (CH 2) 2 -CH 3 (272) R: -O- (CH 2) 3 -CH 3 (273) R: -O- (CH ₂ -O-CH _{2) 2} -CH
_{3 (274) R: -O-} CO-CH = CH 2 (275) R: -O- (CH 2) 2 -O-CO-CH =
_{CH 2 (276) R: -O} -CO-C (CH 3) = CH 2 (277) R: -O- (CH 2) 2 -O-CO-C (C
_{H 3) = CH 2 (278} ) R: -O-CO- (CH 2) 2 -O-CO-
CH = CH ₂ (279) R: —O—CO— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂

[0082]

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(280) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0084]

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(281) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0086]

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(282) R: —H (283) R: —CH ₃ (284) R: — (CH ₂ ) ₂ —CH ₃ (285) R: — (CH ₂ ) ₅ —CH ₃ (286) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (287) R :-( CH 2} ) 2 -O-CO-C (C
_{H 3) = CH 2 (288} ) R :-( CH 2) 4 -O-CO-CH = CH
_{2 (289) R: -OH (} 290) R: -O- (CH 2) 2 -CH 3 (291) R: -O- (CH 2) 3 -CH 3 (292) R: -O- (CH ₂ -O-CH _{2) 2} -CH
_{3 (293) R: -O-} CO-CH = CH 2 (294) R: -O- (CH 2) 2 -O-CO-CH =
CH ₂ (295) R: —O—CO—C (CH ₃ ) ＝ CH ₂ (296) R: —O— (CH ₂ ) ₂ —O—CO—C (C
_{H 3) = CH 2 (297} ) R: -O-CO- (CH 2) 2 -O-CO-
CH = CH ₂ (298) R: —O—CO— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂

[0088]

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(299) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0090]

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(300) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0092]

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[0093] (301) R: -H (302 ) R: -CH 3 (303) R :-( CH 2) 2 -CH 3 (304) R :-( CH 2) 5 -CH 3 (305) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (306) R :-( CH 2} ) 2 -O-CO-C (C
_{H 3) = CH 2 (307} ) R :-( CH 2) 4 -O-CO-CH = CH
_{2 (308) R: -OH (} 309) R: -O- (CH 2) 2 -CH 3 (310) R: -O- (CH 2) 3 -CH 3 (311) R: -O- (CH ₂ -O-CH _{2) 2} -CH
_{3 (312) R: -O-} CO-CH = CH 2 (313) R: -O- (CH 2) 2 -O-CO-CH =
CH ₂ (314) R: —O—CO—C (CH ₃ ) = CH ₂ (315) R: —O— (CH ₂ ) ₂ —O—CO—C (C
H ₃ ) = CH ₂ (316) R: —O—CO— (CH ₂ ) ₂ —O—CO—
CH = CH ₂ (317) R: —O—CO— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂

[0094]

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(318) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0096]

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(319) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0098]

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[0099] (320) R: -H (321 ) R: -CH 3 (322) R :-( CH 2) 2 -CH 3 (323) R :-( CH 2) 5 -CH 3 (324) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (325) R :-( CH 2} ) 2 -O-CO-C (C
_{H 3) = CH 2 (326} ) R :-( CH 2) 4 -O-CO-CH = CH
_{2 (327) R: -OH (} 328) R: -O- (CH 2) 2 -CH 3 (329) R: -O- (CH 2) 3 -CH 3 (330) R: -O- (CH ₂ -O-CH _{2) 2} -CH
_{3 (331) R: -O-} CO-CH = CH 2 (332) R: -O- (CH 2) 2 -O-CO-CH =
_{CH 2 (333) R: -O} -CO-C (CH 3) = CH 2 (334) R: -O- (CH 2) 2 -O-CO-C (C
_{H 3) = CH 2 (335} ) R: -O-CO- (CH 2) 2 -O-CO-
CH = CH ₂ (336) R: —O—CO— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂

[0100]

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(337) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0102]

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(338) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0104]

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(339) R: -C≡C-H (340) R: -C≡C-CH ₃ (341) R: -C≡C- (CH ₂ ) ₂ -CH ₃ (342) R:- C≡C— (CH ₂ ) ₅ —CH ₃ (343) R: —C≡C— (CH ₂ ) ₂ —O—CO—C
H = CH ₂ (344) R: —C≡C— (CH ₂ ) ₂ —O—CO—C
(CH ₃ ) = CH ₂ (345) R: —C≡C— (CH ₂ ) ₄ —O—CO—C
H = CH ₂ (346) R: —C≡C—OH (347) R: —C≡C—O— (CH ₂ ) ₂ —CH ₃ (348) R: —C≡C—O— (CH ₂ ) ₃ —CH ₃ (349) R: —C≡C—O— (CH ₂ —O—CH ₂ )
_{2 -CH 3 (350) R:} -C≡C-O-CO-CH = CH 2 (351) R: -C≡C-O- (CH 2) 2 -O-CO
—CH ＝ CH ₂ (352) R: —C≡CO—CO—C (CH ₃ ) = C
H ₂ (353) R: —C≡CO— (CH ₂ ) ₂ —O—CO
_{-C (CH 3) = CH 2} (354) R: -C≡C-O-CO- (CH 2) 2 -O
—CO—CH ＝ CH ₂ (355) R: —C≡CO—CO— (CH ₂ ) ₂ —O
_{-CO-C (CH 3) =} CH 2

[0106]

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(356) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0108]

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(357) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0110]

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[0111] (358) R: -H (359 ) R: -CH 3 (360) R :-( CH 2) 2 -CH 3 (361) R :-( CH 2) 5 -CH 3 (362) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (363) R :-( CH 2} ) 2 -O-CO-C (C
H ₃ ) = CH ₂ (364) R: —COOH (365) R: —CO—O— (CH ₂ ) ₂ —CH ₃ (366) R: —CO—O— (CH ₂ ) ₃ —CH ₃ ( 367) R: -CO-O- ( CH 2 -O-CH 2) 2
_{-CH 3 (368) R: -CO} -O- (CH 2) 2 -O-CO-
CH = CH ₂ (369) R: —CO—O— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂ (370) R: —CH ₂ —OH (371) R: —CH ₂ —O— (CH ₂ ) ₂ —CH ₃ (372) R: —CH ₂ —O— (CH _{2) 3 -CH 3 (373)} R: -CH 2 -O- (CH 2 -O-CH 2)
_{2 -CH 3 (374) R:} -CH 2 -O-CO-CH = CH 2 (375) R: -CH 2 -O- (CH 2) 2 -O-CO
_{-CH = CH 2 (376) R} : -CH 2 -O-CO-C (CH 3) = C
_{H 2 (377) R: -CH} 2 -O- (CH 2) 2 -O-CO
_{-C (CH 3) = CH 2} (378) R: -CH 2 -O-CO- (CH 2) 2 -O
_{-CO-CH = CH 2 (379} ) R: -CH 2 -O-CO- (CH 2) 2 -O
_{-CO-C (CH 3) =} CH 2

[0112] _{(380) R: -SO 3 H} (381) R: -SO 3 - (CH 2) 2 -CH 3 (382) R: -SO 3 - (CH 2) 3 -CH 3 (383) R : —SO ₃ — (CH ₂ —O—CH ₂ ) ₂ —
_{CH 3 (384) R: -SO} 3 - (CH 2) 2 -O-CO-C
H = CH ₂ (385) R: —SO ₃ — (CH ₂ ) ₂ —O—CO—C
(CH ₃ ) = CH ₂ (386) R: —CO—CH ₃ (387) R: —CO— (CH ₂ ) ₂ —CH ₃ (388) R: —CO— (CH ₂ ) ₅ —CH ₃ ( _{389) R: -CO- (CH 2} ) 2 -O-CO-CH
ＣＨCH ₂ (390) R: —CO— (CH ₂ ) ₂ —O—CO—C
(CH ₃ ) = CH ₂

(391) R: —NH ₂ (392) R: —NH— (CH ₂ ) ₂ —CH ₃ (393) R: —NH— (CH ₂ ) ₃ —CH ₃ (394) R: —NH _{- (CH 2 -O-CH 2} ) 2 -C
_{H 3 (395) R: -NH} -CO-CH = CH 2 (396) R: -NH- (CH 2) 2 -O-CO-CH
_{= CH 2 (397) R:} -NH-CO-C (CH 3) = CH 2 (398) R: -NH- (CH 2) 2 -O-CO-C
(CH ₃ ) = CH ₂ (399) R: —NH—CO— (CH ₂ ) ₂ —O—CO
_{-CH = CH 2 (400) R} : -NH-CO- (CH 2) 2 -O-CO
_{-C (CH 3) = CH 2} (401) R: -OH (402) R: -O- (CH 2) 2 -CH 3 (403) R: -O- (CH 2) 3 -CH 3 (404 _{) R: -O- (CH 2 -O} -CH 2) 2 -CH
_{3 (405) R: -O-} CO-CH = CH 2 (406) R: -O- (CH 2) 2 -O-CO-CH =
CH ₂ (407) R: —O—CO—C (CH ₃ ) ＝ CH ₂ (408) R: —O— (CH ₂ ) ₂ —O—CO—C (C
_{H 3) = CH 2 (409} ) R: -O-CO- (CH 2) 2 -O-CO-
_{CH = CH 2 (410) R} : -O-CO- (CH 2) 2 -O-CO-
C (CH ₃ ) = CH ₂

[0114]

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(411) R: —O— (CH ₂ ) ₄ —O—
CO-CH = CH ₂

[0116]

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(412) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0118]

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(413) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0120]

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(414) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0122]

