JP2002265475A - Polymerizable liquid crystal compound, and optical isomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal compound which exhibits a liquid crystal property at a temperature of <=100 deg.C and has excellent thermal stability and a large birefringence difference, to provide a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, and to provide an optical isomer prepared by polymerizing these substances. SOLUTION: The polymerizable liquid crystal compound represented by the formula [X is a polymerizable group;1 and Y2 are each identically or differently a bond such as a single bond or a Cn H2n ; (n) is an integer of 1 to 20; rings A to C and A' to C' are each independently a ring structured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polymerizable liquid crystal compound useful as a liquid crystal display, an optical compensator for a liquid crystal display, a polarizing prism, and various other light modulating materials, and a polymerizable liquid crystal compound containing the polymerizable liquid crystal compound. The present invention relates to a liquid crystal composition and an optically anisotropic body using 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. Further, when applying a liquid crystalline polymer 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 method, a low-molecular bifunctional liquid crystalline acrylate compound or composition is twist-nematically aligned and then photopolymerized to fix the alignment state.

[0006] In order to use these optically anisotropic materials for a polymer film having a controlled internal orientation structure, various optically anisotropic materials, a liquid crystal display, etc., good chemical stability, heat resistance, solvent and the like are required. And have a solubility in low-molecular liquid crystals and stability against electric fields and the like.

However, in the conventional technique, although alignment can be performed in a short time, workability is poor because the temperature at which a liquid crystal phase is exhibited is higher than 100 ° C., and unintended thermal polymerization is induced, resulting in uneven alignment. There are drawbacks such as immobilization in a state, loss of optical anisotropy in a high temperature range, and poor solubility with solvents and liquid crystals. Furthermore, when light is modulated using these conventional optically anisotropic materials having a small birefringence difference, the light modulation performance is due to the thickness of the optically anisotropic body and the birefringence difference. I had to make my body thicker.

In a polymer material having a controlled orientation structure,
A material having good workability, heat resistance and high birefringence anisotropy has not been known so far. When an optically anisotropic material having a high birefringence anisotropy is used as an optical waveguide or a light modulation material such as an optical compensator, the optical anisotropic layer is used to transmit light with a minimum thickness. Because it can be converted, it can be thin and lightweight. Therefore, development of an optical anisotropic body and an optical element having a birefringence difference as large as possible has been demanded.

[0009]

An object of the present invention is to provide a polymerizable liquid crystal compound which exhibits liquid crystallinity at a temperature of 100 ° C. or less, has excellent thermal stability, and has a large birefringence difference. An object of the present invention is to provide a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, and an optically anisotropic body obtained by polymerizing the composition.

[0010]

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 is a polymerizable liquid crystal compound represented by the following general formula (I). General formula (I)

[0011]

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(Wherein X represents a polymerizable group, and Y ₁ , Y ₂ and Y ₅ are the same or different and are a single bond, —C _n H _2n —, —C
_{n H 2n O -, - OC} n H 2n -, - (C 2 H 4 O) n -, -
_{(OC 2 H 4) n -} , - (C 3 H 6 O) n -, - (OC 3 H 6)
_{n -, - C n H 2n} COO -, - OOCC n H 2n -, - C n H
_2n OOC-, or -COOC _n H _2n - represents either, n represents an integer from 1 to 20, the ring A~C and A'-C 'are each independently, represent one of the following rings,

[0013]

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A and b are integers of 0 to 2; R _{1 to} R ₆ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group; Or a fluoroalkoxy group, wherein Y ₃ and Y ₄ are each independently a single bond,-
CH ₂ CH ₂ —, —CH ₂ O—, —COO—, —OCO
-, -C≡C-, -CH = CH-, -CF = CF-,-
_{(CH 2) 4 -, -} (CH 2) 6 -, - CH 2 CH 2 CH 2 O
-, or -CH ₂ = CHCH represents ₂ CH _2, c is 1 to 1
Represents an integer of 0)

The polymerizable liquid crystal compound of the present invention is, in particular, a polymerizable liquid crystal compound in which X in the general formula (I) is a (meth) acrylate group, and further includes Y ₁ , Y ₂ and Y ₅
There same or _{different, -C n H 2n -, -} C n H 2n O-, or -OC _n H _2n - is and, n represents the polymerizable liquid crystal compound is an integer from 1 to 20, the general formula (I ) Is a polymerizable liquid crystal compound in which Y ₃ and Y ₄ are each independently a single bond or —C≡C—.

The polymerizable liquid crystal compound of the present invention is preferably
Any one or more of the rings A to C and A ′ to C ′ in the general formula (I) is

[0017]

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Wherein F is a fluorine atom, m is an integer of 1 to 3, and p is an integer of 1 to 3, which is a polymerizable liquid crystal compound which is any aromatic group. is there.

