JP2002128742A - Polymerizable liquid crystal compound and optical isomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal compound exhibiting liquid crystal nature at a low temperature, having excellent thermal stability and developing a large birefringence difference, an optical isomer produced by using the liquid crystal compound and a method for producing the optical isomer. SOLUTION: The polymerizable liquid crystal compound is expressed by general formula (I) (X is a polymerizable group; Y1 and Y2 are each independently (CH2)m, (CH2)mO, O(CH2)m, (CH2)mCOO, OOC(CH2)m, (CH2)mOOC or COO(CH2)m; (m) is an integer of 1-20; and A is an aromatic group having substituent). The invention further relates to an optical isomer composed of the compound and a method for producing the isomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerizable liquid crystal compound useful as a material for a liquid crystal display, an optical compensator for a liquid crystal display, a polarizing prism, and the like, an optically anisotropic substance obtained by polymerizing the compound, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, a polymer film in which the orientation structure of internal molecules is controlled has been demanded as a compensator because of a demand for both improvement of display quality and weight reduction of a liquid crystal display element. (Japanese Unexamined Patent Publication No.
No. 28822, JP-A-4-55813 and JP-A-5-27235).

[0003] In the method using these liquid crystalline polymers, a polymer compound solution exhibiting thermotropic liquid crystallinity is coated on an alignment-treated substrate, and then heat-treated at a temperature at which the polymer liquid crystal exhibits a liquid crystal phase. After the orientation, the polymer compound is kept in a glassy state to fix the orientation.

[0004] However, these polymer films are
If the temperature exceeds the glass transition point of the liquid crystalline polymer, the alignment state is destroyed, so that the use temperature is limited by the glass transition point. In addition, when a liquid crystalline polymer is applied to a substrate that has been subjected to an alignment treatment, it cannot be used for a substrate having poor solvent resistance, such as some plastics, because it is dissolved in a solvent and applied.

As a means for solving these problems, a method for producing an optically anisotropic material using a low-molecular bifunctional liquid crystal acrylate compound has been reported (JP-A-3-140).
No. 29). In this technique, a low molecular bifunctional liquid crystalline acrylate compound or composition is twisted and nematically aligned, and then photopolymerized to fix the alignment state.

[0006] In order to use these optically anisotropic materials for polymer films with controlled internal alignment structure, various optically anisotropic materials, liquid crystal displays, etc., good chemical and thermal stability, solvent and low It must have good solubility in molecular liquid crystals and good stability against electric fields and the like. However, in the above-described conventional technology, although the alignment state can be maintained, there are disadvantages such as poor workability due to a high temperature at which a liquid crystal phase is exhibited, and poor thermal stability and poor solubility with a solvent or liquid crystal. . Further, in order to sufficiently modulate light with a smaller film thickness, development of an optical anisotropic body and an optical element having a larger birefringence difference has been desired.

[0007]

An object of the present invention is to provide a polymerizable liquid crystal compound which exhibits liquid crystallinity at a low temperature, has excellent thermal stability, and has a large birefringence difference. An object of the present invention is to provide an optical isomer and a production method thereof.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have repeatedly searched for the production of a novel polymerizable liquid crystal compound, and have completed the present invention.

That is, the present invention relates to (1) a compound represented by the general formula (I)

[0010]

Embedded image

(Wherein X represents a polymerizable group;₁And Y_TwoBut
Same or different,-(CH_Two)_m-,-(CH_Two)_mO
-, -O (CH_Two)_m-,-(CH_Two)_mCOO-, -OO
C (CH _Two)_m-,-(CH_Two)_mOOC- or -COO
(CH_Two)_mRepresents any one of-, m is an integer from 1 to 20
A is a number, and A represents an aromatic group having a substituent. )
A polymerizable liquid crystal compound,

(2) The polymerizable liquid crystal compound according to (1), wherein A in the general formula (I) is an aromatic group substituted with a halogen atom, an alkyl group or an alkoxyl group;

(3) The polymerizable liquid crystal compound according to (1) or (2), wherein X in the general formula (I) is a (meth) acrylate group;

(4) In formula (I), Y ₁ and Y ₂ are the same or different and are — (CH ₂ ) _m O— or —O (CH ₂ ) _m —, where m is 1 to 20 (1) to (3)
A polymerizable liquid crystal compound according to any one of

(5) A in the general formula (I) is

[0016]

Embedded image

(Wherein F represents a fluorine atom and p represents an integer of 1 to 3) and is an aromatic group represented by any one of (1) to (4). A polymerizable liquid crystal compound;

(6) A method for producing an optically anisotropic substance, wherein the polymerizable liquid crystal compound according to any one of the above (1) to (5) is photopolymerized in the presence of a photopolymerization initiator.

(7) An optically anisotropic substance comprising the polymerizable liquid crystal compound according to any one of the above (1) to (5).

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable liquid crystal compound of the present invention has the general formula (I)

[0021]

Embedded image

(Wherein X represents a polymerizable group;₁And Y_TwoBut
Same or different,-(CH_Two)_m-,-(CH_Two)_mO
-, -O (CH_Two)_m-,-(CH_Two)_mCOO-, -OO
C (CH _Two)_m-,-(CH_Two)_mOOC- or -COO
(CH_Two)_mRepresents any one of-, m is an integer from 1 to 20
A is a number, and A represents an aromatic group having a substituent. )
It is.

Here, X in the polymerizable liquid crystal compound represented by the general formula (I) represents a polymerizable group, specifically, a (meth) acryl group, a (meth) acryloylphenyl group,
-Chloro (meth) acrylate group, acrylamide group,
A polymerizable residue such as a vinyl ether group, a thiol group, an allyl ether group, an epoxy group, an itaconic acid derivative, a styrene derivative, or a cinnamic acid derivative, and more preferably a radically polymerizable (meth) acryl group, An acryloylphenyl group and 2-chloro (meth) acrylate.

In the formula (I), Y ₁ and Y ₂ are the same or different and are represented by — (CH ₂ ) _m —, — (CH ₂ ) _m O—, and — (CH ₂ ) _{m
COO -, - OOC (CH 2} ) m -, - (CH 2) m OOC
— Or —COO (CH ₂ ) _m —, wherein m is an integer of 1 to 20, and more preferably m is 3 to 10.

The aromatic group represented by A is, for example, an aromatic group substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0026]

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(Wherein, n represents an integer of 1 to 3, and p represents an integer of 1 to 3), and is an aromatic group having 1 to 3 substituents.

The feature of the polymerizable liquid crystal compound according to the present invention is that the polymerizable liquid crystal compound has two polymerizable groups, and the rigid liquid crystal skeleton peculiar to the liquid crystal which contributes to the development of liquid crystallinity has an asymmetric tran skeleton. The rigid liquid crystal skeleton includes, for example, a skeleton comprising an aromatic ring, a triple bond, and a 6-membered ring A.
From such characteristics, the polymerizable compound according to the present invention can exhibit a high birefringence and a liquid crystal phase at a low temperature.

The compound of the present invention represented by the general formula (I) can be obtained by a known technique. For example, in the general formula (I), X represents an acrylate group, and Y ₁ and Y ₂ represent — (CH ₂ ) ₈ O— and —O (CH
_{2) 8} -, and an aromatic group A is substituted with a methoxy group

[0030]

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In the case of the polymerizable liquid crystal compound represented by
Equivalent amounts of-(4-bromophenoxy) tetrahydro-2H-pyran and 3-methyl-1-butyn-3-ol are charged, heated under a palladium / copper iodide catalyst, and the reaction solution is further added in the presence of potassium hydroxide. To reflux the toluene to obtain an acetylene derivative.

Next, the obtained acetylene derivative and 2-
After heating with (4-bromo-3-methoxyphenoxy) tetrahydro-2H-pyran under a palladium / copper iodide catalyst, the mixture is stirred with a dilute hydrochloric acid / methanol solution to obtain a phenol derivative having a tran skeleton.

