JP2013166780A - Polymerizable liquid crystal compound, polymerizable liquid crystal composition containing the compound, and polymer of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal compound, which exhibits a liquid crystal phase at a low temperature and hardly crystalizes and has a viscosity that is not extremely high, excellent transparency after polymerization and high mechanical strength, and to provide a polymerizable liquid crystal composition containing the compound, and a polymer of the compound or the composition.SOLUTION: A polymerizable liquid crystal compound includes: at least two polymerizable functional groups in the molecule; 2 to 10 rings which are the same or different from one another and selected from the group consisting of non-polymerizable aromatic rings, aliphatic ring, hetero rings or condensed rings; and at least one of -CHCHCOO- and -CHCHOCO- as a group connecting two rings. A polymerizable liquid crystal composition includes the above polymerizable liquid crystal compound, and a polymer of the above compound or composition is also provided.

Description

  The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the compound, and the polymerizable compound or a polymer of the polymerizable liquid crystal composition.

After aligning a liquid crystal compound having a polymerizable functional group (hereinafter, polymerizable liquid crystal compound) or a polymerizable liquid crystal composition containing at least one such compound in a liquid crystal state, activity such as ultraviolet rays is performed in that state. When irradiated with energy rays, a polymer in which the alignment state structure of liquid crystal molecules is fixed can be produced. The polymer thus obtained has anisotropy of physical properties such as refractive index, dielectric constant, magnetic susceptibility, elastic modulus, and thermal expansion coefficient. It can be applied as a coating agent such as a plate, a polarizing prism, a waveguide, a piezoelectric element, a nonlinear optical element, various optical filters, a pigment using selective reflection of a cholesteric liquid crystal phase, and an optical fiber.
JP-A-8-3111 discloses a polymerizable liquid crystal composition for the above application. Although the polymerizable liquid crystal composition disclosed in the publication has a characteristic of exhibiting liquid crystallinity at room temperature, it has a drawback of insufficient transparency and mechanical strength after polymerization. German published patents DE 4408171 and DE 4226994 disclose polyfunctional polymerizable liquid crystal compounds and polymerizable liquid crystal compositions having two polymerizable functional groups. Since these compounds have a high temperature at which a liquid crystal phase is exhibited, there are disadvantages that many kinds of liquid crystal compounds need to be used to lower the transition point and crystals tend to precipitate at room temperature. PCT International Publication WO 98/23580 and JP-A-10-310612 disclose polymerizable liquid crystal compounds having a plurality of liquid crystal skeletons (mesogens) in one molecule. Such a material has a very high viscosity, and when alignment defects such as disclination occur in the alignment process, it takes a long time to disappear, and there is a problem that productivity deteriorates.

JP-A-8-3111 German Patent Application Publication No. 4408171 German Patent Application No. 4226994 International Publication WO 98/23580 JP-A-10-310612

  The problem in the present invention is that a polymerizable liquid crystal compound having a low temperature showing a liquid crystal phase, hardly crystallizing, having a very low viscosity, excellent in transparency after polymerization, and having high mechanical strength, the compound It is in providing the polymerizable composition to contain and these polymers.

  The present invention focuses on the chemical structure of the polymerizable liquid crystal compound in order to solve the above problems, and as a result, has found that a compound having a specific partial chemical structure is useful. A polymerizable liquid crystal composition containing a compound and these polymers were found.

Invention 1, having two or more polymerizable functional groups in one molecule and 2-10 identical or different rings selected from the group consisting of non-polymerizable aromatic ring, alicyclic ring, heterocyclic ring and condensed ring And a polymerizable liquid crystal compound having at least one of —CH ₂ CH ₂ COO— or —CH ₂ CH ₂ OCO— as a group linking two rings.

  Invention 2, General formula (I)

(Wherein P ¹ and P ² represent a polymerizable functional group, S ¹ and S ² represent a divalent spacer group, X ¹ , X ² and L ¹ each independently represent a linking group; ¹ is a linking group selected from —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, and A ¹ and A ² are The polymerizable liquid crystal compound according to invention 1, characterized by being independently represented by an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, wherein n represents an integer of 1 to 9.

In Invention 3, in Formula (I), X ¹ and X ² each independently represent a single bond, —O—, —S—, —CO—, —COO—, —OCO—, and at least one of L ¹ One is _{-CH 2 CH 2 COO -, -} CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - represents, independently a single bond otherwise, _-CH 2 -, - O _{-, - S -, - CO} -, - OCOO -, - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - C≡C -, - CH = CH _{-, - CF = CF -,} - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH _{2 represents} —CH═CH—, —CH═CH—COO—, —OCO—CH═CH—, and S ¹ and And S ² may be a non-adjacent carbon atom may be substituted with an oxygen atom, and a hydrogen atom may be substituted with an oxygen atom, a halogen atom or a cyano group, or an alkylene group having 2 to 18 carbon atoms, or silicon. The polymerizable liquid crystal compound according to invention 2, which represents a siloxane group having 2 to 18 atoms.

  Invention 4, General formula (II)

Wherein W ¹ and W ² each independently represent a single bond, —O—, —COO—, —OCO—, and Y ¹ and Y ² each independently represent —COO—, —OCO—. , P and q each independently represents an integer of 2 to 18, and the 1,4-phenylene group is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. The polymerizable liquid crystal compound according to any one of Inventions 1 to 3, which may be substituted).

  Invention 5, General formula (III)

(Wherein, ^{P 1} represents a polymerizable functional group, ^{S 1} and ^{S 2} represents a divalent spacer ^group, X ^1, X 2, ^{L 1} each independently represents a linked group, among the ^{L 1} at least one _{-CH 2 CH 2 COO -, -} CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - is from linking group selected, ^{R 1} represents a hydrogen atom or ^{P 1,} And A ¹ and A ² independently represent an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, n represents an integer of 2 to 9, and m represents an integer of 0 to 2. The polymerizable liquid crystal compound according to invention 1, which is represented by:

In Invention 6, General Formula (III), X ¹ and X ² each independently represent a single bond, —O—, —S—, —CO—, —COO—, —OCO—, and at least ^one of L ¹ one is _{-CH 2 CH 2 COO -, -} CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - represents, independently a single bond otherwise, _-CH 2 -, - O—, —S—, —CO—, —OCOO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═ CH—, —CF═CF—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ CH ₂ CH ₂ —, —CH═CH—CH ₂ CH ₂ —, —CH _{2 CH 2 -CH = CH -, -} CH = CH-COO -, - represents OCO-CH = CH-, ¹ and S ² may be substituted carbon atoms that are not adjacent is an oxygen atom, also a hydrogen atom is an oxygen atom, a halogen atom, an alkylene group having 2 to 18 carbon atoms which may be substituted with a cyano group or, 6. The polymerizable liquid crystal compound according to invention 5, wherein the polymerizable liquid crystal compound represents a siloxane group having 2 to 18 silicon atoms.

A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of invention 7 and inventions 1 to 6.
Invention 8, General formula (IV)

(Wherein X ⁷ represents a hydrogen atom or a methyl group, r represents an integer of 0 or 1, 6-membered rings A, B and C are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenyl group, and these 6-membered rings A, B, and C are further substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups, or halogen atoms having 1 to 7 carbon atoms. Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, — CH = CH -, - CF = CF -, - (CH 2) 4 -, - _{H 2 CH 2 CH 2 O -} , - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - CH = CH-COO -, - OCO —CH═CH—, Y ⁵ represents a single bond, —O—, —OCO—, —COO—, —CH═CH—COO—, and Z ¹ represents a hydrogen atom, a halogen atom, a cyano group, or a carbon atom. 8. A polymerizable liquid crystal composition according to invention 7, comprising a polymerizable liquid crystal compound represented by 1 to 20 hydrocarbon groups).

  Invention 9, General formula (VII)

(In the formula, X ⁸ represents a hydrogen atom or a methyl group, s represents an integer of 2 to 18, t represents an integer of 0 or 1, and the 6-membered rings D, E, and F are each independently 1 , 4-phenylene group, 1,4-phenylene group, 1,4-cyclohexylene group, non-adjacent CH group substituted with nitrogen, or one or two non-adjacent CH ₂ groups substituted with oxygen or sulfur atoms Represents a 1,4-cyclohexylene group or a 1,4-cyclohexenyl group, and these 6-membered rings D, E, and F are further an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group. , One or more halogen atoms may be substituted, and Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, — OCO-, -C≡C-, -CH = CH-, -CF = CF _{, - (CH 2) 4 -} , - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH-, —CH═CH—COO—, —OCO—CH═CH—, Y ⁸ represents a single bond, —O—, —OCO—, —COO—, —CH═CH—COO—, and Z ² represents hydrogen. 9. A polymerizable liquid crystal composition according to invention 7 or 8, comprising a polymerizable liquid crystal compound represented by an atom, a halogen atom, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms.

Invention 10. The polymerizable liquid crystal composition according to any one of Inventions 7 to 9, wherein the liquid crystal lower limit temperature is 40 ° C. or lower.
A polymer of the polymerizable liquid crystal compound according to any one of Invention 11, Invention 1 to 6, or the polymerizable liquid crystal composition according to any one of Inventions 7 to 10.

The polymerizable compound of the present invention is characterized by having at least one —CH ₂ CH ₂ COO— or —CH ₂ CH ₂ OCO— as a group linking two rings. By introducing this linking group, it was found that the lower limit temperature of the liquid crystal can be effectively reduced without greatly detracting from the liquid crystal temperature range of the compound, and the present invention has been provided.

  The polymerizable liquid crystal compound of the present invention has a low liquid crystal lower limit temperature of about 60 ° C. In addition, the polymerizable liquid crystal composition of the present invention exhibits liquid crystallinity at room temperature and is difficult to precipitate crystals. Moreover, the polymer film obtained after superposition | polymerization gives the polymer excellent in transparency and mechanical characteristics. In this respect, the polymerizable liquid crystal composition of the present invention facilitates the production of a retardation film, an optical low-pass filter, and the like, and is extremely useful.

Hereinafter, examples of embodiments of the present invention will be described. Examples of the polymerizable functional group that can be used in the polymerizable liquid crystal compound of the present invention include acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, epoxy group, vinyl group, vinyloxy group, ethynyl group, mercapto group, maleimide group, _{ClCH = CHCONH-, CH 2 = CCl-} , CHCl = CH-, RCH = CHCOO- (R is chlorine, fluorine or a hydrocarbon group having 1 to 10 carbon atoms) can be mentioned. Among these, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a mercapto group, and a vinyloxy group are preferable, and an acryloyloxy group is particularly preferable. The aromatic ring, alicyclic ring, heterocyclic ring and condensed ring that can be used in the polymerizable liquid crystal compound of the present invention include benzene, pyridine, pyrazine, pyridazine, pyrimidine, 1,2,4-triazine, 1,3,5-triazine. , Tetrazine, dihydrooxazine, cyclohexane, cyclohexene, cyclohexadiene, cyclohexanone, piperidine, piperazine, tetrahydropyran, dioxane, tetrahydrothiopyran, dithiane, oxathiane, dioxaborinane, naphthalene, dioxanaphthalene, tetrahydronaphthalene, quinoline, coumarin, quinoxaline, decaline Hydronaphthalene, indane, benzoxazole, benzothiazole, phenanthrene, dihydrophenanthrene, perhydrophenanthrene, dioxaperhydrophenanthrene, Luolene, fluorenone, cycloheptane, cycloheptatrienone, cholesten, bicyclo [2.2.2] octane and bicyclo [2.2.2] octene, 1,5-dioxaspiro (5.5) undecane, 1,5- Dithiaspiro (5.5) undecane, triphenylene, torquesen, porphyrin, phthalocyanine can be used. Among these, benzene, cyclohexane, phenanthrene, naphthalene, tetrahydronaphthalene, and decahydronaphthalene are preferable. One or more of these rings may be substituted with an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are desirable, and a methyl group and an ethyl group are particularly preferable. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable. As an alkanoyl group, an acetyl group, a propionyl group, and a butyroyl group are preferable. As a halogen atom, a fluorine atom, a bromine atom, and a chlorine atom are preferable. A fluorine atom and a chlorine atom are particularly preferable. The number of rings is preferably 2 to 10, and more preferably 3 to 6. The selected 2 to 6 rings are bonded by a covalent bond such as a single bond or an ester bond, and at least one of the bonds between the rings is —CH ₂ CH ₂ COO— or —CH _2. there needs to be a CH ₂ OCO-. The shape of the whole molecule is a rod-like, banana-like (bent molecule), or disc-like shape as is known in the technical field of liquid crystal so that it shows liquid crystallinity as a molecule or shows good compatibility with liquid crystal materials. Preferably there is.

The rod-like or banana-like molecule has the general formula (I)

The molecule | numerator represented by is preferable. Here, P ¹ and P ² are preferably independently selected from the examples described above as polymerizable functional groups that can be used in the polymerizable liquid crystal compound of the present invention. A ¹ and A ² are preferably independently selected from the examples described above as a group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring that can be used in the polymerizable liquid crystal compound of the present invention. X ¹ and X ² are preferably each independently selected from a single bond, —O—, —S—, —CO—, —COO—, and —OCO—. At least one of L ¹ is a linking group selected from —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, and —OCOCH ₂ CH ₂ —. The groups are independently a single bond, —CH ₂ —, —O—, —S—, —CO—, —OCOO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO. -, - OCO -, - C≡C -, - CH = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 - , —CH═CH—CH ₂ CH ₂ —, —CH ₂ CH ₂ —CH═CH—, —CH═CH—COO—, —OCO—CH═CH—, preferably a single bond, —CH ₂ CH _{2 -, - CH 2 O -,} - OCH 2 -, - COO -, - OCO _{-, - C≡C -, - CH} = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = It is more preferable to select from CH—CH ₂ CH ₂ —, —CH ₂ CH ₂ —CH═CH—, —CH═CH—COO—, —OCO—CH═CH—. S ¹ and S ^{2 each} represent a divalent spacer group, preferably have flexibility, non-adjacent carbon atoms may be substituted with oxygen atoms, and hydrogen atoms are oxygen atoms, halogen atoms, or cyano groups. It is preferable to select from an optionally substituted alkylene group having 2 to 18 carbon atoms or a siloxane group having 2 to 18 silicon atoms. These divalent spacer groups may be linear or branched, and may have an asymmetric atom. n is an integer of 1 to 9, and is preferably an integer of 2 to 5. When n is an integer of 1 to 2, ^one of L ¹ is selected from —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, and —OCOCH ₂ CH ₂ —. When n is an integer of 3 to 5, 1-2 of L ¹ are —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ -, -OCOCH ₂ CH _2- is preferred, and when n is 6-9, 2-4 of L ¹ are -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO- , —COOCH ₂ CH ₂ — and —OCOCH ₂ CH ₂ — are preferred.

General formula (I) in the rod-shaped or banana-shaped molecule represented by _{^{- (A 1 -L 1) n}} -A 2 - As the skeleton include the following, using the polymerizable liquid crystal compound of the present invention The skeleton that can be formed is not limited to these.