The present invention also relates to the above-mentioned polymerizable liquid crystal compound.
A polymerizable liquid crystal composition containing one or more polymerizable liquid crystal compounds, further containing one or more of the above polymerizable liquid crystal compounds and a polymerizable compound other than the above, and one of the polymerizable liquid crystal compounds. A polymerizable liquid crystal composition containing the above and a polymerizable liquid crystal compound other than the above, and further, a polymerizable liquid crystal compound, or an optically anisotropic body composed of the polymerizable liquid crystal composition.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable liquid crystal compound of the present invention is a compound represented by the following general formula (I). General formula (I)

[0021]

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(Wherein X represents a polymerizable group, and Y ₁ , Y ₂ and Y ₅ are the same or different and are a single bond, —C _n H _2n —, —C
_{n H 2n O -, - OC} n H 2n -, - (C 2 H 4 O) n -, -
_{(OC 2 H 4) n -} , - (C 3 H 6 O) n -, - (OC 3 H 6)
_{n -, - C n H 2n} COO -, - OOCC n H 2n -, - C n H
_2n OOC-, or -COOC _n H _2n - represents one of, n is an integer from 1 to 20, rings A, B and C
Each independently represents any of the following rings,

[0023]

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A and b are integers of 0 to 2; R _{1 to} R ₆ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group; Or a fluoroalkoxy group, wherein Y ₃ and Y ₄ are each independently a single bond,-
CH ₂ CH ₂ —, —CH ₂ O—, —COO—, —OCO
-, -C≡C-, -CH = CH-, -CF = CF-,-
_{(CH 2) 4 -, -} (CH 2) 6 -, - CH 2 CH 2 CH 2 O
-, or -CH ₂ = CHCH represents ₂ CH _2, c is 1 to 1
Represents an integer of 0)

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,
Maleimide group, vinyl ether group, thiol group, allyl ether group, epoxy group, itaconic acid derivative, styrene derivative, polymerizable residues such as cinnamic acid derivative,
More preferred are a (meth) acryl group, a (meth) acryloylphenyl group, and 2-chloro (meth) acrylate which are capable of radical polymerization.

In the general formula (I), Y ₁ , Y ₂ and Y ₅ are the same or different and a single bond, —C _n H _2n —, —C _n H _2n O—, —O
_{C n H 2n -, - (} C 2 H 4 O) n -, - (OC 2 H 4) n -,
_{- (C 3 H 6 O)} n -, - (OC 3 H 6) n -, - C n H 2n C
_{OO -, - OOCC n H 2n} -, - C n H 2n OOC-, or -COOC _n H _2n - represents one of, n is an integer from 1 to 20, more preferably n is 3-10 It is.

In the general formula (I), c is an integer of 1 to 10, more preferably an integer of 1 to 4. General formula (I)
Examples of the rings A to C and A ′ to C ′ are a halogen atom, an alkyl group having 1 to 5 carbon atoms, an aromatic group substituted with an alkoxy group having 1 to 5 carbon atoms, and an aliphatic group. , More preferably,

[0028]

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(Wherein, m represents an integer of 1 to 3, and p represents an integer of 1 to 3).

The polymerizable liquid crystal compound of the present invention is characterized in that it has two polymerizable groups and two rigid liquid crystal skeletons specific to liquid crystals contributing to the development of liquid crystallinity, and the rigidity specific to liquid crystals contributing to the development of liquid crystallinity. Liquid crystal skeletons are linked via siloxane bonds. The rigid liquid crystal skeleton is, for example, 6
Examples of the skeleton include a membered ring A and a ring B, a triple bond, and a ring C. From such characteristics, the polymerizable compound according to the present invention has a high birefringence index difference, and can exhibit a liquid crystal phase at a low temperature of 100 ° C. or less. Can maintain good molecular orientation even in a high temperature range of 120 ° C. or higher.

The compound represented by the general formula (I) of the present invention can be synthesized as follows. For example, in the general formula (I), X is an acrylate group, and Y ₁ and Y ₂ are each-(C
H ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, and Y ₅ is — (C
H ₂ ) ₃ —, Y ₃ is a single bond, Y ₄ is an ester bond, rings A, B, and A ′ and B ′ each represent an aromatic group;
C ′ represents an aromatic group substituted with a methyl group, c is an integer of 2,

[0032]

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In the case of the polymerizable liquid crystal compound represented by
3,4-dihydro-2H-pyran and 4-hydroxy-
An equivalent amount of 4′-biphenylcarboxylic acid is charged and reacted at a low temperature using p-toluenesulfonic acid as a catalyst to obtain an intermediate 1 in which a hydroxyl group is protected.

Next, 4-allyl-2-yl was added to 1 equivalent of 1,1,3,3,5,5-hexamethyltrisiloxane.
After adding 2 equivalents of methylphenol and heating under a platinum catalyst, Intermediate 2 to which siloxane is added is obtained.

The intermediate 1 and the intermediate 2 were reacted by heating in the presence of dicyclohexylcarbodiimide and N-methylaminopyridine, and the reaction product was further stirred with a dilute hydrochloric acid / methanol solution to introduce a siloxane-bonded bis. Biphenol derivatives can be obtained.

The desired polymerizable liquid crystal compound can be obtained by heating the bis-biphenol derivative and 3-bromopropyl 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.

In the general formula (I), X represents an acrylate group, and Y ₁ and Y ₂ represent — (CH ₂ ) ₄ O— and —O
(CH ₂ ) ₄ —, Y ₅ is — (CH ₂ ) ₂ —, n
Is 0, Y ₄ is —C≡C—, and rings B, B ′, C,
C ′ represents an aromatic group, and c is an integer of 2;

[0038]

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In the case of the polymerizable liquid crystal compound represented by the formula:
One equivalent of 1,1,3,3,5,5-hexamethyltrisiloxane is added with 2 equivalents of 4-bromostyrene, and heated under a platinum catalyst to obtain an intermediate 3 to which siloxane is added.

Further, 2- (4-bromo-phenoxy) tetrahydro-2H-pyran and 3-methyl-1-butyne-
An equivalent amount of 3-ol is charged, heated under a palladium / copper iodide catalyst, and the reaction solution is refluxed with toluene in the presence of potassium hydroxide to obtain an acetylene derivative.