The desired polymerizable liquid crystal compound can be obtained by heating the phenol derivative and bromooctyl acrylate at 80 to 100 ° C. in the presence of potassium carbonate. If the reaction temperature is 110 ° C. or higher, the acrylic groups may polymerize with each other, which is not preferable. The polymerizable liquid crystal compound used in the present invention can be synthesized by the same method as described above.

Next, a method for producing an optically anisotropic substance using the polymerizable liquid crystal compound will be described. The compound represented by the general formula (I) can be used alone, or in the form of a mixture of several or a mixture with other liquid crystal components. The polymerizable liquid crystal compound of the present invention may be used alone and / or in a mixture of two or more. In the composition,
A liquid crystal compound having a polymerizable functional group other than the present invention may be contained as long as the properties of the optically anisotropic material are not reduced.

In addition to the polymerizable liquid crystal compound used in the present invention, a liquid crystal compound having no polymerizable functional group and / or a polymerizable compound can be added as long as the properties of the optically anisotropic material are not reduced. . As the liquid crystal compound having no polymerizable functional group, a nematic liquid crystal compound, a smectic liquid crystal compound, a cholesteric liquid crystal compound, and the like can be used without particular limitation as long as they are generally recognized as liquid crystals in this field. Examples of the polymerizable compound include an acrylic monomer having a polymerizable group, a urethane oligomer having a polymerizable group, a polyester oligomer, and an epoxy acrylate oligomer.

These liquid crystal compounds or polymerizable compounds may be appropriately selected and added in combination, but the orientation and mechanical strength of the optically anisotropic substance and the liquid crystallinity of the obtained polymerizable liquid crystal composition are not lost. Thus, it is necessary to adjust the amount of each component added.

As a means for polymerizing the polymerizable liquid crystal compound and / or polymerizable liquid crystal composition of the present invention, active energy rays such as heat and / or ultraviolet rays can be used. In the case of thermal polymerization, it is preferable to use a thermal polymerization initiator as the polymerization initiator. As the thermal polymerization initiator, any known and commonly used thermal polymerization initiator can be used without particular limitation.

As the thermal polymerization initiator, for example,
Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane,
peroxides such as n-butyl-4,4'-di (tert-butylperoxy) valerate and dicumyl peroxide; azo compounds such as 7-azobisisobutylnitrile; tetramethylthiuram disulfide; .

Active energy rays are preferable because the manufacturing process is easy. When ultraviolet rays are used as the active energy rays, it is preferable to add a photopolymerization initiator as a polymerization initiator to the composition. Photopolymerization initiators can be broadly classified into two types: photoinitiators for radical polymerization and photoinitiators for cationic polymerization.

Examples of the former include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-
Acetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;

Benzoin based compounds such as benzoin and benzoin isobutyl ether; acylphosphine oxide systems such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;

Further, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4 '
-Dichlorobenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4- Benzophenones such as methoxybenzophenone;

2-isopropylthioxanthone, 2,4
Aminobenzophenones such as -dimethylthioxanthone, 2,4-diethylthioxanthone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphor Quinone and the like.

The latter include iron arene complexes, arylsulfonium salts, aryliodonium salts and the like.

The amount of the polymerization initiator to be added is 0.01 to 10% by weight, preferably 1 to 5% by weight in the polymerizable liquid crystal compound and / or the polymerizable liquid crystal composition. When a radical polymerization type photoinitiator is added to the polymerizable liquid crystal compound and / or the polymerizable liquid crystal composition of the present invention, the composition is cured only by the addition of the above radical polymerization type photoinitiator. It is preferable to use a photosensitizer in combination.

Examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate,
Amines such as ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy) and 2-ethylhexyl 4-dimethylaminobenzoate Is mentioned. The compounding amount of the photosensitizer is 0.01% in the polymerizable liquid crystal compound and / or the polymerizable liquid crystal composition.
10 to 10% by weight, preferably 0.05 to 5% by weight.

To the polymerizable liquid crystal compound and / or polymerizable liquid crystal composition used in the present invention, an optically active compound is added for the purpose of introducing a twisted nematic alignment or a cholesteric alignment spiral structure into the optically anisotropic material. You may. The optically active compound that can be used here need not itself exhibit liquid crystallinity, and may or may not have a polymerizable group. The direction of the twist can be appropriately selected according to the purpose of use.