^{(Wherein, L 2, L 3, L} 4, L 5 _{is, -CH 2 CH 2 COO -,} - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, a single bond, _{-CH 2 -, - O -,} - S -, - CO -, - OCOO -, - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - C≡ C—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ CH ₂ CH ₂ —, —CH═CH—CH ₂ CH _2- , —CH ₂ CH ₂ —CH═CH—, —CH═CH—COO—, —OCO—CH═CH—, wherein the 1,4-phenylene group is an alkyl group having 1 to 7 carbon atoms, One or more of them may be substituted with an alkoxy group, an alkanoyl group, a cyano group or a halogen atom. One or more carbon atoms in the 1,4-phenylene group may be substituted with a nitrogen atom, and the entire 1,4-phenylene group may be replaced with a 1,4-cyclohexyl group or a naphthalene-2,6-diyl group. , Decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl may be substituted, and these rings are alkyl groups having 1 to 7 carbon atoms, alkoxy groups , An alkanoyl group, or a cyano group, may be substituted with one or more halogen atoms, and a carbon atom in the ring may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom)

Examples of the divalent spacer group of S ¹ and S ² include the following, but the spacer group that can be used in the polymerizable liquid crystal compound of the present invention is not limited thereto.

 (In the formula, m1 represents an integer of 2 to 18, m2 represents an integer of 1 to 6, m3 represents an integer of 1 to 3, and m4 represents an integer of 1 to 9)

  Of the rod-like or banana-like molecules represented by the above general formula (I), rod-like molecules are more preferable. As such a rod-like molecule, a compound represented by the general formula (II) is particularly preferable.

Wherein W ¹ and W ² each independently represent a single bond, —O—, —COO—, —OCO—, and Y ¹ and Y ² each independently represent —COO—, —OCO—. , P and q each independently represents an integer of 2 to 18, and the 1,4-phenylene group is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. (May be replaced)
The compound represented by the general formula (II) is preferable because the minimum liquid crystal lower temperature tends to be particularly low. p and q are each independently preferably an integer of 3 to 8, particularly preferably an integer of 3 to 6. Specific examples of the compound represented by the general formula (II) are listed below, but the polymerizable liquid crystal compound of the present invention is not limited to these.

(Wherein p and q each independently represents an integer of 2 to 18)

In addition, the disk-shaped molecule includes the general formula (III)

The molecule | numerator represented by is preferable. Here, P ¹ is preferably independently selected from the examples described above as polymerizable functional groups that can be used in the polymerizable liquid crystal compound of the present invention. A ¹ and A ² are preferably independently selected from the examples described above as a group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring that can be used in the polymerizable liquid crystal compound of the present invention. At least one of L ¹ is a linking group selected from —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, and —OCOCH ₂ CH ₂ —. The groups are independently a single bond, —CH ₂ —, —O—, —S—, —CO—, —OCOO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO. -, - OCO -, - C≡C -, - CH = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 - , —CH═CH—CH ₂ CH ₂ —, —CH ₂ CH ₂ —CH═CH—, —CH═CH—COO—, —OCO—CH═CH— are preferably selected. X ¹ and X ² are preferably each independently selected from a single bond, —O—, —S—, —CO—, —COO—, and —OCO—. S ¹ and S ^{2 each} represent a divalent spacer group, preferably have flexibility, a carbon atom that is not adjacent may be substituted with an oxygen atom, and a hydrogen atom is an oxygen atom, a halogen atom, or a cyano group It is preferably selected from an alkylene group having 2 to 18 carbon atoms which may be substituted with or a siloxane group having 2 to 18 silicon atoms. These divalent spacer groups may be linear or branched, and may have an asymmetric atom. n is an integer of 2 to 9, and m represents an integer of 0 to 2. R ¹ represents a hydrogen atom or the same meaning as P ¹ .

In the discotic molecule represented by the general formula (III), examples of the skeleton excluding -S ¹ -P ¹ and -S ² -R ¹ include the following, but the polymerizable liquid crystal compound of the present invention The skeleton which can be used in is not limited to these.

  Next, the polymerizable liquid crystal composition of the present invention will be described. The polymerizable liquid crystal composition of the present invention preferably contains at least 30% by mass of the polymerizable liquid crystal compound of the present invention, more preferably 50% by mass or more, and particularly preferably 70% by mass or more. preferable. The polymerizable liquid crystal composition of the present invention particularly preferably contains two or more polymerizable liquid crystal compounds of the present invention.

In addition to the polymerizable liquid crystal compound of the present invention, the polymerizable liquid crystal composition of the present invention can contain a known polymerizable liquid crystal compound. In this case, any compound can be used without particular limitation as long as it is a compound having a skeleton that is generally recognized as a liquid crystal skeleton in this technical field and a polymerizable functional group in the molecule. However, it is particularly preferable that the liquid crystal skeleton has at least two or three six-membered rings. Examples of the polymerizable functional group include acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, epoxy group, vinyl group, vinyloxy group, ethynyl group, mercapto group, maleimide group, ClCH═CHCONH—, CH ₂ ═CCl—. , CHCl═CH—, RCH═CHCOO— (wherein R represents chlorine, fluorine, or a hydrocarbon group having 1 to 10 carbon atoms), acryloyloxy group, methacryloyloxy group, vinyloxy group, mercapto group More preferred is an acryloyloxy group. In the case of a compound having a plurality of polymerizable functional groups in one molecule, the types of polymerizable functional groups may be different. For example, in the case of a compound having two polymerizable functional groups, one may be an acryloyloxy group and the other may be a vinyloxy group. As the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in one molecule, the general formula (IV)

(Wherein X ⁷ represents a hydrogen atom or a methyl group, r represents an integer of 0 or 1, 6-membered rings A, B and C are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH2 groups are substituted with oxygen or sulfur atoms, 1,4 -Represents a cyclohexenyl group, and these 6-membered rings A, B, and C are further substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups, or halogen atoms having 1 to 7 carbon atoms. Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH. = CH -, - CF = CF -, - (CH 2) 4 -, - _{H 2 CH 2 CH 2 O -} , - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - CH = CH-COO -, - OCO -CH = CH-, Y5 represents a single bond, -O-, -OCO-, -COO-, -CH = CH-COO-, Z1 represents a hydrogen atom, a halogen atom, a cyano group, a carbon atom 1 to It preferably contains a liquid crystalline (meth) acrylate represented by 20).

  Among the monofunctional polymerizable liquid crystal compounds represented by the general formula (IV), the general formula (V)

(式中、Ｘ^７は水素原子又はメチル基を表し、Ｒ^２は炭素原子数１〜１０のアルキル基を表す)で表される化合物や、一般式（ＶＩ)

(Wherein X ⁷ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms), or a compound represented by the general formula (VI)

(式中、Ｘ^７は水素原子又はメチル基を表し、Ｒ^２は炭素原子数１〜１０のアルキル基を表す)で表されるものが好ましい。これら一般式（Ｖ）と一般式（ＶＩ)の化合物は、単独で用いても良いし、組み合わせて用いても良い。組み合わせて用いる場合、一般式（Ｖ）と一般式（ＶＩ)の化合物の濃度を等しくするのが好ましい。

(In the formula, X ⁷ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms). These compounds of general formula (V) and general formula (VI) may be used alone or in combination. When used in combination, it is preferable to make the concentrations of the compounds of general formula (V) and general formula (VI) equal.