Next, 2 equivalents of the obtained acetylene derivative and 1 equivalent of the above intermediate 3 are reacted by heating under a palladium / copper iodide catalyst, and the reaction product is stirred with a dilute hydrochloric acid / methanol solution. As a result, a phenol derivative intermediate 4 having a siloxane bond and a tran skeleton is obtained.

The phenol derivative and bromobutyl acrylate are mixed with 80 to 100 in the presence of potassium carbonate.
By heating at ℃, the desired polymerizable liquid crystal compound can be obtained. 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 easily synthesized by the above method or the like. Next, a method for producing an optically anisotropic substance using the polymerizable liquid crystal compound will be described.

The polymerizable liquid crystal composition of the present invention comprises one or more compounds represented by the general formula (I), another polymerizable compound, another liquid crystal component, or another polymerizable liquid crystal compound. Can be used in the form of a mixture of the polymerizable liquid crystal compounds of the present invention alone and / or in a composition obtained by mixing two or more of them to lower the properties of the present invention such as liquid crystallinity, polymerizability, and optical anisotropy. A polymerizable liquid crystal compound other than the present invention, a non-liquid crystal polymerizable compound, and a non-polymerizable liquid crystal compound may be blended within a range not to be performed.

Examples of the liquid crystal compound having no polymerizable functional group include nematic liquid crystal compounds, smectic liquid crystal compounds, and cholesteric liquid crystal compounds, which are generally recognized as liquid crystals in this field, and can be used without any particular limitation. Examples of the non-liquid crystal 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 polymerizable compounds or liquid crystal compounds may be appropriately selected and added in combination. However, the orientation and mechanical strength of the optically anisotropic substance and the liquid crystallinity of the resulting polymerizable liquid crystal composition are not lost. In addition, it is necessary to adjust the addition amount of each component.

As a means for polymerizing the polymerizable liquid crystal compound and the polymerizable liquid crystal composition of the present invention, 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; .

The method using energy rays as the polymerization means is preferable because the production process is easy. When using ultraviolet rays as energy rays, it is preferable to add a photopolymerization initiator as a polymerization initiator to the polymerizable liquid crystal 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 compounds such as benzoin and benzoin isobutyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4,4'-
Dichlorobenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-
Benzophenones such as 4-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.

As the latter, iron arene complexes, arylsulfonium salts, aryliodonium salts and the like can be mentioned. The amount of the polymerization initiator to be added depends on the polymerizable liquid crystal compound and / or
Alternatively, the content is 0.01 to 10% by weight, preferably 1 to 5% by weight in 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. To
It is preferable to use a photosensitizer in combination.

Examples of such photosensitizers 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.

When a maleimide group is used as the polymerizable group of the polymerizable liquid crystal compound of the present invention, it is possible to sufficiently cure even without adding a photopolymerization initiator or adding a very small amount.

The polymerizable liquid crystal compound and / or polymerizable liquid crystal composition used in the present invention contains an optically active compound for the purpose of introducing a twisted nematic alignment or a cholesteric alignment spiral structure into an optically anisotropic body. It may be added. 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 preferred amount of the optically active compound varies depending on the use of the optically anisotropic substance. Chiral nematic orientation,
Alternatively, when a helical structure having a cholesteric orientation is introduced and used as, for example, a visual compensator for a liquid crystal display device, the pitch (P) of the helical structure is adjusted so that the wavelength of the selectively reflected light derived from the cholesteric structure deviates from the visible light region. 0.25
It is preferable to adjust the pitch of the spiral structure to 0.25 μm or less, for example, when used as a reflector having a specific wavelength, 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.

The alignment means can be achieved by rubbing the substrate surface with a cloth or the like, irradiating ultraviolet rays, or obliquely depositing SiO ₂ on the substrate surface. 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 has been rubbed with a cloth or the like and a method of irradiating the substrate with ultraviolet rays are preferable from the viewpoint of simplicity.

The substrate which 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 proper orientation cannot be obtained by rubbing these substrates with a cloth or the like, a polyimide thin film or a polyvinyl alcohol thin film or the like is formed on the substrate surface according to a known method, and even if this is rubbed with a cloth or the like. good.

As a method of polymerizing the polymerizable liquid crystal compound of the present invention, a method of polymerizing by irradiating an energy ray is preferable since low-temperature curing and rapid polymerization are expected. Energy rays include ultraviolet rays, electron beams, α rays, β
Rays, ionizing radiation such as gamma rays, visible light, microwaves,
The term refers to high frequency or the like, but any energy species may be used as long as radical active species can be generated.

Examples of lamps that generate ultraviolet light include ultrahigh-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, and short arc lamps. What is necessary is just to select in consideration of the absorption wavelength of the compound which generates an active species.

In particular, a photopolymerization method, particularly 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.

[0066]

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".

The heat resistance test was performed using a cooling and heating apparatus LK for a microscope.
Was evaluated by ^first measuring the polarized Raman scattering light ^- 1600 and 2200cm at room temperature and 120 ° C. using a microscopic Raman spectroscopy RM-2000 (Renishou Co.) using -600PM (Rincome Co.).

(Example 1) 4-bromostyrene 25 was placed in a four-necked flask equipped with a Dimroth reflux tube and a thermometer.
g, hexachloroplatinic acid hexahydrate (500 ppm) and toluene (50 ml) were charged and heated to 80 ° C. Then 1,
8.7 g of 1,3,3-tetramethyldisiloxane was added dropwise. After the addition, the flask was kept at 100 ° C. and stirred 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).