Examples of these optically active compounds include cholesteryl pelargonate having a cholesteryl group as an optically active group, cholesterol stearate, and “CB-1 having a 2-methylbutyl group as an optically active group.
5 "," C-15 "(above, manufactured by BDH)," S108
2 "(Merck)," CM-19 "," CM-2 "
0 "," CM "(manufactured by Chisso)," S-811 "having a 1-methylheptyl group as an optically active group (manufactured by Merck)," CM-21 "," CM-22 "(manufactured by Chisso) And the like).

The preferable addition amount of the optically active compound varies depending on the use of the optically anisotropic substance. Chiral nematic orientation,
Alternatively, a helical structure with a cholesteric orientation is introduced. For example, when the helical structure is used as a visual compensator for a liquid crystal display device, the pitch of the helical structure is adjusted so that the wavelength of the selectively reflected light derived from the cholesteric structure is out of the visible light region. P) is 0.2
It is preferable to adjust the pitch to be 5 μm or less or 0.5 μm or more. For example, when used as a reflector having a specific wavelength, the pitch of the helical structure is 0.25 so that the wavelength of the selectively reflected light is in the visible light region. It is preferable to adjust the thickness to 0.5 μm.

Next, a method for producing an optically anisotropic body obtained by polymerizing the polymerizable liquid crystal compound of the present invention or the polymerizable liquid crystal composition containing them will be described. The polymerizable liquid crystal compound of the present invention, or a polymerizable liquid crystal composition containing them is applied on a substrate having an alignment means, or at least one of the two substrates having an alignment means, the polymerizable liquid crystal compound or It can be obtained by polymerizing by heat and / or light irradiation in an aligned state with a polymerizable liquid crystal composition interposed.

As a method of the alignment means, a method in which the substrate surface is rubbed with a cloth or the like, or a method in which SiO _{2 is} applied to the substrate surface
Can be achieved by using oblique vapor deposition.
In the case where a substrate that has been subjected to such an alignment treatment is not used, a method using an electric field or a magnetic field can be used. These alignment means may be used alone or in combination. Among them, a method using a substrate whose substrate surface is rubbed with a cloth or the like is preferable because of its simplicity.

The substrate that can be used at this time can be an organic material or an inorganic material. Specific examples include organic materials such as polyethylene terephthalate, polycarbonate, polyimide, polymethyl methacrylate, polyethylene, polyethersulfone, and polytetrafluoroethylene, and inorganic materials such as silicon and glass.

When a polarizing film is used as a substrate, an optically anisotropic body can be directly incorporated into the polarizing film. The optically anisotropic body thus obtained is used as an elliptically polarizing film as a component of a liquid crystal display. Can be suitably used.

When it is not possible to obtain an appropriate orientation by rubbing these substrates with a cloth or the like, a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is rubbed with a cloth or the like. You may.

As a method for polymerizing the polymerizable liquid crystal compound of the present invention, heat and / or active energy rays can be used. However, since low-temperature curing and rapid polymerization are expected, irradiation with active energy rays can be used. A polymerization method is desirable. Active energy rays are ultraviolet rays, electron beams,
It refers to ionizing radiation such as α-rays, β-rays, and γ-rays, visible light, microwaves, high-frequency waves, and the like, but may be any energy species as long as radical active species can be generated.

Examples of the device that generates ultraviolet light include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, and a short arc lamp. May be selected in consideration of the absorption wavelength of the compound that generates.

In particular, a photopolymerization method, especially a polymerization method using ultraviolet rays, is more preferable from the viewpoint of production. The polymerizable liquid crystal compound of the present invention, or the polymerizable liquid crystal composition containing the same may be irradiated from either the coated substrate surface or the uncoated substrate surface, but when irradiating the uncoated substrate surface, The substrate used must have transparency. Further, the optically anisotropic body manufactured according to the present invention may be used after being peeled off from the substrate, or may be used while being carried on the substrate without being peeled off.