  As specific examples of the compound represented by the general formula (IV), the structures and phase transition temperatures of the compounds of the formulas (a-1) to (a-25) are shown below. However, compounds that can be used in the liquid crystal composition of the present invention are not limited thereto. (Wherein the cyclohexane ring represents a transcyclohexane ring, the number represents a phase transition temperature, C represents a crystalline phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase)

  In addition to the monofunctional polymerizable liquid crystal compound represented by the general formula (IV), the liquid crystal composition of the present invention may contain another monofunctional polymerizable liquid crystal compound. As specific examples of such compounds, the structures and phase transition temperatures of the compounds of formulas (a-26) to (a-35) are shown below. However, compounds that can be used in the liquid crystal composition of the present invention are not limited thereto. (Wherein the cyclohexane ring represents a transcyclohexane ring, the number represents a phase transition temperature, C represents a crystalline phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase)

  Furthermore, the general formula (VII)

(In the formula, X ⁸ represents a hydrogen atom or a methyl group, s represents an integer of 2 to 18, t represents an integer of 0 or 1, and the 6-membered rings D, E, and F are each independently 1 , 4-phenylene group, 1,4-phenylene group, non-adjacent CH group substituted with nitrogen, 1,4-cyclohexylene group, one or two non-adjacent CH ₂ groups substituted with oxygen or sulfur atoms Represents a 1,4-cyclohexylene group or a 1,4-cyclohexenyl group, and these 6-membered rings D, E, and F are further an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group. , One or more halogen atoms may be substituted, and Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, — OCO-, -C≡C-, -CH = CH-, -CF = CF- _{- (CH 2) 4 -,} - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - CH = CH—COO—, —OCO—CH═CH—, Y ⁸ represents a single bond, —O—, —OCO—, —COO—, —CH═CH—COO—, and Z ² represents a hydrogen atom. And a monofunctional polymerizable liquid crystal compound represented by a halogen atom, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms. In such a compound, s is preferably an integer of 2 to 12, more preferably an integer of 2 to 8, and particularly preferably an integer of 2 to 6. As specific examples of the compound represented by the general formula (VII), structures of the compounds of the formulas (a-36) to (a-50) are shown below. However, compounds that can be used in the liquid crystal composition of the present invention are not limited thereto.

(In the formula, s and X ⁸ represent the same meaning as in general formula (VII), and R ³ represents a hydrocarbon group having 1 to 20 carbon atoms.)
Examples of the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in one molecule include compounds of formula (a-51) to formula (a-60). However, compounds that can be used in the liquid crystal composition of the present invention are not limited thereto.

(Wherein, X ⁹ and X ¹⁰ each independently represent a hydrogen atom or a methyl group, and u and v each independently represent an integer of 2 to 18)
Moreover, you may contain the bifunctional polymerizable liquid crystal compound which has a 2 or more liquid crystal frame | skeleton in a molecule | numerator like Formula (a-61) currently disclosed by Unexamined-Japanese-Patent No. 10-310612.

(Wherein w represents an integer of 2 to 18)

  Moreover, you may contain the trifunctional polymerizable liquid crystal compound like Formula (a-62) currently disclosed by USP5593617.

(式中、ｍは４〜１１の整数を表す)
また、ＵＳＰ５５６７３４９に開示されている式（ａ−６３)のような４官能重合性液晶化合物を含有しても良い。

(In the formula, m represents an integer of 4 to 11)
Moreover, you may contain the tetrafunctional polymerizable liquid crystal compound like Formula (a-63) currently disclosed by USP5567349.

(式中、ｗは４〜１２の整数を、ｗ'は２〜１２の整数を表す)

(Wherein, w represents an integer of 4 to 12, and w ′ represents an integer of 2 to 12)

  The polymerizable liquid crystal composition of the present invention may contain a liquid crystal compound having no polymerizability. Examples of liquid crystal compounds having no polymerizability include general formulas (VIII) and (IX)

(Wherein R ⁴ , R ⁵ and R ⁶ are each independently an optionally substituted fluorine-substituted alkyl group or alkoxy group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, or the number of carbon atoms. Represents an alkyl group having 1 to 12 carbon atoms substituted with an alkenyloxy group having 3 to 16 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein ring G, ring H, ring I, ring J and ring K are each 1,4-phenylene group, 2-methyl-1,4-phenylene group, 3-methyl-1,4-phenylene group, naphthalene-2,6-diyl group, which may be independently substituted with a fluorine atom, Phenanthrene-2,7-diyl group, fluorene-2,7-diyl group, trans-1,4-cyclohexylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene − , 6-diyl group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group or pyridazine- 2,5-diyl group, j and k each independently represent 0, 1 or 2, Y ⁹ , Y ¹⁰ , Y ¹¹ and Y ¹² each independently represent a single bond, —CH ₂ CH ₂ — , — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH— or —C≡C—, wherein Z ⁴ is a cyano group, a fluorine atom , A chlorine atom, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, a hydrogen atom, a 3,3,3-trifluoroethoxy group, R ⁴ or —OR ⁴ , wherein R ⁴ has 1 to 12 carbon atoms. Or an alkyl group of 2 to 12 Represents an alkenyl group, Z ^3, Z ⁵ may be mentioned a hydrogen atom, a fluorine atom or a chlorine atom). When such a non-polymerizable liquid crystal compound is contained, it is preferable to contain one or more compounds selected from general formula (VIII) and general formula (IX). R ⁴ , R ⁵ , and R ⁶ are each independently a fluorine-substituted alkyl group or alkoxy group having 2 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 3 to 8 carbon atoms. An alkenyloxy group or an alkyl group having 2 to 8 carbon atoms substituted with an alkoxy group having 1 to 5 carbon atoms is preferred, and ring G, ring H, ring I, ring J and ring K are each independently fluorine. 1,4-phenylene group, trans-1,4-cyclohexylene group and pyrimidine-2,5-diyl group which may be substituted by an atom are preferable, and Y ⁹ , Y ¹⁰ , Y ¹¹ and Y ¹² are respectively Independently, a single bond, —COO—, —OCO—, —CH═CH— or —C≡C— is preferable, and a single bond, —COO— or —OCO— is more preferable. Moreover, it is preferable that two of Z ³ , Z ⁴ , and Z ⁵ are fluorine atoms, the other one is a hydrogen atom, and Z ⁴ is a cyano group. In the polymerizable liquid crystal composition of the present invention, the component composed of the non-polymerizable liquid crystal compound is preferably designed so that the component itself exhibits a nematic liquid crystallinity or a chiral smectic C phase. In the case of designing to exhibit a chiral smectic C phase, it is preferable to design to contain a pyrimidine as a ring structure and a compound having an ester structure as a linking group.

  When the polymerizable liquid crystal composition of the present invention is used as a passive element, that is, an element whose characteristics do not change even when an electric field or a magnetic field is applied, for example, as a material for a retardation film or an optical low-pass filter, it has polymerizability. 0-30 mass% is preferable, as for content of the liquid crystalline compound which has not been performed, 0-20 mass% is more preferable, and 0-10 mass% is especially preferable. When the polymerizable liquid crystal composition of the present invention is used as an active element, that is, an element that changes its characteristics by application of an electric field or a magnetic field and functions as an optical switch, for example, as a material for a polymer stabilizing element. Is preferably 5 to 99 mass%, more preferably 40 to 98 mass%, and particularly preferably 80 to 98 mass%. There is no particular limitation on the liquid crystalline compound having no polymerizability that can be added, and any compound recognized as a liquid crystalline compound in this technical field can be used. Since a liquid crystalline compound having a halogen atom such as an atom can be easily controlled in orientation by application of an electric field, it is preferable to use such a compound. In particular, when a polymerizable liquid crystal composition is designed so as to have only a halogen atom such as a fluorine atom as a polar group, a liquid crystal composition exhibiting a high retention rate suitable for driving by an active element such as a TFT (thin film transistor) or TFD (thin film diode). This is particularly preferable because a product can be obtained.

Furthermore, the polymerizable liquid crystal composition of the present invention may be added with a compound having a polymerizable functional group and not exhibiting liquid crystallinity. 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 of the present invention preferably exhibits a liquid crystal phase at room temperature, typically 25 ° C., when applied to the production of an optical element.

  The liquid crystal composition of the present invention may be any composition that exhibits a phase that is generally recognized as a liquid crystal phase in this technical field. Among such compositions, those exhibiting a nematic phase, a smectic A phase, a (chiral) smectic C phase, a cholesteric phase, and a discotic phase are preferable as the liquid crystal phase. Among these, the nematic phase is particularly preferable because it has good orientation. When a (chiral) smectic C phase is indicated, the smectic A phase is higher than the temperature range of the (chiral) smectic C phase, and the nematic phase is higher than the temperature range of the smectic A phase. Each of the liquid crystal compositions that are expressed is preferable because it tends to obtain good alignment.

  The minimum liquid crystal temperature of the polymerizable liquid crystal composition of the present invention is desirably 40 ° C. or lower. The lower the liquid crystal lower limit temperature, the lower the temperature, the lower the temperature, and the lower the temperature, the more the alignment can be fixed by irradiation with active energy rays such as ultraviolet rays. From this, the liquid crystal lower limit temperature is more preferably 30 ° C. or less, and particularly preferably 25 ° C. or less.

  The clearing point of the polymerizable liquid crystal composition of the present invention is preferably adjusted to 90 ° C. or less, more preferably 80 ° C. or less, still more preferably 60 ° C. or less, particularly preferably 55 ° C. or less, and very preferably 50 ° C. or less. preferable. In this way, even when the liquid crystal composition of the present invention needs to be in an isotropic liquid phase in the injection step or the like, it is not necessary to raise the temperature to over 90 ° C., resulting in undesirable thermal polymerization. Induction can be avoided.

  A photopolymerization initiator can be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the polymerization reactivity. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. The addition amount is preferably 0.01 to 5% by mass, more preferably 0.02 to 1% by mass, and particularly preferably 0.03 to 1% by mass with respect to the liquid crystal composition. In addition, a stabilizer can be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, and nitroso compounds. . 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.

  A chiral compound can be added to the polymerizable liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton inside. The chiral compound used for such a purpose does not need to exhibit liquid crystal properties per se, and may or may not have a polymerizable functional group. Moreover, the direction of the spiral can be appropriately selected depending on the intended use of the polymer. As such a chiral compound, for example, “CB-” manufactured by BD H. Co. (BDH; UK) having cholesteryl group as a chiral group, cholesterol stearate, and 2-methylbutyl group as a chiral group. 15 ”,“ C-15 ”,“ S-1082 ”manufactured by Merck (Germany),“ CM-19 ”,“ CM-20 ”,“ CM ”manufactured by Chisso; 1-methylheptyl as a chiral group Examples thereof include “S-811” manufactured by Merck Co., which has a group, “CM-21” manufactured by Chisso Corporation, “CM-22”, and the like. A preferable addition amount in the case of adding a chiral compound depends on the use of the liquid crystal composition, but is a value obtained by dividing the thickness (d) of the polymer obtained by polymerization by the helical pitch (P) in the polymer (d / P) is preferably in an amount ranging from 0.1 to 100, and more preferably in an amount ranging from 0.1 to 20.

  In addition, when the polymerizable liquid crystal composition of the present invention is used for a raw material of a polarizing film or an alignment film, a printing ink, a paint, a protective film or the like, a metal, a metal complex, a dye, or a pigment depending on the purpose. , Dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc. Can also be added.

Next, the polymer of the present invention will be described. The polymer produced by polymerizing the polymerizable liquid crystal compound or polymerizable liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal compound or polymerizable 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. In addition, the polymer produced by polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention is useful because it has anisotropy in physical properties. Such a polymer is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal compound or polymerizable 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, Alternatively, 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 deposited or sandwiched between the substrates.

  Methods for supporting a polymerizable liquid crystal compound or polymerizable liquid crystal composition on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, printing method, etc. Can be mentioned. Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, and cellosolves. 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 polymer obtained by polymerizing the polymerizable liquid crystal material and the substrate are not good in adhesion.

  Examples of a method for sandwiching the polymerizable liquid crystal compound or the polymerizable liquid crystal composition between the substrates include an injection method using a capillary phenomenon. It is also effective to depressurize the space formed between the substrates and then inject a polymerizable 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, the patterning of the alignment can be easily achieved, so that the molecular orientation inside the polymer can be precisely controlled.

  As a 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. In addition, the polyimide thin film that gives a pretilt angle used in a normal twisted nematic (TN) element or a super twisted nematic (STN) element can control the molecular orientation structure inside the polymer more precisely. Are particularly preferred. 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 the alignment state of the polymerizable liquid crystal compound or the polymerizable liquid crystal composition, various alignment states generally known in the technical field of liquid crystal can be adopted. Examples of orientation states include homogeneous (horizontal) orientation, tilted homogeneous orientation, homeotropic (vertical) orientation, tilted homeotropic orientation, hybrid orientation, twisted nematic orientation, and super twisted nematic orientation. . Moreover, you may pattern by changing the orientation state for the combination of these orientations or every place. In the case of tilted homogeneous alignment and tilted homeotropic alignment, it means that the angle between the substrate surface and the major axis of the liquid crystal molecule is other than 0 degree or 90 degrees in both cases. The angle formed between the substrate surface and the major axis of the liquid crystal molecules may be selected depending on the application and function of the polymer to be produced. When the angle formed between the substrate surface and the major axis of the liquid crystal molecule is set in the range of 10 to 80 degrees, more preferably in the range of 20 to 70 degrees, the produced polymer is an optical for improving the viewing angle of the liquid crystal display widely. It can be used as a member. Further, even when the alignment state of the liquid crystal composition is hybrid alignment, the produced polymer can be used as an optical member for widely improving the viewing angle of the liquid crystal display. In addition, when the angle between the substrate surface and the major axis of the liquid crystal molecules is set to 30 to 60 degrees, more preferably 40 to 50 degrees, and particularly preferably 45 degrees, the polymer to be produced has an efficiency of polarization separation. Can be given well. Such a polymer is useful as a polarization separation element or an optical low-pass filter. In addition, when the alignment state of the liquid crystal composition is hybrid alignment, the produced polymer is useful as a polarizing optical element or an optical low-pass filter. On the other hand, an alignment structure having a helical structure represented by twisted nematic alignment, super twisted nematic alignment, and cholesteric alignment is also useful. When the twist angle is set to 60 to 270 degrees, it is useful for optical compensation of a liquid crystal display element. In addition, when the helical pitch is adjusted and set so as to selectively reflect a specific wavelength region, the produced polymer can be used as a notch filter or a reflective color filter, which is useful. Further, if the wavelength region that selectively reflects is set to the infrared region, it is also useful as a heat ray cut filter. In addition, when it is in a homogeneous orientation or homeotropic orientation state, the anisotropy of the refractive index is larger than that obtained by stretching the plastic. is there. There is also a possibility that an optical compensator can be built in the liquid crystal cell. This characteristic is important when it is used for optical compensation of a reflective liquid crystal display element, and in particular, its use as a quarter wavelength plate is extremely important.

As a method for polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of 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 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. 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, in the case of producing a polymer 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. Is preferred. 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 photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm ² or more, a polymerizable liquid crystal compound or a polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

The polymer of the present invention obtained by 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 polymer 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 polymer 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.

Example 1 Synthesis of polymerizable liquid crystal compound (1)
While stirring a mixture of 138.1 g of 4-hydroxybenzoic acid, 136.1 g of 6-chloro-1-hexanol, 84.0 g of sodium hydroxide, 25.0 g of potassium iodide, 440 ml of ethanol, and 440 ml of water at 80 ° C. Heated for 32 hours. After cooling the resulting reaction solution to room temperature, 1000 ml of saturated brine was added to the reaction solution, and dilute hydrochloric acid was added until the aqueous layer of the reaction solution became weakly acidic. The reaction solution was extracted by adding 1000 ml of ethyl acetate. After the organic layer was washed with water, the organic solvent was distilled off under reduced pressure and further air-dried to obtain 223.9 g of the compound of formula (s-1).

  A mixture of 110.0 g of the compound of formula (s-1), 133.1 g of acrylic acid, 27.0 g of p-toluenesulfonic acid, 6.0 g of hydroquinone, 420 ml of toluene, 180 ml of n-hexane and 260 ml of tetrahydrofuran was heated and stirred. The resulting water was refluxed for 6 hours while distilling off the produced water. The reaction solution was cooled to room temperature, and extracted with 1000 ml of saturated brine and 800 ml of ethyl acetate. After the organic layer was washed with water, the organic solvent was distilled off under reduced pressure to obtain 231.4 g of a crude product. Next, recrystallization from a mixture of 400 ml of n-hexane and 100 ml of toluene was performed twice to obtain 111.8 g of the compound of the formula (s-2).

  10.6 g of compound of formula (s-2), 4.0 g of 2- (4-hydroxyphenyl) ethyl alcohol, 0.5 g of 4-dimethylaminopyridine, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride A mixture of 7.0 g of salt, 0.5 g of 4-dimethylaminopyridine and 150 ml of methylene chloride was stirred at room temperature for 20 minutes. To this reaction solution, 10.6 g of the compound of the formula (s-2), 7.0 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.5 g of 4-dimethylaminopyridine, 50 ml of methylene chloride And a further 8 hours at room temperature. After completion of the reaction, the reaction solution was washed with water, and the organic layer was distilled off under reduced pressure to obtain 24.5 g of a crude product. The obtained crude product was subjected to silica gel column chromatography (Rf = 1.0) using ethyl acetate as a developing solvent, and recrystallization from 60 ml of ethanol, recrystallization from a mixed solvent consisting of 60 ml of methanol and 25 ml of methylene chloride. Purification was performed to obtain 13.5 g of a polymerizable liquid crystal compound of the formula (s-3).

When the temperature of the polymerizable liquid crystal compound of the formula (s-3) was raised, it transitioned to a nematic phase at 61 ° C. and a phase transition to an isotropic liquid phase at 81 ° C.

(Example 2) Synthesis of polymerizable liquid crystal compound (2)
A mixture consisting of 91.3 g of methyl 4-hydroxybenzoate, 68.1 g of 3-chloro-1-propanol, 99.0 g of potassium carbonate, and 360 ml of dimethylformamide was heated to reflux at 80 ° C. for 16 hours while stirring. The obtained reaction solution was cooled to room temperature, 800 ml of saturated brine was added to the reaction solution, and diluted hydrochloric acid was added until the aqueous layer of the reaction solution became weakly acidic. The reaction solution was extracted by adding 1000 ml of tetrahydrofuran. The organic solvent was distilled off under reduced pressure to obtain 133.1 g of a crude product of the formula (s-4).

  A mixture consisting of 133.1 g of the crude product of formula (s-4), 50.0 g of sodium hydroxide, 100 ml of methanol and 100 ml of water was heated to reflux with stirring for 4 hours. After cooling the reaction solution to room temperature, the reaction solution was neutralized by adding hydrochloric acid. Next, 1000 ml of saturated brine was added to the reaction solution, and further 1000 ml of tetrahydrofuran was added for extraction. The organic solvent was distilled off under reduced pressure to obtain 118.5 g of a crude product. Next, recrystallization was performed using a mixed solvent composed of 200 ml of toluene and 100 ml of tetrahydrofuran to obtain 88.0 g of the compound of the formula (s-5).

A mixture of 44.0 g of the compound of the formula (s-5), 96.8 g of acrylic acid, 20.0 g of p-toluenesulfonic acid, 4.0 g of hydroquinone, 200 ml of toluene, 1504 ml of hexane, and 150 ml of tetrahydrofuran is formed by heating and stirring. The incoming water was refluxed for 8 hours while distilling off with a Dean-Stark water separator. After cooling the reaction solution to room temperature, 1000 ml of saturated brine was added to the reaction solution to wash the reaction solution. After adding 900 ml of ethyl acetate to the organic layer, the organic layer was washed twice with 300 ml of saturated aqueous sodium hydrogen carbonate solution. Further, the organic layer was washed with 1000 ml of water three times, and then the organic solvent was distilled off under reduced pressure to obtain 54.2 g of a crude product. Purification by recrystallization from a mixed solvent of 300 ml of toluene and 200 ml of hexane and recrystallization from a mixed solvent of 200 ml of toluene and 100 ml of hexane gave 45.3 g of the compound of the formula (s-6).

  12.3 g of compound of formula (s-6), 3.2 g of 2- (4-hydroxyphenyl) ethyl alcohol, 0.6 g of 4-dimethylaminopyridine, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride A mixture of 9.4 g of salt and 150 ml of tetrahydrofuran was stirred at room temperature for 6 hours. Extraction was performed by adding 200 ml of saturated brine and 400 ml of ethyl acetate to the reaction solution. After the organic layer was washed with water, the organic solvent was distilled off under reduced pressure to obtain 15.7 g of a crude product. The resulting crude product was recrystallized from silica gel column chromatography using a mixed solvent of toluene and ethyl acetate (volume ratio of ethyl acetate: toluene = 1: 5, Rf = 0.50) as a developing solvent and 40 ml of methanol. To obtain 3.0 g of a polymerizable liquid crystal compound of the formula (s-7).

When the temperature of the polymerizable liquid crystal compound of the formula (s-7) was raised, the phase transitioned to a nematic phase at 60 ° C. and the phase transition to an isotropic liquid phase at 84 ° C.

(Example 3) Preparation of polymerizable liquid crystal composition (1)
50 parts by mass of a polymerizable liquid crystal compound of the compound (a-1)

And 50 parts by mass of a polymerizable liquid crystal compound of the compound (a-4)

A composition (A) consisting of The composition (A) exhibited a nematic liquid crystal phase at room temperature (25 ° C.). The nematic phase-isotropic liquid phase transition temperature was 46 ° C. Also, in the 1.662 (refractive index of extraordinary light) _{n e} measured at 589 nm, (refractive index of ordinary light) _{n o} is 1.510, the birefringence was 0.152.

  A composition (B) comprising 30 parts by mass of the polymerizable liquid crystal compound (s-7) synthesized in Example 2 and 70 parts by mass of the composition (A) was prepared. This composition (B) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 56 ° C. Further, no crystal was precipitated for 3 hours or more.

(Example 4) Preparation of polymerizable liquid crystal composition (2)
A composition (C) comprising 40 parts by mass of the polymerizable liquid crystal compound (s-7) synthesized in Example 2 and 60 parts by mass of the composition (A) was prepared. This composition (C) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 60 ° C. Further, no crystals were precipitated for 1 hour or longer.

(Example 5) Preparation of polymerizable liquid crystal composition (3)
A composition (D) comprising 50 parts by mass of the polymerizable liquid crystal compound (s-7) synthesized in Example 2 and 50 parts by mass of the composition (A) was prepared. This composition (D) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 64 ° C. Further, no crystals were precipitated for 1 hour or longer.

(Example 6) Preparation of polymerizable liquid crystal composition (4)
A composition (E) comprising 60 parts by mass of the polymerizable liquid crystal compound (s-7) synthesized in Example 2 and 40 parts by mass of the composition (A) was prepared. This composition (E) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 67 ° C. Further, no crystal was deposited for 30 minutes or more.

(Example 7) Preparation of polymerizable liquid crystal composition (5)
A composition (F) comprising 70 parts by mass of the polymerizable liquid crystal compound (s-7) synthesized in Example 2 and 30 parts by mass of the composition (A) was prepared. This composition (F) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 71 ° C. Further, no crystal was deposited for 30 minutes or more.

(Example 8) Preparation of polymerizable liquid crystal composition (6)
A composition (G) comprising 20 parts by mass of the polymerizable liquid crystal compound (s-3) synthesized in Example 1 and 80 parts by mass of the composition (A) was prepared. This composition (G) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 56 ° C. Further, no crystal was precipitated for 48 hours or more. The 1.671 (refractive index of extraordinary light) _{n e} measured at 589 nm, (refractive index of ordinary light) _{n o} is 1.507, the birefringence was 0.164. The viscosity at 20 ° C. was 56.3 cp.

(Example 9) Preparation of polymerizable liquid crystal composition (7)
A composition (H) comprising 40 parts by mass of the polymerizable liquid crystal compound (s-3) synthesized in Example 1 and 80 parts by mass of the composition (A) was prepared. This composition (H) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 62 ° C. Further, no crystals were precipitated for 1 hour or longer. The 1.675 (refractive index of extraordinary light) _{n e} measured at 589 nm, (refractive index of ordinary light) _{n o} is 1.504, the birefringence was 0.171.

(Example 10) Preparation of polymerizable liquid crystal composition (8)
A composition (I) comprising 60 parts by mass of the polymerizable liquid crystal compound (s-3) synthesized in Example 1 and 80 parts by mass of the composition (A) was prepared. This composition (I) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 68 ° C. Further, no crystal was deposited for 30 minutes or more.

(Example 11) Preparation of polymerizable liquid crystal composition (10)
A polymerizable liquid crystal composition (J) comprising 99 parts by mass of the polymerizable liquid crystal composition (D) prepared in Example 5 and 1 part by mass of a photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) was prepared. This composition (J) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 62 ° C. Further, no crystals were precipitated for 1 hour or longer.

(Example 12) Preparation of polymerizable liquid crystal composition (11)
A polymerizable liquid crystal composition (K) comprising 99 parts by mass of the polymerizable liquid crystal composition (E) prepared in Example 6 and 1 part by mass of a photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) was prepared. This composition (K) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 65 ° C. Further, no crystal was deposited for 30 minutes or more.

(Example 13) Preparation of polymerizable liquid crystal composition (12)
When the polymerizable liquid crystal compound (s-3) obtained in Example 1 and the polymerizable liquid crystal compound (s-7) obtained in Example 2 were mixed, they were well compatible at an arbitrary ratio. The polymerizable liquid crystal composition comprising 50 parts by mass of the polymerizable liquid crystal compound (s-3) and 50 parts by mass of the polymerizable liquid crystal compound (s-7) exhibited a nematic phase at room temperature. In addition, no crystals were deposited for 30 minutes or more.

(Comparative Example 1) Preparation of polymerizable liquid crystal composition 20 parts by mass of the compound of the formula (s-8) (This compound showed a crystalline phase at room temperature. The phase transition temperature was 87 ° C for the crystal-smectic phase, smectic. Phase-nematic phase is 91 ° C., nematic phase-isotropic liquid phase is 110 ° C.)

A composition (L) comprising 80 parts by mass of the composition (A) was prepared. The composition (L) exhibited a nematic liquid crystal phase at room temperature (25 ° C.), and the nematic phase-isotropic liquid phase transition temperature was 64 ° C. In this polymerizable liquid crystal composition (L), crystals were precipitated within 15 minutes. A polymerizable liquid crystal composition (M) comprising 99 parts by mass of the composition (L) and 1 part by mass of a photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) was prepared. The composition (M) exhibited a nematic phase at room temperature, and the nematic-isotropic liquid phase transition temperature was 60 ° C. In this polymerizable liquid crystal composition (M), crystals were precipitated within 15 minutes.

  From the comparison between Examples 3 to 13 and Comparative Example 1, it can be seen that the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention hardly precipitates crystals.

(Example 14) Production of polymer (1)
The composition (J) prepared in Example 11 was injected at room temperature into an anti-parallel alignment liquid crystal glass cell having a cell gap of 50 microns (a glass cell subjected to alignment treatment so that the liquid crystal was uniaxially aligned). It was confirmed that uniform uniaxial orientation was obtained after the injection. Next, ultraviolet rays of 1 mW / cm ² were irradiated for 10 minutes using UVGL-25 manufactured by Ultra Violet at room temperature (25 ° C.) to polymerize the composition (J) to obtain a polymer. The obtained polymer had different refractive indexes depending on the direction, and it was confirmed that it functions as an optical anisotropic body. The haze of the polymer as it was in the glass cell was 1.8%. Furthermore, the glass liquid crystal cell was disassembled, and the obtained polymer alone was taken out and examined for heat resistance. As a result, the orientation was not disturbed even at 150 ° C., and it was confirmed that there was no problem. Further, the obtained polymer was not gel-like and excellent in mechanical properties.

(Example 15) Production of polymer (2)
The composition (K) prepared in Example 12 was injected at room temperature into an anti-parallel alignment liquid crystal glass cell having a cell gap of 50 microns (a glass cell subjected to alignment treatment so that the liquid crystal was uniaxially aligned). After injection, it was confirmed that uniform uniaxial orientation was rapidly obtained. Next, ultraviolet rays of 1 mW / cm ² were irradiated for 10 minutes using UVGL-25 manufactured by Ultra Violet at room temperature (25 ° C.) to polymerize the composition (K) to obtain a polymer. The obtained polymer had different refractive indexes depending on the direction, and it was confirmed that it functions as an optical anisotropic body. The haze of the polymer as it was in the glass cell was 1.7%. Furthermore, the glass liquid crystal cell was disassembled, and the obtained polymer alone was taken out and examined for heat resistance. As a result, the orientation was not disturbed even at 150 ° C., and it was confirmed that there was no problem. Further, the obtained polymer was not gel-like and excellent in mechanical properties.

(Comparative example 2) Production of polymer The composition (M) prepared in the comparative example was placed at room temperature on an anti-parallel alignment liquid crystal glass cell having a cell gap of 50 microns (a glass cell subjected to alignment treatment so that the liquid crystal was uniaxially aligned). And injected. It was confirmed that uniform uniaxial orientation was obtained after the injection. Next, ultraviolet rays of 1 mW / cm ² were irradiated for 10 minutes using UVGL-25 manufactured by Ultra Violet at room temperature (25 ° C.) to polymerize the composition (M) to obtain a polymer. The obtained polymer had different refractive indexes depending on the direction, and it was confirmed that it functions as an optical anisotropic body. The haze of the polymer as it was in the glass cell was 13.5%.

  From Examples 14 and 15 and Comparative Example 2, it can be seen that when a polymer is produced using the polymerizable liquid crystal composition of the present invention, a highly transparent material with reduced haze is obtained.

Invention 1 , General Formula (I)

(Wherein P ¹ and P ² represent a polymerizable functional group, S ¹ and S ² represent a divalent spacer group, X ¹ , X ² and L ¹ each independently represent a linking group, X ¹ and X ² each independently represents a single bond, —O—, —CO—, —COO—, —OCO—, and at least one of L ¹ is —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — , and the others are independently a single bond, —CH ₂ —, —O— , —CO—, —OCOO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₄ —, —CH _{2 CH 2 CH 2 O -,} - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - _{H 2 CH 2 -CH = CH -} , - CH = CH-COO -, - OCO-CH = CH- represents, ^{S 1} and ^{S 2} may be substituted carbon atoms that are not adjacent is an oxygen atom, also A hydrogen atom represents an alkylene group having 2 to 18 carbon atoms which may be substituted with an oxygen atom, a halogen atom or a cyano group, or a siloxane group having 2 to 18 silicon atoms , and A ¹ and A ² are independently aromatic ring, alicyclic, represent 及 beauty condensed ring, n represents the heavy polymerizable liquid crystal compound characterized by being represented by an integer of 3-9) on.

Invention 2 , A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to invention 1.
Invention 3 , General formula (IV)

(Wherein X ⁷ represents a hydrogen atom or a methyl group, r represents an integer of 0 or 1, 6-membered rings A, B and C are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenyl group, and these 6-membered rings A, B, and C are further substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups, or halogen atoms having 1 to 7 carbon atoms. Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, — CH = CH -, - CF = CF -, - (CH 2) 4 -, - _{H 2 CH 2 CH 2 O -} , - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - CH = CH-COO -, - OCO —CH═CH—, Y ⁵ represents a single bond, —O—, —OCO—, —COO—, —CH═CH—COO—, and Z ¹ represents a hydrogen atom, a halogen atom, a cyano group, or a carbon atom. The polymerizable liquid crystal composition according to invention 2, comprising a polymerizable liquid crystal compound represented by 1 to 20 hydrocarbon groups).

Invention 4 , General formula (VII)

(In the formula, X ⁸ represents a hydrogen atom or a methyl group, s represents an integer of 2 to 18, t represents an integer of 0 or 1, and the 6-membered rings D, E, and F are each independently 1 , 4-phenylene group, 1,4-phenylene group, 1,4-cyclohexylene group, non-adjacent CH group substituted with nitrogen, or one or two non-adjacent CH ₂ groups substituted with oxygen or sulfur atoms Represents a 1,4-cyclohexylene group or a 1,4-cyclohexenyl group, and these 6-membered rings D, E, and F are further an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group. , One or more halogen atoms may be substituted, and Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, — OCO-, -C≡C-, -CH = CH-, -CF = CF _{, - (CH 2) 4 -} , - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH-, —CH═CH—COO—, —OCO—CH═CH—, Y ⁸ represents a single bond, —O—, —OCO—, —COO—, —CH═CH—COO—, and Z ² represents hydrogen. The polymerizable liquid crystal composition according to invention 2 or 3, comprising a polymerizable liquid crystal compound represented by an atom, a halogen atom, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms.

Invention 5 The polymerizable liquid crystal composition according to any one of Inventions 2 to 4 , wherein the lower limit temperature of the liquid crystal is 40 ° C. or lower.
Invention 6 , Polymerizable liquid crystal compound according to invention 1 or polymer of polymerizable liquid crystal composition according to any one of inventions 2 to 5 .

Claims (11)

2 or more polymerizable functional groups in one molecule and 2-10 identical or different rings selected from the group consisting of non-polymerizable aromatic ring, alicyclic ring, heterocyclic ring and condensed ring, A polymerizable liquid crystal compound having at least one of —CH ₂ CH ₂ COO— or —CH ₂ CH ₂ OCO— as a group linking two rings. Formula (I)

(Wherein P ¹ and P ² represent a polymerizable functional group, S ¹ and S ² represent a divalent spacer group, X ¹ , X ² and L ¹ each independently represent a linking group; ¹ is a linking group selected from —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, and A ¹ and A ² are The polymerizable liquid crystal compound according to claim 1, wherein the polymerizable liquid crystal compound is independently represented by an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, and n represents an integer of 1 to 9. In the general formula (I), X ¹ and X ² each independently represent a single bond, —O—, —S—, —CO—, —COO—, —OCO—, and at least one of L ¹ is — CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — are represented, and the others are independently a single bond, —CH ₂ —, —O—, — _{S -, - CO -, -} OCOO -, - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - C≡C -, - CH = CH -, - CF═CF—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ CH ₂ CH ₂ —, —CH═CH—CH ₂ CH ₂ —, —CH ₂ CH ₂ —CH = CH -, - CH = CH -COO -, - OCO-CH = CH- represents, ^{S 1} and ^{S 2} Non-adjacent carbon atoms may be substituted with oxygen atoms, hydrogen atoms may be substituted with oxygen atoms, halogen atoms, cyano groups, C2-C18 alkylene groups, or silicon atoms. The polymerizable liquid crystal compound according to claim 2, which represents -18 siloxane groups. Formula (II)

Wherein W ¹ and W ² each independently represent a single bond, —O—, —COO—, —OCO—, and Y ¹ and Y ² each independently represent —COO—, —OCO—. , P and q each independently represents an integer of 2 to 18, and the 1,4-phenylene group is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. The polymerizable liquid crystal compound according to any one of claims 1 to 3, which may be substituted). Formula (III)

(Wherein, ^{P 1} represents a polymerizable functional group, ^{S 1} and ^{S 2} represents a divalent spacer ^group, X ^1, X 2, ^{L 1} each independently represents a linked group, among the ^{L 1} at least one _{-CH 2 CH 2 COO -, -} CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - is from linking group selected, ^{R 1} represents a hydrogen atom or ^{P 1,} And A ¹ and A ² independently represent an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, n represents an integer of 2 to 9, and m represents an integer of 0 to 2. The polymerizable liquid crystal compound according to claim 1, wherein In the general formula (III), X ¹ and X ² each independently represent a single bond, —O—, —S—, —CO—, —COO—, —OCO—, and at least one of L ¹ is _{, - - -CH 2 CH 2 COO} CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - represents, independently a single bond _otherwise, -CH 2 _-, - _{O-, -S -, - CO -, -} OCOO -, - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - C≡C -, - CH = CH-, _{-CF = CF -, - (CH} 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 - CH = CH -, - CH = CH-COO -, - OCO-CH = CH- represents, S ¹ and S ² Non-adjacent carbon atoms may be substituted with oxygen atoms, hydrogen atoms may be substituted with oxygen atoms, halogen atoms, cyano groups, C2-C18 alkylene groups, or silicon atoms. 6. The polymerizable liquid crystal compound according to claim 5, which represents -18 siloxane groups.   A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of claims 1 to 6. Formula (IV)

(Wherein X ⁷ represents a hydrogen atom or a methyl group, r represents an integer of 0 or 1, 6-membered rings A, B and C are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH2 groups are substituted with oxygen or sulfur atoms, 1,4 -Represents a cyclohexenyl group, and these 6-membered rings A, B, and C are further substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups, or halogen atoms having 1 to 7 carbon atoms. Y ³ and Y ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH. = CH -, - CF = CF -, - (CH 2) 4 -, - _{H 2 CH 2 CH 2 O -} , - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - CH = CH-COO -, - OCO —CH═CH—, Y ⁵ represents a single bond, —O—, —OCO—, —COO—, —CH═CH—COO—, and Z ¹ represents a hydrogen atom, a halogen atom, a cyano group, or a carbon atom. The polymerizable liquid crystal composition according to claim 7, comprising a polymerizable liquid crystal compound represented by 1 to 20 hydrocarbon groups). Formula (VII)

(In the formula, X ⁸ represents a hydrogen atom or a methyl group, s represents an integer of 2 to 18, t represents an integer of 0 or 1, and the 6-membered rings D, E, and F are each independently 1 , 4-phenylene group, 1,4-phenylene group, 1,4-cyclohexylene group, non-adjacent CH group substituted with nitrogen, or one or two non-adjacent CH ₂ groups substituted with oxygen or sulfur atoms Represents a 1,4-cyclohexylene group or a 1,4-cyclohexenyl group, and these 6-membered rings D, E, and F are further an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group. , One or more halogen atoms may be substituted, and Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, — OCO-, -C≡C-, -CH = CH-, -CF = CF _{, - (CH 2) 4 -} , - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH-, —CH═CH—COO—, —OCO—CH═CH—, Y ⁸ represents a single bond, —O—, —OCO—, —COO—, —CH═CH—COO—, and Z ² represents hydrogen. The polymerizable liquid crystal composition according to claim 7 or 8, comprising a polymerizable liquid crystal compound represented by an atom, a halogen atom, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms.   The polymerizable liquid crystal composition according to any one of claims 7 to 9, wherein a liquid crystal lower limit temperature is 40 ° C or lower.   The polymer of the polymerizable liquid crystal compound according to any one of claims 1 to 6 or the polymer of the polymerizable liquid crystal composition according to any one of claims 7 to 10.