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[0123] (415) R: -H (416 ) R: -CH 3 (417) R :-( CH 2) 2 -CH 3 (418) R :-( CH 2) 5 -CH 3 (419) R _{:-( CH 2) 2 -O-CO} -CH = CH
_{2 (420) R :-( CH 2} ) 2 -O-CO-C (C
_{H 3) = CH 2 (421} ) R: -COOH (422) R: -CO-O- (CH 2) 2 -CH 3 (423) R: -CO-O- (CH 2) 3 -CH 3 ( 424) R: -CO-O- ( CH 2 -O-CH 2) 2
_{-CH 3 (425) R: -CO} -O- (CH 2) 2 -O-CO-
CH = CH ₂ (426) R: —CO—O— (CH ₂ ) ₂ —O—CO—
_{C (CH 3) = CH 2} (427) R: -CH 2 -OH (428) R: -CH 2 -O- (CH 2) 2 -CH 3 (429) R: -CH 2 -O- (CH _{2) 3 -CH 3 (430)} R: -CH 2 -O- (CH 2 -O-CH 2)
_{2 -CH 3 (431) R:} -CH 2 -O-CO-CH = CH 2 (432) R: -CH 2 -O- (CH 2) 2 -O-CO
_{-CH = CH 2 (433) R} : -CH 2 -O-CO-C (CH 3) = C
_{H 2 (434) R: -CH} 2 -O- (CH 2) 2 -O-CO
_{-C (CH 3) = CH 2} (435) R: -CH 2 -O-CO- (CH 2) 2 -O
_{-CO-CH = CH 2 (436} ) R: -CH 2 -O-CO- (CH 2) 2 -O
_{-CO-C (CH 3) =} CH 2

(437) R: -SO ₃ H (438) R: -SO _3- (CH ₂ ) ₂ -CH ₃ (439) R: -SO _3- (CH ₂ ) ₃ -CH ₃ (440) R : —SO ₃ — (CH ₂ —O—CH ₂ ) ₂ —
_{CH 3 (441) R: -SO} 3 - (CH 2) 2 -O-CO-C
_{H = CH 2 (442) R} : -SO 3 - (CH 2) 2 -O-CO-C
(CH ₃ ) = CH ₂ (443) R: —CO—CH ₃ (444) R: —CO— (CH ₂ ) ₂ —CH ₃ (445) R: —CO— (CH ₂ ) ₅ —CH ₃ ( _{446) R: -CO- (CH 2} ) 2 -O-CO-CH
ＣＨCH ₂ (447) R: —CO— (CH ₂ ) ₂ —O—CO—C
(CH ₃ ) = CH ₂

(448) R: —NH ₂ (449) R: —NH— (CH ₂ ) ₂ —CH ₃ (450) R: —NH— (CH ₂ ) ₃ —CH ₃ (451) R: —NH _{- (CH 2 -O-CH 2} ) 2 -C
_{H 3 (452) R: -NH} -CO-CH = CH 2 (453) R: -NH- (CH 2) 2 -O-CO-CH
_{= CH 2 (454) R:} -NH-CO-C (CH 3) = CH 2 (455) R: -NH- (CH 2) 2 -O-CO-C
(CH ₃ ) = CH ₂ (456) R: —NH—CO— (CH ₂ ) ₂ —O—CO
_{-CH = CH 2 (457) R} : -NH-CO- (CH 2) 2 -O-CO
_{-C (CH 3) = CH 2} (458) R: -OH (459) R: -O- (CH 2) 2 -CH 3 (460) R: -O- (CH 2) 3 -CH 3 (461 _{) R: -O- (CH 2 -O} -CH 2) 2 -CH
_{3 (462) R: -O-} CO-CH = CH 2 (463) R: -O- (CH 2) 2 -O-CO-CH =
CH ₂ (464) R: —O—CO—C (CH ₃ ) ＝ CH ₂ (465) R: —O— (CH ₂ ) ₂ —O—CO—C (C
H ₃ ) = CH ₂ (466) R: —O—CO— (CH ₂ ) ₂ —O—CO—
CH = CH ₂ (467) R: —O—CO— (CH ₂ ) ₂ —O—CO—
C (CH ₃ ) = CH ₂

[0126]

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(468) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0128]

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(469) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0130]

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(470) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0132]

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(471) R: -O- (CH ₂ ) ₄ -O-
CO-CH = CH ₂

[0134]

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(472) R: —OH (473) R: —O— (CH ₂ ) ₂ —CH ₃ (474) R: —O— (CH ₂ ) ₃ —CH ₃ (475) R: —O— _{(CH 2 -O-CH 2)} 2 -CH
_{3 (476) R: -O-} CO-CH = CH 2 (477) R: -O- (CH 2) 2 -O-CO-CH =
_{CH 2 (478) R: -O} -CO-C (CH 3) = CH 2 (479) R: -O- (CH 2) 2 -O-CO-C (C
_{H 3) = CH 2 (480} ) R: -O-CO- (CH 2) 2 -O-CO-
CH = CH ₂ (481) R: —O—CO— (CH ₂ ) ₂ —O—CO—
_{C (CH 3) = CH 2} (482) R: -C≡C-C (CH 3) 2 -OH (483) R: -C≡C-Si (CH 3) 3 (484) R: -C≡ _{C- (CH 2) 2 -CH 3} (485) R: -C≡C- (CH 2) 2 -O-CO-C
_{H = CH 2 (486) R} : -CH = CH- (CH 2) 2 -CH 3 (487) R: -CH = CH- (CH 2) 2 -O-CO
-CH = CH ₂

[0136]

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(488) R: -O-CO-CH = CH ₂

[0138]

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(489) R: -O-CO-CH = CH ₂

[0140]

