JP2000119222A - Liquid crystalline (meth)acrylate compound, liquid crystal composition containing the same compound and optically anisotropic body obtained by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the novel subject compound useful as optical, indicating and recording materials, an optical compensator for liquid crystal displays and a polarization prism material. SOLUTION: This liquid crystalline (meth)acrylate compound is expressed by formula I (L1 and L2 are each H or methyl; the six-membered rings A and B are each 1,4-phenylene, 1,4-cyclohexylene or the like; the six-membered ring C is 1,3-phenylene or the like; Y1 and Y2 are each a single bond, CH2CH2 or the like; X1 and X2 are each a single bond, O or OCO; Sp1 and Sp2 are each a 1-20C spacer group), e.g. a compound expressed by formula II. The compound of formula I is obtained, e.g. when X1 and Y2=OCO; Y1 = a single bond; X2=COO; L1=L2=L; the 6 membered rings A, B=6 membered rings A', B'; Sp1, Sp2=Sp, by heating a compound of formula III and a compound of formula IV in the presence of an acid catalyst such as p-toluenesulfonic acid at >=230 deg.C to obtain a compound of formula V, which is condensed with an alcohol derivative using a condensing agent, a basic catalyst, etc. to form an ester derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel liquid crystalline (meth) acrylate compound which is used as an optical compensator or a polarizing prism material for optical, display and recording materials, liquid crystal displays, and a liquid crystal composition containing the compound. And an optically anisotropic body using the same.

[0002]

2. Description of the Related Art In recent years, liquid crystal materials have been used in TN (twisted nematic) type and STN (super twisted nematic).
In addition to application to display media using reversible motion of liquid crystal molecules, such as display elements represented by nematic), the orientation and the anisotropy of physical properties such as refractive index, dielectric constant, and magnetic susceptibility Application to optically anisotropic materials such as a retardation plate, a polarizing plate, a polarizing prism, and various optical filters is being studied by utilizing the properties. The optically anisotropic material using such a liquid crystal material as a constituent material needs stable and uniform optical characteristics. To this end, it is necessary to semipermanently fix the alignment state structure of liquid crystal molecules in a liquid crystal state. Required.

As means for semi-permanently fixing the alignment state structure of liquid crystal molecules in a liquid crystal state, a liquid crystal compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound is prepared in a liquid crystal state. There is known a method of polymerizing a polymer by irradiating it with an energy ray such as an ultraviolet ray after the orientation. A liquid crystal material having a polymerizable functional group applicable to such a technique is disclosed in
102205, JP-A-62-70406,
It is disclosed in Japanese Patent Publication No. 8-3586, Japanese Patent Application Laid-Open No. Hei 4-227611, German Published Patent Application DE 42 26 994, and the like. However, since these materials have a high temperature at which a liquid crystal phase is exhibited, undesired thermal polymerization is induced in the alignment step, and it is not possible to produce an optical anisotropic material having excellent uniformity, or the produced optical anisotropic material has a problem. However, there is a problem that the heat resistance is not sufficient.

[0004] As a solution to these problems, 2
A liquid crystal material having one or more polymerizable functional groups and exhibiting a liquid crystal phase at room temperature is disclosed in German Offenlegungsschrift DE 4
No. 408171, PCT International Publication WO97 / 1467
4, JP-A-8-245520, JP-A-8-104
870 and the like. However, most of these materials have three or more 6-membered rings such as a benzene ring and a cyclohexane ring in a liquid crystal skeleton, and have a problem that the molecular weight is as large as about 500 to 1000. The (average) molecular weight of the non-polymerizable liquid crystal material used in the field of liquid crystal display is about 250 to 450, whereas such a large (average) molecular weight increases the viscosity and increases the uniformity. This causes a problem that it takes time to obtain a proper alignment state. In particular, in the case of using an orientation division technique for changing the orientation state for each region, if the viscosity is high, it may take 30 minutes or more for the orientation to stabilize. There is a problem that is greatly deteriorated.

It exhibits a liquid crystal phase at room temperature, has excellent heat resistance of the optically anisotropic body after polymerization, and has an (average) molecular weight of about 250-4.
A polymerizable liquid crystal material as small as about 50 is disclosed in JP-A-8-31.
No. 11 discloses this. However, when an optically anisotropic body having a film thickness of 30 μm or more is produced using this polymerizable liquid crystal material, there is a problem that the optically anisotropic body becomes cloudy and transparency is deteriorated.

[0006]

Accordingly, an object of the present invention is to provide a liquid crystal (meth) acrylate compound capable of obtaining an optically anisotropic material having excellent transparency after polymerization, a liquid crystal composition containing the compound, Further, the (average) molecular weight is as low as about 250 to 450, a uniform alignment state can be obtained quickly, a liquid crystal phase is exhibited at room temperature, and after polymerization, the optical properties are excellent in uniformity, heat resistance and transparency. An object of the present invention is to provide a liquid crystal composition capable of obtaining an anisotropic substance, and an optical isomer obtained from the liquid crystal composition.

[0007]

Means for Solving the Problems The present inventors have earnestly studied the correlation between the chemical structure of a polymerizable liquid crystal material and the liquid crystal temperature range, and the correlation with the transparency of an optically anisotropic material obtained after polymerization. The present inventors have found that the above problem can be solved by using a liquid crystalline (meth) acrylate compound having a specific chemical structure, and have completed the present invention. That is,
The liquid crystal (meth) acrylate compound of the present invention is represented by the following general formula (I).

[0008]

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(Wherein L ¹ and L ² each independently represent a hydrogen atom or a methyl group, and the 6-membered rings A and B each independently represent a 1,4-phenylene group, one or
A 1,4-phenylene group in which two CH groups are substituted with nitrogen,
1,4-cyclohexylene group, 1,4 wherein one or two non-adjacent CH ₂ groups are substituted with an oxygen atom or a sulfur atom
-Cyclohexylene group, or cyclohexene-1,4-
Represents a diyl group, and these 6-membered rings A and B may be further substituted by one or more of an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom; The membered ring C is a 1,3-phenylene group, 1,3 in which one or two non-adjacent CH groups are substituted with nitrogen.
A phenylene group, a 1,3-cyclohexylene group, a 1,3-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with an oxygen atom or a sulfur atom, or a cyclohexene-1,3-diyl group; And the 6-membered ring C may be further substituted with an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom, and Y ¹ and Y ² are each independently a single atom. Bond, -CH
_{2 CH 2 -, - CH 2} O-, -OCH 2 -, -COO-,
-OCO-, -C≡C-, -CH = CH-, -CF = C
_{F -, - (CH 2)} 4 -, -CH 2 CH 2 CH 2 O -, - O
_{CH 2 CH 2 CH 2 -,} -CH = CH-CH 2 CH 2 -, -
_{CH 2 CH 2 -CH = CH -} , - CH = CH-COO-,
Represents -OCO-CH = CH-, -OCO-COO-,
X ¹ and X ² each independently represent a single bond, —O—, —COO
—, —OCO—, and Sp ¹ and Sp ² represent a spacer group having 1 to 20 carbon atoms. )

In the liquid crystal (meth) acrylate compound of the present invention, L ¹ and L ² are hydrogen atoms, and the 6-membered rings A and B are 1,4-phenylene groups in the general formula (I). A 6-membered ring C is a 1,3-phenylene group,
¹ , Sp ² is an alkylene group having 2 to 12 carbon atoms, Y ¹ is a single bond, and Y ² is —COO—,
OCO- and X ¹ and X ² are preferably -O-. Further, the liquid crystal composition of the present invention contains the above liquid crystalline (meth) acrylate compound, and exhibits a liquid crystal phase. Further, the liquid crystal composition of the present invention preferably further contains a liquid crystalline (meth) acrylate compound represented by the following general formula (II).

[0011]

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(Wherein L ³ represents a hydrogen atom or a methyl group, n represents an integer of 0 or 1, and the 6-membered rings D, E, and F each independently represent a 1,4-phenylene group, A 1,4-phenylene group in which one or two non-adjacent CH groups are substituted with nitrogen, a 1,4-cyclohexylene group, or a 1- or 2-non-adjacent CH ₂ group substituted with an oxygen atom or a sulfur atom , 4-cyclohexyl group or cyclohexene-
A 1,4-diyl group, and these 6-membered rings D, E, F
May be further substituted by one or more of an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom, and Y ³ and Y ⁴ each independently represent a single bond,- CH ₂ CH ₂ —, —CH ₂ O—, —OC
H _2- , -COO-, -OCO-, -C≡C-, -CH
= CH -, - CF = CF -, - (CH 2) 4 -, - CH 2
_{CH 2 CH 2 O -, -} OCH 2 CH 2 CH 2 -, - CH = C
_{H-CH 2 CH 2 -,} - CH 2 CH 2 -CH = CH -, - C
H = CH-COO-, -OCO-CH = CH-,
Y ⁵ is a single bond, -O-, -OCO-, -COO-, -C
H = represents CH-COO-, Z ¹ represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms. )

The liquid crystal composition of the present invention preferably exhibits a liquid crystal phase at 25 degrees Celsius. Further, the optical anisotropic body of the present invention is characterized by being composed of a polymer of the above liquid crystal composition.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A liquid crystalline (meth) acrylate compound represented by the general formula (I) can be used, for example, in JP-A-8-31.
No. 11 has a molecular weight of about 250 to
When an optically anisotropic body is produced using a liquid crystal composition added in a small amount to a polymerizable liquid crystal material as small as about 450, the (average) molecular weight and the viscosity are not significantly increased as compared with a case where no optical isotropic substance is added. Transparency can be improved.
The molecular weight of the liquid crystalline (meth) acrylate represented by the general formula (I) is about 500 to 1000, but since the amount added is small, a remarkable increase in the (average) molecular weight can be avoided.

It is not always clear why the addition of the liquid crystalline (meth) acrylate compound represented by the general formula (I) improves the transparency of the optically anisotropic body obtained by polymerization. However, -X ² -Sp ² -OCOC (L ² ) = C
It is considered that the structural feature that the side chain group represented by H ₂ is located at the meta position with respect to the linking group Y ² is related. As in the compound of the present invention, the extension direction of the side chain group is
When the liquid crystal skeleton is not parallel to the major axis direction, the linearity of the molecule is reduced. It is considered that the reduced linearity induced some change in the alignment state of the liquid crystal molecules in the photopolymerization process. Also, as the linearity of the molecule decreases, the crystallinity decreases. Thereby, even when the compound of the present invention is added to a liquid crystal composition exhibiting a liquid crystal phase at room temperature,
It is difficult to increase the crystal phase-liquid crystal phase transition temperature. That is, even when added to a polymerizable liquid crystal composition as disclosed in JP-A-8-3111, the liquid crystal phase at room temperature is hardly damaged.

In the liquid crystal (meth) acrylate compound represented by the general formula (I) of the present invention (hereinafter referred to as the compound of the present invention), L ¹ and L ² each independently represent a hydrogen atom or a methyl group. Represents The reactivity is higher when hydrogen atoms are selected as L ¹ and L ² than when a methyl group is selected. Therefore, it is preferable to select a hydrogen atom when a material in which photopolymerization proceeds rapidly is required, and when it is necessary to adjust the reactivity to a low level, a methyl group is added to one or both of L ¹ and L ^2. It is preferred to choose.

The 6-membered rings A and B are each independently 1,4
A phenylene group, a 1,4-phenylene group in which one or two non-adjacent CH groups are substituted with nitrogen, a 1,4-cyclohexylene group, and one or two non-adjacent CH ₂ groups are an oxygen atom or a sulfur atom Represents a 1,4-cyclohexylene group or a cyclohexene-1,4-diyl group. These 6-membered rings A and B further have 1 to 7 carbon atoms.
May be substituted with one or more of an alkyl group, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom.

When a compound having a large birefringence is required, the conjugated system must extend in the major axis direction of the molecule. Therefore, the unsubstituted 1,4-phenylene is used as the 6-membered rings A and B. Alkyl group having 1 to 7 carbon atoms, alkoxy group, alkanoyl group, cyano group, 1,4-phenylene group substituted by one or more halogen atoms, or one or two non-adjacent CH groups Is preferably selected as a 1,4-phenylene group substituted with nitrogen. Conversely, when a compound having a small birefringence is required, the 6-membered rings A and B may be an unsubstituted 1,4-cyclohexylene group or an alkyl group having 1 to 7 carbon atoms, an alkoxy group, or an alkanoyl. Group, cyano group, or halogen atom
Cyclohexene-1,4-cyclohexylene group in which one or more substituted 1,4-cyclohexylene groups or 1,4-cyclohexylene groups in which one or two non-adjacent CH ₂ groups are further substituted with an oxygen atom or a sulfur atom; It is preferred to choose a diyl group.

The introduction of a substituent into the 6-membered ring A or B has the effect of lowering the liquid crystal temperature, but at the same time increases the molecular weight. Therefore, the halogen atom as the substituent is particularly preferably a fluorine atom having a relatively small atomic weight. Also,
When an alkyl group, an alkoxy group, or an alkanoyl group is selected as a substituent, the number of carbon atoms is more preferably 5 or less, and particularly preferably 3 or less.

Similarly, when a compound having a large birefringence is required for the 6-membered ring C, it can be an unsubstituted 1,3-phenylene group or an alkyl, alkoxy, or alkanoyl group having 1 to 7 carbon atoms. , A cyano group, or a halogen atom
It is preferable to select a 1,3-phenylene group substituted by one or more, or a 1,3-phenylene group in which one or two non-adjacent CH groups are substituted with nitrogen. When a compound having a small birefringence is required, as the 6-membered ring C, an unsubstituted 1,3-cyclohexylene group or an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, Or a 1,3-cyclohexylene group substituted with one or more halogen atoms, or a 1,3-cyclohexylene group in which one or two non-adjacent CH ₂ groups are further substituted with an oxygen atom or a sulfur atom; It is preferred to choose a cyclohexene-1,3-diyl group.

The effect brought about by introducing a substituent into the 6-membered ring C depends on the position of the introduction. When introduced into the para position relative to the connecting group Y ^2, since not subtracted the linearity of the molecules, the effect of reducing the liquid crystal temperature is not. However, when a fluorine atom or a cyano group is introduced at this position, the dielectric constant in the molecular long axis direction can be increased.For example, when an optically anisotropic material is produced, an electric field is used as an alignment means of a liquid crystal composition. Can be suitably used. In addition, when an alkyl group, alkoxy group, or alkanoyl group having 1 to 7 carbon atoms is introduced at the para position, the liquid crystal temperature range can be widened. For this purpose, C2
Or more, and more preferably 3 or more carbon atoms.
When a substituent is introduced at a position other than the para-position, the effect of reducing the liquid crystal temperature is brought about. However, at the same time, the molecular weight also increases. Therefore, the halogen atom as the substituent is particularly preferably a fluorine atom having a relatively small atomic weight. When an alkyl group, an alkoxy group, or an alkanoyl group is selected, the number of carbon atoms is more preferably 5 or less, and particularly preferably 3 or less.

Y ¹ and Y ² are each independently a single bond;
_{-CH 2 CH 2 -, - CH} 2 O-, -OCH 2 -, -CO
O-, -OCO-, -C≡C-, -CH = CH-, -C
F = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O-
_{, -OCH 2 CH 2 CH 2 -} , -CH = CH-CH 2 CH
_{2 -, - CH 2 CH 2} -CH = CH -, - CH = CH-C
OO-, -OCO-CH = CH--OCO-COO-. When a compound having a large birefringence is required, the conjugated system must extend in the major axis direction of the molecule.
¹ and Y ² are a single bond, -COO-, -OCO-, -C≡C
It is preferable to select-, -CH = CH-, -CF = CF-. Conversely, if the birefringence small compound is _{required, -CH 2 CH 2 -, -} CH 2 O-, -OCH 2 -, -
(CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ C
H ₂ CH ₂ - preferably selected.

Sp ¹ and Sp ² each independently represent a spacer group having 1 to 20 carbon atoms. Examples of the spacer group include a linear alkylene group, a branched alkylene group, a linear alkylene group in which non-adjacent carbon atoms are substituted with an oxygen atom, a carbonyl group, an ester group, a branched alkylene group, and the like. Further, a hydrogen atom in these spacer groups may be substituted with a halogen atom such as a fluorine atom. As the spacer group, from the viewpoint of reducing the viscosity, it is preferable to select an unsubstituted linear alkylene chain and a branched alkylene chain, and an unsubstituted linear alkylene chain is particularly preferable. The number of carbon atoms is
2-12 are preferable, 2-8 are more preferable, 3-6
Is particularly preferred. When the number of carbon atoms increases, the molecular weight tends to increase and the viscosity tends to increase. When the number of carbon atoms decreases, the liquid crystal temperature of the compound tends to increase.

X ¹ and X ² each independently represent a single bond,
Represents -COO-, -OCO-, -O-. In order to minimize degradation of the compound due to hydrolysis, it is preferable to select -O-.

The selection of the substituents L ¹ , L ² , 6-membered rings A, B, C and the linking groups Y ¹ , Y ² , X ¹ , X ² , Sp ¹ , Sp ² is based on the birefringence of the compound. However, an object of the compound of the present invention is to realize a liquid crystal composition capable of producing an optically anisotropic body having excellent transparency by adding a small amount without significantly increasing the (average) molecular weight. Because there is
Care must be taken not to deviate from this purpose. Particularly preferred chemical structures of the present invention (formulas (1) to (15)
0)) is exemplified below. (In the formula, L ¹ and L ² represent a hydrogen atom or a methyl group, s and t represent integers of 1 to 20, and the cyclohexane ring represents a transcyclohexane ring.)

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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The compounds of the present invention exemplified above are represented by the formula (I) wherein -X ² -Sp ² -OCOC (L ² ) =
Except for the feature that the side chain group represented by CH ₂ is located at the meta position with respect to the linking group Y ² , the chemical structure itself is not special in the technical field of liquid crystal materials. There is no. Therefore, in the synthesis of the compound of the present invention, a synthesis method established in the technical field of a conventional liquid crystal compound or liquid crystal (meth) acrylate can be applied almost as it is. For example, a method disclosed in Japanese Patent Publication No. 6-507987 or Japanese Patent Publication No. H8-3111 can be used.

Among the compounds exemplified above, in the general formula (I), the 6-membered rings A and B are substituted with unsubstituted 1,4-
A phenylene group or an alkyl group having 1 to 7 carbon atoms,
An alkoxy group, an alkanoyl group, a cyano group, or a 1,4-phenylene group substituted by one or more halogen atoms, wherein the 6-membered ring C is an unsubstituted 1,3-phenylene group or a group having 1 to 7 carbon atoms. An alkyl group, an alkoxy group, an alkanoyl group, or a cyano group, a 1,3-phenylene group substituted with one or more halogen atoms, Y ¹ is a single bond, and Y ² is —COO— or —OCO—. Those having a liquid crystal skeleton such that the compound has a liquid crystal temperature range of 1
This is useful because it is easy to suppress the temperature to 00 ° C. or lower and the production is easy. Among them, especially the 6-membered rings A and B
Is an unsubstituted 1,4-phenylene group, a 6-membered ring C is an unsubstituted 1,3-phenylene group, Y ¹ is a single bond, and Y ² is -CO
O- or -OCO- compounds have high industrial value because they are particularly easy to produce. Such a compound can be synthesized, for example, by the following method.

[0043]

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(Wherein X is a halogen atom, 6-membered ring A ′,
B ′ is an unsubstituted 1,4-phenylene group or an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a 1,4-phenylene group substituted with one or more halogen atoms; 6-membered ring C ′ is unsubstituted 1,3-
A phenylene group or an alkyl group having 1 to 7 carbon atoms,
An alkoxy group, an alkanoyl group, a cyano group, or a 1,3-phenylene group substituted with one or more halogen atoms; L ¹ and L ² each represent a hydrogen atom or a methyl group;
¹ and Sp ² represent a spacer group having 1 to 20 carbon atoms. )

As shown here, the biphenyl derivative of the general formula (III) is bonded to a spacer group to which a hydroxyl group is added by using a base such as sodium hydroxide or potassium carbonate. A compound is obtained and esterified with (meth) acrylic acid using an acid catalyst such as p-toluenesulfonic acid to obtain a compound of the general formula (V). Then, a hydroxyl group-provided spacer group is bonded to the hydroxybenzoic acid derivative (VI) using a base such as sodium hydroxide or potassium carbonate to obtain a compound of the general formula (VII). Esterification with (meth) acrylic acid using an acid catalyst such as sulfonic acid gives a compound of the general formula (VIII). The resulting compounds of the general formulas (V) and (VIII) are ester-condensed with a condensing agent such as dicyclohexylcarbodiimide (DCC) using a base catalyst such as dimethylaminopyridine (DMAP), or The carboxyl group of the formula (VIII) is converted to an acyl halide group with a thionyl halide or the like, and ester-condensed with a compound of the general formula (V) using a base catalyst such as pyridine,
The compound of the present invention represented by the general formula (IX) can be synthesized.
Further, the compound of the present invention can also be synthesized by the following method.

[0046]

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(Wherein X is a halogen atom, 6-membered ring A ′,
B ′ is an unsubstituted 1,4-phenylene group or an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group, a 1,4-phenylene group substituted with one or more halogen atoms, 6-membered ring C ′ is unsubstituted 1,3-
A phenylene group or an alkyl group having 1 to 7 carbon atoms,
An alkoxy group, an alkanoyl group, a cyano group, or a 1,3-phenylene group substituted with one or more halogen atoms; L ¹ and L ² each represent a hydrogen atom or a methyl group;
¹ and Sp ² represent a spacer group having 1 to 20 carbon atoms. )

As shown here, the biphenyl derivative of the general formula (X) is bonded to a spacer group to which a hydroxyl group has been added by using a base such as sodium hydroxide or potassium carbonate. A compound is obtained and esterified with (meth) acrylic acid using an acid catalyst such as p-toluenesulfonic acid to obtain a compound of the general formula (XII). Then, a hydroxyl group-provided spacer group is bonded to the hydroquinone derivative (XIII) using a base such as sodium hydroxide or potassium carbonate to obtain a compound of the general formula (XIV). By esterifying with (meth) acrylic acid using an acid catalyst such as
A compound of general formula (XV) is obtained. The resulting compounds of the general formulas (XII) and (XV) are ester-condensed with a condensing agent such as dicyclohexylcarbodiimide (DCC) using a base catalyst such as dimethylaminopyridine (DMAP), or The carboxyl group of the formula (XII) is converted to an acyl halide group with a thionyl halide or the like, and ester-condensed with a compound of the general formula (XV) using a base catalyst such as pyridine to obtain a compound of the general formula (XVI)
Can be synthesized. Further, the compound of the present invention can also be synthesized by the following method.

[0049]

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(Wherein L represents a hydrogen atom or a methyl group, and the 6-membered rings A ′ and B ′ are an unsubstituted 1,4-phenylene group or an alkyl group having 1 to 7 carbon atoms, an alkoxy group, An alkanoyl group, a cyano group, or a halogen atom
One or more substituted 1,4-phenylene groups and 6-membered ring C ′ may be unsubstituted 1,3-phenylene groups or 1 to 3 carbon atoms.
1,3-, 1- or 3-substituted alkyl, alkoxy, alkanoyl, cyano, or halogen atoms
L ¹ and L ² represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² represent a spacer group having 1 to 20 carbon atoms. )

As shown herein, a biphenyl derivative of the general formula (XVII) and a benzoic acid derivative of the general formula (XVIII) are combined with a condensing agent such as dicyclohexylcarbodiimide (DCC) and a base catalyst such as dimethylaminopyridine (DMAP). Or a carboxyl group of the general formula (XVIII) is converted to an acyl halide group with a thionyl halide or the like, and the compound of the general formula (XVII) is esterified with a base catalyst such as pyridine. By condensing, a compound of the general formula (XIX) is obtained. afterwards,
The compound of general formula (XX) is obtained by deprotecting the acetyl group using a base such as benzylamine. The carboxylic acid derivative of the general formula (XXI) is ester-condensed with a condensing agent such as dicyclohexylcarbodiimide (DCC) using a base catalyst such as dimethylaminopyridine (DMAP). The group of the present invention represented by the general formula (XXII) is converted by converting the group into an acyl halide group with a thionyl halide or the like, and performing ester condensation with the compound of the general formula (XX) using a base catalyst such as pyridine. Compounds can be synthesized. Further, the compound of the present invention can also be synthesized by the following method.

[0052]

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Wherein L represents a hydrogen atom or a methyl group, and the 6-membered rings A ′ and B ′ are an unsubstituted 1,4-phenylene group or an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group. Group, cyano group, or halogen atom
One or more substituted 1,4-phenylene groups and 6-membered ring C ′ may be unsubstituted 1,3-phenylene groups or 1 to 3 carbon atoms.
1,3-, 1- or 3-substituted alkyl, alkoxy, alkanoyl, cyano, or halogen atoms
Represents a phenylene group, and Sp ¹ and Sp ² represent a spacer group having 1 to 20 carbon atoms. )

As shown here, the biphenyl derivative of the general formula (XXIII) and the benzoic acid derivative of the general formula (XXIV)
230 in the presence of an acid catalyst such as p-toluenesulfonic acid.
The compound of the general formula (XXV) is obtained by heating at a temperature of not less than ° C. To this, an alcohol derivative of the general formula (XXVI) is subjected to ester condensation using a condensing agent such as dicyclohexylcarbodiimide (DCC) and a base catalyst such as dimethylaminopyridine (DMAP), or
The carboxyl group of (XXV) is converted into an acyl group with a thionyl halide or the like, and ester-condensed with a compound of the general formula (XXVI) using a base catalyst such as pyridine to give a compound represented by the general formula (XXVII). Can be synthesized.

The liquid crystal composition of the present invention may be any composition which shows a phase which is generally recognized as a liquid crystal phase in this technical field. Among such liquid crystal compositions, a nematic phase, a smectic A phase, and a (chiral) smectic C as a liquid crystal phase.
And a cholesteric phase are preferred. Among them, the nematic phase is particularly preferable because the viscosity tends to be low and a stable alignment state tends to be promptly obtained in the alignment step in the production of the optically anisotropic body. Further, in the case of showing a (chiral) smectic C phase, the smectic A phase is shown in a temperature range higher than the temperature range of the (chiral) smectic C phase, and in the case of showing a smectic A phase, the temperature of the smectic A phase is shown. A liquid crystal composition that expresses a nematic phase in a temperature region above the region,
It is preferable because good uniaxial orientation characteristics can be obtained.

The object of the liquid crystal composition of the present invention is to produce an optically anisotropic substance by irradiating ultraviolet rays in a temperature range of a liquid crystal phase to polymerize a (meth) acrylate compound in the composition. Therefore, in order to avoid undesired thermal polymerization during the ultraviolet irradiation step and to produce an optically anisotropic material having excellent uniformity, the liquid crystal composition of the present invention is used at room temperature or near room temperature, that is, typically, It preferably exhibits a liquid crystal phase at 25 ° C. For example, when the liquid crystal composition of the present invention is irradiated with ultraviolet rays in the (chiral) smectic C phase to polymerize the (meth) acrylate compound in the composition, at room temperature or near room temperature, that is, typically at 25 ° C. Those which express a (chiral) smectic C phase are preferred.

The concentration of the compound represented by formula (I) in the liquid crystal composition of the present invention is preferably 5 to 40% by weight, and
0 to 30% by weight is more preferable, and 15 to 25% by weight is particularly preferable. When the concentration is less than 5% by weight, the effect of improving the transparency of the optically anisotropic material produced using the liquid crystal composition of the present invention is hardly obtained. When the concentration exceeds 40% by weight, the average molecular weight in the liquid crystal composition is reduced. Tends to be higher.

For the purpose of suppressing an increase in viscosity and quickly obtaining a stable alignment state in the alignment step in the production of an optically anisotropic substance, the (average) molecular weight of the liquid crystal composition of the present invention is about 250 to 250.
Preferably it is suppressed to 450. It is also important to adjust the clearing point (the temperature at which the liquid crystal phase transitions to the isotropic liquid phase) in order to quickly obtain a stable alignment state. If the clearing point is lowered, the orientation treatment is inevitably performed in a state of high fluidity, and the effect of rapidly stabilizing the orientation can be obtained. The clearing point is preferably at most 80 ° C, more preferably at most 70 ° C, particularly preferably at most 60 ° C.

In the step of coating the liquid crystal composition on the substrate or in the step of injecting the liquid crystal composition into the liquid crystal cell during the production of the optically anisotropic material of the present invention, a uniform alignment state is obtained quickly.
Temporarily bringing a liquid crystal composition into an isotropic liquid phase state is an effective means. When the clearing point is higher than 60 ° C. to 80 ° C., undesirable thermal polymerization is induced in the isotropic liquid phase state, and there is a risk that an optically anisotropic body having good uniformity cannot be produced. From this point, it is effective to adjust the transparent point as described above.

The liquid crystal composition of the present invention further comprises the above general formula (II) wherein L ³ represents a hydrogen atom or a methyl group;
n represents an integer of 0 or 1, and the 6-membered rings D, E, and F each independently represent a 1,4-phenylene group, a 1,4-phenyl group in which one or two non-adjacent CH groups are substituted with nitrogen. A phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexyl group in which one or two non-adjacent CH ₂ groups are substituted with an oxygen atom or a sulfur atom, or cyclohexene-1,
Represents a 4-diyl group, and these 6-membered rings D, E, and F are further substituted by one or more of an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —
, -COO-, -OCO-, -C≡C-, -CH = C
H -, - CF = CF - , - (CH 2) 4 -, - CH 2 CH 2
_{CH 2 O -, - OCH 2} CH 2 CH 2 -, -CH = CH-
_{CH 2 CH 2 -, -CH 2} CH 2 -CH = CH -, - CH
ＣＨCH—COO—, —OCO—CH ＝ CH—, and Y
⁵ is a single bond, -O-, -OCO-, -COO-, -CH
= Represents a CH-COO-, Z ¹ represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms)
It is preferable to include a liquid crystalline (meth) acrylate compound represented by the formula:

The liquid crystalline (meth) acrylate compound represented by the general formula (II) has the following formula from the viewpoint of suppressing viscosity.
n is particularly preferably 0, and Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH
_2- , -COO-, -OCO-, -C−C-, -CH =
CH -, - CF = CF- is particularly preferred, Y ⁵ is single bond, -O -, - OCO -, - COO- are particularly preferred,
Z ¹ is particularly preferably a halogen atom, a cyano group, or a hydrocarbon group having 1 to 5 carbon atoms.

The general formula (I) in the liquid crystal composition of the present invention
The concentration of the liquid crystalline (meth) acrylate compound represented by I) is preferably from 60 to 95% by weight, and more preferably from 70 to 90% by weight.
Is more preferable, and 75 to 85% by weight is particularly preferable.
If the concentration is less than 60% by weight, the viscosity tends to increase, and if the concentration exceeds 95% by weight, the transparency of the optically anisotropic material produced using the liquid crystal composition tends to deteriorate. . As specific examples of the compound of the general formula (II), the structures and phase transition temperatures of the compounds of the formulas (151) to (175) are shown below. However, the polymerizable liquid crystal compound that can be used in the liquid crystal composition of the present invention is not limited to these. (In the formula, a cyclohexane ring represents a transcyclohexane ring, a number represents a phase transition temperature, and at the phase transition temperature, C represents a crystal phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase. .)

[0063]

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[0064]

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[0065]

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[0066]

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Further, a liquid crystal compound having no polymerizable functional group can be added to the liquid crystal composition of the present invention according to the intended use. However, from the viewpoint of ensuring the heat resistance of the optically anisotropic body manufactured using the liquid crystal composition, the amount of addition is preferably set to 10% by weight or less. In addition, a compound having a polymerizable functional group and having no liquid crystallinity can be added to the liquid crystal composition of the present invention.
As such a compound, any compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field, but acrylate compounds, methacrylate compounds, vinyl ether compounds Is particularly preferred.

As described above, the liquid crystal composition of the present invention comprises:
In addition to the liquid crystalline (meth) acrylate represented by the general formula (I), a liquid crystal compound having a polymerizable functional group, a liquid crystal compound having no polymerizable functional group, and a polymerizable compound having no liquid crystallinity are appropriately combined. It may be added, but it is necessary to adjust the addition amount of each component so that at least the liquid crystallinity of the obtained liquid crystal composition is not lost and the viscosity is not significantly increased.

Further, a polymerization initiator such as a thermal polymerization initiator and a photopolymerization initiator can be added to the liquid crystal composition of the present invention for the purpose of improving the polymerization reactivity. Examples of the thermal polymerization initiator include benzoyl peroxide, bisazobutyronitrile and the like. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, and benzyl ketals. When the thermal polymerization initiator or the photopolymerization initiator is added, the amount added is preferably 10% by weight or less, particularly preferably 5% by weight or less, based on the liquid crystal composition.
A range of 1.5% by weight is more preferred.

Further, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve the storage stability. Examples of usable stabilizers include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechol and the like. When the stabilizer is used, the amount added is preferably 1% by weight or less based on the liquid crystal composition.
Particularly preferred is 0.5% by weight or less.

Further, a chiral (optically active) compound can be added to the liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton therein. The chiral compound used for such a purpose need not itself exhibit liquid crystallinity, and may or may not have a polymerizable functional group. The direction of the helix can be appropriately selected depending on the intended use of the polymer. Such chiral compounds include, for example,
Cholesteryl pelargonic acid having a cholesteryl group as an optically active group, and cholesterol stearate; "CB-15" manufactured by BDH (BDH, UK) having a 2-methylbutyl group as an optically active group,
"C-15", "S-108" manufactured by Merck (Germany)
2 ", Chisso's" CM-19 "," CM-20 ",
“CM”: “S-811” manufactured by Merck and having 1-methylheptyl group as an optically active group, “CM” manufactured by Chisso
-21 "and" CM-22 ". The preferable amount of the chiral compound to be added depends on the use of the liquid crystal composition, but the value (d) obtained by dividing the thickness (d) of the polymer obtained by polymerization by the helical pitch (P) in the polymer.
/ P) is preferably in the range of 0.1 to 20.

When the liquid crystal composition of the present invention is used as a raw material for a polarizing film or alignment film, or as a printing ink or paint, a metal, a metal complex, a dye, a pigment, a pigment, an Activators, gelling agents, ultraviolet absorbers, antioxidants, ion exchange resins, metal oxides of titanium oxide, and the like can also be added.

The optically anisotropic body of the present invention can be produced by polymerizing the liquid crystal composition of the present invention in an oriented state. For example, the substrate is rubbed with a cloth or the like, or the substrate on which an organic thin film is formed is rubbed with a cloth or the like, or a substrate having an orientation film obliquely vapor-deposited with SiO ₂ is supported by means such as coating. Or the method of polymerizing the liquid crystal of the present invention after being sandwiched between substrates. Examples of other alignment treatment methods include the use of flow alignment of the liquid crystal composition and the use of an electric or magnetic field. These alignment means may be used alone or in combination. Among them, a method using a substrate whose surface has been rubbed with a cloth or the like is particularly preferable because of its simplicity.

The material constituting the substrate can be used regardless of an organic material or an inorganic material. Examples of the organic material serving as the substrate material include, for example, polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride,
Examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetylcellulose, cellulose, polyetheretherketone, and the like. Examples of inorganic materials include silicon, glass, and calcite.

If it is not possible to obtain a proper orientation by rubbing these substrates with a cloth or the like, an organic thin film such as 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 rub. In addition, the usual twisted nematic (T
N) element or super twisted nematic (S
The polyimide thin film giving a pretilt angle used in the TN) element is particularly preferable because the molecular orientation structure inside the optically anisotropic body can be controlled more precisely.

When the alignment state is controlled by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the above-mentioned polyimide thin film on the electrode. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. This method is an organic thin film having a functional group that undergoes a photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that isomerized by light, or an organic thin film such as a polyimide;
Preferably, the alignment film is formed by irradiating polarized ultraviolet light. By applying a photomask to this photoalignment method, patterning of the alignment can be easily achieved, so that the molecular orientation inside the optically anisotropic body can be precisely controlled.

As a method of polymerizing the liquid crystal composition of the present invention, rapid polymerization is desirable, and a method of photopolymerizing by irradiating light energy such as ultraviolet rays or electron beams is preferable. As a light source for photopolymerization,
A polarized light source or a non-polarized light source may be used. When photopolymerization is performed in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency. Also,
The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular, when an optically anisotropic material is to be produced by photopolymerization, the temperature is as low as possible at room temperature or a temperature close to room temperature, that is, typically at 25 ° C., from the viewpoint of avoiding unintentional thermal polymerization. It is preferable to carry out polymerization.

The optically anisotropic body of the present invention obtained by polymerization can be subjected to a heat treatment for the purpose of reducing the initial change in properties and stably exhibiting properties. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours. The optically anisotropic body of the present invention produced by such a method may be used after being peeled off from the substrate, or may be used without being peeled off.

[0079]

The present invention will be described below in more detail with reference to Examples of the present invention. However, the invention is not limited to these examples.

Example 1 Synthesis of Liquid Crystalline Acrylate Compound (Part 1) 12,4 g of 4,4′-biphenol, 6-chloro-1
Hexanol 88.0 g, sodium hydroxide 25.7
g, potassium iodide 25.0 g, ethanol 480 ml
And 440 ml of water while stirring.
Heated at 0 ° C for 4 hours. After cooling the obtained reaction solution to room temperature, dilute hydrochloric acid was added until the aqueous layer of the reaction solution became weakly acidic.
The precipitated crystals were collected by filtration using a glass filter, and the crystals were washed with 2000 ml of water to obtain 900 g of a crude product. 900 ml of this crude product
The purification was carried out by recrystallization once from methanol once and twice from 300 ml methanol to obtain 50.0 g of a compound represented by the following formula (a).

[0081]

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A mixture of 48.0 g of the compound of the formula (a), 48.3 g of acrylic acid, 15.0 g of p-toluenesulfonic acid, 2.5 g of hydroquinone, 220 ml of toluene, 90 ml of tetrahydrofuran and 130 ml of n-hexane was heated and stirred. The mixture was refluxed for 4 hours while distilling off generated water. After the reaction solution was cooled to room temperature, 1000 ml of saturated saline and 700 ml of ethyl acetate were added to the reaction solution for extraction. After washing the organic layer with water, ethyl acetate was distilled off under reduced pressure to obtain 60.9 g of a crude product. The obtained crude product was recrystallized from a mixed solvent of 60 ml of toluene and 120 ml of hexane to obtain 41.8 g of a crude product from which most of acrylic acid as an impurity was removed. 31.8 g of this was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and toluene (volume ratio: ethyl acetate: toluene = 1: 4, Rf = 0.52) as a developing solvent. 19.0 g of a compound represented by the following formula (b) was obtained.

[0083]

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15.0 g of 3-hydroxybenzoic acid, 6-
Chloro-1-hexanol 14.8 g, sodium hydroxide 9.1 g, potassium iodide 0.5 g, ethanol 45
ml and 45 ml of water while stirring.
Heated at C for 16 hours. After cooling the obtained reaction solution to room temperature, 500 ml of saturated saline was added to the reaction solution, and dilute hydrochloric acid was added until the aqueous layer of the reaction solution became weakly acidic. 300 ml of ethyl acetate was added to the reaction solution for extraction. After washing the organic layer with water, ethyl acetate was distilled off under reduced pressure to obtain 25.4 g of a crude product of the following formula (c).

[0085]

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A mixture consisting of 20.0 g of the crude product of the formula (c), 24.3 g of acrylic acid, 4.0 g of p-toluenesulfonic acid, 0.5 g of hydroquinone, 100 ml of toluene and 100 ml of n-hexane was heated and stirred. The mixture was refluxed for 4 hours while distilling off generated water. After cooling the reaction solution to room temperature, the reaction solution was mixed with 500 ml of a saturated saline solution and ethyl acetate 3 times.
00 ml was added for extraction. After washing the organic layer with water,
The organic solvent was distilled off under reduced pressure to obtain 25.2 g of a crude product. The obtained crude product was diluted with 100 ml of hexane and 20 ml of ethyl acetate.
l from a mixture of 50 ml of hexane and 20 ml of ethyl acetate, 100 ml of hexane
And recrystallized from a mixture of ethyl acetate and 20 ml of ethyl acetate in a total of three times to obtain a compound 9.5 represented by the formula (d).
g was obtained.

[0087]

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While stirring a mixture of 1.00 g of the compound of the formula (b), 0.86 g of the compound of the formula (d), 0.12 g of N, N-dimethylaminopyridine and 20 ml of tetrahydrofuran, 10 ml of tetrahydrofuran was added thereto with stirring. Dissolved dicyclohexylcarbodiimide 0.6
4 g was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. To this was added 100 ml of toluene, and the precipitated dicyclohexylurea was filtered off. After the obtained organic layer was washed with water, toluene was distilled off under reduced pressure to obtain 2.7 g of a crude product. This was mixed with a mixed solvent consisting of ethyl acetate and toluene (ethyl acetate: toluene = 1: 10, Rf =
Purified by silica gel column chromatography using 0.69) as a developing solvent and recrystallization from 12 ml of methanol to give a liquid crystalline acrylate compound represented by the formula (e) (hereinafter referred to as a liquid crystalline acrylate compound (e)). )
0.9 g was obtained.

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The liquid crystal acrylate compound (e) has a phase transition temperature of 54 ° C. between the C phase (crystal phase) and the Sx phase (smectic phase of unknown assignment), and the Sx phase-I phase (isotropic liquid phase). The transition temperature was 61 ° C. In addition, ¹ H-NMR
(300 MHz, CDCl ₃ ) data is δ1.23
~ 1.93 (m, 16H), 4.02 (t, 2H),
4.04 (t, 2H), 4.17 (t, 4H), 5.8
0 (d, 2H), 6.12 (dd, 2H), 6.40
(D, 2H), 6.95 to 7.82 (m, 12H).

Example 2 Synthesis of Liquid Crystalline Acrylate Compound (Part 2) 18.4 g of isovanillic acid, 14.8 g of 6-chloro-1-hexanol, 9.1 g of sodium hydroxide, 0.2 g of potassium iodide, ethanol A mixture of 45 ml and 45 ml of water was heated at 80 ° C. for 16 hours with stirring. After cooling the obtained reaction solution to room temperature, 500 ml of saturated saline was added to the reaction solution, and dilute hydrochloric acid was added until the aqueous layer of the reaction solution became weakly acidic. 300 m of ethyl acetate was added to the reaction solution.
1 was added for extraction. After the organic layer was washed with water, ethyl acetate was distilled off under reduced pressure to obtain 27.0 g of a crude product represented by the following formula (f).
I got

[0092]

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A mixture consisting of 25.0 g of the crude product of the formula (f), 26.9 g of acrylic acid, 4.0 g of p-toluenesulfonic acid, 0.5 g of hydroquinone, 100 ml of toluene and 100 ml of n-hexane was heated and stirred. The mixture was refluxed for 3 hours while distilling off generated water. After cooling the reaction solution to room temperature, the reaction solution was mixed with 500 ml of a saturated saline solution and ethyl acetate 3 times.
00 ml was added for extraction. After washing the organic layer with water,
The organic solvent was distilled off under reduced pressure to obtain 31.8 g of a crude product. 80 ml of hexane and 20 ml of ethyl acetate were obtained.
Was purified by recrystallization from a mixture of the above, to obtain 15.8 g of a compound represented by the formula (g).

[0094]

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0.95 g of the compound of the formula (g), 0.12 g of N, N-dimethylaminopyridine, 1-ethyl-3-
While stirring a mixture composed of 0.62 g of (3-dimethylaminopropyl) carbodiimide hydrochloride and 20 ml of tetrahydrofuran, 1.00 g of the compound of the above formula (b) dissolved in 10 ml of tetrahydrofuran was added thereto.
Dropped over minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 9 hours.
200 ml of saturated saline and 100 ml of ethyl acetate were added to the reaction solution.
Was added to perform extraction. After washing the organic layer with water, the organic solvent was distilled off under reduced pressure to obtain 1.80 g of a crude product. This is subjected to silica gel column chromatography using a mixed solvent of ethyl acetate and toluene (ethyl acetate: toluene = 1: 7, Rf = 0.52 in a volume ratio) as a developing solvent, and recrystallization twice from 15 ml of methanol. To obtain a liquid crystal acrylate compound represented by the following formula (h) (hereinafter referred to as liquid crystal acrylate compound (h)).
88 g were obtained.

[0096]

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As for the phase transition temperature of the liquid crystalline acrylate compound (h), the transition temperature between the C phase (crystal phase) and the I phase (isotropic liquid phase) was 102 ° C.

Example 3 Preparation of Liquid Crystal Composition (Part 1) 50 parts by weight of a liquid crystal acrylate compound represented by the following formula (i):
And a liquid crystal composition (A) comprising 50 parts by weight of a liquid crystal acrylate represented by the following formula (j).

[0099]

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The liquid crystal composition (A) exhibited a nematic liquid crystal phase at room temperature (25 ° C.). The N (nematic phase) -I (isotropic liquid phase) transition temperature was 46 ° C. Also, 589
n _e (refractive index of extraordinary light) measured in nm is 1.662
In, (refractive index of ordinary light) n _o is 1.510, the birefringence was 0.152. The average molecular weight was 293.6.

A liquid crystal composition (B) comprising 10 parts by weight of the liquid crystal acrylate compound (e) synthesized in Example 1 and 90 parts by weight of the liquid crystal composition (A) was prepared. Liquid crystal composition (B)
Exhibited a nematic liquid crystal phase at room temperature (25 ° C.). N
(Nematic phase) -I (isotropic liquid phase) transition temperature is 40
° C. Further, in the 1.6541 (refractive index of extraordinary light) n _e measured at 589 nm, (refractive index of ordinary light) n _o is 1.5153, the birefringence index was 0.1388. The average molecular weight was 309.8.

Example 4 Preparation of Liquid Crystal Composition (Part 2) Liquid Crystalline Acrylate Compound (e) 2 synthesized in Example 1
A liquid crystal composition (C) comprising 0 parts by weight and 80 parts by weight of the liquid crystal composition (A) was prepared. The liquid crystal composition (C) was prepared at room temperature (2
(5 ° C.) and exhibited a nematic liquid crystal phase. The N (nematic phase) -I (isotropic liquid phase) transition temperature was 36 ° C.
Further, in the 1.6460 (refractive index of extraordinary light) n _e measured at 589 nm, n _o (ordinary refractive index) of the 1.520
7. The birefringence was 0.1253. The average molecular weight is
327.9.

(Example 5) Preparation of optically anisotropic liquid crystal comprising 99 parts by weight of the liquid crystal composition (C) prepared in Example 4 and 1 part by weight of a photopolymerization initiator "Irgacure 651" (manufactured by Ciba Geigy). Composition (D) was prepared. The liquid crystal composition (D) was injected at room temperature into an antiparallel alignment liquid crystal glass cell having a cell gap of 50 μm (a glass cell subjected to an alignment treatment so as to uniaxially align the liquid crystal). It was confirmed that the orientation was stabilized within 1 minute after the injection and a uniform uniaxial orientation was obtained. Next, at room temperature, UVP U
The liquid crystal composition (D) was polymerized by irradiating with UV light of 1 mW / cm ² for 10 minutes using VGL-25 to obtain an optically anisotropic body. The parallel light transmittance of the optically anisotropic body in the glass cell was 85.4%, and the haze was 3.9%.

(Comparative Example) 99 parts by weight of the liquid crystal composition (A) containing no liquid crystalline acrylate compound of the present invention prepared in Example 3 and a polymerization initiator "Irgacure 65"
A liquid crystal composition (E) comprising 1 part by weight of "1" (manufactured by Ciba Geigy) was prepared. The liquid crystal composition (E) was injected at room temperature into an antiparallel-aligned liquid crystal glass cell having a cell gap of 50 microns (a glass cell subjected to an alignment treatment so that the liquid crystal was uniaxially aligned). After injection, the orientation is stable within 1 minute,
It was confirmed that uniform uniaxial orientation was obtained. next,
1 mW / c using UVP-25 UVGL at room temperature
The liquid crystal composition (E) was polymerized by irradiating ultraviolet rays of m ² for 10 minutes to obtain an optically anisotropic body. The parallel light transmittance of the optically anisotropic body in the glass cell was 75.9%, and the haze was 11.0%.

From the results of Example 4 and Comparative Example 1, when the liquid crystal composition containing the liquid crystal acrylate compound of the present invention was used, a uniform alignment state was quickly obtained, and the optical anisotropy produced after polymerization was obtained. It can be seen that the transparency of the body is improved.

[0106]

As described above, the liquid crystalline (meth) acrylate compound of the present invention has the structural feature represented by the above general formula (I). The transparency of the optical isomer obtained by polymerizing the composition can be improved. In the formula (I), L ¹ and L ² are hydrogen atoms, the six-membered rings A and B are 1,4-phenylene groups, and the six-membered ring C is 1,3-phenylene group. , Sp ¹ and Sp ² have 2 to 1 carbon atoms.
An alkylene group having 2; Y ¹ is a single bond;
Y ² is —COO—, —OCO—, and X ¹ and X ² are —
When O—, the liquid crystal temperature range of the compound alone is 100
It is easy to suppress the temperature to not more than ℃, and the production is also easy.

Further, since the liquid crystal composition of the present invention contains the above liquid crystalline (meth) acrylate compound, the transparency of the optical isomer obtained by polymerizing the liquid crystal composition can be improved. . When the liquid crystal compound of the present invention further contains a liquid crystalline (meth) acrylate compound represented by the general formula (II), the (average) molecular weight is about 2
It becomes as low as about 50 to 450, a uniform alignment state can be quickly obtained, and since it exhibits a liquid crystal phase at room temperature, an optically anisotropic body having excellent heat resistance can be obtained after polymerization.
An optically anisotropic body having excellent uniformity and transparency can be obtained.

The optical anisotropic body of the present invention is excellent in uniformity, heat resistance and transparency because it is composed of a polymer of the above liquid crystal composition. As described above, the optically anisotropic body using the liquid crystal (meth) acrylate compound of the present invention has improved transparency, and includes a retardation plate, a polarizing plate,
It is very useful as a material for optical functional films such as polarizing prisms and various optical filters.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 20/26 C08F 20/26 4J100 C09K 19/12 C09K 19/12 19/14 19/14 19/16 19 / 16 19/18 19/18 19/20 19/20 19/30 19/30 19/34 19/34 19/38 19/38 (72) Inventor Hiroshi Shimizu 1-81-31 Midorigaoka, Ikeda-shi, Osaka F-term in Osaka Institute of Technology (reference) 4C022 GA04 4C055 AA01 BA01 CA03 CA17 CA53 CB01 CB04 DA01 4C062 AA22 4H006 AA01 AA03 AB64 BJ50 BP30 4H027 BA01 BA13 BD01 BD02 BD12 BE04 CB02 CF02 FA02 4J100 DA

Claims (6)

[Claims] 1. A compound represented by the following general formula (I):
(Meth) acrylate compound. Embedded image(Where L¹ , L^Two Are each independently a hydrogen atom or
Represents a methyl group, and the 6-membered rings A and B each independently represent
1,4-phenylene group, one or two non-adjacent CHs
A 1,4-phenylene group in which the group is substituted by nitrogen,
A cyclohexylene group, one or two non-adjacent CHs_Two 
1,4-cycloalkyl having a group substituted by an oxygen atom or a sulfur atom
Hexylene group or cyclohexene-1,4-diyl group
These 6-membered rings A and B further have 1 carbon atom
To 7 alkyl groups, alkoxy groups, alkanoyl groups,
Even if it is substituted with one or more ano groups or halogen atoms
Good, 6-membered ring C is 1,3-phenylene group, one or adjacent
1,3-phenyl having two CH groups not substituted with nitrogen
A len group, a 1,3-cyclohexylene group, one or adjacent
Not two ch_Two Group is substituted with an oxygen or sulfur atom
1,3-cyclohexylene group or cyclohexene-
Represents a 1,3-diyl group, and the 6-membered ring C further has a carbon atom
Alkyl group, alkoxy group, alkanoyl of formulas 1 to 7
Group, a cyano group, or a halogen atom
K, Y¹ , Y^Two Are each independently a single bond, -CH_TwoC
H_Two-, -CH_TwoO-, -OCH_Two-, -COO-,-
OCO-, -C≡C-, -CH = CH-, -CF = CF
-,-(CH_Two)_Four-, -CH_TwoCH_TwoCH _TwoO-, -OC
H_TwoCH_TwoCH_Two-, -CH = CH-CH_TwoCH_Two-, -C
H_TwoCH_Two-CH = CH-, -CH = CH-COO-,-
OCO-CH = CH-, -OCO-COO-, and X
¹ , X^Two Are each independently a single bond, -O-, -COO
-, -OCO-, Sp¹ , Sp^Two Is 1 carbon atom
To 20 spacer groups. ) 2. In the general formula (I), L ¹ , L ²
Is a hydrogen atom, the six-membered rings A and B are 1,4-phenylene groups, the six-membered ring C is a 1,3-phenylene group,
p ¹ and Sp ² are alkylene groups having 2 to 12 carbon atoms, Y ¹ is a single bond, Y ² is —COO—,
Is -OCO-, X ^1, claim 1 liquid crystal according to X ² is characterized in that it is a -O- (meth) acrylate compound. 3. A liquid crystal composition comprising the liquid crystalline (meth) acrylate compound according to claim 1 or 2 and exhibiting a liquid crystal phase. 4. The liquid crystal composition according to claim 3, comprising a liquid crystalline (meth) acrylate compound represented by the following general formula (II). Embedded image (In the formula, L ³ represents a hydrogen atom or a methyl group, n represents an integer of 0 or 1, and the 6-membered rings D, E, and F each independently represent a 1,4-phenylene group, one or an adjacent group. A 1,4-phenylene group in which two CH groups are substituted with nitrogen,
4-cyclohexylene group, one or two non-adjacent C
H ₂ represents a 1,4-cyclohexyl group or a cyclohexene-1,4-diyl group in which an oxygen atom or a sulfur atom is substituted, and these 6-membered rings D, E, and F further have 1 to 1 carbon atoms. 7 may be substituted by one or more of an alkyl group, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom, and Y ³ and Y ⁴ are each independently a single bond,-
_{CH 2 CH 2 -, - CH} 2 O -, - OCH 2 -, -COO
-, -OCO-, -C≡C-, -CH = CH-, -CF
_{= CF -, - (CH 2} ) 4 -, - CH 2 CH 2 CH 2 O-,
_{-OCH 2 CH 2 CH 2 -,} - CH = CH-CH 2 CH
_{2 -, - CH 2 CH 2} -CH = CH -, - CH = CH-C
OO -, - OCO-CH = CH- represent, Y ⁵ is single bond, -O -, - OCO -, - COO -, - CH = CH-
Represents COO-, Z ¹ represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms. ) 5. The liquid crystal composition according to claim 4, which exhibits a liquid crystal phase at 25 degrees Celsius. 6. An optically anisotropic material comprising a polymer of the liquid crystal composition according to claim 3. Description: