JP2014240469A - Polymerizable compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound which shows excellent solubility with another liquid crystal compound in constituting a polymerizable liquid crystal composition and which shows excellent heat resistance and mechanical strength when the polymerizable liquid crystal composition is cured.SOLUTION: The polymerizable compound is expressed by formula (I); and a liquid crystal composition including the above compound as a constituent is provided. Further, an optical anisotropic material or a liquid crystal device using the liquid crystal composition is provided. Since the above polymerizable compound has excellent solubility with other liquid crystal compounds, the polymerizable compound is useful as a constituent of a polymerizable composition. A polymerizable composition comprising the above polymerizable compound shows a wide temperature range of a liquid crystal phase; and an optical anisotropic material using the polymerizable composition has high heat resistance and is useful for a polarizing plate, a retardation plate or the like.

Description

  TECHNICAL FIELD The present invention relates to a polymerizable compound, a liquid crystal composition containing the compound, an optical anisotropic body which is a cured product of the liquid crystal composition, or a polymer stable liquid crystal display element obtained by polymerizing the liquid crystal composition. It is.

  In recent years, with the progress of the information society, the importance of optical compensation films used for deflecting plates and retardation plates, which are essential for liquid crystal displays, has been increasing, and optical compensation films that are required to have high durability and high functionality. Reports an example of polymerizing a polymerizable liquid crystal composition. Optical anisotropic materials used for optical compensation films, etc. are not only optical properties but also important factors such as compound polymerization rate, solubility, melting point, glass transition point, polymer transparency, mechanical strength, surface hardness and heat resistance. It becomes. Furthermore, a PSA (Polymer Sustained Alignment) type liquid crystal display device and a PSVA (Polymer Stabilized Vertical Alignment) type liquid crystal display device have a cured product obtained by polymerizing a polymerizable compound in a liquid crystal cell in order to control the tilt of liquid crystal molecules. In addition, it has been put to practical use as a liquid crystal display element because it exhibits high-speed response and high contrast.

  As a compound constituting a polymerizable liquid crystal composition, a compound having a structure in which 1,4-phenylene groups are linked by an ester bond (see Patent Document 1) and a compound having a fluorene group (see Patent Document 2) have been conventionally used. Proposed. However, the polymerizable compounds described in Patent Documents 1 and 2 have problems such as low solubility in the liquid crystal composition, and the polymerizable compound has an asymmetric structure in order to improve the solubility in the liquid crystal composition. Is disclosed (see Patent Document 3). Further, in a PSA type liquid crystal display device, an acrylate-based polymerizable compound having a biphenyl skeleton is generally known (see Patent Document 4).

Japanese National Patent Publication No. 10-513457 JP 2005-60373 A JP-T-2001-527570 JP 2003-307720 A

  However, since the polymerizable compound described in Patent Document 4 has a biphenyl skeleton, it has to be irradiated with ultraviolet rays for a long time in order to polymerize with little absorption in the ultraviolet region of 300 nm. Moreover, although the polymerizable compound described in Patent Document 3 is certainly improved in terms of solubility in the liquid crystal composition as compared with the conventional polymerizable compound, the solubility itself is not yet sufficient, Furthermore, it has been confirmed that new problems such as low heat resistance and low mechanical strength occur.

  Accordingly, an object of the present invention is to provide a polymerizable compound having excellent solubility in a liquid crystal composition and / or excellent heat resistance and mechanical strength when the inside of the liquid crystal composition is cured. And In addition, when the liquid crystal composition containing the polymerizable compound according to the present invention is used for a liquid crystal display element, the liquid crystal having improved display characteristics such as productivity and reliability improvement by improving the curability of the polymerizable liquid crystal composition. An object is to provide a display element. Furthermore, the present invention can also be applied to an IPS (in-plane switching) type liquid crystal display device.

  As a result of studying various substituents in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-mentioned problems, and have completed the present invention. That is, the present invention provides a polymerizable compound represented by a specific general formula (I), an optical anisotropic body using the liquid crystal composition, or a liquid crystal display element.

  The polymerizable compound according to the present invention is useful as a constituent member of the polymerizable composition because it has excellent solubility with other liquid crystal compounds. The composition containing the polymerizable compound according to the present invention has a wide liquid crystal phase temperature range, and the optical anisotropic body using the composition containing the polymerizable compound has high heat resistance, and is a deflecting plate and retardation plate. It is useful for such applications. Since the polymerizable compound according to the present invention has a wide ultraviolet absorption region, it can be polymerized by light or heat without adding a polymerization initiator, and can be polymerized without using a photoinitiator. Since an optical anisotropic body composed of a polymer of a liquid crystal composition containing such a polymerizable compound does not contain an impurity derived from a photoinitiator, both reliability and productivity can be achieved.

  The liquid crystal display device using the liquid crystal composition containing the polymerized compound according to the present invention has a small amount of residual monomer, and the image sticking property and the stability of the pretilt angle are greatly improved as compared with the conventional liquid crystal display device. A liquid crystal display element can be provided.

  The first of the present invention is the following general formula (I)

(In the general formula (I), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a hydrogen atom, an alkyl having 1 to 8 carbon atoms. A group, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkoxy group having 1 to 8 carbon atoms, a halogen atom, a cyano group or a nitro group;
S ¹ and S ² each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkylene group is an oxygen atom, -COO-, -OCO- or -OCOO- may be substituted,
L ¹ represents —CH═CH—COO— or —C ₂ H ₄ COO—,
L ² and L ³ are each independently a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —CO—, —COO—, —OCO. ^{_{-, - OCOOCH 2 -, -}} CH 2 OCOO -, - CO-NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - CH = CH -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO-, _{-OCOCH 2 -, - CH 2 COO} -, - CH = CH -, - CF = CH -, - CH = CF -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ — or —C≡C— (wherein R ^{1 1} represents an alkyl group having 1 to 4 carbon atoms).
M ¹ is 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2, 6-diyl group, pyrazine-2,5-diyl and 1,3-dioxane-2,5-diyl group, and M ¹ is unsubstituted or substituted by a substituent. Examples of the substituent in which a hydrogen atom in the group of M ¹ is substituted include an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, and 1 to 8 carbon atoms. An alkoxy group, a halogenated alkoxy group having 1 to 8 carbon atoms, a halogen atom, a cyano group or a nitro group,
R ¹ represents the following formula (R-I) to formula (R-IX)

In the formulas (RI) to (R-IX), R ^{2 to} R ⁶ are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. 1 to 5 halogenated alkyl groups, W is a single bond, —O— or a methylene group, p, t and q are each independently 0, 1 or 2,
Z is 1,2-phenylene group, 1,3-phenylene group, 1,2-cyclohexylene group, naphthalene-2,3-diyl group, naphthalene-1,2-diyl group, naphthalene-1,8-diyl group 1,2,4,5-benzenetetrayl group, 1,4,5,8-naphthalenetetrayl group, single bond, or the following formula (i) or formula (ii):

Z may be unsubstituted or substituted by a substituent, and examples of the substituent in which a hydrogen atom in the group of Z is substituted include an alkyl group, a halogenated alkyl group, an alkoxy group, an ester group (—COO -R ^Z R ^z: C 1 -C 10 alkyl group), a halogen atom, a cyano group or a nitro group,
m represents 0, 1 or 2, and n represents 2 or 4. When m represents 2, two M ¹ and L ² may be the same or different, and when n represents 2 and 4, two or four R ¹ and M ¹ are present. , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , L ¹ , L ² , L ³ , S ¹ , S ² , and m are the same or different. May be. ).

In the general formula (I), S ¹ and S ² each independently represent a spacer group or a single bond, and the spacer group is preferably an alkylene group having 1 to 10 carbon atoms or a single bond, 6 alkylene group or a single bond is more preferable, and the methylene group may be replaced with an oxygen atom, —COO—, —OCO—, or —OCOO—, assuming that the alkylene group does not directly bond oxygen atoms. S ² is more preferably an alkylene group having 2 to 6 carbon atoms or a single bond.

In the general formula (I), L ¹ represents —CH═CH—COO— or —C ₂ H ₄ COO—, and, when large absorbance is required, increases the conjugation of π electrons —CH ═CH—COO— is more preferable, and L ² and L ³ are each independently a single bond, —C ₂ H ₄ —, —O—, —OCH ₂ —, —CH ₂ O—, —COO—, — _{OCO -, - OCOOCH 2 -,} - CH 2 OCOO -, - CH = CH-COO -, - OOC-CH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO _{-, - C 2 H 4 COO} -, - CF 2 O- or -C≡C- are preferred, inexpensive to manufacture, in terms of liquid crystal alignment property, a single bond, -COO -, - OCO -, - CH 2 O _{-, - OCH 2 -, -} C 2 H 4 -, - C≡C- or -O- more favorable Properly, a single _{bond, -COO -, - OCO -,} - CH 2 O -, - OCH 2 - or -O- is more preferred. L ³ is more preferably a single bond, —COO—, —OCO— or —O—.

In the general formula (I), M ¹ is 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group, pyridine-2, 5-diyl group or pyrimidine-2,5-diyl group is preferable, 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group or tetrahydronaphthalene-2,6-diyl group And M ¹ may be unsubstituted or substituted by a substituent, and the substituent in which the hydrogen atom in the group of M ¹ is substituted includes an alkyl group having 1 to 6 carbon atoms, A halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, or a nitro group is preferable. M ¹ is unsubstituted and more preferably a 1,4-phenylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, or a naphthalene-2,6-diyl group.

In the general formula (I), R ¹ represents a polymerizable group, and specific examples of the polymerizable group include the structures shown below.

(In the formulas (RI) to (R-IX), R ^{2 to} R ⁶ are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. A halogenated alkyl group, W is a single bond, —O— or a methylene group, and p, t and q are each independently 0, 1 or 2.)
These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when ultraviolet polymerization is carried out as a polymerization method, the formula (RI), formula (R-II), formula (R-IV), formula (R-VI), formula (R-VII) or formula (R -IX) is preferred, formula (RI), formula (R-IV), formula (R-VI) or formula (R-VII) is more preferred, and formula (RI) is more preferred.

  The formula (RI) is more preferably any one of the following formulas (R-1) to (R-3).

  The formula (R-II) is more preferably the following formula (R-4) or formula (R-5).

  As the formula (III), the following formula (R-6) is more preferable.

  As said formula (IV), following formula (R-7) or (R-8) is more preferable.

  As the formula (V), the following formula (R-9) or formula (R-10) is more preferable.

  As the formula (VI), the following formula (R-11) is preferable.

  As the formula (VII), the following formula (R-12) or formula (R-13) is more preferable.

As the ^{R 1,} formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R-11), formula ( R-13) or formula (R-IX) is more preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula (R-13) is more preferred. Even more preferred is formula (R-1) or (R-2).

  In the general formula (I), Z is 1,2-phenylene group, 1,3-phenylene group, 1,2-cyclohexylene group, naphthalene-2,3-diyl group, 1,2,4,5-benzene. More preferred are a tetrayl group, 1,4,5,8-naphthalenetetrayl group or a single bond, 1,2-phenylene group, 1,3-phenylene group, 1,2-cyclohexylene group, naphthalene-2,3. -Diyl group, 1,2,4,5-benzenetetrayl group or 1,4,5,8-naphthalenetetrayl group is more preferable, 1,2-phenylene group, 1,2-cyclohexylene group, naphthalene- A 2,3-diyl group or a 1,2,4,5-benzenetetrayl group is more preferable because the polymerizable groups are close to each other in the liquid crystal composition, so that polymerization is easily promoted.

In the general formula (I), m is preferably 0 or 1, and n represents 2 and 4. When n represents 2 and 4, two or four M ¹ , X ¹ , X ² , L ¹ , L ² , L ³ , S ¹ , S ² , m and R ¹ are the same May be different.

A particularly preferable form of the polymerizable compound represented by the general formula (I) according to the present invention is preferably a chemical structure in which the distance between the same or different polymerizable groups R ¹ is shortened. Examples thereof include compounds represented by the following general formula (IA) having such a cis form.

(In the above general formula (IA), Z represents 1,2-phenylene group, 1,3-phenylene group, 1,2-cyclohexylene group, naphthalene-2,3-diyl group, naphthalene-1,2 -Diyl group, naphthalene-1,8-diyl group, 1,2,4,5-benzenetetrayl group, 1,4,5,8-naphthalenetetrayl group, single bond or the following formula (i) or formula ( ii):

Z may be unsubstituted or substituted by a substituent, and examples of the substituent in which a hydrogen atom in the group of Z is substituted include an alkyl group, a halogenated alkyl group, an alkoxy group, an ester group (—COO -R ^Z R ^z: C 1 -C 10 alkyl group), a halogen atom, a cyano group or a nitro group,
U ^1a and U ^1b are independently of each other a single bond, formulas (L-1) to (L-3):

(In the above formulas (L-1) to (L-3), p and q are integers of 0 or more and 12 or less.)
One of the
U ^2a and U ^2b are each independently a single bond or a carbonyl group,
U ^3a and U ^3b are each independently a single bond or —O—C (═O) —,
S / D is a single bond or a double bond,
p ^1a , p ^2a , p ^1b and p ^2b are integers of 0 or more and 12 or less,
R ^1a and R ^1b and X ^{1 to} X ⁸ are independently of each other, R ^1a and R ^1b are the same as R ^{1 in the} general formula (I), and X ^{1 to} X ⁸ are the same as in the general formula (I). X ^{1 to} X ⁸ in the above.
In the case where l is 1 or 2, two or four X ^{1 to} X ⁸ may be the same or different. It is preferable that it is a compound represented by this.

  More specifically, the compounds represented by the general formula (I) according to the present invention are particularly preferably compounds represented by the following formulas (I-1) to (I-26).

(In the above formulas (I-1) to (I-26), p and q each independently represent an integer of 0 to 12, but in the case of 0, the oxygen atom bonded to the aromatic ring is removed. .)
The polymerizable compound according to the present invention is represented by the formulas (I-1), (I-3), (I-5), and (I-6) among the above formulas (I-1) to (I-26). (I-7), (I-13), and (I-24) are preferable, and formulas (I-1), (I-3), (I-6), (I-7), and (I-13) are preferable. More preferred are formulas (I-3), (I-6) and (I-7).

  The compound of the present invention can be synthesized by the synthesis method described below.

(Production Method 1) Production of Compound Represented by General Formula (I-1) A biphenyl derivative (S-1) is obtained by a Mizorogi-Heck reaction of 4-bromo-4′-hydroxybiphenyl and tertiary butyl acrylate with a palladium catalyst. And a biphenyl derivative (S-2) having an acryloyl group is obtained by an esterification reaction with acryloyl chloride. Furthermore, the tertiary butyl group is eliminated with trifluoroacetic acid to obtain a biphenyl derivative (S-3) converted into a carboxylic acid group.

  Next, 1,2-hydroxybenzene and 6-chlorohexanol are etherified in the presence of a base such as potassium carbonate to obtain a compound (S-4) having a hydroxyl group. Furthermore, the target compound (I-1) can be obtained by esterifying (S-3) and (S-4) with a dehydration condensing agent such as dicyclohexylcarbodiimide.

(Production Method 2) Production of Compound Represented by General Formula (I-5) 2-Fluoro-4-bromobiphenyl and acetyl chloride are subjected to Friedel-Craft reaction using aluminum chloride (III), and then formic acid and hydrogen peroxide are reacted. A hydroxybiphenyl compound (S-6) substituted with a fluorine atom by formic acid with hydrogen oxide water is obtained. Further, a biphenyl derivative (S-7) is obtained by a Mizorogi-Heck reaction with tertiary butyl acrylate by a palladium catalyst. Subsequently, etherification reaction is performed in the presence of 6-chlorohexyl acrylate and a base such as potassium carbonate to obtain a biphenyl derivative (S-8) having an acryloyl group. Further, the biphenyl derivative (S-9) obtained by removing the tertiary butyl group and converting it to a carboxylic acid group with trifluoroacetic acid is obtained.

  Subsequently, (S-4) and (S-9) obtained by etherification reaction of 1,2-hydroxybenzene and 6-chlorohexanol are subjected to esterification reaction using a dehydration condensing agent such as dicyclohexylcarbodiimide. (I-5) can be obtained.

(Manufacturing method 3) Manufacture of the compound represented by general formula (I-9) The biphenyl derivative (S-10) is obtained by the catalytic hydrogen reduction which used palladium carbon for the biphenyl derivative (S-1) which has a hydroxyl group. Further, a biphenyl derivative (S-11) having an acryloyl group is obtained by an esterification reaction with acryloyl chloride. Furthermore, the tertiary butyl group is eliminated with trifluoroacetic acid to obtain a biphenyl derivative (S-12) converted into a carboxylic acid group.

  Next, (S-13) and (S-12) obtained by an esterification reaction of isophthalic acid and 6-chlorohexanol using potassium carbonate or the like are obtained by an esterification reaction using a dehydration condensing agent such as dicyclohexylcarbodiimide. The target compound (I-9) can be obtained.

(Production Method 4) Production of Compound Represented by General Formula (I-14) Hydroxybenzyl alcohol and chloromethyl methyl ether (MOM-Cl) are etherified in the presence of a base such as potassium carbonate to protect methoxymethyl ether The (MOM protected) compound (S-14) is obtained. Next, etherification using Mitsunobu reaction with protocatechuic acid butyl ester, and further, a compound (S-15) having two phenolic hydroxyl groups by demethoxymethyl ether group with hydrochloric acid is obtained.

  Biphenyl derivative (S-10), 6-chlorohexyl acrylate, and ether are reacted in the presence of a base such as potassium carbonate to obtain biphenyl derivative (S-16) having an acryloyl group. Further, the biphenyl derivative (S-17) obtained by removing the tertiary butyl group and converting it to a carboxylic acid group with trifluoroacetic acid is obtained. Subsequently, the target compound (I-14) can be obtained by esterifying the obtained (S-17) and (S-15) with a dehydrating condensing agent such as dicyclohexylcarbodiimide.

(Production Method 5) Production of Compound Represented by General Formula (I-21) 3-Ethyl-3-hydroxymethyloxetane (trade name EOXA, manufactured by Toagosei Co., Ltd.) and 1-bromo-3-chloropropane are mixed with sodium hydroxide. The oxetane derivative (S-18) is obtained by etherification reaction in the presence of a base such as Subsequently, 4-bromo-4′-hydroxybiphenyl is etherified in the presence of a base such as potassium carbonate to obtain a biphenyl derivative (S-19) having an oxetane group.

  A tetrafunctional acrylate (S-20) is obtained by esterification reaction of pyromellitic acid and hydroxyethyl acrylate using a dehydration condensing agent such as dicyclohexylcarbodiimide. Furthermore, the target compound (I-21) can be obtained by the Mizorogi-Heck reaction by a palladium catalyst with the biphenyl derivative (S-19) having an oxetane group.

  The polymerizable compound of the present invention can be used in nematic liquid crystals, smectic liquid crystals, chiral nematics, chiral smectics, and cholesteric liquid crystal compositions. In the liquid crystal composition of the present invention, other polymerizable compounds may be added in an arbitrary range other than using one or more compounds represented by the general formula (I) of the present invention. As the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention, those having the formula (RI) as the polymerizable functional group are more preferable, and acryloyloxy group (R-1) or methacryloyl. Those having an oxy group (R-2) are particularly preferred. Further, as the polymerizable liquid crystal compound, those having two or more polymerizable functional groups in the molecule are preferable. When the liquid crystal composition of the present invention is a cholesteric liquid crystal, addition of a chiral compound is preferable. Furthermore, for use in a PSA (Polymer Sustained Alignment) type liquid crystal display device, a PSVA (Polymer Stable Vertical Vertical Alignment) type liquid crystal display device, and a PS-IPS (In-Plane switching) type liquid crystal display device, a non-polymerizable liquid crystal composition. Add to product.

  Specific examples of the polymerizable compound other than the invention of the present application are not limited except that the compound represented by the general formula (I) is contained, but as a polymerizable liquid crystal compound used in combination, a compound represented by the formula (R -I) (for example, those having acryloyloxy group (R-1) or methacryloyloxy group (R-2)) are preferred, and those having two or more polymerizable functional groups in the molecule are more preferred.

  The polymerizable compound according to the present invention may contain a polymerizable compound other than the polymerizable compound represented by the general formula (I), and the polymerizable compound according to the present invention is a liquid crystal composition having no polymerizable group. Or a polymerizable compound represented by the general formula (I) alone, or a liquid crystal composition containing the polymerizable compound represented by the general formula (I) and another polymerizable compound But you can.

  In the present invention, the other polymerizable compound used in combination with the polymerizable compound represented by the general formula (I) preferably exhibits liquid crystallinity, specifically, the general formula (III):

(In the above general formula (III), R ¹¹ is a polymerizable group,
S ¹¹ each independently represents a single bond or an alkylene group having 1 to 12 carbon atoms, wherein one or more —CH ₂ — in the alkylene group is one in which oxygen atoms are not directly bonded to each other. As a methylene group may be replaced by an oxygen atom, -COO-, -OCO- or -OCOO-,
L ¹¹ and L ¹² are each independently a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —OCOOCH ₂ —, _{^{-CH 2 OCOO -, - CO-}} NR 13 -, - NR 13 -CO -, - CH = N -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - OOC-CH = CH—, —COOC ₂ H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO—, —C ₂ H ₄ COO—, —OCOCH ₂ —, —CH ₂ COO—, —CH═CH—, _{-C 2 H 4 -, - CF} = CH -, - CH = CF -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF ₂ CF ₂ — or —C≡C—, wherein R ¹³ is an alkyl group having 1 to 4 carbon atoms Represents)
M ¹¹ and M ¹² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6- A diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, wherein M ¹ and M ¹ are each independently unsubstituted or an alkyl group, halogenated An alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen group, a cyano group, or a nitro group may be substituted,
l ¹¹ represents 0, 1, 2 or 3, and when l ¹¹ represents 2 or 3, two or three L ¹² and M ¹² may be the same or different;
A ¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanate group (—SCN), a trifluoromethoxy group, an alkyl group having 1 to 12 carbon atoms, one methylene group or adjacent Two or more methylene groups that are not present may be substituted with an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —OCOO, —CH═CH—, —C≡C—, or A ^11. It is ^(wherein, L ^{13, S 12} and ^{R 12 L 11,} the same meaning as ^{S 11} and ^{R 11.) -L 13 -S 12} -R 12 compounds represented by are preferred.

In the general formula (III), L ¹¹ , L ¹² and L ¹³ each independently represent a single bond, —O—, —COO— or —OCO—, and M ¹¹ and M ¹² each independently And compounds represented by 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, preferable.

  Specifically, the compound represented by general formula (III) is preferably a compound represented by general formula (III-1) to general formula (III-23).

(In the above general formulas (III-1) to (III-43), a and b each independently represent an integer of 0 to 12, and when a is 0, oxygen bonded to the aromatic ring. Atoms are removed.)
When the liquid crystal composition of the present invention is a chiral smectic liquid crystal or a cholesteric liquid crystal, a chiral compound is usually added. Specific compounds are represented by general formulas (IV-1) to (IV-8). 0.5-50 mass% is preferable with respect to a liquid crystal composition, and, as for the compounding quantity of the said chiral compound, 2-30 mass% is more preferable.

(In the above formulas (IV-1 to IV-8), a and b represent an integer of 0 to 12, but in the case of 0, the oxygen atom bonded to the aromatic ring is removed.)
The polymerizable compound of the present invention may be added to a liquid crystal composition having no polymerizable group, such as an ordinary liquid crystal device such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, TFT. (Thin film transistor) Nematic liquid crystal composition and ferroelectric liquid crystal composition used for liquid crystal and the like can be mentioned.

  The compound represented by the general formula (I) is provided with liquid crystal alignment ability by polymerization of the polymerizable compound in the polymerizable compound-containing liquid crystal composition, and transmits light through the birefringence of the liquid crystal composition. It is used in a liquid crystal display element that controls It is particularly effective for PSA (Polymer Sustained Alignment) type liquid crystal display devices, PSVA (Polymer Stabilized Vertical Alignment) type liquid crystal display devices, PS-IPS (in-plane switching) type liquid crystal display devices and FFS that control the tilt of liquid crystal molecules. As a driving method, it is useful for AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element) and STN-LCD (super twisted nematic liquid crystal display element), but is particularly useful for AM-LCD. .

  The second of the present invention is a liquid crystal composition containing the polymerizable compound and the non-polymerizable liquid crystal compound. The liquid crystal composition according to the present invention preferably contains at least one polymerizable compound represented by the general formula (I), more preferably contains 1 to 5 species, more preferably 1 to 3 species. More preferably, it contains a seed. In addition, if the content of the compound represented by the general formula (I) is small, the alignment regulating force for the non-polymerizable liquid crystal compound is weak, and if it is too large, the energy required for polymerization increases and the polymer does not polymerize and remains. Since the amount of the polymerizable compound to be increased increases, the lower limit value is preferably 0.01% by mass, more preferably 0.03% by mass, and the upper limit value is 2.0% by mass. Preferably, it is 1.0 mass%.

  In the liquid crystal composition according to the present invention, the non-polymerizable liquid crystal composition preferably contains at least one of the seven types of liquid crystal compounds described below. Specifically, the liquid crystal composition according to the present invention includes a general formula (V), a general formula (VIa), a general formula (VIb), a general formula (VIc), a general formula (VIIa), a general formula (VIIb), and It is preferable to include at least one compound selected from the group consisting of general formula (VIIc).

  The liquid crystal composition according to the present invention has a general formula (V):

(In the general formula (V), R ²¹ and R ²² each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one existing in these groups. of -CH 2 _- or nonadjacent two or more -CH 2 _- may be substituted by -O- or -S-, also at least one hydrogen atom present in the group May be substituted with a fluorine atom or a chlorine atom,
M ²¹ , M ²² and M ²³ are independently of each other (a) a trans-1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent — CH ₂ — may be replaced by —O— or —S—).
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by a nitrogen atom), 3-fluoro- 1,4-phenylene group and 3,5-difluoro-1,4-phenylene group, and (c) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine- Selected from the group consisting of 2,5-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Represents a group, o represents 0, 1 or 2, L ²¹ and L ²² each independently represent a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH _{2. O -, - OCF 2 -,} - CF 2 O -, - CH = C -, - CH = N-N = CH- or an ^{-C≡C-, if L 22} there are a plurality may be different may be the ^{same, if M 23} there are a plurality of different may be the same May be. ) May be included as appropriate.

  In the liquid crystal composition containing the polymerizable compound represented by the general formula (I) according to the present invention (hereinafter also referred to as a polymerizable compound-containing liquid crystal composition), the content of the compound represented by the general formula (V) Is preferably 30% by mass, for example, as one embodiment of the present invention, with respect to the total amount (100% by mass) of the liquid crystal composition of the present invention. Or in another embodiment of this invention, it is preferable that it is 20 mass%. Moreover, in another embodiment of this invention, it is preferable that it is 10 mass%. Moreover, in another embodiment of this invention, it is preferable that it is 5 mass%.

  Furthermore, in the polymerizable compound-containing liquid crystal composition according to the present invention, the upper limit of the content of the compound represented by the general formula (V) is based on the total amount (100% by mass) of the liquid crystal composition of the present invention. In the embodiment of the present invention, it is preferably 95% by mass. Furthermore, in another embodiment of this invention, it is preferable that it is 80 mass%.

  The liquid crystal composition according to the present invention has a general formula (VIa), a general formula (VIb), and a general formula (VIc):

(In the above general formula (VIa) to general formula (VIc), R ³¹ , R ³² and R ³³ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. , one -CH 2 present in the group _- or nonadjacent two or more -CH 2 _- may be substituted by -O- or -S-, also present in these groups One or more hydrogen atoms may be substituted with fluorine atoms or chlorine atoms,
M ³¹ , M ³² , M ³³ , M ³⁴ , M ³⁵ , M ³⁶ , M ³⁷ and M ³⁸ are independent of each other,
(D) trans-1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- May be)
(E) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =), 3-fluoro -1,4-phenylene group and 3,5-difluoro-1,4-phenylene group, and (f) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine Selected from the group consisting of -2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group The hydrogen atoms contained in the above groups (d), (e) and (f) are each independently a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom. May be replaced,
L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ and L ³⁸ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH _{2) 4 -, - OCH 2} -, - CH 2 O -, - OCF 2 -, - CF 2 O- or represents ^{-C≡C-, M 32, M 34,} M 35, M 37, M 38, When there are a plurality of L ³¹ , L ³³ , L ³⁵ , L ³⁶ , and / or L ³⁸ , they may be the same or different,
X ³¹ , X ³² , X ³³ , X ³⁴ , X ³⁵ , X ³⁶ and X ³⁷ each independently represent a hydrogen atom or a fluorine atom, and Y ³¹ , Y ³² and Y ³³ independently represent a hydrogen atom, fluorine Represents an atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group, or difluoromethoxy group,
At least one of X ³¹ , X ³² , or Y ³¹ is a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a difluoromethoxy. Or at least one of hydrogen atoms contained in M ³¹ or M ³² represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a chlorine atom,
At least one of X ³³ , X ³⁴ , X ³⁵ or Y ³² is a fluorine atom, chlorine atom, cyano group, thiocyanato group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group or difluoro. A methoxy group, or at least one of hydrogen atoms contained in M ³³ , M ³⁴ or M ³⁵ represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
At least one of X ³⁶ , X ^{37 and} Y ³³ is a fluorine atom, chlorine atom, cyano group, thiocyanate group, trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group or difluoromethoxy group. Or at least one of the hydrogen atoms contained in M ³⁶ , M ³⁷ and M ³⁸ represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, and c, d, e, f and g independently represents 0, 1 or 2, but d + e and f + g are 2 or less. ) May be included as appropriate.

  In the liquid crystal composition containing the polymerizable compound represented by the general formula (I) according to the present invention (hereinafter also referred to as a polymerizable compound-containing liquid crystal composition), it is represented by the general formulas (VIa) to (VIc). The lower limit of the content of the compound is preferably, for example, 30% by mass as one embodiment of the present invention with respect to the total amount (100% by mass) of the liquid crystal composition of the present invention. Or in another embodiment of this invention, it is preferable that it is 20 mass%. Moreover, in another embodiment of this invention, it is preferable that it is 10 mass%. Moreover, in another embodiment of this invention, it is preferable that it is 5 mass%.

  Furthermore, in the polymerizable compound-containing liquid crystal composition according to the present invention, the upper limit of the content of the compounds represented by the general formulas (VIa) to (VIc) is the total amount (100% by mass) of the liquid crystal composition of the present invention. On the other hand, it is preferable that it is 95 mass% in embodiment of this invention. Furthermore, in another embodiment of this invention, it is preferable that it is 80 mass%.

  The liquid crystal composition according to the present invention has a general formula (VIIa), a general formula (VIIb), and a general formula (VIIc):

(In the above formulas (VIIa) to (VIIc), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 10 carbon atoms or 2 carbon atoms. represents 10 alkenyl group of from one -CH 2 present in the group _- or nonadjacent two or more -CH 2 _- may be substituted by -O- or -S- In addition, one or more hydrogen atoms present in these groups may be substituted with fluorine atoms or chlorine atoms,
M ⁴¹ , M ⁴² , M ⁴³ , M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ are independent of each other,
(G) trans-1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- May be)
(H) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═);
(I) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and a group selected from the group consisting of decahydronaphthalene-2,6-diyl group, the above groups (d), (e) and (f) Each hydrogen atom contained may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or —C≡C— represents M ⁴² , M ⁴³ , M ⁴⁵ , M ⁴⁶ , M ⁴⁸ , M ⁴⁹ , L ⁴¹ , L ⁴³ , L ⁴⁴ , L ⁴⁶ , L ⁴⁷ and / or a plurality of L ⁴⁹ , they may be the same or different,
X ⁴¹ and X ⁴² each independently represent a trifluoromethyl group, a trifluoromethoxy group or a fluorine atom, and X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ and X ⁴⁸ are each independently a hydrogen atom. , A trifluoromethyl group, a trifluoromethoxy group, or a fluorine atom, wherein any one of X ⁴¹ and X ⁴² represents a fluorine atom, and at least one of X ⁴³ , X ^44, and X ⁴⁵ represents a fluorine atom. , X ⁴⁶ , X ⁴⁷ and X ⁴⁸ represent a fluorine atom, but X ⁴⁶ and X ⁴⁷ do not represent a fluorine atom at the same time, and X ⁴⁶ and X ⁴⁸ do not represent a fluorine atom at the same time. G is -CH ₂ - or an -O-, h, i, j, r, s, and t are independently from each other, represent 0, 1 or 2, h + i, j + r and s + t is 2 or less That. ) May be included as appropriate.

  In the liquid crystal composition containing the polymerizable compound represented by the general formula (I) according to the present invention (hereinafter also referred to as a polymerizable compound-containing liquid crystal composition), it is represented by the general formulas (VIIa) to (VIIc). The lower limit of the content of the compound is preferably, for example, 30% by mass as one embodiment of the present invention with respect to the total amount (100% by mass) of the liquid crystal composition of the present invention. Or in another embodiment of this invention, it is preferable that it is 20 mass%. Moreover, in another embodiment of this invention, it is preferable that it is 10 mass%. Moreover, in another embodiment of this invention, it is preferable that it is 5 mass%.

  Furthermore, in the polymerizable compound-containing liquid crystal composition according to the present invention, the upper limit of the content of the compounds represented by the general formulas (VIIa) to (VIIc) is the total amount (100% by mass) of the liquid crystal composition of the present invention. On the other hand, it is preferable that it is 95 mass% in embodiment of this invention. Furthermore, in another embodiment of this invention, it is preferable that it is 80 mass%.

  The liquid crystal composition is a compound selected from the group consisting of a compound represented by the general formula (V), a general formula (VIa), a general formula (VIb) and a compound represented by the general formula (VIc), or the general formula (VIIa). And those containing at least one compound selected from the group consisting of compounds represented by general formula (VIIb) and general formula (VIIc). One or two compounds represented by general formula (V) are preferable. Liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by general formula (VIa), general formula (VIb) and general formula (VIc) A compound selected from the group consisting of compounds represented by formula (V), one or more of the compounds represented by formula (V), and further represented by formula (VIIa), formula (VIIb), and formula (VIIc) One or The liquid crystal composition containing the above species are preferred.

  It is preferable that the composition for optical anisotropic bodies according to the present invention contains the polymerizable compound according to the present invention and a solvent.

  The solvent used in the composition is not particularly limited, and a solvent in which the polymerizable compound exhibits good solubility can be used. For example, aromatic hydrocarbons such as toluene, xylene and mesitylene, ester solvents such as methyl acetate, ethyl acetate and propyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, 1,2-dimethoxyethane And ether solvents such as anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, γ-butyrolactone, and chlorobenzene. These can be used alone or in combination of two or more. Moreover, the below-mentioned additive can also be added.

  The ratio of the solvent is not particularly limited as long as it does not significantly impair the applied state, since the optically anisotropic composition used in the present invention is usually applied. The ratio (weight ratio) between the solid content and the solvent is preferably 0.1: 99.9 to 80:20, and more preferably 1:99 to 60:40 in view of applicability.

  Moreover, since the composition for optical anisotropic bodies of the present invention is polymerized in an aligned state, an additive such as a surfactant or a polymer that promotes alignment may be used as necessary. The surfactant for promoting orientation used in the optical anisotropic composition of the present invention is soluble in the composition and segregates at the air interface opposite to the substrate when the composition is applied and dried. The surfactant to be used is not particularly limited, but a surfactant having a smaller surface tension than the compound having a polymerizable functional group is preferable. Examples of such surfactants include fluorine-containing nonionic surfactants, organosilane surfactants, polyacrylate surfactants, and the like. The surfactant may have a polymerizable group in order to form a stronger film when polymerized.

  The polymer for promoting orientation used in the optical anisotropic composition of the present invention is also soluble in the composition, and segregates at the air interface opposite to the substrate when the composition is applied and dried. As long as it is a material, the polymer to be used is not particularly limited, but a polymer having a smaller surface tension than the compound having a polymerizable functional group is preferable. Examples of such a polymer include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, chlorinated liquid paraffin, and polyvinylidene fluoride.

  The polymer preferably has a mass average molecular weight of 200 to 1,000,000, more preferably 300 to 100,000, and particularly preferably 400 to 10,000.

  The composition for optical anisotropic body of the present invention can be applied uniformly, to obtain a cholesteric reflective film having a uniform film thickness, or a general-purpose additive can be used according to each purpose. For example, additives such as a leveling agent, a thixo agent, a surfactant, an ultraviolet absorber, an infrared absorber, an antioxidant, and a surface treatment agent can be added to such an extent that the liquid crystal alignment ability is not significantly reduced.

  The optical anisotropic body according to the present invention is preferably constituted by polymerizing the composition for optical anisotropic bodies containing the polymerizable compound, and the liquid crystal display element according to the present invention includes the optical anisotropic body. It is preferable to use a body.

  The polymer-stabilized liquid crystal display element according to the present invention preferably uses the liquid crystal composition according to the present invention, and uses the polymerizable liquid crystal composition according to the present invention, and the polymerizable compound in the polymerizable liquid crystal composition. It is preferable that the liquid crystal display element is provided with a liquid crystal alignment ability by polymerizing.

  The configuration of the liquid crystal display element according to the present invention includes a first substrate having a common electrode made of a transparent conductive material, a pixel electrode made of a transparent conductive material, and a thin film transistor for controlling the pixel electrode provided in each pixel. A second substrate including the formed thin film transistor layer; and a liquid crystal composition filled between the first substrate and the second substrate, wherein no voltage is applied to the liquid crystal molecules in the liquid crystal composition. A liquid crystal display element whose orientation is substantially perpendicular to the substrate, wherein the liquid crystal composition of the present invention is used as the liquid crystal composition.

  The first substrate and the second substrate may be sandwiched between a pair of polarizing plates. Furthermore, a color filter may be provided between the first substrate and the common electrode.

  That is, a liquid crystal display element according to the present invention includes a second polarizing plate, a second substrate, an electrode layer including a thin film transistor (or also referred to as a thin film transistor layer), an alignment film, a layer including a liquid crystal composition, An alignment film, a common electrode, a color filter, a first substrate, and a first polarizing plate are sequentially stacked.

  The two substrates (first substrate and second substrate) of the liquid crystal cell used in the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic, one of which is silicon or the like. Opaque material may be used. A transparent substrate having a transparent electrode layer such as a common electrode or a pixel electrode can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

  The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  The first and second substrates on which the transparent electrode (layer) and the thin film transistor layer are formed are opposed so that the transparent electrode (layer) and the like are inside. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be 1-100 micrometers, and 1.5 to 10 micrometers is more preferable. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

  A method for introducing a liquid crystal composition containing a polymerizable compound into a liquid crystal composition containing space containing a liquid crystal composition formed by bonding two substrates facing each other as described above is a normal vacuum. An injection method or an ODF method can be used. However, in the method of introducing the polymerizable monomer-containing liquid crystal composition by the vacuum injection method, although the drop mark does not occur, there is a problem that the injection mark remains, but in the present invention, the ODF method is used. The display element can be suitably used.

  In the present invention, as a method of polymerizing the polymerizable compound, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating current to the polymerizable compound-containing liquid crystal composition. The alternating current to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the MVA mode liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89 degrees from the viewpoint of alignment stability and contrast.

  Moreover, it is a compound which has a polymerizable functional group, Comprising: The compound which does not show liquid crystallinity can also be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.

  The liquid crystal composition according to the present invention can be polymerized by heat and light without adding a polymerization initiator, but the addition of a photopolymerization initiator is preferred. The concentration of the photopolymerization initiator to be added is preferably 0.1 to 10% by mass, more preferably 0.2 to 10% by mass, and particularly preferably 0.4 to 5% by mass. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.

  In addition, a stabilizer may be added to the liquid crystal composition according to the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the amount added is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.

  In addition, when the liquid crystal composition according to the present invention is used for a retardation film, a raw material for a polarizing film or an alignment film, or a printing ink and paint, a protective film, etc., depending on the purpose, a metal, a metal complex, Dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, titanium oxide and other metals An oxide or the like can also be added.

Next, the optical anisotropic body of the present invention will be described. The optical anisotropic body produced by polymerizing the polymerizable compound-containing liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable compound-containing liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. Moreover, the optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic body is, for example, a substrate obtained by rubbing the surface of the polymerizable compound-containing liquid crystal composition of the present invention with a cloth or the like, or a substrate obtained by rubbing a substrate surface on which an organic thin film is formed with a cloth or the like, or It can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film on which SiO ₂ is obliquely vapor-deposited or sandwiched between the substrates.

  Examples of methods for supporting a polymerizable compound-containing liquid crystal composition on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. Can do. In coating, the polymerizable compound-containing liquid crystal composition may be used as it is or an organic solvent may be added. Organic solvents include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, dichloromethane, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone, γ-butyllactone, acetoxy-2-ethoxyethane, propylene glycol monomethyl Examples include acetate and N-methylpyrrolidinones. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. Moreover, the addition amount is preferably 90% by mass or less. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. Providing an intermediate layer such as a polyimide thin film on the substrate is also effective as a means for improving the adhesion when the adhesion between the optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal material and the substrate is not good. .

  Examples of the method for filling the liquid crystal composition according to the present invention between the substrates include an injection method utilizing capillary action. It is also effective to depressurize the space formed between the substrates and then inject a liquid crystal material.

Examples of the alignment treatment other than the rubbing treatment or the oblique deposition of SiO ₂ include the use of fluid orientation of a liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. This method can be applied to, for example, an organic thin film having a functional group that undergoes photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that is isomerized by light, or an organic thin film such as polyimide. An alignment film is formed by irradiating polarized ultraviolet rays. By applying an optical mask to this photo-alignment method, patterning of the alignment can be easily achieved, so that the molecular orientation inside the optical anisotropic body can be precisely controlled.

  As the shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

  When appropriate orientation cannot be obtained 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. Also good. Moreover, the polyimide thin film which gives the pretilt angle used in the normal TN liquid crystal device or STN liquid crystal device is particularly preferable because the molecular orientation structure inside the optical anisotropic body can be controlled more precisely.

  In the case where 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 aforementioned polyimide thin film on the electrode.

As a method of polymerizing the liquid crystal composition according to the present invention, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation is in the temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular, when an optical anisotropic body is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. It is preferable to make it. The intensity of the active energy ray is preferably 0.1 mW / cm ^{2 to 2} W / cm ² . When the intensity is 0.1 mW / cm ² or less, a great amount of time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

  The optical anisotropic body of the present invention obtained by the above polymerization can be subjected to heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. 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 optical anisotropic body of the present invention produced by such a method may be peeled off from the substrate and used alone or without peeling. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “mass%”.

Example 1
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 10 g (40.1 mmol) of 4-bromo-4′-hydroxybiphenyl, 6.2 g (48.2 mmol) of tertiary butyl acrylate, 4.8 g of triethylamine (48 mmol), 530 mg of palladium acetate, and 300 ml of dimethylformamide were charged, and the reaction was performed by heating the reactor to 100 ° C. in a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 11 g of the compound represented by the formula (1).

  Next, a reaction vessel equipped with a stirrer, a cooler and a thermometer was charged with 3 g (10.1 mmol) of the compound represented by the above formula (1), 1 g (11 mmol) of acrylic acid chloride, and 50 ml of dichloromethane, and nitrogen gas. The reactor was cooled below 5 ° C. under atmosphere. Next, 1.2 g (12 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, dichloromethane was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 3.6 g of a compound represented by the formula (2).

  Further, 3.6 g of the compound represented by the above formula (2) was dissolved in 10 ml of dichloromethane in a reaction vessel equipped with a stirrer, a cooler and a thermometer, and then 10 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. did. After confirming the completion of the reaction, 200 ml of toluene was added to precipitate crystals. The precipitate was filtered to obtain 2.4 g of a compound represented by the formula (3).

  Next, 5.5 g (10 mmol) of 1,2-hydroxybenzene, 4.1 g (30 mmol) of potassium carbonate, 3 g (22 mmol) of 6-chlorohexanol, and 100 ml of dimethylformamide were added to a stirrer, a condenser and a thermometer. And was allowed to react at 90 ° C. for 4 hours. After completion of the reaction, the mixture was washed with ethyl acetate and pure water, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out with a double amount (weight ratio) silica gel column to obtain 2.5 g of a compound represented by the formula (4).

  Next, 1 g (3.4 mmol) of the compound represented by the above formula (4), 2 g (6.8 mmol) of the compound represented by the above formula (3), 90 mg of dimethylaminopyridine, and 30 ml of dichloromethane were charged, and 5 in an ice-cooled bath. The reaction vessel was kept below ℃, and 940 mg (7.5 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtration of the reaction solution, 50 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column, and 1.2 g of the desired compound represented by the formula (5) was obtained by recrystallization from dichloromethane / methanol. This compound exhibited a liquid crystal phase at a wide temperature from 99 ° C. to 131 ° C. or higher.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 1.48-1.60 (m, 8H), 1.72-1.77 (m, 4H), 1.82-1.89 (m, 4H) ), 4.00 (t, 4H), 4.29 (t, 4H), 6.02 (d, 2H), 6.31-6.38 (m, 2H), 6.44-6.50 ( m, 2H), 6.66 (d, 2H), 6.89 (s, 4H), 7.20-7.29 (m, 6H), 7.59-7.62 (m, 10H), 7 .76 (d, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 25.9, 28.8, 29.3, 64.8, 69.0, 118.0, 120.9, 121.8, 126.8, 127 .3, 127.6, 128.4, 130.7, 132.7, 142.3, 143.8, 158.5, 165.9, 166.8
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
Melting point: 99 ° C
(Example 2)
To a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 12.8 g (96 mmol) of aluminum (III) chloride and 100 ml of dichloromethane were added and stirred. Next, 8.4 g (110 mmol) of acetyl chloride was slowly added dropwise over 90 minutes, and further 80 ml of a dichloromethane solution of 20 g (80 mmol) of 4-bromo-2-fluorobiphenyl was slowly added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by further stirring for 2 hours. The reaction solution was slowly poured into 500 ml of ice water, extracted with dichloromethane, and the organic layer was washed with pure water and saturated brine. After the solvent was distilled off, drying was performed to obtain 23 g of a compound having an acetyl group introduced. Next, 23 g of the compound having the acetyl group introduced therein and 300 ml of formic acid were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and 20 ml of 34.5% hydrogen peroxide solution was added, followed by heating under reflux for 6 hours. It was. After completion of the reaction, 450 ml of a 10% aqueous sodium hydrogen sulfite solution was added to decompose the peroxide. The precipitated solid was filtered, dissolved with ethyl acetate, and the organic layer was washed with water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 18 g of a compound represented by the formula (6).

  In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 10 g (37.4 mmol) of the compound represented by the above formula (6), 5.7 g (44.8 mmol) of tertiary butyl acrylate, 5.6 g of triethylamine (56 mmol), 410 mg of palladium acetate, and 300 ml of dimethylformamide were charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 10.5 g of a compound represented by the formula (7).

  Next, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 10.5 g (33.4 mmol) of the compound represented by the above formula (7), 3.6 g (40 mmol) of acrylic acid chloride, and 100 ml of dichloromethane were added. The reactor was charged and cooled to 5 ° C. or lower under a nitrogen gas atmosphere. Next, 4 g (40 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, dichloromethane was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 10.5 g of a compound having an acrylic group.

  Furthermore, 10.5 g of the compound having an acrylic group was dissolved in 20 ml of dichloromethane in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and then 30 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. After confirming the completion of the reaction, toluene is added to precipitate crystals. The precipitate was filtered to obtain 8.9 g of a compound represented by the formula (8).

  Next, 5.5 g (10 mmol) of 1,2-hydroxybenzene, 4.1 g (30 mmol) of potassium carbonate, 2.1 g (22 mmol) of 3-chloropropanol, and 100 ml of dimethylformamide were added to a stirrer, a condenser, The reaction vessel equipped with a thermometer was charged and reacted at 90 ° C. for 4 hours. After completion of the reaction, the mixture was washed with ethyl acetate and pure water, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 2.0 g of the compound represented by the formula (9).

  Subsequently, 5.5 g (17.6 mmol) of the compound represented by the above formula (8) and 2 g (8.8 mmol) of the compound represented by the formula (9) were added to a reaction vessel equipped with a stirrer, a cooler, and a thermometer. Then, 250 mg of dimethylaminopyridine and 150 ml of dichloromethane were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 2.7 g (21 mmol) of diisopropylcarbodiimide was slowly added dropwise in an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out with a double amount (weight ratio) silica gel column, and 6.1 g of the desired compound represented by the formula (10) was obtained by recrystallization with dichloromethane / methanol. This compound exhibited a liquid crystal phase at a temperature from 144 ° C. to 153 ° C. or higher.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 2.17-2.28 (m, 4H), 4.12 (t, 4H), 4.49 (t, 4H), 6.03-6. 18 (m, 2H), 6.32-6.44 (m, 2H), 6.62 (d, 2H), 6.65 (m, 2H), 6.94 (s, 4H), 7.21 -7.23 (m, 4H), 7.31-7.34 (m, 4H), 7.42-7.44 (m, 4H), 7.56-7.58 (m, 2H), 7 .61 (d, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 28.7, 61.5, 65.6, 114.2, 119.0, 121.2, 121.4, 127.4, 129.7, 132 .5, 142.3, 143.8, 148.3, 164.8, 166.8
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
Melting point: 144 ° C
Example 3
In a reaction vessel equipped with a stirrer, a cooler and a thermometer, 5 g (16.8 mmol) of the compound represented by the formula (1) described in Example 1 2.8 g (20 mmol) of potassium carbonate, 3-chloropropyl 3 g (20 mmol) of acrylate and 50 ml of dimethylformamide were charged and reacted at 90 ° C. for 4 hours. After completion of the reaction, the mixture was washed with ethyl acetate and pure water, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed with a double amount (weight ratio) silica gel column to obtain 5.6 g of a compound represented by the formula (11).

  Furthermore, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 5.6 g of the compound represented by the above formula (11) was dissolved in 10 ml of dichloromethane, and then 20 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. did. After confirming the completion of the reaction, toluene was added to precipitate crystals. The precipitate was filtered to obtain 4.5 g of a compound represented by the formula (12).

  Next, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 10.5 g (33.4 mmol) of the compound represented by the above formula (12) and the compound 5 represented by the formula (4) described in Example 1 .2 g (16.7 mmol), dimethylaminopyridine 400 mg, and dichloromethane 150 ml were kept in an ice-cooled bath at 5 ° C. or lower, and 5 g (40 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. . After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out with a double amount (weight ratio) silica gel column, and 13 g of the desired compound represented by the formula (13) was obtained by recrystallization with dichloromethane / methanol. This compound exhibited a liquid crystal phase at a temperature from 114 ° C. to 119 ° C. or higher.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 1.45 to 1.60 (m, 8H), 1.73-1.77 (m, 4H), 1.83 to 1.87 (m, 4H) ), 2.15-2.20 (m, 4H), 3.99 (t, 4H), 4.02 (t, 4H), 4.22 (t, 4H) 4.36 (t, 4H), 5.82 (d, 2H), 6.10-6.17 (m, 2H), 6.39-6.47 (m, 4H), 6.89 (s, 4H), 6.94 (d, 4H), 7.51-7.55 (m, 12H), 7.65 (m, 6H), 7.67 (d, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 25.9, 28.7, 28.8, 29.3, 61.3, 64.4, 64.5, 69.0, 113.9, 114 7, 117.5, 120.9, 126.8, 127.9, 128.1, 128.4, 130.7, 132.5, 132.6, 142.3, 144.0, 148.9 , 158.5, 165.9, 166.9
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1662-1622, 809 cm ⁻¹
Melting point: 114 ° C
Example 4
Pyromellitic acid 5 g (20 mmol), hydroxyethyl acrylate 9.3 g (80 mmol), dimethylaminopyridine 1.2 g, dichloromethane 150 ml were charged in a reaction vessel equipped with a stirrer, a cooler and a thermometer, and an ice-cooled bath. 940 mg (96 mmol) of diisopropylcarbodiimide was slowly added dropwise in an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtration of the reaction solution, 50 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 11 g of a compound represented by the formula (14).

  Then, 5 g (7.7 mmol) of the compound represented by the above formula (14) and 7.6 g (31 mmol) of 4-bromo-4′-hydroxybiphenyl in a reaction vessel equipped with a stirrer, a cooler, and a thermometer. Then, 6.2 g (62 mmol) of triethylamine, 10 g (31 mmol) of tetrabutylammonium bromide, 250 mg of palladium acetate, and 300 ml of dimethylformamide were charged, and the reaction was performed by heating the reactor to 70 ° C. in a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column to obtain 7.6 g of a compound represented by the formula (15).

  Further, 5 g (3.8 mmol) of the compound represented by the above formula (15), 1.5 g (16.6 mmol) of acrylic acid chloride and 50 ml of dichloromethane were placed in a reaction vessel equipped with a stirrer, a cooler and a thermometer. The reactor was charged and cooled to 5 ° C. or lower under a nitrogen gas atmosphere. Thereafter, 1.7 g (16.6 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, dichloromethane was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 4 g of the desired compound represented by the formula (16).

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 4.48 (m, 8H), 4.56 (m, 8H), 5.90 (d, 4H), 6.10-6.30 (m, 4H), 6.40-6.50 (m, 4H) 6.66 (d, 4H), 7.15 (m, 8H), 7.44-7.49 (m, 12H), 7.59- 7.62 (m, 8H), 7.76 (m, 8H), 8.24 (s, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 61.8, 63.3, 116.2, 122.1, 126.9, 127.5, 127.8, 129.5, 129.6, 134 .1, 140.0, 145.1, 150.2, 164.3, 166.5
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
(Example 5)
Benzyloxyphenol 10 g (50 mmol), dodecanedicarboxylic acid 5.75 g (25 mmol), dimethylaminopyridine 300 mg, dichloromethane 150 ml were charged and kept in an ice-cooled bath at 5 ° C. or lower in an atmosphere of nitrogen gas. Diisopropylcarbodiimide 7.56 (60 mmol) was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtration of the reaction solution, 50 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified with a double amount (weight ratio) silica gel column, and dispersed and washed with methanol to obtain 13 g of a compound represented by the formula (17).

  Next, 13 g of the compound represented by the above formula (17) was dissolved in 80 ml of tetrahydrofuran and charged into a 250 ml autoclave. Further, 20 ml of ethanol and 600 mg of 5% palladium carbon were added, and the mixture was reacted at a hydrogen pressure of 0.4 Mpa for 6 hours. After the reaction solution was filtered, the filtrate was concentrated to obtain 9 g of a compound represented by the formula (18).

  Next, in a reaction vessel equipped with a stirrer, a condenser and a thermometer, 9 g (22 mmol) of the compound represented by the above formula (18) and 16 g (43.4 mmol) of the compound represented by the following formula (19), Charge 260 mg of dimethylaminopyridine and 150 ml of dichloromethane, and keep the reaction vessel at 5 ° C or lower with an ice-cooled bath. In an atmosphere of nitrogen gas, 6.5 g (50 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate.

After distilling off the solvent, purification was carried out with a double amount (weight ratio) silica gel column, and 13 g of the desired compound represented by the formula (20) was obtained by recrystallization with dichloromethane / methanol. This compound exhibited a liquid crystal phase at temperatures from 152 ° C. to 200 ° C. or higher.

¹ H-NMR (solvent: deuterated chloroform): δ: 1.26 to 1.30 (m, 12H), 1.52 (t, 4H), 2.11 (m, 4H), 2.20-2. 25 (m, 4H), 2.30 (t, 4H), 4.10-4.15 (m, 4H), 4.20-4.25 (m, 4H), 6.31 (s, 2H) 6.40 (m, 2H), 6.44-6.48 (m, 2H), 7.02-7.05 (m, 4H), 7.24-7.26 (m, 8H), 7 .44-7.48 (m, 6H), 7.59 (m, 4H), 7.62-7.68 (m, 4H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 18.3, 25.0, 25.9, 28.8, 29.3, 29.6, 33.5, 34.2, 61.8, 64 , 9, 114.9, 115.5, 122.0, 122.2, 126.9, 127.8, 129.3, 129.7, 132.4, 134.1, 136.0, 142.3 , 143.8, 148.1, 158.5, 165.9, 166.8
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
(Example 6)
A polymerizable liquid crystal composition (Composition 1) having the following composition was prepared.

The polymerizable liquid crystal composition had good compatibility stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 3% to prepare a polymerizable liquid crystal composition (Composition 2). When the cyclohexanone solution of composition 2 was spin-coated on polyimide-coated glass and irradiated with 4 mW / cm ² of ultraviolet light for 120 seconds using a high-pressure mercury lamp, composition 2 remained in a uniform alignment state. Polymerization yielded an optically anisotropic body. The surface hardness (according to JIS-SK-5400) of this optical anisotropic body was H. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 90%, and the retardation reduction rate was 10%.

(Comparative Example 1)
A polymerizable liquid crystal composition (Composition 3) having the following composition was prepared.

  The polymerizable liquid crystal composition showed a nematic liquid crystal phase, but the solubility was poor and crystals were precipitated at room temperature for 1 hour.

(Comparative Example 2)
A polymerizable liquid crystal composition (Composition 4) having the following composition was prepared.

  The polymerizable liquid crystal composition had good storage stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 3% to prepare a polymerizable liquid crystal composition (Composition 5). Using this composition 5, an optical anisotropic body was obtained in the same manner as in Example 6. It was confirmed that the obtained optical anisotropic body was subjected to rubbing treatment and the composition 5 was polymerized while maintaining a uniform alignment state. The surface hardness (according to JIS-SK-5400) of this optical anisotropic body was F. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 82%, and the phase difference reduction rate was 18%.

  Thus, it is clear that the composition 5 of Comparative Example 2 has a larger retardation reduction rate of the optically anisotropic body that can be produced and is inferior in heat resistance than the composition 2 of the present invention. Further, the surface hardness F was insufficient.

(Example 6)
A liquid crystal composition LC-1 containing the compound shown below was prepared. The constituent compounds and the ratios contained are as follows.

Properties of liquid crystal properties Tni represents a nematic phase-isotropic liquid phase transition temperature (° C.), Δn represents a refractive index anisotropy at 20 ° C., and Δε represents a dielectric anisotropy at 25 ° C.

  The liquid crystal properties of the LC-1 were as follows.

Tni: 85 ° C., Δε: 5.5, Δn: 0.090
0.3% of the compound represented by the formula (5) synthesized in Example 1 was added to the liquid crystal composition LC-1. The polymerizable compound-containing liquid crystal composition was excellent in storage stability with no precipitation even when stored at −10 ° C. for 1 week. This polymerizable compound-containing composition was injected into a glass cell with polyimide subjected to an alignment treatment of 3.5 μm, and after irradiation with 10 J of ultraviolet rays, the liquid crystal composition was extracted from the glass cell, and the residual monomer was analyzed by high performance liquid chromatography. However, it was below the detection limit.

(Example 7)
A liquid crystal composition LC-2 containing the compound shown below was prepared. The constituent compounds and the ratios contained are as follows.

Properties of liquid crystal properties Tni represents a nematic phase-isotropic liquid phase transition temperature (° C.), Δn represents a refractive index anisotropy at 20 ° C., and Δε represents a dielectric anisotropy at 25 ° C.

  The liquid crystal properties of the LC-1 were as follows.

Tni: 78.3 ° C., Δε: −2.59, Δn: 0.101
0.15 parts by mass of the compound represented by the formula (5) synthesized in Example 1 was added to the liquid crystal composition LC-2 (100 parts by mass). The polymerizable compound-containing liquid crystal composition was excellent in storage stability with no precipitation even when stored at −10 ° C. for 1 week. This polymerizable compound-containing composition was injected into a glass cell with polyimide subjected to an alignment treatment of 3.5 μm, and after irradiation with 10 J of ultraviolet rays, the liquid crystal composition was extracted from the glass cell, and the residual monomer was analyzed by high performance liquid chromatography. However, it was below the detection limit.

Claims (11)

Formula (I):

(In the general formula (I), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a hydrogen atom, an alkyl having 1 to 8 carbon atoms. A group, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkoxy group having 1 to 8 carbon atoms, a halogen atom, a cyano group or a nitro group;
S ¹ and S ² each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkylene group is an oxygen atom, -COO-, -OCO- or -OCOO- may be substituted,
L ¹ represents —CH═CH—COO— or —C ₂ H ₄ COO—,
L ² and L ³ are each independently a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —CO—, —COO—, —OCO. ^{_{-, - OCOOCH 2 -, -}} CH 2 OCOO -, - CO-NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - CH = CH -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO-, _{-OCOCH 2 -, - CH 2 COO} -, - CH = CH -, - CF = CH -, - CH = CF -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ — or —C≡C— (wherein R ^{1 1} represents an alkyl group having 1 to 4 carbon atoms).
M ¹ is 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2, 6-diyl group, pyrazine-2,5-diyl and 1,3-dioxane-2,5-diyl group, and M ¹ is unsubstituted or substituted by a substituent. Examples of the substituent in which a hydrogen atom in the group of M ¹ is substituted include an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, and 1 to 8 carbon atoms. An alkoxy group, a halogenated alkoxy group having 1 to 8 carbon atoms, a halogen atom, a cyano group or a nitro group,
R ¹ represents the following formula (R-I) to formula (R-IX)

In the formulas (RI) to (R-IX), R ^{2 to} R ⁶ are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. 1 to 5 halogenated alkyl groups, W is a single bond, —O— or a methylene group, p, t and q are each independently 0, 1 or 2,
Z is 1,2-phenylene group, 1,3-phenylene group, 1,2-cyclohexylene group, naphthalene-2,3-diyl group, naphthalene-1,2-diyl group, naphthalene-1,8-diyl group 1,2,4,5-benzenetetrayl group, 1,4,5,8-naphthalenetetrayl group, single bond, or the following formula (i) or formula (ii):

Z may be unsubstituted or substituted by a substituent, and examples of the substituent in which a hydrogen atom in the group of Z is substituted include an alkyl group, a halogenated alkyl group, an alkoxy group, an ester group (—COO -R ^Z R ^z: C 1 -C 10 alkyl group), a halogen atom, a cyano group or a nitro group,
m represents 0, 1 or 2, and n represents 2 or 4. When m represents 2, two M ¹ and L ² may be the same or different, and when n represents 2 and 4, two or four R ¹ and M ¹ are present. , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , L ¹ , L ² , L ³ , S ¹ , S ² , and m are the same or different. May be. A polymerizable compound represented by In the general formula (I), L ² and L ³ are independently of each other —O—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —C ₂ H ₄ —, — C≡C— or a single bond,
M ¹ represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a naphthalene-2,6-diyl group, or a tetrahydronaphthalene-2,6-diyl group, and M ¹ has 1 to 8 carbon atoms. An alkyl group, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkoxy group having 1 to 8 carbon atoms, a halogen atom, a cyano group, or a nitro group. It ’s okay,
Z is unsubstituted or substituted by an alkyl group, halogenated alkyl group, alkoxy group, halogenated alkoxy group, halogen, or cyano group, 1,2-phenylene group, 1,2-cyclohexylene group, naphthalene- 2,3-diyl group, 1,2,4,5-benzenetetrayl group, 1,4,5,8-naphthalenetetrayl group,
The polymerizable compound according to claim 1, wherein m represents 0 or 1.   The polymerizable compound according to claim 1, wherein m represents 0 in the general formula (I). In the general formula (I), S ² is a single bond or an alkylene group having 1 to 6 carbon atoms,
L ³ is a single bond, or —O—, —COO—, —OCO—,
Z is unsubstituted or substituted by an alkyl group, halogenated alkyl group, alkoxy group, halogenated alkoxy group, halogen, or cyano group, or a 1,2-phenylene group, naphthalene-2,3-diyl group, or The polymerizable compound according to any one of claims 1 to 3, which represents a 1,2,4,5-benzenetetrayl group and m represents 0. The polymerizable compound according to claim 1, wherein, in the general formula (I), R ¹ independently represents the formula (RI). The polymerizable compound according to claim ¹ , wherein, in the general formula (I), S ¹ represents a single bond and m = 0.   A liquid crystal composition containing the polymerizable compound according to claim 1.   The composition for optical anisotropic bodies containing the polymeric compound and solvent in any one of Claim 1 to 6.   An optical anisotropic body composed of a polymer of a liquid crystal composition containing the polymerizable compound according to claim 7.   A liquid crystal display element using the optical anisotropic body according to claim 8.   A polymer-stabilized liquid crystal display device comprising the liquid crystal composition according to claim 7.