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[0141] (490) R: -H (491 ) R: -O- (CH 2) 2 -CH 3 (492) R: -O- (CH 2) 2 -O-CO-CH =
CH ₂

[0142]

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[0143] (493) R: -H (494 ) R: -O- (CH 2) 2 -CH 3 (495) R: -O- (CH 2) 2 -O-CO-CH =
CH ₂

[0144]

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[0145] (496) R: -H (497 ) R: -O- (CH 2) 2 -CH 3 (498) R: -O- (CH 2) 2 -O-CO-CH =
CH ₂

The above aromatic compounds can be synthesized with reference to a known method for constructing an aromatic ring (for example, described in a new experimental chemistry course) or a method for introducing a substituent into an aromatic ring. The tolan skeleton, stilbene skeleton and biphenyl skeleton contained in the aromatic compound respectively form the Sonogasira reaction (Sonogasira reaction).
reaction), Heck reaction and Suzuki reaction.

[0147]

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An aromatic ring having an alkyl group or an acyl group as a substituent is, for example, a Friedel-Crafts reaction (Fr
It can be synthesized by using iedel-Crafts reaction).

[0149]

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Two or more alignment temperature lowering agents may be used in combination. The amount of the alignment temperature lowering agent used is also determined in consideration of the influence on the alignment temperature and the intrinsic birefringence of the discotic liquid crystal composition. The alignment temperature lowering agent is preferably used in an amount of 1 to 50% by weight, more preferably 2 to 40% by weight, and more preferably 3 to 30% by weight of the amount of the discotic liquid crystalline compound. Most preferably, it is used.

[Optical Anisotropic Layer] The optically anisotropic layer is formed from a discotic liquid crystal composition containing the above-mentioned alignment temperature lowering agent and discotic liquid crystalline molecules. Discotic liquid crystalline molecules are described in various literatures (C. Destrade et.
al., Mol. Crysr. Liq. Cryst., vol. 71, page 111
(1981); edited by The Chemical Society of Japan, quarterly chemistry review, No. 22,
Liquid Crystal Chemistry, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne
et al., Angew. Chem. Soc. Chem. Comm., page 1794.
(1985); J. Zhang et al., J. Am. Chem. Soc., Vol. 11
6, page 2655 (1994)). For the polymerization of discotic liquid crystal molecules, see JP-A-8-272.
84 publication. In order to fix the discotic liquid crystal molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystal molecules. However, when a polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain an oriented state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. Therefore, discotic liquid crystal molecules are
The compound represented by the following formula (I) is preferable.

(I) D (-LQ) _{n wherein} D is a discotic core; L is a divalent linking group; Q is a polymerizable group; and n is 4 to 12 Is an integer. An example of the discotic core (D) of the above formula is shown below. In each of the following examples, LQ (or QL) means a combination of a divalent linking group (L) and a polymerizable group (Q).

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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In the above formula, the divalent linking group (L) is
Alkylene group, alkenylene group, arylene group, -CO
It is preferably a divalent linking group selected from the group consisting of-, -NH-, -O-, -S- and a combination thereof. The divalent linking group (L) is an alkylene group, an alkenylene group, an arylene group, -CO-, -NH-, -O-
And a group obtained by combining at least two divalent groups selected from the group consisting of and -S-.
The divalent linking group (L) is most preferably a group obtained by combining at least two divalent groups selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -CO- and -O-. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms. The alkylene group, alkenylene group and arylene group may have a substituent (eg, an alkyl group, a halogen atom, a cyano, an alkoxy group, an acyloxy group). Examples of the divalent linking group (L) are shown below. The left side is bonded to the discotic core (D), and the right side is bonded to the polymerizable group (Q). AL represents an alkylene group or an alkenylene group, and AR represents an arylene group.

L1: -AL-CO-O-AL- L2: -AL-CO-O-AL-O- L3: -AL-CO-O-AL-O-AL- L4: -AL-CO-O -AL-O-CO-L5: -CO-AR-O-AL-L6: -CO-AR-O-AL-O-L7: -CO-AR-O-AL-O-CO-L8: -CO -NH-AL-L9: -NH-AL-O-L10: -NH-AL-O-CO-L11: -O-AL-L12: -O-AL-O-L13: -O-AL-O- CO-

L14: -O-AL-O-CO-NH-AL
-L15: -O-AL-S-AL- L16: -O-CO-AL-AR-O-AL-O-CO- L17: -O-CO-AR-O-AL-CO- L18: -O -CO-AR-O-AL-O-CO-L19: -O-CO-AR-O-AL-O-AL-OC
O-L20: -O-CO-AR-O-AL-O-AL-OA
L-O-CO-L21: -S-AL-L22: -S-AL-O-L23: -S-AL-O-CO-L24: -S-AL-S-AL-L25: -S-AR -AL-

In order to optically compensate for a liquid crystal cell in which rod-like liquid crystal molecules are twisted in the STN mode, it is preferable that the discotic liquid crystal molecules are also twisted. When an asymmetric carbon atom is introduced into the AL (alkylene group or alkenylene group), the discotic liquid crystal molecule can be twisted and aligned in a helical manner. Further, even when a compound (chiral agent) having an asymmetric carbon atom and exhibiting optical activity is added to the optically anisotropic layer, the discotic liquid crystal molecules can be twisted in a helical manner.