[0058]

EXAMPLES Examples of the present invention will be shown below, and the present invention will be described more specifically. However, the invention is not limited to these examples. In the following examples, “parts” means “parts by weight” unless otherwise specified. The UV illuminance was measured using a Ushio Electric
VD-365PD "with a Unimeter UIT-150".

Example 1 In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 10 g of 2- (4-bromophenoxy) tetrahydro-2H-pyran, 3-methyl-1
-Butin-3-ol 4.9 g, tetrakistriphenylphosphine palladium 570 mg, copper iodide 190 m
g, 15 ml of triethylamine and 50 ml of DMF were charged and stirred. Next, the flask was heated to 90 ° C. and reacted for 3 hours. After completion of the reaction, the reaction solution was washed with a saturated saline solution, dried over sodium sulfate, and the solvent was distilled off to obtain an intermediate (a).

Next, the intermediate (a) synthesized above was placed in a four-necked flask equipped with Dean Stark and a thermometer.
4 g, 50 ml of toluene and 200 mg of potassium hydroxide were charged, the flask was heated to 120, and the toluene was refluxed for 3 hours. Thereafter, the reaction solution was filtered, the filtrate was washed with saturated saline, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 2.1 g of an intermediate (b) having an acetylene group.

4 equipped with a Dimroth reflux tube and a thermometer
1.9 g of the intermediate (b), 2.7 g of 2- (4-bromo-2-fluorophenoxy) tetrahydro-2H-pyran, 100 mg of tetrakistriphenylphosphine palladium, 35 mg of copper iodide, 10 ml of triethylamine in a one-necked flask 30 ml of DMF was charged and stirred. Next, the flask was heated to 90 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was washed with a saturated saline solution, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 4 g of an intermediate (c) having a tran skeleton.

Then, 3.8 g of the intermediate (c) and 20 g of tetrahydrofuran were placed in an eggplant flask equipped with a dropping funnel.
ml and stirred. Then, a 5% hydrochloric acid aqueous solution was added dropwise, and the mixture was stirred for 30 minutes. 100 ml of ethyl acetate was added to the reaction solution, washed with pure water and saturated saline, dried over sodium sulfate, the solvent was distilled off, and purified by a silica gel column to obtain 2.1 g of an intermediate (d) having a tran skeleton.

Further, 1.9 of the intermediate (d) was placed in a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel and a thermometer.
g, 7 g of potassium carbonate and 50 ml of DMF.
Stirred at C for 1 hour. Then, a DMF solution of 4.1 g of 4-bromobutyl acrylate was added dropwise. After completion of the dropwise addition, the flask was kept at 100 ° C. and stirred for 4 hours to complete the reaction. After completion of the reaction, the organic layer was washed with pure water and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (A- 2.5 g of 1) was obtained.

[0064]

Embedded image

Also, from the infrared absorption spectrum, 3200
It was confirmed that the absorption of phenolic hydroxyl groups at ３3600 cm ⁻¹ had disappeared, and it was completely etherified.

(Physical properties) 1H-NMR (solvent: deuterated chloroform): δ: 7.45 (2H), 7.26 (2H), 6.92-6.83 (3H), 6.42
(2H), 6.10 (2H), 5.86 (2H), 4.26 (4H), 4.10 (2H), 4.01 (2H),
1.91 (8H),

¹³ C-NMR (solvent: deuterated chloroform):
δ: 165.9,133.0,130.6,128.7,120,114.6,72.0,69.9,6
8.9,64.6,29.0,28.6,25.8

Infrared absorption spectrum (IR) (KBr) c
m ^-1 : 2930,2861, 2215,1734,1634,1606,1197,817,807.
5 elemental analysis: C = 66.3% (66.7), H = 6.3% (6.47)

The obtained polymerizable liquid crystal compound (A-1) was
In a temperature-lowering state of 2 ° C./min, a phase transition from an isotropic phase liquid state to a smectic phase was performed at 29 ° C., and a phase transition was performed at 5 ° C. to a crystalline phase. Further, a non-polymerizable liquid crystal compound “RO-57”
1 "(manufactured by Dainippon Ink and Chemicals, Inc.), and the birefringence difference (Δn) of the polymerizable liquid crystal compound (A-1) of the present invention was measured using an Appe refractometer (manufactured by Atago). The value was as high as 23. No change was observed after the heat test at 120 ° C.