4 equipped with a Dimroth reflux tube and a thermometer
In a one-necked flask, 10 g of the intermediate (a) 4 g of 3-methyl-1-butyn-3ol, 550 mg of tetrakistriphenylphosphine palladium, 180 mg of copper iodide, 10 ml of triethylamine, dimethylformamide (hereinafter, referred to as
DMF) 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, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 4.5 g of an intermediate (b).

Next, the intermediate (b) synthesized above was placed in a four-necked flask equipped with Dean Stark and a thermometer.
3.5 g, toluene 50 ml, potassium hydroxide 44 mg
Was charged, and the flask was heated to 120 ° C. to reflux toluene for 3 hours. Thereafter, the reaction solution was filtered, the filtrate 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 2.6 g of an intermediate (c).

4 equipped with a Dimroth reflux tube and a thermometer
2.6 g of the intermediate (c), 3.7 g of 2- (4-bromo-2-fluorophenoxy) tetrahydro 2H-pyran, 150 mg of tetrakistriphenylphosphine palladium, 51 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 4.2 g of an intermediate (d).

Then, 4.2 g of the intermediate (d) and 20 m of tetrahydrofuran were placed in an eggplant flask equipped with a dropping funnel.
and stirred. Then, 1 / 10N hydrochloric acid aqueous solution was added to 1
The mixture was added dropwise and stirred for 30 minutes. Ethyl acetate 100
The mixture was washed with pure water and saturated saline, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by a silica gel column to obtain 2 g of an intermediate (e) having a siloxane bond and a tolan bond.

Further, intermediate (e) 1.0 was placed in a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel and a thermometer.
g, potassium carbonate 1.3 g and DMF 30 ml,
Stirred at 25 ° C. for 1 hour. Then, a DMF solution of 0.8 g of 6-brohexyl 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, 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: -1) was obtained in an amount of 0.9 g.

[0074]

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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) ¹ H-NMR (solvent: deuterated chloroform): δ: 7.32 (4H),
7.16 (2H), 7.08 (6H), 6.79 (2H), 6.27 (2H), 6.03 (2H), 5.73
(2H), 4.07 (4H), 3.94 (4H), 2.59-2.53 (4H), 1.79-1.74 (4
H), 1.74-1.70 (4H), 1.48-1.36 (8H), 0.80 (4H), 0.00

¹³ C-NMR (solvent: deuterated chloroform):
δ; 165.9,158,131.1,130.1,128.2,127.5,114.4,88.3,6
8.8, 64.8, 29.0, 28.6, 28.1, 25.3, 25.2, 19.6 Infrared absorption spectrum (IR) (KBr) cm ^-1 : 2937,2
860, 2215, 1916, 1726, 1635, 1606, 1197, 817, 807.5 Elemental analysis: C = 70.2% (70.56), H = 6.9% (7.02)

The obtained polymerizable liquid crystal compound (A-1) was
At a temperature drop of 2 ° C./min, a phase transition from an isotropic phase liquid state to a nematic phase at 82 ° C. and a crystal phase at 75 ° C. In addition, a non-polymerizable liquid crystal compound “RO-571”
The difference in birefringence (Δn) of a composition obtained by adding 5% by weight and 10% by weight of the polymerizable liquid crystal compound (A-1) of the present invention to (Dai Nippon Ink Chemical Co., Ltd.) was measured using an Appe refractometer (ATAGO And the extrapolation of Δn of the polymerizable liquid crystal compound (A-1) showed a high value of 0.20. Also 120
No change was observed after the heat test at ℃.

(Example 2) In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 4.2 g of the intermediate (c) of (Example 1), 2- (4-bromophenyl-4'-phenoxy) ) 7.2 g of tetrahydro 2H-pyran, 250 mg of tetrakistriphenylphosphine palladium,
82 mg of copper iodide, 15 ml of triethylamine, DMF
50 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.
Purification was performed using a silica gel column to obtain 8 g of an intermediate (f).

Next, 4.0 g of the intermediate (f) and tetrahydrofuran 20 were placed in an eggplant flask equipped with a dropping funnel.
ml and stirred. Next, 1 ml of a 1 / 10N aqueous hydrochloric acid solution was added dropwise, and the mixture was stirred for 30 minutes. Ethyl acetate 10
0 ml was added, washed with pure water and saturated saline, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by a silica gel column to obtain 2.8 g of an intermediate (g) having a siloxane bond and a tolan skeleton. .

Further, 2.8 of the intermediate (g) was placed in a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel and a thermometer.
g, potassium carbonate 3.4 g, DMF 50 ml,
Stirred at 25 ° C. for 1 hour. Then, a DMF solution of 1.9 g of 6-brohexyl 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- 3.0 g of 2) was obtained.