The polymerizable group (Q) in the formula (I) is determined according to the type of the polymerization reaction. Examples of the polymerizable group (Q) are shown below.

[0165]

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The polymerizable group (Q) is an unsaturated polymerizable group (Q1
To Q7), an epoxy group (Q8) or an aziridinyl group (Q9), more preferably an unsaturated polymerizable group, and more preferably an ethylenically unsaturated polymerizable group (Q
1 to Q6) are most preferred. In the formula (I), n is an integer of 4 to 12. Specific numbers are determined according to the type of discotic core (D).
The combination of a plurality of L and Q may be different, but is preferably the same.

Two or more discotic liquid crystalline molecules may be used in combination. For example, the polymerizable discotic liquid crystal molecules and the non-polymerizable discotic liquid crystal molecules described above can be used in combination. The non-polymerizable discotic liquid crystal molecule is preferably a compound in which the polymerizable group (P) of the polymerizable discotic liquid crystal molecule is changed to a hydrogen atom or an alkyl group. That is, the non-polymerizable discotic liquid crystalline molecule is preferably a compound represented by the following formula (II). (II) D (-LR) _{n wherein} D is a discotic core; L is a divalent linking group; R is a hydrogen atom or an alkyl group;
Is an integer of 4 to 12. An example of the discotic core (D) of formula (II) is that LP (or PL) is replaced by LR (or R
Except for changing to L), it is the same as the example of the polymerizable discotic liquid crystal molecule described above. Further, a divalent linking group (L)
Is the same as the example of the polymerizable discotic liquid crystal molecule described above. The alkyl group represented by R has 1 to 4 carbon atoms.
It is preferably 0, more preferably 1 to 30. A chain alkyl group is more preferable than a cyclic alkyl group, and a straight-chain alkyl group is more preferable than a branched chain alkyl group. R is particularly preferably a hydrogen atom or a linear alkyl group having 1 to 30 carbon atoms.

The optically anisotropic layer is formed of a discotic liquid crystal molecule, an alignment temperature lowering agent or the following polymerizable initiator and optional additives (eg, a plasticizer, a monomer, a surfactant, a cellulose ester, It is formed by applying a discotic liquid crystal composition (coating solution) containing a 3,5-triazine compound, a chiral agent) on the alignment film. As the solvent used for preparing the discotic liquid crystal composition,
Organic solvents are preferably used. Examples of the organic solvent include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethylsulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate),
Ketones (eg, acetone, methyl ethyl ketone) and ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane) are included. Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination. The discotic liquid crystal composition can be applied by a known method (eg, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method).

The discotic liquid crystal molecules are preferably oriented substantially uniformly, and more preferably are fixed in a state where they are substantially uniformly oriented. Most preferably, it is fixed. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization reactions are preferred. Examples of photopolymerization initiators include α
-Carbonyl compounds (U.S. Pat.
369670), acyloin ethers (described in US Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (described in US Pat. No. 272251)
No. 2), polynuclear quinone compounds (US Pat. No. 304)
Nos. 6127 and 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (described in US Pat. No. 3,549,367), an acridine and phenazine compound (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,221,970). The amount of the photopolymerization initiator used is preferably 0.01 to 20% by weight, more preferably 0.5 to 5% by weight of the solid content of the coating solution. Light irradiation for the polymerization of discotic liquid crystalline molecules preferably uses ultraviolet light.
The irradiation energy is 20 mJ / cm ^{2 to} 50 J / cm
² , preferably 100 to 800 mJ / cm
More preferably, it is ² . Light irradiation may be performed under heating conditions to promote the photopolymerization reaction.

The thickness of the optically anisotropic layer is from 0.1 to 20.
μm, more preferably 0.5 to 15 μm, and most preferably 1 to 10 μm. As described above, the alignment state of liquid crystal molecules in the optically anisotropic layer is determined according to the type of display mode of the liquid crystal cell. Specifically, the alignment state of liquid crystal molecules is determined by the types of liquid crystal molecules, types of alignment films, and additives in the optically anisotropic layer (eg, plasticizer, binder, surfactant).
Controlled by the use of

[Transparent Support] As the transparent support of the optical compensation sheet, an optically isotropic polymer film is generally used. The support is transparent when the light transmittance is 8
It means 0% or more. Specifically, the optical isotropy has an in-plane retardation (Re) of preferably 10 nm or less, more preferably 5 nm or less. The retardation in the thickness direction (Rt
h) is preferably 40 nm or less, and 20 nm
It is more preferred that: The in-plane retardation (Re) and the thickness direction retardation (Rth) of the transparent support are defined by the following formulas. Re = (nx−ny) × d Rth = [{(nx + ny) / 2} −nz] × d where nx and ny are in-plane refractive indices of the transparent support, and nz is the thickness of the transparent support. Is the refractive index in the direction, and d is the thickness of the transparent support.