(Example 2) The procedure of Example 1 was repeated, except that 8.9 g of 6-bromohexyl acrylate was used instead of 4.1 g of 4-bromobutyl acrylate. 8 g of a white crystalline polymerizable liquid crystal compound (A-2) represented by

[0071]

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From the infrared absorption spectrum, 3200 to 36
The absorption of the phenolic hydroxyl group at 00 cm ^-1 disappeared, confirming that the phenolic hydroxyl group was completely etherified.

(Physical properties) 1H-NMR (solvent: deuterated chloroform): δ: 7.45 (2
H), 7.26 (2H), 6.92-6.83 (3H), 6.42 (2H), 6.10 (2H), 5.86 (2H
H), 4.26 (4H), 4.10 (2H), 4.01 (2H), 1.86-1.67 (4H), 1.55-
1.45 (4H)

¹³ C-NMR (solvent: deuterated chloroform):
δ: 166.0,133.2,130.6,128.7,120,114.6,72.0,69.9,6
8.9,64.6,29.0,28.6,25.8,23.5

Infrared absorption spectrum (IR) (KBr) c
m ^-1 : 2932,2860, 2215,1734,1634,1606,1197,817,807.
5 Elemental analysis: C = 70.5% (71.6), H = 6.4% (6.95)

The obtained polymerizable liquid crystal compound (A-2) was
In a temperature-lowering state of 2 ° C./min, a phase transition from an isotropic phase liquid state to a smectic phase was carried out at 42 ° C., and a phase transition was carried out at 22 ° C. to a crystalline phase. Further, a non-polymerizable liquid crystal compound “RO-57”
1 "(manufactured by Dainippon Ink and Chemicals, Inc.), and the birefringence difference (Δn) of the polymerizable liquid crystal compound (A-1) of the present invention was measured using an Appe refractometer (manufactured by Atago). A high value of 22 was shown. No change was observed after the heat test at 120 ° C.

(Example 3) In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 1.9 g of the intermediate (b) synthesized in Example 1 and 2- (4-bromo-3-methylphenoxy) 2.6 g of tetrahydro 2H-pyran, 100 mg of tetrakistriphenylphosphine palladium, 35 mg of copper iodide, 10 ml of triethylamine, DMF3
0 ml was charged and stirred. Next, the flask was heated to 90 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was washed with a saturated saline solution, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by a silica gel column to obtain 3.0 g of an intermediate (e) having a tran skeleton.

Next, 3.5 g of the intermediate (e) and 20 g of tetrahydrofuran 20 were placed in an eggplant flask equipped with a dropping funnel.
ml and stirred. Then, a 5% hydrochloric acid aqueous solution was added dropwise, and the mixture was stirred for 30 minutes. The reaction solution was added with 100 ml of ethyl acetate, washed with pure water and saturated saline, dried over sodium sulfate, and the solvent was distilled off.
1.8 g of an intermediate (f) having a tran skeleton was obtained.

Further, the intermediate (f) 1.8 was placed in a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel and a thermometer.
g, 7 g of potassium carbonate and 50 ml of DMF.
Stirred at C for 1 hour. Then, a DMF solution of 3.8 g of 6-bromohexyl acrylate was added dropwise. After dropping,
The flask was kept at 100 ° C. and stirred for 4 hours to complete the reaction. After completion of the reaction, the mixture was washed with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, the residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (A) represented by the following formula: -3) was obtained in an amount of 2.0 g.

[0080]

Embedded image

From the infrared absorption spectrum, 3200 to 36
The absorption of the phenolic hydroxyl group at 00 cm ^-1 disappeared, confirming that the phenolic hydroxyl group was completely etherified.