[0082]

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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) ¹ H-NMR (solvent: deuterated chloroform): δ: 7.46-7.30 (16H), 7.06 (4H), 6.82 (4H), 6.3
2 (2H), 6.03 (2H), 5.72 (2H), 4.07 (4H), 3.94 (4H), 2.59-2.4
9 (4H), 1.76-1.72 (4H), 1.69-1.66 (4H), 1.44-1.36 (8H), 0.
80 (4H), 0.00

¹³ C-NMR (solvent: deuterated chloroform):
δ: 165.8,158.5,145,139.131.1,130.1,128.2,127.5,11
4.4, 88.3, 68.8, 64.8, 29.0, 28.6, 28.1, 25.3, 25.2, 19.6 Infrared absorption spectrum (IR) (KBr) cm ^-1 : 2937,2
860, 2215, 1916, 1726, 1635, 1606, 1197, 817, 807.5 Elemental analysis: C = 78.2% (79.00), H = 7.2% (7.43)

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 made at 189 ° C., and a phase transition was made to a crystal phase at 88 ° C. Further, a non-polymerizable liquid crystal compound “RO-
571 "(manufactured by Dainippon Ink and Chemicals, Inc.) and the birefringence difference (Δn) of a composition obtained by adding 5% by weight and 10% by weight of the polymerizable liquid crystal compound (A-2) of the present invention to an Appe refractometer. (Manufactured by Atago Co.) and polymerizable liquid crystal compound (A-2)
Was extrapolated to Δn, indicating a high value of 0.30.
No change was observed after the heat test at 120 ° C.

Example 3 4-bromostyrene was placed in a four-necked flask equipped with a Dimroth reflux tube and a thermometer.
6 g, 84 mg of hexachloroplatinic acid hexahydrate and 50 ml of toluene were charged and heated to 80 ° C. Then 1,1,
15 g of 3,3,5,5-hexamethyltrisiloxane was added dropwise. After the addition, the flask was kept at 100 ° C. and stirred 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 (h).

4 equipped with a Dimroth reflux tube and a thermometer
In a one-necked flask, 10 g of intermediate (h) 3.2 g of 3-methyl-1-butyn-3ol, 440 mg of tetrakistriphenylphosphine palladium, 140 mg of copper iodide,
10 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, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 6 g of an intermediate (i).

Next, the intermediate (i) synthesized above was placed in a four-necked flask equipped with Dean Stark and a thermometer.
5.4 g, toluene 50 ml, potassium hydroxide 200 m
g, and heat the flask to 120 ° C.
Reflux for 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 2.2 g of an intermediate (j) having an acetylene group.

4 equipped with a Dimroth reflux tube and a thermometer
2.2 g of Intermediate (j), 3.4 g of 2- (4-bromo-2-fluorophenyl-4'-phenoxy) tetrahydro2H-pyran, 110 mg of tetrakistriphenylphosphine palladium, 110 mg of copper iodide in a one-necked flask 36m
g, 10 ml of triethylamine and 30 ml of DMF were 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 of hydrochloric acid, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 5 g of an intermediate (k).

Next, 5 g of the intermediate (k) and 20 ml of tetrahydrofuran were placed in an eggplant flask equipped with a dropping funnel.
And stirred. Next, 1mN hydrochloric acid aqueous solution was added for 1m.
The mixture was added dropwise and stirred for 30 minutes. Ethyl acetate 100m
l, washed with pure water and saturated saline, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by a silica gel column to obtain 3 g of an intermediate (l) having a siloxane bond and a tran skeleton.

Further, intermediate (l) 3.0 was placed in a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel and a thermometer.
g, 3 g of potassium carbonate and 30 ml of DMF.
Stirred at C for 1 hour. Then, a DMF solution of 1.8 g of 6-brohexyl 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, 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: 2.2 g of -3) was obtained.

[0093]

Embedded image

Further, 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) ¹ H-NMR (solvent: deuterated chloroform): δ: 7.38-7.33 (8H), 7.28-7.17 (6H), 7.06 (4
H), 6.85 (4H), 6.30 (2H), 6.01 (2H), 5.68 (2H), 4.06 (4H), 3.
88 (2H), 2.55 (4H), 1.70 (4H), 1.58 (4H), 1.42-1.33 (8H),
0.8 (4H)

¹³ C-NMR (solvent: deuterated chloroform):
δ: 166.0,136.2,130.0,127.7,120,114.3,67.6,64.3,2
8.9, 28.3, 25.8 Infrared absorption spectrum (IR) (KBr) cm ^-1 : 2932,2
860, 2215, 1734, 1634, 1606, 1197, 817, 807.5 Elemental analysis: C = 70.1% (71.3), H = 6.86% (6.70)

The polymerizable liquid crystal compound (A-3) obtained was
At a temperature drop of 2 ° C. per minute, a phase transition from an isotropic phase liquid state to a nematic phase is performed at 118 ° C., and a phase transition is performed from a nematic phase state to a smectic phase at 108 ° C.
At 0 ° C., the phase transitioned to the crystalline phase. Further, the polymerizable liquid crystal compound (A-3) of the present invention was 5% by weight and 1% by weight of the non-polymerizable liquid crystal compound “RO-571” (manufactured by Dainippon Ink and Chemicals, Inc.).
The birefringence difference (Δn) of the composition to which 0% by weight was added was measured by an Appe refractometer (manufactured by Atago Co., Ltd.), and the Δn of the polymerizable liquid crystal compound (A-3) was extrapolated to 0.31. It showed a high value. No change was observed after the heat test at 120 ° C.

Example 4 A four-necked flask equipped with a Dimroth reflux tube and a thermometer was charged with 24.8 g of 4-allyl-2-methoxyphenol, 84 mg of hexachloroplatinic acid hexahydrate and 50 ml of toluene, and charged at 80 ° C. Heated. Next, 15 g of 1,1,3,3,5,5-hexamethyltrisiloxane was added dropwise. After dropping, add 1 flask
The mixture was kept at 00 ° C and stirred 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 (m).