Depending on the type of liquid crystal display mode, an optically anisotropic polymer film may be used as the transparent support. That is, in some cases, the optical anisotropy of the optically anisotropic layer is added to the optical anisotropy of the transparent support to correspond to the optical anisotropy of the liquid crystal cell (optical compensation). When an optically anisotropic transparent support is used for such a purpose, the in-plane retardation (Re) of the transparent support is used.
Is preferably at least 20 nm, more preferably at least 30 nm. Further, the retardation (Rth) in the thickness direction is preferably 80 nm or more, and more preferably 120 nm or more.

The material for forming the transparent support is determined depending on whether it is an optically isotropic support or an optically anisotropic support. In the case of an optically isotropic support, glass or cellulose ester is generally used. In the case of an optically anisotropic support, a synthetic polymer (eg, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin) is generally used. The optical anisotropy is obtained by stretching the synthetic polymer film. The cellulose ester or synthetic polymer film is preferably formed by a solvent casting method. The thickness of the transparent support is preferably from 20 to 500 μm, more preferably from 50 to 200 μm. In order to improve the adhesion between the transparent support and the layer provided thereon (adhesive layer, alignment film or optically anisotropic layer), the transparent support is subjected to a surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet light). (UV) treatment, flame treatment). An adhesive layer (undercoat layer) may be provided on the transparent support.

[Alignment Film] The alignment film may be formed by rubbing an organic compound (preferably a polymer), obliquely depositing an inorganic compound, forming a layer having microgrooves, or by using a Langmuir-Blodgett method (LB film). (Eg, ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate). In addition, the application of an electric field,
There is also known an alignment film in which an alignment function is generated by applying a magnetic field or irradiating light. An alignment film formed by rubbing a polymer is particularly preferable. The rubbing treatment is performed by rubbing the surface of the polymer layer several times with paper or cloth in a certain direction. The type of polymer used for the alignment film is determined according to the type of display mode of the liquid crystal cell. In a display mode in which many of the rod-like liquid crystal molecules in the liquid crystal cell are substantially vertically aligned (eg, VA, OCB, HAN), the liquid crystal molecules in the optically anisotropic layer are substantially horizontally aligned. An alignment film having the function of causing the alignment is used. In a display mode (eg, STN) in which most of the rod-like liquid crystal molecules in the liquid crystal cell are substantially horizontally aligned, the liquid crystal molecules have a function of substantially vertically aligning the liquid crystal molecules in the optically anisotropic layer. An alignment film is used.
In a display mode (eg, TN) in which many of the rod-like liquid crystal molecules in the liquid crystal cell are substantially obliquely oriented, it has a function of substantially obliquely aligning the liquid crystal molecules of the optically anisotropic layer. An alignment film is used. For specific types of polymers, there are descriptions in the literature on optical compensation sheets using discotic liquid crystalline molecules corresponding to the various display modes described above. The thickness of the alignment film is preferably 0.01 to 5 μm, and more preferably 0.05 to 1 μm.

[Liquid Crystal Display Device] The present invention can be applied to liquid crystal cells of various display modes. As described above, the optical compensation sheet using discotic liquid crystal molecules is TN
(Twisted Nematic), IPS (In-Plane Switchin)
g), FLC (Ferroelectric Liquid Crystal), OC
B (Optically Compensatory Bend), STN (Supper
Twisted Nematic), VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) have already been proposed. The present invention is effective for a liquid crystal display device of any display mode. A polarizing element generally includes a polarizing film and a protective film. The polarizing film includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film are generally manufactured using a polyvinyl alcohol-based film.
The polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. The protective films are provided on both surfaces of the polarizing film. The transparent support of the optical compensation sheet can also function as a protective film on one side of the polarizing film. As a protective film for the other polarizing film, it is preferable to use a cellulose ester film having high optical isotropy, especially a triacetyl cellulose film.

[0176]

EXAMPLES Example 1 (Preparation of Discotic Liquid Crystal Composition) To 200 mg of the following discotic liquid crystal compound, 20 mg of an alignment temperature lowering agent (129) was added, and the mixture was dissolved in 100 microliter of methyl ethyl ketone. And a discotic liquid crystal composition was prepared.

[0177]

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[0178]

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(Preparation of Alignment Film) The following modified polyvinyl alcohol was dissolved in a mixed solvent of N-methylpyrrolidone and methyl ethyl ketone (volume ratio = 20/80) to prepare a 5% by weight solution. This solution was applied on a glass plate having a thickness of 1.1 mm using a bar coater. 8 coating layers
It was dried with hot air at 0 ° C. for 10 minutes, and the surface was rubbed to form an alignment film.

[0180]

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(Measurement of Alignment Temperature) After the discotic liquid crystal composition is spin-coated on the alignment film, the liquid crystal composition is observed with a polarizing microscope while heating at a rate of 5 ° C./min. I asked. The orientation temperature is 125 ° C.
Met.

(Preparation of Wedge Cell) A glass plate provided with an alignment film was cut, and the width was 20 mm, the length was 40 mm, and the height was 0.85 m.
m wedge cells were fabricated.

(Measurement of Intrinsic Birefringence) To a discotic liquid crystal composition, 30 μl of a 2% by weight solution of TEMPO (2,2,6,6-tetramethyl-1-piperidinoyloxy-free radical) in methyl ethyl ketone was added. One liter was added to make a complete solution. Next, methyl ethyl ketone was removed under reduced pressure to obtain a solid substance of the liquid crystal composition. The wedge cell, a solid was poured in N _D phase temperature, it was uniformly aligned. When the wedge cell was observed with a polarizing microscope in which a 550 nm interference filter was inserted in the light source, a black streak was observed in a region showing a retardation that was an integral multiple of 550 nm. The temperature is lowered to a level just before the streaks become unreadable (20 ° C. or higher).
The value of the maximum intrinsic birefringence (Δn) at 0 nm was determined. Δn was 0.135.

[Comparative Example 1] A discotic liquid crystal composition was prepared and evaluated in the same manner as in Example 1 except that the alignment temperature lowering agent (129) was not added. The results are shown in Table 1.

Example 2 A discotic liquid crystal composition was prepared in the same manner as in Example 1 except that the same amount of the alignment temperature lowering agent (231) was used instead of the alignment temperature lowering agent (129). evaluated. The results are shown in Table 1.

[0186]

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Example 3 A discotic liquid crystal composition was prepared in the same manner as in Example 1, except that the same amount of the alignment temperature lowering agent (431) was used in place of the alignment temperature lowering agent (129). evaluated. The results are shown in Table 1.

[0188]

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Comparative Example 2 A discotic liquid crystal composition was prepared in the same manner as in Example 1, except that the same amount of the alignment temperature lowering agent (x) was used instead of the alignment temperature lowering agent (129). evaluated. The results are shown in Table 1.

[0190]

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[Comparative Example 3] A discotic liquid crystal composition was prepared in the same manner as in Example 1 except that the same amount of the alignment temperature reducing agent (y) was used instead of the alignment temperature reducing agent (129). evaluated. The results are shown in Table 1.

[0192]

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[0193]

Table 1 Table 1 Liquid crystal composition Orientation temperature lowering agent Orientation temperature Temperature drop Intrinsic birefringence relative value 比較 Comparative Example 1 None 155 ° C 0 ° C 0.144 100% Example 1 (129) 125 ° C -30 ° C 0.135 94% Example 2 (231) 125 ° C -30 ° C 0.138 96% Example 3 (431) 122 ° C- 33 ° C. 0.144 100% Comparative Example 2 (x) 127 ° C.-28 ° C. 0.128 89% Comparative Example 3 (y) 125 ° C.-30 ° C. 0.125 87% ─────────── ───────────────────────── (Note) Temperature drop: difference from the orientation temperature of Comparative Example 1 Relative value: Comparative Example 1 Percentage of organic birefringence

Example 4 (Preparation of Optical Compensation Sheet) Thickness 100 μm, size 27
A 0 mm × 100 mm triacetyl cellulose film (Fujitac, manufactured by Fuji Photo Film Co., Ltd.) was used as a transparent support. The following polyacrylic acid copolymer 100
Parts by weight and 20 parts by weight of triethylamine are dissolved in a mixed solvent of methanol and water (volume ratio = 30/70),
A 5% by weight solution was prepared. This solution was applied to a thickness of 1 μm on a transparent support using a bar coater. The coating layer was dried with hot air at 100 ° C. for 5 minutes, and its surface was rubbed to form an alignment film. On the alignment film, a coating solution having the following composition was applied by an extrusion method.

[0195]

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<< Coating Liquid for Optically Anisotropic Layer >>デ ィ ス 91 parts by weight of the discotic liquid crystalline compound used in Example 1 20 parts by weight Cellulose acetate butyrate having a degree of acetylation of 2.0%, a degree of butyrylation of 50.0%, and a number average molecular weight of 30,000 (CAB-551-0.2, manufactured by Eastman Chemical Company) 0.25 parts by weight Cellulose acetate butyrate having a degree of acetylation of 3.0%, a degree of butyrylation of 50.0%, and a number average molecular weight of 40,000 (CAB-531-1, manufactured by Eastman Chemical Company) 0.25 parts by weight Orientation temperature lowering agent (431) 9 parts by weight Photopolymerization initiator (Irgacure 369, Japan Manufactured Bagaigi Ltd.) 3 parts Methyl ethyl ketone 120 parts by weight ────────────────────────────────────

[0197]

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The Δnd of the obtained optical compensation sheet was set to a wavelength of 5
It was 880 nm when measured at 50 nm. The twist angle of the discotic liquid crystal molecules was 240 °. Furthermore, when the alignment state of the discotic liquid crystal molecules was observed with a polarizing microscope, all the molecules were uniformly aligned (monodomain alignment).

Separately, an optical compensatory sheet in which the discotic liquid crystalline compound is substantially vertically oriented but not twisted was prepared in the same manner except that the chiral agent was removed from the coating liquid for the optically anisotropic layer. did. The in-plane retardation (R) of this sheet was measured using an ellipsometer.
e) was measured, and the average inclination angle was determined from the angle dependence to be 85 to 90 °. When the Δnd of the obtained optical compensation sheet was measured at a wavelength of 550 nm,
It was 80 nm. The twist angle of the discotic liquid crystal molecules was 240 °. Furthermore, when the alignment state of the discotic liquid crystal molecules was observed with a polarizing microscope, all the molecules were uniformly aligned (monodomain alignment).

Example 5 (Production of Liquid Crystal Display) Twist Angle: 240 °, Δnd
Was bonded below the 880 nm STN liquid crystal cell so that one optical compensation sheet prepared in Example 4 was on the liquid crystal cell side. On the surface where the optical compensation sheet and the liquid crystal cell are bonded, the director of the discotic liquid crystal molecules (the normal direction of the disc surface) and the director of the rod-like liquid crystal molecules of the liquid crystal cell (the long axis direction) match. The orientations of the liquid crystal cell and the optical compensation sheet were adjusted. Further, a pair of polarizing plates were attached in a crossed Nicol arrangement to produce an STN liquid crystal display device. ST obtained
When a voltage was applied to the N-type liquid crystal display, a normally black mode was set. When the visual characteristics were measured,
An angle range having a contrast ratio of 5 or more was obtained at 120 ° or more on the left and right and 150 ° or more at the top and bottom.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a basic configuration of a transmission type liquid crystal display device.

FIG. 2 is a schematic diagram showing a basic configuration of a reflection type liquid crystal display device.

[Explanation of symbols]

 BR Backlight RP Reflector 1, 1a, 1b Polarizer 2, 2a, 2b Transparent support of optical compensation sheet 3, 3a, 3b Optically anisotropic layer of optical compensation sheet 4a Lower substrate of liquid crystal cell 4b of liquid crystal cell Upper substrate 5 Rod-shaped liquid crystalline molecules

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H049 BA02 BA25 BA42 BA47 BB03 BB46 BB49 BB50 BC09 BC22 2H091 FA11X FA11Z FB02 GA01 HA07 HA09 HA10 LA11 LA30 4H027 BA08 BD02 BD07 BD12 BD21 BD24 BE02 CB03 CE03 DM02 DM03

Claims (5)

[Claims] 1. A discotic liquid crystal composition comprising a discotic liquid crystal molecule and an alignment temperature lowering agent, wherein the alignment temperature of the discotic liquid crystal composition is such that the alignment temperature lowering agent is excluded from the discotic liquid crystal composition. Lower than the orientation temperature of the obtained composition, and the difference in orientation temperature is 1
The maximum intrinsic birefringence of 0 ° C. or higher and measured at a wavelength of 550 nm of the discotic liquid crystal composition was measured at a wavelength of 550 nm of a composition obtained by removing the alignment temperature lowering agent from the discotic liquid crystal composition. A discotic liquid crystal composition having a maximum intrinsic birefringence of 90% or more. 2. The discotic liquid crystal composition according to claim 1, wherein the alignment temperature lowering agent is an aromatic compound. 3. The discotic liquid crystal composition according to claim 1, wherein the discotic liquid crystal composition contains the alignment temperature lowering agent in an amount of 1 to 50% by weight based on the amount of the discotic liquid crystal compound. 4. An optical compensatory sheet comprising a transparent support, an alignment film and an optically anisotropic layer formed of discotic liquid crystalline molecules, which are laminated in this order, wherein the optically anisotropic layer comprises Tick liquid crystal molecules and an alignment temperature lowering agent, the alignment temperature of the discotic liquid crystal composition is lower than the alignment temperature of the composition obtained by excluding the alignment temperature lowering agent from the discotic liquid crystal composition, the alignment temperature of the The difference is 10 ° C. or more, and the maximum intrinsic birefringence measured at a wavelength of 550 nm of the discotic liquid crystal composition is at a wavelength of 550 nm of a composition obtained by removing the alignment temperature lowering agent from the discotic liquid crystal composition. A discotic liquid crystal composition having a measured maximum intrinsic birefringence of 90% or more is coated on an alignment film, and heated at a temperature higher than the alignment temperature. An optical compensatory sheet comprising a layer formed by orienting liquid crystal molecules. 5. An optical device comprising a liquid crystal cell, two polarizing elements disposed on both sides thereof, and one or two optical compensation sheets disposed between the liquid crystal cell and one or both polarizing elements. A transmission type liquid crystal display device in which a compensation sheet is laminated in order from a polarizing element side, a transparent support, an alignment film, and an optically anisotropic layer formed from discotic liquid crystalline molecules, The layer contains discotic liquid crystal molecules and an alignment temperature reducing agent, and the alignment temperature of the discotic liquid crystal composition is lower than the alignment temperature of the composition obtained by removing the alignment temperature reducing agent from the discotic liquid crystal composition. The difference in orientation temperature is 10 ° C. or more,
In addition, the maximum intrinsic birefringence measured at a wavelength of 550 nm of the discotic liquid crystal composition is the maximum intrinsic birefringence measured at a wavelength of 550 nm of a composition obtained by removing the alignment temperature lowering agent from the discotic liquid crystal composition. A liquid crystal display device comprising a layer formed by coating a discotic liquid crystal composition of 90% or more on an alignment film, and heating at a temperature higher than the alignment temperature to align the discotic liquid crystal molecules. .