(Physical properties) 1H-NMR (solvent: deuterated chloroform): δ: 7.45 (2
H), 7.26 (2H), 7.1-6.9 (3H), 6.42 (2H), 6.11 (2H), 5.86 (2
H), 4.26 (4H), 4.10 (2H), 4.01 (2H), 2.8 (3H), 1.86-1.67 (4
H), 1.55-1.45 (4H)

¹³ C-NMR (solvent: deuterated chloroform):
δ: 166.0, 136.2, 130.0, 128.7, 120, 72.0, 69.9, 68.9, 64.
6,29.0,28.6,25.8,23.5,21.0

Infrared absorption spectrum (IR) (KBr) c
m ^-1 : 2932,2860, 2215,1734,1634,1606,1197,817,807.
5 Elemental analysis: C = 73.8% (74.4), H = 7.12% (7.57)

The obtained polymerizable liquid crystal compound (A-3) was
At a temperature drop of 2 ° C./min, a phase transition from an isotropic phase liquid state to a smectic phase was made at 55 ° C., and a phase transition was made to a crystal phase at 48 ° C. Further, a non-polymerizable liquid crystal compound “RO-57”
1 "(manufactured by Dainippon Ink and Chemicals, Inc.), and the birefringence difference (Δn) of the polymerizable liquid crystal compound (A-1) of the present invention was measured using an Appe refractometer (manufactured by Atago). The value was as high as 20. No change was observed after the heat test at 120 ° C.

Comparative Example 1 In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 2.5 g of the intermediate (b) synthesized in Example 1 above, 2- (4-bromo-phenoxy) tetrahydro 2H 3.2 g of pyran, 100 mg of tetrakistriphenylphosphine palladium, 35 mg of copper iodide, 10 ml of triethylamine, 30 m of DMF
l and stirred. The flask was then heated to 90 ° C.
Allowed to react for hours. After completion of the reaction, the reaction solution was washed with a saturated saline solution, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 4 g of an intermediate (g) having a trans skeleton.

Then, 4 g of the intermediate (g) and 20 ml of tetrahydrofuran were placed in an eggplant flask equipped with a dropping funnel.
And stirred. Then, a 5% hydrochloric acid aqueous solution was added dropwise to the solution.
For a minute. The reaction mixture was added with 100 ml of ethyl acetate, washed with pure water and saturated saline, dried over sodium sulfate, the solvent was distilled off, and purified by a silica gel column to obtain 2 g of an intermediate (h) having a tran bond.

Further, 2 g of the intermediate (h) was placed in a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel and a thermometer.
7 g of potassium carbonate and 50 ml of DMF were charged and stirred at 25 ° C. for 1 hour. Next, a DMF solution of 4.5 g of 6-bromohexyl acrylate was added dropwise. After completion of the dropwise addition, the flask was kept at 100 ° C. and stirred for 4 hours to complete the reaction. After completion of the reaction, the mixture was washed with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, the residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (B- 3.2 g of 1) was obtained.

[0089]

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From the infrared absorption spectrum, 3200 to 36
The absorption of the phenolic hydroxyl group at 00 cm ^-1 disappeared, confirming that the phenolic hydroxyl group was completely etherified.

(Physical properties) 1H-NMR (solvent: deuterated chloroform): δ: 7.45 (4
H), 7.26 (4H), 6.42 (2H), 6.10 (2H), 5.85 (2H), 4.26 (4H), 4.
10 (2H), 4.01 (2H), 1.86-1.67 (4H), 1.50-1.40 (4H)

¹³ C-NMR (solvent: deuterated chloroform):
δ: 166.0, 130.0, 128.7, 120, 72.0, 69.9, 68.9, 64.6, 29.
0,28.6,25.8,23.5,21.0

Infrared absorption spectrum (IR) (KBr) c
m ^-1 : 2932,2860, 2215,1734,1634,1606,1197,817,807.
5 Elemental analysis: C = 73.8% (74.4), H = 7.10% (7.38)

The obtained polymerizable liquid crystal compound (B-1) was
At a temperature drop of 2 ° C./min, a phase transition from an isotropic liquid state to a crystalline phase occurred at 75 ° C.

(Example 4) 40 parts of the polymerizable liquid crystal compound (A-1) obtained in Example 1, 60 parts of a polymerizable liquid crystal compound "UCL-001" (manufactured by Dainippon Ink and Chemicals, Inc.) other than the present invention,
A polymerizable liquid crystal composition was prepared by mixing 2 parts by weight of "Irgacure 651" (manufactured by Ciba Specialty Chemical Co.) as a polymerization initiator. This compound was a composition showing a nematic phase at room temperature.

Next, the above polymerizable composition was injected into a glass cell having a thickness of 20 μm on which a polyimide alignment film subjected to a homogeneous alignment treatment was formed, and then irradiated with ultraviolet light of 400 W / m ² for 60 seconds. An anisotropic body was prepared. According to the measurement of the degree of orientation by Raman scattering measurement, this optically anisotropic body maintained a uniform homogeneous orientation, and there was no problem in heat resistance at 120 ° C.

(Example 5) 30 parts of the polymerizable liquid crystal compound (A-2) obtained in Example 2, 70 parts of a polymerizable liquid crystal compound "UCL-001" (manufactured by Dainippon Ink and Chemicals, Inc.) other than the present invention,
A polymerizable liquid crystal composition was prepared by mixing 2 parts by weight of “Irgacure 651” (manufactured by Ciba Specialty Chemical Co.) as a polymerization initiator. This compound was a composition showing a nematic phase at room temperature.

Next, after injecting the above polymerizable composition into a glass cell having a thickness of 20 μm on which a polyimide alignment film having been subjected to a homogeneous alignment treatment is formed, the glass cell is irradiated with ultraviolet rays of 400 W / m ² for 60 seconds. An anisotropic body was prepared. By measuring the degree of orientation by Raman scattering measurement, this optically anisotropic body maintained uniform homogeneous orientation, and there was no problem in the heat resistance test at 120 ° C.

[0099]

The present invention provides a polymerizable liquid crystal compound which exhibits liquid crystallinity at a low temperature, has excellent thermal stability, and has a large birefringence difference, an optical isomer using the same, and a method for producing the same. can do.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/13 505 G02F 1/13 505 4J100 1/13363 1/13363 F-term (Reference) 2H049 BA06 BA42 BC22 2H088 EA47 HA16 HA23 MA20 2H091 FA07X FA11X FA11Z LA30 4H006 AA01 AA03 AB64 BJ50 BP30 4J011 SA01 SA06 SA21 SA31 SA63 4J100 AT08P BA02P BA04P BA05P BA06P BA15P BB07P BC43P CA01 DA63 DA66 JA43

Claims (7)

[Claims] 1. A compound of the general formula (I)(Wherein, X represents a polymerizable group;₁And Y_TwoAre the same or different
,-(CH_Two)_m-,-(CH_Two)_mO-, -O (CH
_Two)_m-,-(CH_Two)_mCOO-, -OOC (CH _Two)
_m-,-(CH_Two)_mOOC- or -COO (CH_Two)_m
And m represents an integer of 1 to 20;
Represents an aromatic group having a substituent. )
Liquid crystal compounds. 2. The polymerizable liquid crystal compound according to claim 1, wherein A in the general formula (I) is an aromatic group substituted with a halogen atom, an alkyl group, or an alkoxyl group. 3. The polymerizable liquid crystal compound according to claim 1, wherein X in the general formula (I) is a (meth) acrylate group. 4. In the general formula (I), Y ₁ and Y ₂ are the same or different and are — (CH ₂ ) _m O— or —O (CH ₂ ) _m —, wherein m is from 1 to 20. The polymerizable liquid crystal compound according to claim 1, which is an integer. 5. A of the general formula (I) is: (Wherein F represents a fluorine atom and p represents an integer of from 1 to 3).
The polymerizable liquid crystal compound according to any one of the above. 6. A method for producing an optically anisotropic body, comprising photopolymerizing the polymerizable liquid crystal compound according to claim 1 in the presence of a photopolymerization initiator. 7. An optically anisotropic body comprising the polymerizable liquid crystal compound according to claim 1.