In a four-necked flask equipped with a reflux tube for ester synthesis and a thermometer, 27 g of acrylic acid, 40 g of 2- (4-hydroxyphenyl) ethyl alcohol, 1.3 g of p-toluenesulfonic acid, 100 mg of hydroquinone,
150 ml of toluene was charged and uniformly dissolved at 80 ° C. Thereafter, the flask was heated to 90 ° C., and the pressure was reduced to 350 mmHg with a vacuum pump, and the reaction was performed for 4 hours. After heating the flask to 100 ° C., the pressure was reduced to 100 mmHg to complete the reaction. After completion of the reaction, the reaction solution was washed with pure water and saturated saline, dried over sodium sulfate, and the solvent was distilled off.
24 g of intermediate (n) was purified by silica gel column
Obtained.

4 equipped with a Dimroth reflux tube and a thermometer
12.8 g of trans 1,4-cyclohexanecarboxylic acid, 15.3 g of Dotite WSC (manufactured by Dojindo Laboratories), 1.0 g of dimethylaminopyridine, and 350 ml of dichloromethane were charged and stirred in a one-necked flask. The flask was kept at 5 ° C. or lower, and a dichloromethane solution of 15 g of the intermediate (n) was added dropwise. After completion of the dropwise addition, the flask was returned to room temperature and stirred for 6 hours to complete the reaction. The reaction solution is washed with a 1 / 10N hydrochloric acid solution and saturated saline, dried over sodium sulfate, the solvent is distilled off, and purified by a silica gel column to give an intermediate (o) having an acryl group and a carboxyl group.
Was obtained 24 g.

4 equipped with a Dimroth reflux tube and a thermometer
In a one-necked flask, 10.7 g of the intermediate (m), 7.7 g of Dotite WSC (manufactured by Dojindo Laboratories), 0.5 g of dimethylaminopyridine, and 250 ml of dichloromethane were charged and stirred. The flask was kept at 5 ° C. or lower, and the intermediate (o) 1
3.8 g of dichloromethane solution were added dropwise. After completion of the dropwise addition, the flask was returned to room temperature and stirred for 6 hours to complete the reaction. The reaction solution is washed with a 1 / 10N hydrochloric acid solution and saturated saline, dried over sodium sulfate, the solvent is distilled off, purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (A) represented by the following formula: 8.2 g of -4) was obtained.

[0102]

Embedded image

Further, from the infrared absorption spectrum, 3200
The absorption of phenolic hydroxyl groups at 基 3600 cm ⁻¹ disappeared, confirming that the esterification was complete.

(Physical properties) ¹ H-NMR (solvent: deuterated chloroform): δ: 7.26 (8H), 7.17 (2H), 7.02 (4H), 6.45 (2H),
6.1 (2H), 5.8 (2H), 4.36 (4H), 3.80 (6H), 2.98 (4H), 2.58 (4
H), 2.55 (4H), 2.27 (8H), 1.70-1.58 (12H), 0.8 (4H)

¹³ C-NMR (solvent: deuterated chloroform):
δ: 166.0, 154.0, 136.2, 130.0, 128.3, 127.7, 120, 114.3,
67.6, 64.3, 42.3, 34.4, 28.9, 28.3, 25.8 Infrared absorption spectrum (IR) (KBr) cm ^-1 : 2935,2
862,1734,1634,1606,1199,817,808 Elemental analysis: C = 63.1% (64.4), H = 6.99% (7.09)

The polymerizable liquid crystal compound (A-4) obtained was
At a temperature drop of 2 ° C./min, a phase transition from an isotropic phase liquid state to a nematic phase was made at 105 ° C., and a phase transition was made to a crystalline phase at 70 ° C. Further, a non-polymerizable liquid crystal compound “RO-5”
71 "(manufactured by Dainippon Ink and Chemicals, Inc.) and a birefringence difference (Δn) of a composition obtained by adding 5% by weight and 10% by weight of the polymerizable liquid crystal compound (A-4) of the present invention to an Appe refractometer. (Atago Co., Ltd.), Δ of polymerizable liquid crystal compound (A-4)
Extrapolation of n gave 0.17. 120 ° C
No change was observed after the heat resistance test.

Comparative Example 1 A four-necked flask equipped with a reflux tube was charged with 15.2 g of hydroquinone and 57 kg of potassium carbonate.
g and DMF (300 ml) were added and stirred at room temperature for 1 hour. Then, a DMF solution of 25 g of 6-bromo 1-hexanol was added dropwise. After the addition, the flask was kept at 100 ° C. and stirred for 5 hours to terminate the reaction. Methylene chloride was added to the reaction solution, the reaction solution was washed with pure water and saturated saline, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 30 g of an intermediate (p).

In a four-necked flask equipped with a reflux tube for ester synthesis, 5.7 g of acrylic acid and intermediate (p) 11
g, p-toluenesulfonic acid 0.3 g as a catalyst, hydroquinone 10 mg as a polymerization inhibitor, toluene 25
0 ml was charged and uniformly dissolved at 80 ° C. afterwards,
Heat the flask to 90 ° C and use a vacuum pump to
g and the reaction was carried out for 4 hours. Keep the flask at 100 ° C
After heating, the pressure was reduced to 100 mmHg to complete the reaction. After completion, the reaction solution was washed with pure water and saturated saline, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 6 g of an intermediate (q).

4 equipped with a Dimroth reflux tube and a thermometer
2.0 g of trans-1,4-cyclohexanecarboxylic acid, 5 g of Dotite WSC (manufactured by Dojindo Laboratories), 0.3 g of dimethylaminopyridine, and 250 ml of dichloromethane were charged and stirred in a one-necked flask. The flask was kept at 5 ° C. or lower, and a dichloromethane solution of 6 g of the intermediate (q) was added dropwise. After completion of the dropwise addition, the flask was returned to room temperature and stirred for 6 hours to complete the reaction. The reaction solution is washed with a 1 / 10N hydrochloric acid solution and saturated saline, dried over sodium sulfate, the solvent is distilled off, purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound represented by the following formula ( B-1) is 1
0 g was obtained.

[0110]

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 esterification was completed.

(Physical properties) ¹ H-NMR (solvent: deuterated chloroform): δ; 6.9 (4H), 6.8 (4H), 6.3 (2H), 6.0 (2H), 5.8
(2H), 4.26 (4H), 3.90 (4H), 2.5 (2H), 2.3 (4H), 1.86-1.67
(4H), 1.50-1.40 (10H)

¹³ C-NMR (solvent: deuterated chloroform):
δ: 166.0, 153.1, 130.0, 128.7, 120, 72.0, 68.9, 64.6, 29.
0,28.6,25.8,23 Infrared absorption spectrum (IR) (KBr) cm ^-1 : 2930,2
870,1746,1716,1635,1508,810 Elemental analysis: C = 67.9% (68.6), H = 7.20% (7.28)

The polymerizable liquid crystal compound (B-1) obtained was
At a temperature drop of 2 ° C. per minute, a phase transition from an isotropic phase liquid state to a nematic phase is performed at 124 ° C., and a phase transition from a nematic phase state to a smectic phase is performed at 113 ° C.
At 2 ° C., a phase transition to a crystalline phase occurred. Further, 5% by weight of the polymerizable liquid crystal compound (B-1) of the present invention was added to the non-polymerizable liquid crystal compound “RO-571” (manufactured by Dainippon Ink and Chemicals, Inc.).
The birefringence difference (Δn) of the composition to which 0% by weight was added was measured by an Appe refractometer (manufactured by Atago Co., Ltd.), and extrapolated to Δn of the polymerizable liquid crystal compound (B-1). Indicated.

(Example 5) 30 parts of the polymerizable liquid crystal compound (A-2) obtained in Example 2 was used as a polymerizable liquid crystal compound other than the present invention at a temperature of 46 ° C to change the phase transition from an isotropic liquid to a nematic phase. The phase transition to the crystal phase was performed at 5 ° C., and the birefringence difference was 0.15.
Is

[0116]

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A liquid crystal mixture “UCL-001” represented by the formula:
A polymerizable liquid crystal composition was prepared by mixing 70 parts (manufactured by Dainippon Ink and Chemicals, Inc.) and 2 parts by weight of “Irgacure 651” (manufactured by Ciba Specialty Chemical) as a polymerization initiator. The composition is cooled at a rate of 2 ° C. per minute,
A phase transition from an isotropic liquid state to a nematic phase was performed at 74 ° C., a phase transition was performed from a nematic phase state to a smectic phase at 20 ° C., and a phase transition was performed at 10 ° C. to a crystalline phase. The difference in birefringence (Δn) was measured with an Appe refractometer (manufactured by Atago Co., Ltd.).

Next, the above polymerizable composition was injected in an isotropic state into a glass cell having a thickness of 20 μm on which a polyimide alignment film subjected to a homogeneous alignment treatment was formed.
An optically anisotropic body was produced by irradiating with UV light of W / m ² at room temperature for 60 seconds. By measuring the degree of orientation by Raman scattering measurement,
This optically anisotropic body maintained uniform homogeneous orientation, and there was no problem in a heat resistance test at 120 ° C.

(Example 6) 30 parts of the polymerizable liquid crystal compound (A-3) obtained in Example 3, 70 parts of a polymerizable liquid crystal compound "UCL-001" (manufactured by Dainippon Ink and Chemicals) 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 composition undergoes a phase transition from an isotropic liquid state to a nematic phase at 62 ° C., a phase transition from a nematic phase to a smectic phase at 10 ° C., and a crystal phase at 0 ° C. at a temperature of 2 ° C./min. Phase transition. The birefringence index difference (Δn) was measured by an Appe refractometer (manufactured by Atago Co., Ltd.) and found to be 0.20.

Next, the above polymerizable composition was injected into a glass cell having a thickness of 20 μm on which a polyimide alignment film having been subjected to a homogeneous alignment treatment was formed in an isotropic state.
An optically anisotropic body was produced by irradiating with UV light of W / m ² at room temperature for 60 seconds. By measuring the degree of orientation by Raman scattering measurement,
This optically anisotropic body maintained uniform homogeneous orientation, and there was no problem in a heat resistance test at 120 ° C.

Example 7 50 parts of the polymerizable liquid crystal compound (A-3) obtained in Example 3 was used as a non-polymerizable compound at 64 ° C.
Performs a phase transition from an isotropic liquid to a nematic phase at −10 ° C.
And the birefringence difference is 0.22,

[0122]

Embedded image

A cyano-based liquid crystal composition represented by the formula “RO-5”
A polymerizable liquid crystal composition was prepared by mixing 50 parts of “71” (manufactured by Dainippon Ink and Chemicals, Inc.) and 2 parts by weight of “Irgacure 651” (manufactured by Ciba Specialty Chemical) as a polymerization initiator. This composition underwent a phase transition from an isotropic phase liquid state to a nematic phase at 80 ° C. and a crystal phase at 7 ° C. at a temperature of 2 ° C./min. Birefringence index difference (Δ
When n) was measured with an Appe refractometer (manufactured by Atago Co., Ltd.), it was found to be 0.26.

Next, the above polymerizable composition was injected in an isotropic phase into a glass cell having a thickness of 20 μm on which a polyimide alignment film subjected to a homogeneous alignment treatment was formed.
An optically anisotropic body was produced by irradiating with W / m ² ultraviolet rays at room temperature for 60 seconds. By measuring the degree of orientation by Raman scattering measurement,
This optically anisotropic body maintained uniform homogeneous orientation.

(Comparative Example 2) 30 parts of the polymerizable liquid crystal compound (B-1) obtained in Comparative Example 1, 70 parts of the polymerizable liquid crystal compound “UCL-001” (manufactured by Dainippon Ink and Chemicals) other than the present invention,
2 parts by weight of "Irgacure 651" (manufactured by Ciba Specialty Chemical) as a polymerization initiator were mixed, but could not be dissolved.

Comparative Example 3 Polymerizable liquid crystal compound “UCL-001” other than the present invention (manufactured by Dainippon Ink and Chemicals, Inc.) 50
Part, non-polymerizable cyano liquid crystal mixture "RO-571"
A polymerizable liquid crystal composition was prepared by mixing 50 parts (manufactured by Dainippon Ink and Chemicals, Inc.) and 2 parts by weight of "Irgacure 651" (manufactured by Ciba Specialty Chemical) as a polymerization initiator. The composition is heated at 2 ° C./min.
At 5 ° C., a phase transition from an isotropic phase liquid state to a nematic phase was performed, and at 0 ° C., a phase transition to a crystalline phase was performed. When the birefringence difference (Δn) was measured with an Appe refractometer (manufactured by Atago Co.), it was 0.18.
showed that.

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, in an isotropic state,
An optically anisotropic body was produced by irradiating with UV light of W / m ² at room temperature for 60 seconds. This optically anisotropic material was a cured film whose orientation was greatly reduced by Raman scattering measurement and was scattered white.

[0128]

Industrial Applicability The present invention provides a novel polymerizable liquid crystal compound which exhibits liquid crystallinity at a low temperature of 100 ° C. or less, has excellent thermal stability, good solubility, and a large birefringence difference. Provided are a polymerizable composition containing a compound, and an optically anisotropic substance using the same.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/13 500 G02F 1/13 500 4J027 1/1335 1/1335 1/13363 1/13363 // C07C 69 / 017 C07C 69/017 69/653 69/653 69/75 69/75 A F term (reference) 2H049 BA06 BA42 BC09 2H091 FA07X FA07Z FA11X FA11Z FB02 FB12 LA04 4H006 AA01 AA03 AB64 BJ20 BJ50 BR10 4H027 BA13 BD01 BD07 CD04 CG VN01 VP02 VP03 VQ30 VR23 VR41 VU25 4J027 AB36 AE10 AF05 AF06 AG36 AJ08 BA06 BA07 CB03 CB09 CB10 CC02 CC04 CC05 CC06

Claims (10)

[Claims] 1. A polymerizable liquid crystal compound represented by the following general formula (I). General formula (I) (Wherein, X represents a polymerizable group, and Y ₁ , Y ₂ and Y ₅ are the same or different and are each a single bond, —C _n H _2n —, —C _n H _2n O—,
_{-OC n H 2n -, - (} C 2 H 4 O) n -, - (OC 2 H 4) n
_{-, - (C 3 H 6} O) n -, - (OC 3 H 6) n -, - C n H
_{2n COO -, - OOCC n H} 2n -, - C n H 2n OOC-,
Or -COOC _n H _2n - represents either, n represents 1-2
An integer up to 0, rings AC and A′-C ′ each independently represent any of the following rings: a and b are integers of 0 to 2, R _{1 to} R ₆ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group, or Represents a fluoroalkoxy group, Y
₃ and Y ₄ are each independently a single bond, -CH ₂ CH
_{2 -, - CH 2 O -} , - COO -, - OCO -, - C≡C
-, - CH = CH -, - CF = CF -, - (CH 2)
_{4 -, - (CH 2)} 6 -, - CH 2 CH 2 CH 2 O-, or -
Represents _{CH 2 = CHCH 2 CH 2,} c represents an integer of 1 to 10) 2. The polymerizable liquid crystal compound according to claim 1, wherein X in the general formula (I) is a (meth) acrylate group. Wherein Y _1, Y ₂ and Y ₅ in the general formula (I) are the same or _{different, -C n H 2 n -,} - C n H 2n O -, - OC n H
_2n- , wherein n is an integer from 1 to 20.
Or the polymerizable liquid crystal compound according to 2. 4. The polymerizable liquid crystal compound according to claim 1, wherein Y ₃ and Y _{4 in} the general formula (I) each independently represent a single bond or —C≡C—. . 5. One or more of the rings A to C and A ′ to C ′ in the general formula (I) are represented by the following formula: (Wherein F represents a fluorine atom, m represents an integer of 1 to 3, and p represents an integer of 1 to 3), and is an aromatic group. The polymerizable liquid crystal compound according to one of the above. 6. A polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound according to claim 1. 7. A polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound according to claim 1 and a polymerizable compound other than the above. 8. A polymerizable liquid crystal composition comprising one or more of the polymerizable liquid crystal compounds according to claim 1 and a polymerizable liquid crystal compound other than the above. 9. An optically anisotropic substance comprising the polymerizable liquid crystal compound according to claim 1. 10. An optically anisotropic body comprising the polymerizable liquid crystal composition according to claim 6. Description: