JP6183575B2 - Polymerizable compound and liquid crystal display device using the same - Google Patents

Description

  The present invention relates to a compound having a polymerizable group, a polymerizable composition containing the compound, and a liquid crystal display device using the polymerizable composition.

  LCD TVs, smartphones and tablet PCs are oversupplied and price competition is intensifying, and LCD manufacturers are forced to lower costs. In order to break through this situation, major LCD manufacturers are conducting research and development aimed at higher performance and higher added value. Of these, the field sequential full-color method, which has excellent color reproducibility, has attracted particular attention, and high-speed response of 1 ms or less is required.

  However, just using nematic liquid crystal, which is the mainstream at present, has a response speed as slow as about 10 to several ms and cannot be used in the new system. In contrast, a ferroelectric liquid crystal (FLC) using a smectic liquid crystal can respond at a high speed of several hundred μs. However, even if FLC is used, there are only two states of light and dark, so that it is not easy to display halftones necessary for full color display. Another problem is that there is a disturbance in alignment due to a decrease in contrast due to alignment defects and weak impact resistance (Patent Document 1).

  In addition, we are also developing a method using polymer stabilization technology in nematic liquid crystals. Adds several mass% of polymerizable (liquid crystal) compound to the liquid crystal using the principle that the time to return from ON to OFF becomes faster when a three-dimensional polymer network that does not cause light scattering is formed in the liquid crystal and vertically aligned. Thus, it has been confirmed that by polymerizing at a low temperature, the drive voltage increases and the response speed becomes 1 ms or less. However, the problem is that the drive voltage becomes too large.

  On the other hand, several polymerizable compounds (liquid crystals) can be mixed to form a polymerizable liquid crystal composition, and then aligned and polymerized in a liquid crystal state to produce a film-like polymer having a uniform orientation. This can be used for a polarizing plate, a phase difference plate, and the like. Such a film can be provided with transparency, mechanical strength, surface hardness, heat resistance, weather resistance, storage stability, and the like by using an appropriate polymerizable liquid crystal composition. However, the problem is that the adhesion of the film itself to various substrates (or alignment films) is low (Patent Document 2). In some cases, the problem can be solved by the addition of an additive, but new problems have arisen in that the optical characteristics are lowered due to the lowered liquid crystallinity and the manufacturing process is complicated.

JP 2002-31821 A Special table 2007-50613 gazette

  The problem to be solved by the present invention is to provide a polymerizable compound, to a polymer-stabilized liquid crystal display element capable of high-speed response and low-voltage driving using the polymerizable compound and various substrates or alignment films. It is to provide a polymerizable liquid crystal film having high adhesion.

  The present invention relates to the general formula (I)

(In the formula, P represents a polymerizable group, Sp represents a spacer group or a single bond, and A ¹ and A ² are each independently unsubstituted or substituted by one or more L's. Represents an aromatic or non-aromatic cyclic group having 3 to 20 carbon atoms, and any carbon atom of the cyclic group may be substituted with a hetero atom, but a plurality of A ¹ and / or A ² appear. Each may be the same or different, and L is a P-Sp- group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, amino group, a hydroxyl group, a mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, or one -CH ₂ Or nonadjacent two or more -CH ₂ - each independently is -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —, —CH═CH—, —CF═CF— or —C≡C—, but a plurality of L are present They may be the same or different, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and Z ¹ and Z ² are each independently —O—, —S—, _{-CH 2 -, - OCH 2 -} , - CH 2 O -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF _{CH 2 -, - CO -,} - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - OCO —NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF _{2 -, - CF 2 S -,} - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 _{CH 2 -, - OCO-CH} 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO _{-, - CH 2 -OCO -,} - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N N = CH -, - CF = CF -, - C≡C- or represents a single bond, or different an each identical ^{if Z 1} and / or ^{Z 2} appears more, B is —O— or —CH ₂ —, wherein m and n each independently represents an integer of 0 to 5, m + n represents an integer of 1 to 5, and R ¹ represents a P-Sp- group, a hydrogen atom, Fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, hydroxyl group, -N (Y ² ) ₂ , -Si (Y ² ) ₃ , or one- CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S. May be substituted by -CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- Represents a linear or branched alkyl group having 1 to 20 carbon atoms, optional hydrogen atom in the alkyl group may be substituted by a fluorine atom, Y ² is a hydrogen atom, or a C 1 -C 20 represents a linear or branched alkyl group, and when a plurality of Y ² are present, they may be the same or different, and when a plurality of P and Sp appear, they are the same or different. May be. ), A composition containing the compound, a polymer obtained by polymerizing the composition, and a liquid crystal display device.

  The compound of the present invention is useful as a constituent member of a polymerizable composition used for a polymer-stabilized liquid crystal display element because it exhibits high-speed response and low-voltage drive when the polymerizable composition is heated. Moreover, since the polymer (optical anisotropic body) using the composition containing the compound of the present invention is excellent in adhesion to various base materials or alignment films, it is useful for optical materials.

  The present invention provides a compound represented by the general formula (I), a composition containing the compound, a polymer obtained by polymerizing the composition, a liquid crystal display device using the polymer, and A polymerizable liquid crystal film is provided.

  In the general formula (I), P represents a polymerizable group, but the following formula (P-1) to formula (P-18)

Preferably, these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-3), formula (P-7), formula (P-11) or formula (P-13) is more preferred, and formula (P-1), formula (P-2) or formula (P-3) is more preferred. More preferred is formula (P-1) or (P-2). In general formula (I), when a plurality of P are present, they may be the same or different.

In the general formula (I), Sp represents a spacer group or a single bond, but one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—. Preferably represents an alkylene group having 1 to 20 carbon atoms or a single bond, which may be replaced by -OCO- or -OCO-O-, one -CH ₂ -or two or more non-adjacent ones It is more preferable that —CH ₂ — each independently represents an alkylene group having 1 to 12 carbon atoms that may be independently replaced by —O—, —COO— or —OCO—, and one —CH ₂ — or More preferably, two or more —CH ₂ — that are not adjacent to each other independently represent an alkylene group having 1 to 12 carbon atoms that may be independently replaced by —O—, and one —CH ₂ — or Two or more non-adjacent —CH ₂ An alkylene group having 1 to 8 carbon atoms in which-may be independently replaced by -O- is still more preferable, and an alkylene group having 1 to 8 carbon atoms is particularly preferable. In the general formula (I), when a plurality of Sp are present, they may be the same or different.

In the general formula (I), B represents —O— or —CH ₂ —, but preferably represents —O—.

In the general formula (I), A ¹ and A ² are each independently an aromatic or non-aromatic cyclic group having 3 to 20 carbon atoms which may be unsubstituted or substituted by one or more of the following L Any carbon atom of the cyclic group may be substituted with a hetero atom, and when a plurality of A ¹ and / or A ² appear, they may be the same or different from each other. 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group substituted by one or two substituents L , Cyclohexane-1,4-diyl group, 1,4-cyclohexenylene group, bicyclo [2.2.2] octane-1,4-diyl group, spiro [3.3] heptane-2,6-diyl group 1,3-Dioxane-2,5-diyl group , Piperidine-2,5-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, indane-2,5-diyl group, thiophene- It preferably represents a 2,5-diyl group or a fluorene-2,7-diyl group, and is a 1,2-phenylene group, a 1,3-phenylene group which is unsubstituted or substituted by 1 to 2 substituents L, 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, cyclohexane-1,4-diyl group, 1,3-dioxane-2,5diyl group, indane-2, More preferably, it represents a 5-diyl group, a thiophene-2,5-diyl group or a fluorene-2,7-diyl group, and is a 1,4-phenylene group which is unsubstituted or substituted by 1 to 2 substituents L , Na The array type 2,6-diyl group, more preferably represent a cyclohexane-1,4-diyl group or 1,3-dioxane-2,5-diyl group, ^{A 1} is unsubstituted or one to two substituents L It is particularly preferable that A ² represents a 1,4-phenylene group or 1,3-dioxane-2,5diyl which is unsubstituted or substituted by 1 to 2 L. The group is particularly preferred, but it is particularly preferred that A ² directly linked to the ring having B represents a 1,4-phenylene group which is unsubstituted or substituted by 1 to 2 Ls.

In the general formula (I), the substituent L is a P—Sp— group (P and Sp each represent the above-mentioned group), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, Nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH _2- or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO. -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -CH = CH-, -CF = CF- or -C≡C-, but when a plurality of substituents L appear Each may be the same or different, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, but a P-Sp- group, a fluorine atom, a chlorine atom or one —CH ₂ -Or two or more non-adjacent —CH ₂ — are preferably each independently a linear alkyl group having 1 to 10 carbon atoms which may be replaced by —O—, and P—Sp— More preferably, it represents a group, a fluorine atom, a chlorine atom, a methyl group, an ethyl group or a methoxy group.

In the general formula (I), Z ¹ and Z ² are each independently —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CH. _{2 CF 2 -, - CF 2} CH 2 -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH-, —NH—CO—, —OCO—NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —SCH ₂ —, —CH ₂ S—, — CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═ _{CH -, - COO-CH 2} CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OC _{-, - COO-CH 2 -} , - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N ═CH—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond, and when multiple occurrences of Z ¹ and / or Z ² are the same or different may be _{but, -COO -, - OCO -,} - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or It preferably represents a single bond, and more preferably represents —COO—, —OCO— or a single bond. In particular, Z ² directly connected to the ring having B preferably represents a single bond.

  In the general formula (I), m and n each independently represent an integer of 0 to 5, m + n represents an integer of 1 to 5, m + n preferably represents an integer of 1 to 4, and m + n is 1 It is more preferable that the integer of 3 is represented, and it is more preferable that m + n represents 1 or 2.

In the general formula (I), R ¹ is a P—Sp— group (P and Sp are the above-mentioned groups, respectively), a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and pentafluorosulfuranyl. Group, nitro group, cyano group, hydroxyl group, —N (Y ² ) ₂ , —Si (Y ² ) ₃ , or one —CH ₂ — or two or more —CH ₂ — not adjacent to each other. Each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH- Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —NH—CO— or —C≡C—, wherein any hydrogen atom in the alkyl group is a fluorine atom. may be substituted, Y ² is a hydrogen atom, or a carbon atom number of 1 to 20 linear or branched Represents an alkyl group, or different an each identical if Y ² appears more, R ¹ is P-Sp- groups, a hydrogen atom, a fluorine atom, a chlorine atom, or one trifluoromethyl group —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently replaced with —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O—. preferably represents a straight-chain or branched alkyl group having from good carbon atoms 1 even 20 is, P-Sp- groups or one -CH 2 _- or two or more -CH nonadjacent More preferably, each _2- represents a linear alkyl group having 1 to 12 carbon atoms which may be independently replaced by -O-.

  As the compound represented by the general formula (I), compounds represented by the following general formulas (i-1) to (i-5) are more preferable.

(In the formula, P, Sp, A ¹ , A ² , Z ¹ , Z ² , B and R ¹ each independently represent the same as defined in the general formula (I).)
Of the compounds represented by general formulas (i-1) to (i-5), compounds represented by general formula (i-2) and general formula (i-5) are more preferable.

  The compounds represented by the general formulas (i-1) to (i-5) are preferably compounds represented by the following general formulas (ia-1) to (ia-5-5-2), respectively.

(In the formula, P, Sp, and L are the same as defined in formula (I), a is independently an integer of 0 to 2, and Z ^1a and Z ^2a are —COO; _{-, - OCO -, - COO} -CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or a single ^{bond, R 1a} is P-Sp- groups or one -CH ₂ - or adjacent have not more than one -CH ₂ - are each independently linear -O- from good carbon atoms 1 be replaced 12 Represents an alkyl group.)
The groups represented by the following formula (a-1) contained in the compounds represented by the general formulas (ia-1) to (ia-5-2) include the following formulas (a-2) to (a A group selected from -7) is preferred.

(L represents the same as defined in formula (I).)
The compounds represented by the general formula (ia-2), general formula (ia-5-1), and general formula (ia-5-2) are represented by the following general formulas (ib-2-1) to (ib-5). The compound represented by 2-1) is particularly preferable.

(In the formula, P, Sp, and L are the same as those defined in the general formula (I), but when a plurality of P and Sp appear, they may be the same or different, and a And Z ^2a represents the same as defined in the general formulas (ia-1) to (ia-5-2), and R ^1b represents one —CH ₂ — or two or more non-adjacent ones. represents -CH 2 _- are each independently -O- from good carbon atoms 1 be replaced in 12 linear alkyl group).
Among the compounds represented by the general formula (ib-2-1) to the general formula (ib-5-2-1), the general formula (ib-2-2) and the general formula (ib-5-1-2) ), A compound represented by the general formula (ib-5-2-1) is preferable, and a compound represented by the general formula (ib-2-2) or the general formula (ib-5-2-1) is particularly preferable. .

  Specifically, the compounds represented by the general formula (I) are preferably compounds represented by the following formulas (I-1) to (I-56).

The compound of this invention can be manufactured with the following manufacturing methods.
(Production method 1) Production of a compound represented by the following formula (i-a2)

(In the formula, P, Sp and L are the same as defined in formula (I), and a and R ^1a are defined in formulas (ia-1) to (ia-5-2)). And PG represents a protecting group.)
The hydroxyl group of the compound represented by formula (S-1) is protected with a protecting group (PG). The kind of the protective group (PG) is not particularly limited as long as it gives the compound represented by the general formula (S-2) in the reaction process and can stably protect the hydroxyl group in the subsequent steps. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODARA W. GREENE co-authored, A John Wiley & Son, Inc.) Groups are preferred.

  By reacting the compound represented by the general formula (S-2) with, for example, methanesulfonyl chloride (MsCl), a compound represented by the general formula (S-3) can be obtained. In the next reaction, diethyl malonate is alkylated. If it gives the compound represented by general formula (S-4) by converting, it will not be limited to this.

  The compound represented by the general formula (S-4) is obtained by reacting the compound represented by the general formula (S-3) with diethyl malonate.

  A compound represented by the general formula (S-5) can be obtained by reducing the compound represented by the general formula (S-4) with, for example, lithium aluminum hydride. However, the present invention is not limited to this as long as it provides the compound.

  The compound represented by the general formula (S-5) and the compound represented by the general formula (S-6) are subjected to dehydration condensation using, for example, para-toluenesulfonic acid as an acid catalyst, to thereby obtain the general formula (S-7). However, it is not limited to this as long as the compound represented by (S-7) is obtained by dehydration condensation.

  The protecting group (PG) of the compound represented by formula (S-7) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-8) in the reaction process. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition) , PETER G.M.WUTS, THEODARA W.GREENE, A John Wiley & Sons, Inc., Publication).

  A compound represented by the general formula (ia-2) is obtained by reacting the compound represented by the general formula (S-8) with a compound that forms a polymerization group.

  (I-a1) and (i-a3) to (i-a5-2) can also be produced by the same method.

  As reaction conditions of each process, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic Chemistry (Industritory Chemistry) der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co. K), Fiesers' Reagents for Organic Synthesis, Re, et al., John Wiley & S. et al., John Wiley & S. et al. Like The conditions that have been.

In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, liquid separation treatment and the like. In the case of using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, ion exchange resin and the like can be mentioned.
<Polymerizable liquid crystal composition for polymer stabilized liquid crystal display element>
[Liquid Crystal Compound]
The polymerizable liquid crystal composition used by mixing with the polymerizable compound represented by the above general formula (I) of the present invention to constitute a polymer stabilized liquid crystal display element is represented by the general formula (LC). It is preferable to contain a liquid crystal compound.

In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C, so that the oxygen atoms are not directly adjacent. ≡C— may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Alkyl group R ^LC may be respectively branched chain groups, may be straight chain groups, but is preferably a linear group.

In the general formula (LC), A ^LC1 and A ^LC2 each independently represent a group selected from the group consisting of the following group (a), group (b) and group (c).
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom),
(C) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group or chroman-2,6-diyl group.

One or two or more hydrogen atoms contained in the group (a), group (b) or group (c) may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ , respectively. Good.

In the general formula (LC), Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —. _{, -CH 2 O -, - OCF} 2 -, - CF 2 O -, - COO- or an -OCO-.

In general formula (LC), ^YLC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C, so that the oxygen atom is not directly adjacent. ≡C—, —CF ₂ O—, —OCF ₂ — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.

In general formula (LC), a represents an integer of 1 to 4. When a represents 2, 3 or 4, and there are a plurality of ^ALC1s in the general formula (LC), the plurality of ^ALC1s may be the same or different, and there are a plurality of ^ZLCs A plurality of Z ^LCs may be the same or different.

  The compound represented by the general formula (LC) is preferably one or more compounds selected from the group of compounds represented by the following general formula (LC1) and general formula (LC2).

In general formula (LC1) or (LC2), R ^LC11 and R ^LC21 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more CH ₂ groups in the alkyl group are One of the alkyl groups may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that the oxygen atoms are not directly adjacent. Alternatively, two or more hydrogen atoms may be optionally substituted with a halogen atom. As the compound represented by the general formula (LC1) or (LC2), R ^LC11 and R ^LC21 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or the number of carbon atoms. An alkenyl group having 2 to 7 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable, and is further linear. The alkenyl group preferably represents the following structure.

(In the formula, it shall be bonded to the ring structure at the right end.)
In general formula (LC1) or (LC2), A ^LC11 and A ^LC21 each independently represent any one of the following structures. In the structure, one or more CH ₂ groups in the cyclohexylene group may be substituted with an oxygen atom, and one or more CH groups in the 1,4-phenylene group are nitrogen atoms. And one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ .

As the compound represented by the general formula (LC1) or (LC2), ^ALC11 and ^ALC21 each independently preferably have one of the following structures.

In the general formula (LC1) or ^{(LC2), X LC11, X} LC12, X LC21 ~X LC23 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a -CF ₃ or -OCF ^{_3, Y LC11} and Y ^LC21 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, a cyano group, —CF ₃ , —OCH ₂ F, —OCHF ₂ or —OCF ₃ . As the compound represented by the general formula (LC1) or (LC2), Y ^LC11 and Y ^LC21 are each independently preferably a fluorine atom, a cyano group, —CF ₃ or —OCF ₃ , and a fluorine atom or —OCF ₃ is More preferred is a fluorine atom.

In general formula (LC1) or (LC2), Z ^LC11 and Z ^LC21 each independently represent a single bond, —CH═CH—, ^{—CF═CF—} , ^—C≡C— , —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or —OCO— is represented. As the compound represented by the general formula (LC1) or (LC2), Z ^LC11 and Z ^LC21 are each independently a single bond, —CH ₂ CH ₂ —, ^—COO— , ^—OCO— , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O— is preferred, and a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —OCF ₂ — or —CF ₂ O— is more preferred, and a single bond , —OCH ₂ — or —CF ₂ O— is more preferable.

In general formula (LC1) or (LC2), m ^LC11 and m ^LC21 each independently represent an integer of 1 to 4. As the compound represented by the general formula (LC1) or (LC2), ^mLC11 and ^mLC21 are preferably independently 1, 2 or 3, respectively, and when importance is attached to storage stability at low temperature and response speed. 1 or 2 is more preferable, and 2 or 3 is more preferable when improving the upper limit of the nematic phase upper limit temperature. When a plurality of A ^LC11 , A ^LC21 , Z ^LC11 and Z ^LC21 are present in the general formula (LC1) or (LC2), they may be the same or different.

  The compound represented by the general formula (LC) is also preferably one or two or more compounds selected from the group of compounds represented by the following general formula (LC3) to general formula (LC5).

^(Wherein represents ^{R LC31, R LC32, R LC41} , R LC42, alkyl groups ^{R LC51} and ^{R LC52} is 1-15 carbon atoms independently, one in the alkyl group or two or more —CH ₂ — may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that the oxygen atom is not directly adjacent. one or more hydrogen atoms in the group may be optionally substituted by a halogen ^{atom, a LC31, a LC32, a} LC41, a LC42, a LC51 and ^{a LC52} each independently any of the following Structure

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). indicates ^{whether, Z LC31, Z LC32, Z} LC41, Z LC42, Z LC51 and ^{Z LC52} each independently represent a single bond, -CH = CH -, - C≡C -, - CH 2 CH 2 -, - ( CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, Z ⁵ represents —CH ₂ — or an oxygen atom, and X ^LC41 represents It represents a hydrogen atom or a fluorine ^{atom, m LC31, m L 32, m LC41, m LC42,} m LC51 and ^{m LC52} represent each independently ^{0~3, m LC31 + m LC32,} m LC41 + m LC42 and ^m LC51 ^{+ m LC52} is 1, 2 or ^{3, A LC31} ~ When a plurality of A ^LC52 and Z ^{LC31 to} Z ^LC52 are present, they may be the same or different. )
It is preferable to contain one or more compounds selected from the group consisting of the compounds represented by

R ^{LC31 to} R ^LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^{LC31 to} A ^LC52 each independently preferably have the following structure:

Z ^{LC31 to} Z ^LC52 are each independently a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or —OCH ₂ —. preferable.

  As a compound represented by General Formula (LC3), General Formula (LC4), and General Formula (LC5), General Formula (LC3-1), General Formula (LC4-1), and General Formula (LC5-1)

Wherein R ^{31 to} R ³³ are alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, or alkenyloxy groups having 2 to 8 carbon atoms. R ^{41 to} R ⁴³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. Z ^{31 to} Z ³³ are a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCO—, —OCH ₂ —. , —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, X ⁴¹ represents a hydrogen atom or a fluorine atom, and Z ³⁴ represents —CH ₂ — or an oxygen atom. It is preferable to contain at least one compound selected from the group .

In General Formula (LC3-1) to General Formula (LC5-1), R ^{31 to} R ³³ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. Represents an alkoxy group or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl having 2 to 5 carbon atoms More preferably, it represents a group or an alkenyl group having 2 to 4 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, and an alkyl group having 3 carbon atoms. It is particularly preferred to represent.

R ^{41 to} R ⁴³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms. More preferably, it represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, It is particularly preferred to represent an alkoxy group.

Z ^{31 to} Z ³³ are a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCO—, —OCH ₂ —, — CH ₂ O—, —OCF ₂ — or —CF ₂ O— represents a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or — It preferably represents CF ₂ O—, and more preferably represents a single bond or —CH ₂ O—.

  When used in a polymer-stabilized liquid crystal display element, the polymerizable liquid crystal composition is selected from the group of compounds represented by general formula (LC3-1), general formula (LC4-1), and general formula (LC5-1). It is preferable to contain 5% by mass to 50% by mass of the compound, preferably 5% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and more preferably 8% by mass to 27% by mass. It is more preferable to contain, and it is further more preferable to contain 10 mass%-25 mass%.

  Specifically, the compound represented by the general formula (LC3-1) is preferably a compound represented by the following general formula (LC3-11) to general formula (LC3-15).

(In the formula, R ³¹ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^41a represents an alkyl group having 1 to 5 carbon atoms.)
Specifically, the compound represented by the general formula (LC4-1) is preferably a compound represented by the following general formula (LC4-11) to general formula (LC4-14).

(In the formula, R ³² represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^42a represents an alkyl group having 1 to 5 carbon atoms, and X ⁴¹ represents a hydrogen atom or Represents a fluorine atom.)
Specifically, the compound represented by the general formula (LC5-1) is preferably a compound represented by the following general formula (LC5-11) to general formula (LC5-14).

(In the formula, R ³³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^43a represents an alkyl group having 1 to 5 carbon atoms, and Z ³⁴ represents —CH _2. -Or represents an oxygen atom.)
In general formula (LC3-11), general formula (LC3-13), general formula (LC4-11), general formula (LC4-13), general formula (LC5-11), and general formula (LC5-13), R ^{31 to} R ³³ are preferably the same embodiments in general formula (LC3-1) to general formula (LC5-1). R ^{41a to} R ^43a are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

In general formula (LC3-12), general formula (LC3-14), general formula (LC4-12), general formula (LC4-14), general formula (LC5-12), and general formula (LC5-14), R ^{31 to} R ³³ are preferably the same embodiments in general formula (LC3-1) to general formula (LC5-1). R ^{41a to} R ^43a are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

  Among general formulas (LC3-11) to (LC5-14), in order to increase the absolute value of dielectric anisotropy, general formula (LC3-11), general formula (LC4-11), Formula (LC5-11), general formula (LC3-13), general formula (LC4-13) and general formula (LC5-13) are preferred, and general formula (LC3-11), general formula (LC4-11), general formula Formula (LC5-11) is more preferred.

  The liquid crystal layer in the liquid crystal display element of the present invention preferably contains one or more compounds represented by general formulas (LC3-11) to (LC5-14), and contains one or two kinds. It is more preferable to contain 1 type or 2 types of compounds represented by general formula (LC3-1).

  Moreover, as a compound represented by General formula (LC3), General formula (LC4), and General formula (LC5), General formula (LC3-2), General formula (LC3-3), General formula (LC4-2) And general formula (LC5-2)

Wherein R ^{51 to} R ⁵³ are an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. R ^{61 to} R ⁶³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. B ^{1 to} B ^{3 each} represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be fluorine-substituted, Z ^{41 to} Z ⁴³ are a single bond, —CH═CH—, _{-C≡C -, - CH 2 CH 2} -, - (CH 2) 4 -, - COO -, - OCO -, - OCH 2 -, - CH 2 O -, - OCF 2 - or _-CF 2 O- the ^{stands, X 42} represents a hydrogen atom or a fluorine atom, ^{Z 4} It is -CH ₂ - represents an or an oxygen atom).
It is preferable to contain at least one compound selected from the group of compounds represented by:

In General Formula (LC3-2), General Formula (LC3-3), General Formula (LC4-2), and General Formula (LC5-2), R ^{51 to} R ⁵³ are each an alkyl group having 1 to 8 carbon atoms, An alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, but an alkyl group having 1 to 5 carbon atoms or 2 to 5 carbon atoms The alkenyl group is preferably an alkyl group having 2 to 5 carbon atoms or more preferably an alkenyl group having 2 to 4 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms or 2 carbon atoms. It is more preferable to represent an alkenyl group, and it is particularly preferable to represent an alkyl group having 3 carbon atoms.

R ^{61 to} R ⁶³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms. More preferably, it represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, It is particularly preferred to represent an alkoxy group.

B ^{31 to} B ³³ each represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be fluorine-substituted, but an unsubstituted 1,4-phenylene group or a trans-1,4- A cyclohexylene group is preferred, and a trans-1,4-cyclohexylene group is more preferred.

Z ^{41 to} Z ⁴³ are a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCO—, —OCH ₂ —, — CH ₂ O—, —OCF ₂ — or —CF ₂ O— represents a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or — It preferably represents CF ₂ O—, and more preferably represents a single bond or —CH ₂ O—.

  The compound represented by general formula (LC3-2), general formula (LC3-3), general formula (LC4-2), and general formula (LC5-2) is contained in an amount of 10 to 60% by mass in the liquid crystal composition. However, it is more preferable to contain 20 to 50% by mass, more preferably 25 to 45% by mass, more preferably 28 to 42% by mass, and more preferably 30 to 40% by mass. Further preferred.

  Specifically, the compound represented by the general formula (LC3-2) is preferably a compound represented by the following general formula (LC3-21) to general formula (LC3-29).

  Moreover, as a compound represented by general formula (LC3-3), the compound represented by the following general formula (LC3-31)-general formula (LC3-33) is also preferable.

(In the formula, R ⁵¹ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^61a represents an alkyl group having 1 to 5 carbon atoms. Preferred is the same embodiment as R ⁵¹ and R ⁶¹ in 2).
Specifically, the compound represented by the general formula (LC4-2) is preferably a compound represented by the following general formula (LC4-21) to general formula (LC4-26).

(In the formula, R ⁵² represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^62a represents an alkyl group having 1 to 5 carbon atoms, and X ⁴² represents a hydrogen atom or (It represents a fluorine atom, but an embodiment similar to R ⁵² and R ⁶² in formula (LC4-2) is preferred.)
Specifically, the compound represented by the general formula (LC5-2) is preferably a compound represented by the following general formula (LC5-21) to general formula (LC5-26).

(In the formula, R ⁵³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^63a represents an alkyl group having 1 to 5 carbon atoms, and Z ⁴⁴ represents —CH _2. -Represents an oxygen atom, but an embodiment similar to R ⁵³ and R ⁶³ in formula (LC5-2) is preferred.)
General formula (LC3-21), General formula (LC3-22), General formula (LC3-25), General formula (LC4-21), General formula (LC4-22), General formula (LC4-25), General formula In (LC5-21), general formula (LC5-22), and general formula (LC5-25), R ^{51 to} R ⁵³ represent general formula (LC3-2), general formula (LC4-2), and general formula ( Similar embodiments in LC5-2) are preferred. R ^{61a to} R ^63a are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

General formula (LC3-23), general formula (LC3-24) and general formula (LC3-26), general formula (LC4-23), general formula (LC4-24) and general formula (LC4-26), general formula In (LC5-23), general formula (LC5-24), and general formula (LC5-26), R ^{51 to} R ⁵³ represent general formula (LC3-2), general formula (LC4-2), and general formula (LC5- Similar embodiments in 2) are preferred. R ^{61a to} R ^63a are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

  Among general formulas (LC3-21) to (LC5-26), in order to increase the absolute value of dielectric anisotropy, general formula (LC3-21), general formula (Lc3-22) and general formula Formula (LC3-25), Formula (LC4-21), Formula (LC4-22) and Formula (LC4-25), Formula (LC5-21), Formula (LC5-22) and Formula ( LC5-25) is preferred.

The compounds represented by general formula (LC3-2), general formula (LC3-3), general formula (LC4-2) and general formula (LC5-2) can be contained alone or in combination of two or more. compounds B ¹ .about.B ³ represents a 1,4-phenylene group, and ^B 1 .about.B ³ is preferably contains at least one or more compounds which represent a trans-1,4-cyclohexylene group, respectively.

  Other examples of the compound represented by the general formula (LC3) include the following general formula (LC3-a) and general formula (LC3-b).

(Wherein R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 each independently represent the same meaning as R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 in the general formula (LC3), and X ^{LC3b1 to} X ^LC3b6 are Represents a hydrogen atom or a fluorine atom, and at least one of X ^LC3b1 and X ^LC3b2 or X ^LC3b3 and X ^LC3b4 represents a fluorine atom, m ^LC3a1 is 1, 2 or 3, and m ^LC3b1 is 0 or 1 and when there are a plurality of A ^LC31 and Z ^LC31 , they may be the same or different.) Or one or more compounds selected from the group of compounds represented by Is preferred.

R ^LC31 and R ^LC32 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Is preferably represented.

A ^LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group. , 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.

Z ^LC31 is a single _{bond, -CH 2 O -, - COO} -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.

  As general formula (LC3-a), it is preferable to represent the following general formula (LC3-a1).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 1 carbon atom. It is more preferable that it represents ^˜7 alkyl group, and R ^LC32 represents an alkoxy group having 1 to 7 carbon atoms.

  As general formula (LC3-b), it is preferable to represent the following general formula (LC3-b1) to general formula (LC3-b12), and general formula (LC3-b1), general formula (LC3-b6), and general formula (LC3-b8) and general formula (LC3-b11) are more preferable, general formula (LC3-b1) and general formula (LC3-b6) are more preferable, and general formula (LC3-b1) is represented. Most preferably it represents.

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 2 carbon atoms. Or an alkyl group having 3 carbon atoms, and more preferably R ^LC32 represents an alkyl group having 2 carbon atoms.

  The compound represented by the general formula (LC4) is preferably a compound represented by the following general formula (LC4-a) to general formula (LC4-c), and the compound represented by the general formula (LC5) is: Compounds represented by the following general formula (LC5-a) to general formula (LC5-c) are preferred.

^{(Wherein, R LC41,} R ^LC42 and ^{X LC41} each independently represent the same meaning as ^{R LC41, R LC42} and ^{X LC41} in the general formula ^{(LC4), R LC51} and ^{R LC52} is the general independently It represents the same meaning as ^{R LC51} and ^{R LC52} in formula ^{(LC5), Z LC4a1, Z} LC4b1, Z LC4c1, Z LC5a1, Z LC5b1 and ^{Z LC5c1} each independently represent a single bond, -CH = CH -, - C≡ _{C -, - CH 2 CH 2} -, - (CH 2) 4 -, - COO -, - OCH 2 -, - CH 2 O -, - OCF 2 - or an _-CF 2 O-).
^{R LC41,} R LC42, R ^LC51 and ^{R LC52} each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, the number alkenyl group or a carbon atom of 2 to 7 carbon atoms 2 It preferably represents -7 alkenyloxy groups.

Z ^{LC4a1 to} Z ^LC5c1 each independently preferably represents a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , —CH ₂ CH ₂ —, and more preferably represents a single bond.

  The compound represented by the general formula (LC) is selected from the compounds represented by the following general formula (LC6) (excluding the compounds represented by the general formula (LC1) to the general formula (LC5)). It is also preferable that it is 1 type, or 2 or more types of compounds.

In General Formula (LC6), R ^LC61 and R ^LC62 each independently represent an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C, so that the oxygen atoms are not directly adjacent. ≡C— may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally halogen substituted. As the compound represented by the general formula (LC6), R ^LC61 and R ^LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or 2 to 7 carbon atoms. The alkenyl group is preferably represented by any one of the following structures.

(In the formula, it shall be bonded to the ring structure at the right end.)
In General Formula (LC6), A ^{LC61 to} A ^LC63 each independently represent any of the following structures. In the structure, one or more CH ₂ CH ₂ groups in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —. One or two or more CH groups in the phenylene group may be substituted with a nitrogen atom.

As the compound represented by the general formula (LC6), A ^{LC61 to} A ^LC63 each independently preferably has one of the following structures.

In the general formula (LC6), Z ^LC61 and Z ^LC62 each independently represent a single bond, —CH═CH—, ^—C≡C— , —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—. _{, -OCH 2 -, - CH 2} O -, - OCF 2 - or _-CF 2 O-a represents, MLC61 represents 0-3. As the compound represented by the general formula (LC6), Z ^LC61 and Z ^LC62 are each independently a single bond, —CH ₂ CH ₂ —, ^—COO— , —OCH ₂ —, —CH ₂ O—, —OCF _2. - or _-CF 2 O-are preferred.

The compound represented by the general formula (LC6) is one or more compounds selected from the group consisting of compounds represented by the following general formula (LC6-a1) to general formula (LC6-p1). Is preferred. In the general formulas (LC6-a1) to (LC6-p1), R ^LC61 and R ^LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, carbon An alkenyl group having 2 to 7 atoms or an alkenyloxy group having 2 to 7 carbon atoms is represented.

[Other polymerizable compounds]
In order to constitute a polymerizable liquid crystal composition used in a polymer-stabilized liquid crystal display element, other polymerizable compounds used in addition to the polymerizable compound represented by the above general formula (I) of the present invention include one reactive property. And a monofunctional polymerizable compound having a group and a polyfunctional polymerizable compound having two or more reactive groups such as a bifunctional or trifunctional group. The polymerizable compound having a reactive group may or may not contain a mesogenic moiety.

  In the polymerizable compound having a reactive group, the reactive group is preferably a substituent having a polymerizable property by light. In particular, when the vertical alignment film is formed by thermal polymerization, the reaction of the polymerizable compound having a reactive group can be suppressed during the thermal polymerization of the vertical alignment film material. Substituents are particularly preferred.

  Other polymerizable compounds include the following general formula (P)

(In the general formula (P), Z ^p1 represents a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, and a hydrogen atom in the halogen atom. An optionally substituted alkoxy group having 1 to 15 carbon atoms, a hydrogen atom in which a hydrogen atom may be substituted with a halogen atom, and a hydrogen atom in which a hydrogen atom may be substituted with a halogen atom Represents an alkenyloxy group having 1 to 15 carbon atoms or -Sp ^p2 -R ^p2 ;
R ^p1 and R ^p2 are each independently the following formulas (R-I) to (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, T is a single bond or —COO—, p, t and q are each independently 0, Represents 1 or 2,
Sp ^p1 and Sp ^p2 each represent a spacer group, and Sp ^p1 and Sp ^p2 each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is Represents an integer of 1 to 11, and an oxygen atom is bonded to an aromatic ring).
L ^p1 and L ^p2 are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — COO—, —OCO—, —OCOOCH ₂ —, —CH ₂ OCOO—, —OCH ₂ CH ₂ O—, —CO—NR ^a —, —NR ^a —CO—, —SCH ₂ —, —CH ₂ S— ^{, -CH = CR a -COO -,} - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - COO-CR a = CH-COO -, - COO ^{-CR a = CH-OCO -,} - OCO-CR a = CH-COO -, - OCO-CR a = CH-OCO -, - (CH 2) z -C (= O) -O -, - (CH _{2) z-O- (C =} O) -, - O- (C = O) - (CH 2) z -, - (C = O) -O _{- (CH 2) z -,} - CH = CH -, - CF = CF -, - 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, each R ^a independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, In the formula, z represents an integer of 1 to 4, and
M ^p2 represents 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2, A 5-diyl group, a naphthalene-2,6-diyl group, an indan-2,5-diyl group, or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, but M ^p2 is unsubstituted Or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom , A cyano group, a nitro group or -R ^p1 may be substituted,
M ^p1 represents the following formulas (i-11) to (ix-11):

(In the formula, it binds to Sp ^p1 with ★ and binds to L ^p1 or L ^p2 with ★★),
M ^p3 represents the following formulas (i-13) to (ix-13):

(In the formula, it binds to Z ^p1 with ★ and binds to L ^p2 with ★★),
m ^{p2 to} m ^p4 each independently represents 0, 1, 2 or 3, and m ^p1 and m ^p5 each independently represent 1, 2 or 3, but when a plurality of Z ^p1 are present, May be the same or different. When a plurality of R ^p1 are present, they may be the same or different. When a plurality of R ^p2 are present, they may be the same. They may be different, they may be the same or different when multiple Sp ^p1 are present, and they may be the same or different when multiple Sp ^p2 are present, When a plurality of L ^p1 are present, they may be the same or different, and when a plurality of M ^p2 are present, they may be the same or different. ) Is preferred. Moreover, it is preferable to contain the said polymeric compound 1 type (s) or 2 or more types.

In the general formula (P) according to the present invention, Z ^p1 is preferably -Sp ^p2 -R ^p2 .

In the general formula (P), m ^p1 + m ^p5 is preferably 2 or more.

In the general formula (P), L ^p1 represents a single bond, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, —COOC _{2. H 4 -, - OCOC 2 H} 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - (CH 2) z _{-C (= O) -O -,} - (CH 2) z-O- (C = O) -, - O- (C = O) - (CH 2) z -, - CH = CH-COO-, —COO—CH═CH—, —OCOCH═CH—, — (C═O) —O— (CH ₂ ) z—, —OCF ₂ — or —C≡C—, and L ^p2 represents —OCH _{2 CH 2 O -, - COOC 2} H 4 -, - OCOC 2 H 4 -, - (CH 2) z -C (= O) -O -, - (CH 2) z-O- (C = O) - _{-O- (C = O) - (} CH 2) z -, - (C = O) -O- (CH 2) z -, - CH = CH-COO -, - COO-CH = CH -, - OCOCH _{= CH -, - C 2 H} 4 OCO- or _-C 2 _H 4 is COO-, z in the above formula is preferably an integer of 1 to 4.

In addition, at least one of L ^p1 and L ^{p2 in} the general formula (P) is — (CH ₂ ) _z —C (═O) —O— or — (CH ₂ ) z—O— (C═O). - and _{-O- (C = O) - (} CH 2) z -, - (C = O) -O- (CH 2) is preferably at least one selected from the group consisting of z-.

In the general formula (P), R ^p1 and R ^p2 are each independently the following formulas (R-1) to (R-15):

Is more preferable, it is more preferable that it is in any one of a formula (R-1)-a formula (R-3), and it is especially preferable that it is a formula (R-1).

In the general formula (P), m ^p3 represents 0, 1, 2, or 3. When m ^p2 is 1, L ^p1 is a single bond, and when m ^p2 is 2 or 3, a plurality of L ^p1 is present. At least one is preferably a single bond.

In the general formula (P), m ^p3 represents 0, 1, 2 or 3, and when m ^p3 is 1, M ^p2 is a 1,4-phenylene group, and when m ^p3 is 2 or 3, a plurality of m ^p3 are present. ^{M p2} adjacent to ^{M p1} through at least ^{L p1} of ^{M p2} which is preferably a 1,4-phenylene group.

Further, m ^{p3 in the} general formula (P) represents 0, 1, 2, or 3, and at least one of M ^p2 is a 1,4-phenylene group substituted with one or two or more fluorines. It is preferable.

Further, m ^{p4 in the} general formula (P) represents 0, 1, 2, or 3, and at least one of M ^p3 is a 1,4-phenylene group substituted with one or two or more fluorines. It is preferable.

Further, as the spacer group in the formula ^{(P) (Sp p1, Sp} p2), a single _{bond, -OCH 2 -, - (CH} 2) z O -, - CO -, - C 2 H 4 -, - _{COO -, - OCO -, -} COOC 2 H 4 -, - OCOC 2 H 4 -, - (CH 2) z -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH- _{, -CF 2 -, - CF 2} O -, - (CH 2) z -C (= O) -O -, - (CH 2) z -O- (C = O) -, - O- (C = _{O) - (CH 2) z} -, - (C = O) -O- (CH 2) z -, - O- (CH 2) z -O -, - OCF 2 -, - CH = CH-COO- , —COO—CH═CH—, —OCOCH═CH—, or —C≡C—, and Z is preferably an integer of 1 or more and 10 or less. Arbitrariness.

  The polymerizable compound of the general formula (P) according to the present invention includes a general formula (Pa), a general formula (Pb), a general formula (Pc), a general formula (Pd), a general formula (P Pe) and at least one compound selected from the group consisting of compounds represented by formula (Pf) are preferred.

(In the above general formula (Pa) to general formula (Pf), R ^p1 and R ^p2 are each independently the following formulas (RI) to (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, T is a single bond or —COO—, p, t and q are each independently 0, Represents 1 or 2,
Ring A and Ring B are each independently 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5- Represents a diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indane-2,5-diyl group, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group. Is unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxy halide having 1 to 12 carbon atoms May be substituted with a group, a halogen atom, a cyano group, or a nitro group,
Ring C represents the following formulas (ci) to (c-ix):

(In the formula, it binds to Sp ^p1 with ★ and binds to L ^p5 or L ^p6 with ★★),
Sp ^p1 and Sp ^p4 each represent a spacer group, X ^{p1 to} X ^p4 each independently represent a hydrogen atom or a halogen atom,
L ^p4 , L ^p5 , L ^p6 , L ^p7 , L ^p8 and L ^p10 are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO. _{-, - OCO -, - COOC} 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 _{O -, - (CH 2)} z -C (= O) -O -, - (CH 2) z -O- (C = O) -, - O- (C = O) - (CH 2) z - , — (C═O) —O— (CH ₂ ) _z —, —O— (CH ₂ ) _z —O—, —OCF ₂ —, —CH═CHCOO—, —COOCH═CH—, —OCOCH═CH -Or -C≡C-, wherein z represents an integer of 1 to 8, and z is preferably an integer of 1 to 4,
L ^p3 represents —CH═CHCOO—, —COOCH═CH— or —OCOCH═CH—,
L ^p9 is _{-OCH 2 -, - CH 2 O} -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 _{H 4 OCO -, - C 2} H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - (CH 2) z -C (= O) -O -, - (CH 2 _{) z -O- (C = O)} -, - O- (C = O) - (CH 2) z -, - (C = O) -O- (CH 2) z -, - O- (CH 2 _Z —O—, —OCF ₂ —, —CH═CHCOO—, —COOCH═CH—, —OCOCH═CH— or —C≡C—, wherein z represents an integer of 1-8. However, z is preferably an integer of 1 to 4,
In the compound represented by the general formula (P-a), m ^p6 and m ^p7 each independently represents 0, 1, 2 or 3, m ^p6 + m ^p7 = 2 to 5, and L ^p4 In the presence of multiple rings, they may be the same or different, and when there are multiple rings A and B, they may be the same or different,
In the compound represented by the general formula ( ^Pb ), m ^p8 and m ^p9 each independently represent 0, 1, 2, or 3, and m ^p8 + m ^p9 = 2 to 5, ^p8 = m ^p9 = 1 is preferable, and when there are a plurality of ring A and ring B, they may be the same or different,
In the compound represented by the general formula (Pc), m ^p10 and m ^p11 each independently represent 0, 1, 2, or 3, but preferably m ^p8 = m ^p9 = 0, and ring A , When there are a plurality of rings B, they may be the same or different,
In the compound represented by the general formula (Pd), m ^p12 and m ^p15 each independently represent 1, 2 or 3, m ^p13 represents 0, 1, 2 or 3, and m ^p14 represents , 0 or 1 and m ^p12 + m ^p15 = 3 to 5, when a plurality of R ^p1 are present, they may be the same or different, and when a plurality of R ^p2 are present They may be the same or different, and when there are a plurality of Sp ^p1 , they may be the same or different, and when there are a plurality of Sp ^p4 , they are the same. They may be the same or different when a plurality of L ^p5 are present, and they may be the same when a plurality of rings A and C are present. May be different,
In the compound represented by the general formula (Pe), m ^p16 and m ^p17 each independently represents 0, 1, 2 or 3, m ^p16 + m ^p17 = 2 to 5, and Z ^p2 Is a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, or 1 to carbon atoms in which a hydrogen atom is optionally substituted with a halogen atom. 15 alkoxy groups, alkenyl groups having 1 to 15 carbon atoms in which hydrogen atoms may be substituted with halogen atoms, or alkenyloxy groups having 1 to 15 carbon atoms in which hydrogen atoms may be substituted with halogen atoms represents a group, they are when L ^p8 there are a plurality may be the same or different and each ring a, they will when ring B there are a plurality, be the same or different It may have,
In the compound represented by the above general formula ^{(P-f), m p18} represents 1, 2 or ^{3, m p19} represents 1, 2 or ^3, represents the m ^{p18 +} m p19 = 2~5, When a plurality of L ^p10 are present, they may be the same or different, and when a plurality of rings A and B are present, they may be the same or different. )
The preferable structure of the compound represented by general formula (Pa)-general formula (Pf) based on this invention below is illustrated.

  Preferable examples of the compound represented by the general formula (P-a) include polymerizable compounds represented by the following formulas (P-a-1) to (P-a-31).

  Preferable examples of the compound represented by the general formula (Pb) include polymerizable compounds represented by the following formulas (Pb-1) to (Pb-39).

(In the formula, q ¹ and q ² each independently represent an integer of 1 to 12, and R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.)
The compounds represented by the general formulas (Pb-35) to (Pb-39) are preferable for increasing the solubility with the liquid crystal composition, and are represented by the general formula (Pb-35). Compounds are particularly preferred.

  Preferred examples of the compound represented by the general formula (Pc) include polymerizable compounds represented by the following formulas (Pc-1) to (Pc-52).

  The compound represented by the general formula (P-d) is preferably a compound represented by the following general formula (P-d ').

(In the compound represented by the above general formula (Pd ′), ^mp20 more preferably represents 2 or 3. The other symbols are the same as those in the above general formula (pd), and will be omitted.)
Preferred examples of the compound represented by the general formula (Pd) according to the present invention include polymerizable compounds represented by the following formulas (Pd-1) to (Pd-36).

  Preferable examples of the compound represented by the general formula (Pe) include polymerizable compounds represented by the following formulas (Pe-1) to (Pe-11).

(In the formula, r and s each independently represent an integer of 1 to 11, and R ³⁴ each independently represents a hydrogen atom or a methyl group.)
Preferable examples of the compound represented by the general formula (Pf) include polymerizable compounds represented by the following formulas (Pf-1) to (Pf-8).

(Wherein, q1 and q2 is independently an integer of 1 to 12, ^{R 3} and ^{R 4} each independently represent a hydrogen atom or a methyl group.)
The compounds represented by the general formulas (Pf-1) to (Pf-8) are preferable for improving the solubility with the liquid crystal composition.

  In order to constitute a polymerizable liquid crystal composition used for a polymer-stabilized liquid crystal display element, other polymerizations that do not contain a mesogenic moiety and are used in addition to the polymerizable compound represented by the above general formula (I) of the present invention As a functional compound, the following general formula (X1a)

(In the formula, A ¹ represents a hydrogen atom or a methyl group,
A ² is a single bond or an alkylene group having 1 to 8 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group. May be)
A ³ and A ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group do not have oxygen atoms directly bonded to each other) And each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms).
A ⁴ and A ⁷ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group do not have oxygen atoms directly bonded to each other) And each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group of 1 to 9 carbon atoms)
p represents 0-10,
B ¹ , B ² and B ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are In addition, the oxygen atoms may be independently substituted with an oxygen atom, —CO—, —COO—, or —OCO— as those in which the oxygen atoms are not directly bonded to each other, and one or more of the alkyl groups may be substituted. Each of the hydrogen atoms may be independently substituted with a halogen atom or a trialkoxysilyl group having 3 to 6 carbon atoms. Moreover, it is preferable to contain the said polymeric compound 1 type (s) or 2 or more types.

  The general formula (X1a) is preferably a compound represented by the general formula (II-b).

  The compounds represented by the general formula (II-b) are specifically compounds represented by the following formulas (II-q) to (II-z), (II-aa) to (II-al). It is preferable.

[Polymerization initiator]
As the polymerization method of the polymerizable compound used in the present invention, radical polymerization, anionic polymerization, cationic polymerization, etc. can be used, but polymerization is preferably performed by radical polymerization, radical polymerization by photo-Fries rearrangement, and initiation of photopolymerization. Radical polymerization with an agent is more preferred.
[Liquid crystal composition for polymer stabilized liquid crystal display element]
The polymerizable liquid crystal composition used for constituting the polymer-stabilized liquid crystal display element includes a liquid crystal compound exemplified above, a polymerizable compound represented by the above general formula (I), and the above other polymerizable compounds. Among the total content, the content of the polymerizable compound represented by the general formula (I) and the content of the other polymerizable compound is preferably 1% by mass or more and less than 10% by mass, The lower limit of the content of the polymerizable compound is preferably 2% by mass or more, and the upper limit is preferably less than 9% by mass, more preferably less than 7% by mass, more preferably less than 5% by mass, and more preferably less than 4% by mass. . The polymerizable liquid crystal composition used for constituting the polymer-stabilized liquid crystal display element includes the liquid crystal compound exemplified above, the polymerizable compound represented by the above general formula (I), and the above other polymerizable compounds. Of the total content of the compounds, the total content of the polymerizable compound represented by the general formula (I) and the other polymerizable compounds may contain 10% by mass or more and less than 40% by mass of the polymerizable compound. In this case, the lower limit of the total content of the polymerizable compound represented by the general formula (I) and the other polymerizable compound is preferably 12% by mass or more, more preferably 15% by mass or more, and the upper limit. The value is preferably less than 30%, more preferably less than 25%, more preferably less than 20%, and more preferably less than 15%. Furthermore, the polymerizable liquid crystal composition used for constituting the polymer-stabilized liquid crystal display element includes the liquid crystal compound exemplified above, the polymerizable compound represented by the above general formula (I), and the above other polymerizable compounds. Of the total content of the compounds, the total content of the polymerizable compound represented by the general formula (I) and the other polymerizable compound is preferably 5% by mass or more and less than 15% by mass, and preferably 7% by mass or more. More preferably, it is less than 12%. The polymerizable liquid crystal composition used for constituting the polymer-stabilized liquid crystal display element of the present invention has a total content of the polymerizable compound represented by the general formula (I) and the other polymerizable compound of 1. It is preferable to form a polymer network having a uniaxial optical anisotropy, a uniaxial refractive index anisotropy, or an orientation easy axis direction by setting the mass to 40% by mass or more. It is more preferable that the optical axis or the easy alignment axis of the network and the easy alignment axis of the low-molecular liquid crystal are formed so as to substantially coincide with each other.

  The polymerizable liquid crystal composition used for constituting the polymer-stabilized liquid crystal display element includes a polymerizable compound of the polymerizable compound represented by the general formula (I) and the other polymerizable compound. Of the total amount, the polymerizable compound represented by the general formula (I) is preferably used in the range of 10% by mass to 100% by mass, preferably 20% by mass to 80% by mass, It is more preferable to set it as mass% or more and 70 mass% or less, It is more preferable to set it as 40 mass% or more and 60 mass% or less, It is especially preferable to set it as 45 mass% or more and 55 mass% or less.

  The polymer network includes a polymer binder in which a polymer thin film is formed by aggregating a plurality of polymer networks. The polymer binder has refractive index anisotropy indicating uniaxial orientation, low molecular liquid crystal is dispersed in the thin film, and the uniaxial optical axis of the thin film and the optical axis of the low molecular liquid crystal are in substantially the same direction. The feature is that it is complete. Therefore, unlike a polymer dispersion type liquid crystal or polymer network type liquid crystal which is a light scattering type liquid crystal, light scattering does not occur and a high contrast display can be obtained in a liquid crystal element using polarized light. It is characterized in that the response time of the liquid crystal element is improved by shortening the time. Furthermore, the polymerizable liquid crystal composition used in the present invention is a PSA (Polymer Sustained Alignment) that forms a polymer network layer on the entire liquid crystal element and induces a pretilt by forming a polymer thin film layer on the liquid crystal element substrate. ) Type liquid crystal composition.

  In any concentration, it is preferable to contain at least two kinds of polymerizable compounds having different Tg and adjust Tg as necessary. The polymerizable compound that is a precursor of a polymer having a high Tg is a polymerizable compound having a molecular structure that increases the crosslink density, and preferably has 2 or more functional groups. The precursor of the polymer having a low Tg preferably has a structure in which the number of functional groups is 1, or 2 or more, and an alkylene group or the like is provided as a spacer between functional groups to increase the molecular length. When adjusting the Tg of the polymer network for the purpose of improving the thermal stability and impact resistance of the polymer network, it is preferable to appropriately adjust the ratio of the polyfunctional monomer to the monofunctional monomer. Tg is also related to thermal mobility at the molecular level in the main chain and side chain of the polymer network, and has an influence on electro-optical properties. For example, when the crosslink density is increased, the molecular mobility of the main chain is lowered, the anchoring force with the low molecular liquid crystal is increased, the drive voltage is increased, and the fall time is shortened. On the other hand, when the crosslinking density is lowered so that Tg is lowered, the thermal mobility of the polymer main chain is increased, so that the anchoring force with the low-molecular liquid crystal is lowered, the driving voltage is lowered, and the fall time is increased. The anchoring force at the polymer network interface is influenced by the molecular mobility of the polymer side chain in addition to the above Tg, and the polymer is obtained by using a polymerizable compound having a polyvalent branched alkylene group and a polyvalent alkyl group. The anchoring force of the interface is lowered. In addition, the polymerizable compound having a polyvalent branched alkylene group and a polyvalent alkyl group is effective in inducing a pretilt angle and acts in the direction of reducing the polar anchoring force.

When the polymerizable liquid crystal composition exhibits a liquid crystal phase, the polymerizable compound in the polymerizable liquid crystal composition is polymerized to increase the molecular weight of the polymerizable compound to cause phase separation of the liquid crystal composition and the polymerizable compound. . The form of separation into two phases varies greatly depending on the type of liquid crystal compound contained and the type of polymerizable compound. A phase separation structure may be formed by binodal decomposition in which an infinite number of polymerizable compound phases are generated and grown as island-like nuclei in the liquid crystal phase, and phase separation is caused by fluctuations in concentration between the liquid crystal phase and the polymerizable compound phase. A phase separation structure may be formed by spinodal decomposition. In order to form a polymer network by binodal decomposition, it is preferable that the content of at least low-molecular liquid crystal is 85% by mass or more, and the size is smaller than the wavelength of visible light by using a compound having a high reaction rate of the polymerizable compound. Innumerable nuclei of the polymerizable compound are generated to form a nano-order phase separation structure, which is preferable. As a result, when the polymerization in the polymerizable compound phase proceeds, a polymer network having a void interval shorter than the wavelength of visible light is formed depending on the phase separation structure, whereas the voids in the polymer network are caused by phase separation of the low-molecular liquid crystal phase. However, if the size of the void is smaller than the wavelength of visible light, the liquid crystal display device has high contrast, no light scattering, high contrast, strong influence of anchoring force from the polymer network, and short fall time. Is particularly preferable. The nucleation of the polymerizable compound phase in the binodal decomposition is preferably adjusted as needed as affected by changes in compatibility depending on the type and combination of compounds, reaction rate, temperature and other parameters. The reaction rate, in the case of ultraviolet polymerization, may be adjusted as appropriate to the ultraviolet exposure conditions so as to promote the reactivity depending on the functional group of the polymerizable compound, the type and content of the photoinitiator, and the ultraviolet exposure intensity. An ultraviolet exposure intensity of 20 mW / cm ² or more is preferable. When the low-molecular liquid crystal content is 85% by mass or less, it is preferable to form a polymer network with a phase separation structure by spinodal decomposition. In spinodal decomposition, a phase separation fine structure is obtained by fluctuations in the concentration of two phases with periodicity, so that visible light can be obtained. This is preferable because a uniform gap interval smaller than the wavelength is easily formed. When the proportion of the polymerizable compound is less than 15% by mass, it is preferable to form a phase separation structure by binodal decomposition, and when it is 15% by mass or more, it is preferable to form a phase separation structure by spinodal decomposition. When the content of the polymerizable compound is increased, there exists a phase transition temperature at which the low-molecular liquid crystal phase and the polymerizable compound phase are separated into two phases due to the influence of temperature. An isotropic phase is exhibited at a temperature higher than the two-phase separation transition temperature, but if it is low, separation occurs and a uniform phase separation structure cannot be obtained. When two-phase separation is performed according to temperature, it is preferable to form a phase separation structure at a temperature higher than the two-phase separation temperature. In any of the above cases, a polymer network is formed while maintaining the same alignment state as that of the low-molecular liquid crystal. The formed polymer network exhibits optical anisotropy so as to follow the orientation of the low-molecular liquid crystal. As the form of the liquid crystal layer in the polymer network, a structure in which the liquid crystal composition forms a continuous layer in the three-dimensional network structure of the polymer, a structure in which droplets of the liquid crystal composition are dispersed in the polymer, or both are mixed. Further, there is a structure in which a polymer network layer exists starting from both substrate surfaces, and only a liquid crystal layer is provided in the vicinity of the center of the opposite substrate. In any structure, it is preferable that a pretilt angle of 0 to 90 ° is induced with respect to the liquid crystal element substrate interface by the action of the polymer network. The polymer network to be formed preferably has a function of aligning the coexisting low molecular liquid crystal in the alignment direction indicated by the alignment film of the liquid crystal cell, and further has a function of pretilting the low molecular liquid crystal with respect to the polymer interface direction. It is also preferable. Introducing a polymerizable compound that pretilts a low-molecular liquid crystal with respect to the polymer interface is useful and preferable for lowering the driving voltage of the liquid crystal element. Moreover, it may have refractive index anisotropy, and it is preferable to use a polymerizable compound having a mesogenic group for the function of aligning the liquid crystal in the alignment direction.

  For vertically aligned cells such as VA mode, a polymerizable compound having a polyvalent alkyl group that does not have a mesogenic group that induces vertical alignment or a polyvalent branched alkylene group may be used, and a polymerizable compound having a mesogenic group Is also preferred in combination. When a polymer network is formed in a vertically aligned cell by phase separation polymerization using the polymerizable liquid crystal composition described above, the fibrous or columnar polymer network is in the vertical direction of the low molecular liquid crystal with respect to the liquid crystal cell substrate. It is preferable that they are formed in substantially the same direction. In addition, when a vertical alignment film that induces a pretilt angle by rubbing the liquid crystal on the cell substrate surface so as to induce a tilted alignment is used, the liquid crystal is pretilted and aligned. It is preferable that a fiber-like or columnar polymer network is inclined in the same direction as the low-molecular liquid crystal.

  Furthermore, in the method of inducing the pretilt angle while applying a voltage, when polymerizing while applying a voltage in a voltage range of about 0.9 V to 2 V higher than the threshold voltage of the polymerizable liquid crystal composition, Alternatively, it is more preferable because the columnar polymer network is formed to be inclined so as to induce a desired pretilt angle, preferably 0.1 to 30 °. The fibrous or columnar polymer network formed by any method is characterized in that the two cell substrates are connected to each other. Thereby, the thermal stability of the pretilt angle is improved, and the reliability of the liquid crystal display element can be increased.

  In addition, as a method for inducing the pretilt angle of a low-molecular liquid crystal by forming a fibrous or columnar polymer network in an inclined orientation, the alkylene group between the functional group and the mesogenic group has 6 or more carbon atoms. And a bifunctional acrylate having a small pretilt angle induction angle, a functional group, and a bifunctional acrylate having a large pretilt angle induction angle in which the number of carbon atoms of the alkylene group between the mesogenic groups is 5 or less. A desired pretilt angle can be induced by adjusting the compounding ratio of these compounds.

  Furthermore, a method of forming a fibrous or columnar polymer network by adding a polymerizable compound having a reversible photo-alignment function in a range of at least 0.01% to 1% is mentioned. In this case, the trans form has a rod-like shape similar to that of the low-molecular liquid crystal and affects the alignment state of the low-molecular liquid crystal. The trans isomer contained in the polymerizable liquid crystal composition of the present invention has a low molecular weight that is aligned so that the direction of ultraviolet light travels parallel to the long axis direction of the rod-shaped molecule when ultraviolet light is exposed as parallel light from the top surface of the cell. At the same time, the liquid crystal is aligned so as to be aligned in the molecular long axis direction of the trans form. When ultraviolet rays are exposed while being inclined with respect to the cell, the molecular long axis of the trans body is oriented in the inclined direction, and the liquid crystal is oriented in the inclined direction of the ultraviolet rays. That is, a pre-tilt angle is induced and a photo-alignment function is exhibited. The pretilt angle induced by crosslinking the polymerizable compound at this stage is fixed by a fibrous or columnar polymer network formed by polymerization phase separation. Therefore, the pretilt angle that is important in the VA mode can be induced by a method of separating the polymerization phase while applying a voltage, a method of adding a plurality of polymerizable compounds having different induced pretilt angles, and a reversible photo-alignment function. The liquid crystal element of the present invention can be produced using a method of aligning low-molecular liquid crystals and polymerizable liquid crystal compounds in the direction in which ultraviolet rays travel by using the photo-alignment function exhibited by the polymerizable compound, and separating the polymerization phase as necessary. .

  The polymerizable compound having a photo-alignment function is preferably a photoisomeric compound that absorbs ultraviolet rays to become a trans isomer, and further, the polymerizable compound having a photo-alignment function has a reaction rate of the polymerizable compound having the photo-alignment function. It is preferably slower than the reaction rate of the polymerizable compound other than the above. When UV exposure is performed, the polymerizable compound having a photo-alignment function immediately becomes a trans isomer, and when aligned in the light traveling direction, the surrounding liquid crystal compound including the polymerizable property is aligned in the same direction. At this time, the pretilt angle in the direction in which the UV light travels when the polymer phase separation proceeds and the long axis direction of the low molecular liquid crystal and the easy axis direction of the polymer network are aligned with the easy axis of the polymerizable compound having a photo-alignment function. Is induced.

  Furthermore, in parallel alignment cells such as IPS and FFS modes, the polymer liquid crystal composition is used for the alignment direction of the alignment film having a fibrous or columnar polymer network on the liquid crystal cell substrate surface by phase separation polymerization. The low-molecular liquid crystals are aligned in parallel, but they are formed in the same direction as the refractive index anisotropy or easy-orientation axis direction of the formed fibrous or columnar polymer network and the alignment direction of the low-molecular liquid crystals. Is preferred. Furthermore, it is more preferable that the fibrous or columnar polymer network is present in substantially the entire cell except for the voids in which the low-molecular liquid crystal is dispersed. For the purpose of inducing the pretilt angle with respect to the polymer interface direction, it is preferable to use a polyvalent alkyl group having no mesogenic group, or a polymerizable compound having a polyvalent alkylene group and a polymerizable compound having a mesogenic group. .

  Furthermore, although the electro-optical characteristics are affected by the surface area of the polymer network interface and the gap spacing of the polymer network, it is important not to cause light scattering, and the average gap spacing is preferably smaller than the wavelength of visible light. For example, there is a method of increasing the monomer composition content in order to increase the surface area of the interface and reduce the gap interval. As a result, the polymer phase is formed so that the surface area of the interface is increased by changing the polymerization phase separation structure and making the gap interval fine, and the drive voltage and the fall time are shortened. The polymerization phase separation structure is also affected by the polymerization temperature.

  In the present invention, it is preferable to obtain a phase separation structure having fine voids by polymerizing at a high phase separation rate. The phase separation rate is greatly influenced by the compatibility between the low-molecular liquid crystal and the polymerizable compound and the polymerization rate. Since it largely depends on the molecular structure and content of the compound, it is preferable to adjust the composition as appropriate. When the compatibility is high, it is preferable to use a polymerizable compound having a high polymerization rate. In the case of ultraviolet polymerization, it is preferable to increase the ultraviolet intensity. It is also preferable to increase the content of the polymerizable compound in the polymerizable liquid crystal composition. When the compatibility is low, the phase separation rate is sufficiently high, which is preferable for producing the liquid crystal element of the present invention. As a method for reducing the compatibility, a method of polymerizing at a low temperature can be mentioned. When the temperature is lowered, the degree of alignment order of the liquid crystal is increased and the compatibility between the liquid crystal and the monomer is decreased, so that the polymerization phase separation rate can be increased. Still another method includes a method in which the polymerizable liquid crystal composition is polymerized at a temperature showing a supercooled state. In this case, it is sufficient to make the temperature slightly lower than the melting point of the polymerizable liquid crystal composition. Therefore, it is preferable that the phase separation can be accelerated only by lowering the temperature by several degrees. As a result, the polymer phase separation structure corresponding to the case where a monomer composition content of several tens of percent is added to the liquid crystal, that is, the surface area of the polymer network interface that acts to shorten the fall time is large, and the gap spacing is large. A fine polymer network structure is formed. Therefore, it is preferable that the polymerizable liquid crystal composition of the present invention is appropriately adjusted in consideration of the alignment function, the crosslinking density, the anchoring force, and the gap interval so that the fall time is shortened.

In a liquid crystal device using the polymerizable liquid crystal composition of the present invention, it is necessary to prevent light scattering in order to obtain a high contrast display. It is important to control the phase separation structure to obtain an appropriate polymer network layer structure so as to obtain switching characteristics. The polymer network layer structure will be specifically described as follows.
<Continuous structure of polymer network layer>
A structure in which a polymer network layer is formed on the entire surface of the liquid crystal display element in the liquid crystal phase and the liquid crystal phase is continuous, and the orientation axis of the polymer network and the uniaxial optical axis are substantially in the same direction as the orientation axis of the low-molecular liquid crystal It is preferable that the polymer network is formed so as to induce a pretilt angle of the low-molecular liquid crystal, and light is obtained by reducing the average gap distance of the polymer network to be smaller than the wavelength of visible light and smaller than at least 450 nm. Since scattering does not occur, it is preferable. Furthermore, in order to make the fall time of the response shorter than the response time of the low-molecular liquid crystal alone due to the interaction effect (anchoring force) between the polymer network and the low-molecular liquid crystal, it is preferable to be in the range of 50 nm to 450 nm. In order that the influence of the cell thickness of the liquid crystal is small and the fall time is as long as the cell thickness is large, at least the average gap interval is in the range of around 200 nm and the upper limit is around 450 nm. It is preferable to enter. Increasing the drive gap increases the average gap spacing. However, in order to suppress the increase in drive voltage to 25 V or less and shorten the fall response time, it is sufficient to enter the range from about 250 nm to 450 nm. The fall response time can be improved in the range of about 5 msec to about 1 msec, which is preferable. Further, in order to suppress the drive voltage from increasing within about 5V, it is preferable that the average gap interval is in the range of about 300 nm to 450 nm. Furthermore, it is also possible to control the average gap interval of the polymer network so that the falling response time is a high-speed response of 1 msec or less. Although the drive voltage may increase to 30 V or more, the average gap interval may be set between about 50 nm and about 250 nm, and in order to reduce it to 0.5 msec or less, it is preferable to set from about 50 nm to about 200 nm. The average diameter of the polymer network is in the range of 20 nm to 700 nm, contrary to the average gap spacing. As the content of the polymerizable compound increases, the average diameter tends to increase. Increasing the polymerization phase separation rate by increasing the reactivity increases the density of the polymer network and decreases the average diameter of the polymer network. Therefore, the phase separation conditions may be adjusted as necessary. When the content of the polymerizable compound is 10% or less, the average diameter is preferably 20 nm to 160 nm, and when the average gap distance is 200 nm to 450 nm, the average diameter is 40 nm to 160 nm. preferable. When the polymerizable compound content is greater than 10%, a range of 50 nm to 700 nm is preferable, and a range of 50 nm to 400 nm is more preferable.
<Discontinuous structure of polymer network layer>
In contrast to a structure in which a polymer network layer is formed on the entire surface of a liquid crystal display element and the liquid crystal phase is continuous, if the content of the polymerizable compound is low and the amount necessary for the polymer network layer to cover the entire cell is insufficient, the polymer network Layers are formed discontinuously. When the polarity of the substrate surface such as polyimide alignment film is high, the polymerizable compound tends to gather near the liquid crystal cell substrate interface, and the polymer network layer is formed so that the polymer network grows from the substrate surface and adheres to the substrate interface. A polymer network layer, a liquid crystal layer, a polymer network layer, and a counter substrate are stacked in this order from the surface. Polymer having a laminated structure of polymer network layer / liquid crystal layer / polymer network layer and having a thickness of at least 0.5%, preferably 1%, more preferably 5% or more of the cell thickness in the cell cross-sectional direction When the network layer is formed, the effect of shortening the fall time due to the action of the anchoring force between the polymer network and the low-molecular liquid crystal is exhibited and a favorable tendency is exhibited. However, since the influence of the cell thickness increases, if the fall time becomes longer as the cell thickness is increased, the thickness of the polymer network layer may be increased as necessary. The polymer network structure in the polymer network layer is such that the low-molecular liquid crystal and the easy-orientation axis or uniaxial optical axis are aligned in substantially the same direction, and the low-molecular liquid crystal is formed so as to induce a pretilt angle. Just do it. The average gap distance is preferably in the range of 90 nm to 450 nm.

  For example, when the content of the polymerizable compound is 1% by mass to 6% by mass, it is preferable to use a bifunctional monomer having a mesogenic group having a high anchoring force, and the polymerization rate is low with a structure having a short distance between the functional groups. It is preferable to use a fast bifunctional monomer, and it is preferable to form a polymer phase separation structure at a low temperature of 0 ° C. or lower. When the content of the polymerizable compound is 6% by mass to less than 10% by mass, a combination of the bifunctional monomer and a monofunctional monomer having a low anchoring force is preferable, and a range of 25 ° C. to −20 ° C. is necessary. It is preferable to form a polymer phase separation structure. Furthermore, if the melting point is room temperature or higher, it is preferable to lower the melting point by about 5 ° C. because the same effect as low temperature polymerization can be obtained. When the content of the polymerizable compound is changed from 10% by mass to 40% by mass, the influence of the polymer binder or the polymer network greatly affects the orientation and driving voltage of the low molecular liquid crystal and increases the driving voltage. It is preferable to use a polymerizable compound having a mesogenic group having an orientation function and a relatively weak anchoring force. For example, a polymerizable compound having a weak anchoring force and having a mesogenic group is effective to increase the number of carbon atoms of an alkylene group between the functional group and the mesogenic group, and preferably has 5 to 10 carbon atoms. In addition, when the polymerizable compound exceeds 30% by mass, liquid crystal droplets may be dispersed in the polymer binder. Even in this case, the polymer binder has a refractive index anisotropy and is oriented on the substrate surface. It is preferable that the orientation direction indicated by the film is aligned with the optical axis direction of the polymer binder.

  The higher the concentration of the polymerizable compound in the polymerizable liquid crystal composition, the greater the anchoring force between the liquid crystal composition and the polymer interface, and the higher the τd. On the other hand, when the anchoring force between the liquid crystal composition and the polymer interface increases, τr decreases. In order to make the sum of τd and τr less than 1.5 ms, the concentration of the polymerizable compound in the polymerizable liquid crystal composition is 1% by mass or more and less than 40% by mass, and 2% by mass or more and 15% by mass or less. Preferably, 3 mass% or more and 8 mass% or less are more preferable.

When used in a TFT drive liquid crystal display element, it is necessary to improve the reliability such as suppression of flicker and afterimages caused by printing, and the voltage holding ratio is an important characteristic. The cause of lowering the voltage holding ratio is considered to be ionic impurities contained in the polymerizable liquid crystal composition. In particular, mobile ions strongly influence the voltage holding ratio. Therefore, it is preferable to remove the mobile ions by performing a purification treatment or the like so that at least a specific resistance of 10 ¹⁴ Ω · cm or more is obtained. In addition, when a polymer network is formed by radical polymerization, the voltage holding ratio may decrease due to ionic impurities generated from the photopolymerization initiator, etc., but the polymerization initiator generates a small amount of organic acid and low-molecular byproducts. Is preferably selected.
[Polymer stabilized liquid crystal display element]
The liquid crystal display element of the present invention contains a polymer or copolymer in the liquid crystal composition, and the content of the polymer or copolymer is 1 mass of the total mass of the liquid crystal composition and the polymer or copolymer. The liquid crystal display device has the same structure as the liquid crystal display device according to the prior art except that the content is less than 40% and less than 40% by mass. That is, the polymer-stabilized liquid crystal display element according to the present invention has a structure in which a liquid crystal layer is sandwiched between two transparent substrates having electrodes on at least one side. The liquid crystal display element of the present invention preferably has an alignment layer for aligning the liquid crystal composition on at least one transparent substrate. By applying a voltage to the alignment layer provided on the substrate and the electrode provided on the substrate, the alignment of the liquid crystal molecules is controlled. The polymer network or polymer binder has a uniaxial refractive index anisotropy or an easy axis direction, and the optical axis direction or the easy axis direction of the polymer network or the polymer binder and the easy axis direction of the low molecular liquid crystal are the same direction. Preferably there is. In this respect, it differs from a light scattering polymer network liquid crystal or polymer dispersed liquid crystal that does not have a uniaxial refractive index anisotropy or an orientation easy axis direction. Furthermore, it is preferable that the orientation easy axis direction of the alignment layer is the same as the orientation easy axis direction of the polymer network or the polymer binder. By providing a polarizing plate, a retardation film, etc., display is performed using this orientation state. The liquid crystal display element can be applied to operation modes such as TN, STN, ECB, VA, VA-TN, IPS, FFS, π cell, OCB, and cholesteric liquid crystal. Among these, VA, IPS, FFS, VA-TN, TN, and ECB are particularly preferable. The liquid crystal display element of the present invention is a PSA (Polymer Sustained Alignment) type liquid crystal display element having a polymer or copolymer on the alignment film in that the liquid crystal composition contains a polymer or copolymer. Is different.

  The distance (d) between the substrates of the polymer-stabilized liquid crystal display element of the present invention is preferably in the range of 2 to 5 μm, and more preferably 3.5 μm or less. In general, the birefringence is adjusted so that the product of the birefringence of the liquid crystal composition and the cell thickness is close to 0.275. In the polymerizable liquid crystal composition of the present invention, a polymer network is formed after the polymerization phase separation. Therefore, the birefringence of the liquid crystal display element when an electric field is applied is lowered due to the anchoring force action of the polymer network and the optical properties of the polymer network, so that it is included in the liquid crystal composition, the polymerization composition, or the polymerizable liquid crystal composition. The product of the birefringence (Δn) and the distance (d) between the substrates is particularly preferably in the range of 0.3 to 0.4 μm when the driving voltage is increased within about 5 V due to the formation of the polymer network. A range of 0.30 to 0.35 μm is more preferable for an increase within a range, and a range of 0.29 to 0.33 μm is particularly preferable for an increase within a drive voltage of 1 V. By making the product of the distance (d) between the substrates of the liquid crystal display element and the product of the birefringence (Δn) of the liquid crystal composition and the distance (d) between the substrates within the above ranges, the transmittance is limited to only low-molecular liquid crystals. It is possible to obtain a display that is relatively high and has a high-speed response and favorable color reproducibility. The birefringence of the liquid crystal composition used for the polymerizable liquid crystal composition may be set so that the product of the cell thickness (d) and the birefringence index (Δn) is 1 to 1.9 times with respect to 0.275. preferable.

  The driving voltage of the polymer-stabilized liquid crystal display element of the present invention is not determined only by the dielectric anisotropy or elastic constant of the liquid crystal composition, but greatly by the anchoring force acting between the liquid crystal composition and the polymer interface. Affected. For example, Japanese Patent Application Laid-Open No. 6-222320 discloses the relationship of the following formula as a description regarding the driving voltage of a polymer dispersion type liquid crystal display element.

(Vth represents a threshold voltage, 1Kii and 2Kii represent elastic constants, i represents 1, 2 or 3, Δε represents dielectric anisotropy, and <r> represents a transparent polymer substance interface. (Indicates the average gap distance, A indicates the anchoring force of the transparent polymer substance to the liquid crystal composition, and d indicates the distance between the substrates having transparent electrodes.)
According to this, the driving voltage of the light-scattering liquid crystal display element is determined by the average gap spacing at the interface of the transparent polymer material, the distance between the substrates, the elastic constant / dielectric anisotropy of the liquid crystal composition, and the transparency with the liquid crystal composition. Determined by the anchoring energy between the conductive polymer materials.

  Among these, parameters that can be controlled by the liquid crystal display element of the present invention are liquid crystal properties and anchoring force between polymers. Since the anchoring force largely depends on the molecular structure of the polymer and the molecular structure of the low-molecular liquid crystal, if a polymerizable compound having a strong anchoring force is selected, the response time can be shortened to 1.5 ms or less. At the same time, since the driving voltage increases to 30 V or higher, it is preferable to adjust the composition by appropriately selecting the liquid crystal compound and the polymerizable compound so that the driving voltage is 30 V or lower and the response speed is 1.5 ms or lower. . It is preferable to adjust the composition so that the driving voltage and the response speed are balanced by appropriately blending a polymer precursor having a strong anchoring force and a polymer precursor having a weak anchoring force. On the other hand, as the physical properties of the liquid crystal composition required for lowering the driving voltage, it is particularly preferable that the dielectric anisotropy is 6 or more for P-type liquid crystal and -3 or less for N-type liquid crystal. . The birefringence is preferably 0.09 or more. Furthermore, it is more preferable to make the birefringence of the liquid crystal composition and the refractive index of the fibrous or columnar polymer network as close as possible to eliminate light scattering. However, since the retardation of the liquid crystal element is affected by the concentration of the polymer precursor, it is preferable to use the liquid crystal composition with an increased or decreased birefringence so that the necessary retardation can be obtained.

  The polymer-stabilized liquid crystal display element of the present invention is irradiated with energy rays while the above-described liquid crystal composition is set to −50 ° C. to 30 ° C. to polymerize a polymerizable compound and have a refractive index anisotropy in the liquid crystal composition. Or it is preferable to be obtained by forming a polymer network having an orientation axis direction. The upper limit of the polymerization temperature is 30 ° C, preferably 20 ° C to -10 ° C. It has been found that τd is further accelerated by low temperature polymerization and room temperature polymerization depending on the polymerizable compound composition. This is because 1) the polymerization is performed in a state where the orientation degree of the liquid crystal molecules is increased at a low temperature, and 2) the phase separation is facilitated by reducing the compatibility between the polymer polymerized by the low temperature polymerization and the liquid crystal composition. The phase separation speed is increased and the gap distance of the polymer network becomes fine. 3) Even if a polymerizable compound having a relatively low anchoring force is used, the influence of the anchoring force seems to be strong because the gap gap is fine. This is thought to be due to the formation of a refractive index anisotropic polymer network.

  Furthermore, the polymer-stabilized liquid crystal display device of the present invention is a polymer network or polymer binder having a uniaxial refractive index anisotropy or an orientation easy axis direction, and the optical axis direction or the orientation easy axis direction of the polymer binder is pretilt with respect to the transparent substrate. It is preferably formed to form a corner, and the orientation of the low-molecular liquid crystal is controlled by adjusting the strength of the electric field, and a voltage is applied to the liquid crystal layer described above by tilting it with respect to the substrate surface. However, it is preferable that the polymerizable compound be polymerized by irradiation with energy rays to obtain a polymer having a refractive index anisotropy or an orientation easy axis direction in the liquid crystal composition. In the vertically oriented VA mode, a voltage is applied so that the pretilt angle is within 20 degrees with respect to the normal direction of the substrate, and polymerization is carried out, whereby the portulsion used in the current VA mode cell is used. This is particularly preferable because it not only has an effect corresponding to the fine polymer protrusions of the PSA liquid crystal, but also exhibits a high-speed response that cannot be realized by PSA. In addition, by applying an electric field direction from a plurality of directions to form a polymer, a multi-domain can be formed, and a viewing angle can be improved, which is more preferable. Furthermore, the alignment direction of the low-molecular liquid crystal is regulated by applying photo-alignment treatment or rubbing alignment treatment to the low-molecular liquid crystal to induce a pretilt angle at the substrate interface vertical alignment film interface. The occurrence of orientation defects is preferably suppressed, and it is also preferable to perform the orientation treatment so as to incline in a plurality of directions. The liquid crystal layer is applied with an alternating electric field in a temperature range of −50 ° C. to 30 ° C. as appropriate to a liquid crystal composition containing a polymerizable compound, and irradiated with ultraviolet rays or an electron beam, thereby providing refractive index anisotropy. Is formed in the liquid crystal so that the optical axis direction of the polymer network forms a pretilt angle with respect to the substrate surface. This pretilt angle is a liquid crystal element in which the polymer axis after polymerization is tilted with respect to the substrate surface when the polymer phase is separated in an alignment state induced by applying an electric field due to the dielectric anisotropy of the low-molecular liquid crystal It is more preferable that the polymerizable compound has a high molecular weight.

  The two substrates used in the polymer-stabilized liquid crystal display element of the present invention can be made of a transparent material having flexibility such as glass or plastic. A transparent substrate having a transparent electrode layer 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 or a thin film diode may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. 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. 1.5 to 10 μm is more preferable. When a polarizing plate is used, the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d is adjusted so that the contrast is maximized, and 1/550 nm is reduced depending on the display mode. It is preferable to make it 2 or 1/4. 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 columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like. 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.

  As a method for sandwiching the polymerizable liquid crystal composition between two substrates, a normal vacuum injection method, an ODF method, or the like can be used. In the ODF liquid crystal display device manufacturing process, a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed. A liquid crystal display element can be produced by bonding a front plane and a back plane after dropping a predetermined amount of the polymerizable liquid crystal composition under air. The polymerizable liquid crystal composition used in the present invention can be suitably used because the liquid crystal / monomer composite material can be stably dropped in the ODF process.

  As a method for polymerizing a polymerizable compound, an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, ultraviolet rays or electron beams, which are active energy rays, are irradiated singly or in combination or sequentially. The method of polymerizing by is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. In addition, when polymerization is performed in a state where the polymerizable liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. . In addition, it is preferable to apply an alternating electric field to the polymerizable liquid crystal composition containing the polymerizable compound in a temperature range of −50 ° C. to 20 ° C. and irradiate ultraviolet rays or electron beams. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 100 Hz to 5 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 a horizontal electric field type MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

As for the temperature at the time of irradiation, the polymerizable liquid crystal composition preferably has a temperature range of -50 ° C to 30 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate ultraviolet rays in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and it is preferable to cut and use ultraviolet rays of less than 365 nm as necessary. Intensity of ultraviolet irradiation is ^preferably from ^{0.1mW / cm 2 ~100W / cm 2} , 2mW / cm 2 ~50W / cm 2 is more preferable. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays.
<Polymerizable liquid crystal composition for retardation plate>
The polymerizable compound represented by the general formula (I) of the present invention is mixed with several other polymerizable (liquid crystal) compounds to form a polymerizable liquid crystal composition, and then aligned and polymerized in a liquid crystal state. A film-like polymer having a uniform orientation can be produced, and this can be used for a polarizing plate, a phase difference plate (optical anisotropic body) and the like. The production of such an optical anisotropic body will be described below. Other polymerizable liquid crystal compounds to be mixed with the polymerizable compound represented by the general formula (I) of the present invention include compounds represented by the following general formula.
(Monofunctional polymerizable liquid crystal compound)
As the polymerizable liquid crystal compound (II) having one polymerizable functional group in the molecule, a compound represented by the following general formula (II-1) is preferable.

(Wherein P ² represents a polymerizable functional group, S ¹ represents an alkylene group having 1 to 18 carbon atoms, one —CH ₂ — in the alkylene group or two or more non-adjacent ones. -CH ₂ - are each independently -O -, - COO -, - it may be substituted OCO- or by --OCO-O-, 1 or 2 or more hydrogen atoms possessed by the alkylene group, halogen X ¹ may be substituted by an atom or a CN group, and X ¹ may be —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—. , -S-CO -, - O -CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = _{H -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF—, —C≡C— or a single bond (where P ² —S ¹ and S ¹ —X ¹ are —O—O—, —O—NH—, —S—S— and —O) -S- group is not included.), Q1 represents 0 or 1, MG represents a mesogenic group, R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms. Group represents a straight-chain or branched alkenyl group having 1 to 12 carbon atoms, one of the alkyl group and alkenyl group CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S- CO -, - O-COO - , - CO-NH -, - NH-CO -, - NH -, - N (CH 3) -, - CH = CH-COO -, - CH = CH-OCO- , —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C≡C—, which are substituted on the alkyl group and the alkenyl group. One or two or more hydrogen atoms may be independently substituted with a halogen atom or a cyano group, and when a plurality of hydrogen atoms are substituted, they may be the same or different. However, the compound represented by the above general formula (I) is excluded. )
Here, P ² preferably represents a substituent selected from a polymerizable group represented by the following formula (P-2-1) to formula (P-2-20).

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

Further, S ¹ is preferably represents an alkylene group having 1 to 15 carbon atoms, one -CH 2 in the alkylene group _- or nonadjacent two or more -CH 2 _- are each independently -O-, -COO-, -OCO- or -OCO-O- may be substituted, and one or more hydrogen atoms of the alkylene group may be substituted by a halogen atom or a CN group. good, S ¹ is more preferably an alkylene group having 1 to 12 carbon atoms, one -CH 2 in the alkylene group _- or nonadjacent two or more -CH 2 _- are each independently And may be substituted by -O-, -COO-, -OCO- or -OCO-O-.

X ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH—, —NH—CO—, _{-CF 2 O -, - OCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 _{-, - OCO-CH 2 CH} 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO-, It preferably represents —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. ¹ _{-O -, - OCH 2 -,} - CH 2 O -, - CO -, - COO -, - OCO -, - OCO-O -, - _{F 2 O -, - OCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - More preferably, it represents CH ₂ —OCO—, —CH═CH—, —CF═CF—, —C≡C— or a single bond.
MG represents a mesogenic group and has the general formula (II-b)

(In the formula, B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, tetrahydrothio group, Pyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5- Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2 , 7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthyl Benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group , [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7- Represents a diyl group, and as a substituent, one or more F, Cl, CF ₃ , OCF ₃ , CN group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, 1 to 1 carbon atom An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom An alkenoyl group of 2 to 8 and / or May have a alkenoyloxy group of atom number 2-8, the Z1 and Z2 each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH ₂ O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ — , —OCOCH ₂ CH ₂ —, —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, the number of carbon atoms which may have a halogen atom is 2 10 represents an alkyl group or a single bond, r1 represents 0, 1, 2 or 3, and when a plurality of B1 and Z1 are present, they may be the same or different. The Among these, it is preferable that B1, B2, and B3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, or a 2,6-naphthylene group.

R ²¹ preferably represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, and the alkyl group And one —CH ₂ — in the alkenyl group or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, —O—CO. Replaced by -O-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, or -C≡C- One or two or more hydrogen atoms of the alkyl group and the alkenyl group may be independently substituted with a halogen atom or a cyano group. Even if it ’s different, Good.
Examples of the general formula (II-1) include compounds represented by the following general formulas (II-1-1) to (II-1-4), but are not limited to the following general formulas. is not.

In the formula, each of P ² , S ¹ , X ¹ , q ¹ , and R ²¹ represents the same definition as in the general formula (II-1),
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (II-b), and may be the same or different,
Z11, Z12, Z13 and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-b), and may be the same or different,
The compounds represented by the general formulas (II-1-1) to (II-1-4) are represented by the following formulas (II-1-1-1) to (II-1-1-26). The compounds represented are exemplified, but not limited thereto.

In the formula, R ^c represents a hydrogen atom or a methyl group, m represents an integer of 0 to 18, n represents 0 or 1, and R ²¹ has the same definition as in the general formula (II-1). R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ — in which one —CH ₂ — may be substituted by —O—, —CO—, —COO—, —OCO—. It preferably represents a linear alkyl group of 1 to 6 or a linear alkenyl group of 1 to 6 carbon atoms,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom The alkenoyl group having 2 to 8 carbon atoms and the alkenoyloxy group having 2 to 8 carbon atoms may be contained.

The total content of the polymerizable liquid crystal compound having one polymerizable functional group in the molecule is preferably 0 to 90% by mass and preferably 0 to 85% by mass in the total amount of the polymerizable liquid crystal compound to be used. It is more preferable to contain, and it is especially preferable to contain 0-80 mass%.
(Bifunctional polymerizable liquid crystal compound)
As the polymerizable liquid crystal compound (III) having two polymerizable functional groups in the molecule, a compound represented by the following general formula (III-1) is preferable.

(In the formula, P ² and P ³ each independently represent a polymerizable functional group, S ¹ and S ² each independently represent an alkylene group having 1 to 18 carbon atoms, One —CH ₂ — or two or more non-adjacent —CH ₂ — may each independently be replaced by —O—, —COO—, —OCO— or —OCO—O—, One or more hydrogen atoms of the alkylene group may be substituted with a halogen atom or a CN group, and X ¹ and X ² are each independently —O—, —S—, —OCH ₂ —. , —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—. _{, -SCH 2 -, - CH 2} S -, - CF 2 O -, - OCF 2 -, - CF 2 S-, _{SCF 2 -, - CH = CH} -COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 _{CH 2 -, - CH 2 CH} 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO-, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ² —S ¹ , P ³ — S ² , S ¹ -X ¹ and S ² -X ² do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.), Q 1 and q 2 are Each independently represents 0 or 1, and MG represents a mesogenic group.)
Here, P ² and P ³ each independently preferably represent a substituent selected from a polymerizable group represented by the following formula (P-2-1) to formula (P-2-20). .

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

S ¹ and S ² each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or two or more non-adjacent — CH ₂ — may be independently substituted with —O—, —COO—, —OCO— or —OCO—O—, and one or more hydrogen atoms of the alkylene group may be a halogen atom. Or may be substituted by a CN group, and S ¹ and S ² each independently preferably represents an alkylene group having 1 to 12 carbon atoms, and one —CH ₂ — or Two or more non-adjacent —CH ₂ — may be each independently substituted with —O—, —COO—, —OCO— or —OCO—O—.

X ¹ and X ² are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH. _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- , —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ — _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single It is preferable to represent a bond, and X ¹ and X ² are each independently —O—, —OCH ₂ —, —CH ₂ O—, — CO—, —COO—, —OCO—, —O—CO—O—, —CF ₂ O—, —OCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH _{= CH -, - OCO-CH} = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO _{-CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF -, - C≡C- or may represent a single bond More preferred.
MG represents a mesogenic group and has the general formula (III-b)

(In the formula, B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, tetrahydrothio group, Pyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5- Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2 , 7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthyl Benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group , [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7- Represents a diyl group, and as a substituent, one or more F, Cl, CF ₃ , OCF ₃ , CN group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, 1 to 1 carbon atom An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom An alkenoyl group of 2 to 8 and / or May have a alkenoyloxy group of atom number 2-8, the Z1 and Z2 each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH ₂ O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ — , —OCOCH ₂ CH ₂ —, —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, the number of carbon atoms which may have a halogen atom is 2 10 represents an alkyl group or a single bond, r1 represents 0, 1, 2 or 3, and when a plurality of B1 and Z1 are present, they may be the same or different. The Among these, it is preferable that B1, B2, and B3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, or a 2,6-naphthylene group.

  Examples of the general formula (III-1) include compounds represented by the following general formulas (III-1-1) to (III-1-4), but are not limited to the following general formulas. is not.

In the formula, P ² , S ¹ , X ¹ , q ¹ , X ² , S ² , q ² , and P ³ each represent the same definition as in the general formula (III-1),
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (III-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 and Z2 in the general formula (III-b), respectively, and may be the same or different.

  Among the compounds represented by the general formulas (III-1-1) to (III-1-4), in the compounds represented by the general formulas (III-1-2) to (III-1-4) It is preferable to use a compound having three or more ring structures because the orientation of the obtained optical anisotropic body is good and the curability is good, and the compound represented by formula (III) having three ring structures in the compound is preferable. It is particularly preferable to use a compound represented by -1-2).

  The compounds represented by the general formulas (III-1-1) to (III-1-4) are represented by the following formulas (III-1-1-1) to (III-1-1-21). The compounds represented are exemplified, but not limited thereto.

In the formula, R ^d and R ^e each independently represent a hydrogen atom or a methyl group,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom It may have an alkenoyl group having 2 to 8 carbon atoms or an alkenoyloxy group having 2 to 8 carbon atoms,
m1 and m2 each independently represent an integer of 0 to 18, and n1, n2, n3, and n4 each independently represent 0 or 1.

  The liquid crystal compound having two polymerizable functional groups can be used alone or in combination of two or more, but preferably 1 to 5 types, more preferably 2 to 5 types.

The total content of the polymerizable liquid crystal compound having two polymerizable functional groups in the molecule is preferably 10 to 90% by mass of the total amount of the polymerizable liquid crystal compound to be used, and is preferably 15 to 85% by mass. It is more preferable to contain 20 to 80% by mass.
(Polyfunctional polymerizable liquid crystal compound)
As the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule, it is preferable to use a compound having three polymerizable functional groups. As the polyfunctional polymerizable liquid crystal compound having three polymerizable functional groups in the molecule, a compound represented by the following general formula (IV-1) is preferable.

(Wherein P ^{2 to} P ⁴ each independently represents a polymerizable functional group, S ^{1 to} S ³ each independently represents an alkylene group having 1 to 18 carbon atoms, One —CH ₂ — or two or more non-adjacent —CH ₂ — may each independently be replaced by —O—, —COO—, —OCO— or —OCO—O—, One or more hydrogen atoms of the alkylene group may be substituted with a halogen atom or a CN group, and X ^{1 to} X ³ are each independently —O—, —S—, —OCH ₂ —. , —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—. _{, -SCH 2 -, - CH 2} S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - S _{F 2 -, - CH = CH} -COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 _{CH 2 -, - CH 2 CH} 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO-, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ² —S ¹ , P ³ — ^{S 2, P 4 -S 3,} S 1 -X 1, S 2 -X 2, and ^S 3 ^-X 3 may, -O-O -, - O -NH -, - S-S- and -O- S-group is not included.), Q1 to q4 each independently represents 0 or 1, and MG represents a mesogenic group.)
Here, each of P ^{2 to} P ⁴ independently preferably represents a substituent selected from a polymerizable group represented by the following formula (P-2-1) to formula (P-2-20). .

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

Further, each of S ^{1 to} S ³ independently preferably represents an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or two or more — that are not adjacent to each other. CH ₂ — may be independently substituted with —O—, —COO—, —OCO— or —OCO—O—, and one or more hydrogen atoms of the alkylene group may be a halogen atom. Alternatively, it may be substituted with a CN group, and S ^{1 to} S ³ each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and one —CH ₂ — in the alkylene group or Two or more non-adjacent —CH ₂ — may be each independently substituted with —O—, —COO—, —OCO— or —OCO—O—. X ^{1 to} X ³ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH. _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- , —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ — _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single preferably represents a ^bond, X 1 to X ³ are each _{independently, -O -, - OCH 2 -} , - CH 2 O -, - C _{-, - COO -, - OCO} -, - OCO-O -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF -, - C≡C- or more may represent a single bond preferable.
MG represents a mesogenic group and has the general formula (IV-b)

(In the formula, B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, tetrahydrothio group, Pyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5- Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2 , 7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthyl Benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group , [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7- Represents a diyl group, and as a substituent, one or more F, Cl, CF ₃ , OCF ₃ , CN group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, 1 to 1 carbon atom An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom An alkenoyl group of 2 to 8 and / or May have a alkenoyloxy group of atom number 2-8, the Z1 and Z2 each independently, -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH ₂ O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ — , —OCOCH ₂ CH ₂ —, —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, the number of carbon atoms which may have a halogen atom is 2 10 represents an alkyl group or a single bond, r1 represents 0, 1, 2 or 3, and when a plurality of B1 and Z1 are present, they may be the same or different. The Among these, it is preferable that B1, B2, and B3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, or a 2,6-naphthylene group.
Examples of the general formula (IV-1) include compounds represented by the following general formulas (IV-1-1) to (IV-1-8), but are not limited to the following general formulas. is not.

^{Wherein, P 2, S 1, X} 1, q1, X 2, S 2, q2, P 3, X 3, q4, S 3, q3, P 4 , respectively, the general formula (IV-1) Represents the same definition,
B11, B12, B13, B2, and B3 each represent the same definition as B1 to B3 in the general formula (IV-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 and Z2 in the general formula (IV-b), respectively, and may be the same or different.

  The compounds represented by the general formulas (IV-1-1) to (IV-1-8) are represented by the following formulas (IV-1-1-1) to (IV-1-1-6). The compounds represented are exemplified, but not limited thereto.

In the formula, R ^f , R ^g, and R ^h each independently represent a hydrogen atom or a methyl group, and R ⁱ , R ^j, and R ^k are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and when these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all are unsubstituted, Alternatively, the cyclic group may be substituted with one or two or more halogen atoms, and the cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, 1 to 8 carbon atoms as a substituent. An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and 2 to 2 carbon atoms. 8 alkenyl groups, carbon atoms Number 2-8 alkenyloxy group, alkenoyl group having 2 to 8 carbon atoms, which may have a alkenoyloxy group having from 2 to 8 carbon atoms.
m4 to m9 each independently represents an integer of 0 to 18, and n4 to n10 each independently represents 0 or 1.

  The polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups can be used alone or in combination of two or more.

The total content of the polyfunctional polymerizable liquid crystal compound having 3 or more polymerizable functional groups in the molecule is preferably 0 to 40% by mass in the total amount of the polymerizable liquid crystal compound to be used. More preferably, it is contained in an amount of 0 to 20% by mass.
(Polymerizable compound represented by formula (I))
The polymeric compound represented with general formula (I) which is this invention can be used 1 type, or 2 or more types.

The total content of the polymerizable compound represented by the general formula (I) is based on the coating film obtained from the total amount of the polymerizable liquid crystal compounds represented by the general formula (I) to the general formula (IV). In order to improve adhesion with the material, it is preferably contained in an amount of 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. Moreover, the upper limit of the total content of the polymerizable compound represented by the general formula (I) is 90% of the total amount of the polymerizable liquid crystal compound represented by the general formula (I) to the general formula (IV). % Or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.
(Optical anisotropic body manufacturing method)
(Optical anisotropic)
The optical anisotropic body produced using the polymerizable liquid crystal composition of the present invention is obtained by sequentially laminating a base material, if necessary, an alignment film, and a polymer of the polymerizable liquid crystal composition.
(Base material)
The substrate used for the optical anisotropic body of the present invention is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and is heated during drying after the application of the polymerizable liquid crystal composition of the present invention. If it is the material which has heat resistance which can endure, there will be no restriction | limiting in particular. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. In particular, when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylate, polyether sulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene. Among them, plastic base materials such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and base materials such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and COP (cycloolefin polymer) is used as the polyolefin. It is particularly preferable to use TAC (triacetyl cellulose) as the cellulose derivative and PMMA (polymethyl methacrylate) as the polyacrylate. As a shape of a base material, you may have a curved surface other than a flat plate. These base materials may have an electrode layer, an antireflection function, and a reflection function as needed.

In order to improve the applicability and adhesiveness of the polymerizable liquid crystal composition of the present invention, these substrates may be subjected to surface treatment. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
(Orientation treatment)
In addition, the substrate is usually subjected to an alignment treatment or provided with an alignment film so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. Also good. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
(Application)
Application methods for obtaining the optical anisotropic body of the present invention include applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating method, flexo coating method, ink jet method, and die coating. A publicly known method such as a method, a cap coating method, a dip coating method, or a slit coating method can be used. After applying the polymerizable liquid crystal composition, it is dried as necessary.
(Polymerization process)
Regarding the polymerization operation of the polymerizable liquid crystal composition of the present invention, the liquid crystal compound in the polymerizable liquid crystal composition is generally in a state in which it is horizontally aligned, vertically aligned, hybrid aligned, or cholesteric aligned (planar aligned) with respect to the substrate. It is performed by irradiation with light such as ultraviolet rays or heating. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.
(Polymerization method)
Examples of the method for polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating active energy rays and a thermal polymerization method. However, since the reaction proceeds at room temperature without requiring heating, active energy rays are used. A method of irradiating is preferable, and among them, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.

The temperature at the time of irradiation is preferably set to 30 ° C. or less as much as possible in order to avoid the induction of thermal polymerization of the polymerizable liquid crystal composition so that the polymerizable liquid crystal composition of the present invention can maintain the liquid crystal phase. The liquid crystal composition usually has a liquid crystal phase in the range from the C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as C-N transition temperature) to the NI transition temperature in the temperature rising process. Indicates. On the other hand, in the temperature lowering process, a non-equilibrium state is taken thermodynamically, so that the liquid crystal state may be maintained without being solidified even at a temperature below the CN transition temperature. This state is called a supercooled state. In the present invention, the liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is retained. Specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform the polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light. The ultraviolet irradiation intensity is preferably in the range of 0.05 kW / m ^{2 to} 10 kW / m ² . In particular, a range of 0.2 kW / m ^{2 to 2} kW / m ² is preferable. When the ultraviolet intensity is less than 0.05 kW / m ² , it takes a lot of time to complete the polymerization. On the other hand, when the strength exceeds ² kW / m ² , liquid crystal molecules in the polymerizable liquid crystal composition tend to be photodegraded, or a large amount of polymerization heat is generated to increase the temperature during polymerization. The parameter may change, and the retardation of the film after polymerization may be distorted.

  After only a specific part is polymerized by UV irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized. An optical anisotropic body having a plurality of regions having orientation directions can also be obtained.

  Further, when only a specific portion was polymerized by ultraviolet irradiation using a mask, the alignment was regulated in advance by applying an electric field, magnetic field or temperature to the unpolymerized polymerizable liquid crystal composition, and the state was maintained. An optical anisotropic body having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it.

The optical anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention can be peeled off from the substrate and used alone as an optical anisotropic body, or it can be used as an optical anisotropic body as it is without peeling off from the substrate. You can also In particular, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or by being attached to another substrate.
(Retardation film)
The retardation film of the present invention is prepared in the same manner as the optical anisotropic body of the present invention. When the substrate has a retardation, a retardation film having birefringence obtained by adding the birefringence of the substrate and the birefringence of the retardation film of the present invention is obtained. In the retardation film, the birefringence of the base material and the birefringence of the retardation film may be in the same direction or different directions in the plane of the base material. The liquid crystal device, the display, the optical element, the optical component, the colorant, the marking for security, the member for laser emission, the optical film, and the compensation film are applied in a form suitable for the application.
(Phase difference patterning film)
The retardation patterning film of the present invention is obtained by sequentially laminating a base material, an alignment film, and a polymer of a polymerizable composition solution in the same manner as the optical anisotropic body of the present invention. Are patterned so as to obtain different phase differences. The patterning may be in different directions, such as linear patterning, lattice patterning, circular patterning, polygonal patterning, and the like. The liquid crystal device, display, optical element, optical component, colorant, security marking, laser emission member, optical film, compensation film, and the like are used.
As a method of obtaining a partially different phase difference, an alignment film is provided on the substrate, and the polymerizable composition solution of the present invention is applied and dried during the alignment treatment so that the polymerizable composition is patterned and aligned. To do. Examples of such an alignment treatment include a fine rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, and a fine shape processing treatment. As the alignment film, known and conventional ones are used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by fine rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.

EXAMPLES The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
Example 1 Production of Compound Represented by Formula (I-1)

  To a reaction vessel equipped with a thermometer, a cooler, and a dropping funnel and purged with nitrogen, 20.4 g of sodium hydride (60% oily) and 200 mL of tetrahydrofuran were added. While cooling with ice, 50.0 g of a compound represented by the formula (I-1-1) and 200 mL of tetrahydrofuran were added dropwise. Further, 34.0 g of tetrabutylammonium bromide was added, and then 86.8 g of benzyl bromide was added dropwise while cooling with ice, and the mixture was heated to reflux. After the reaction, the reaction mixture was diluted with toluene, washed successively with water and saturated brine, and purified by column chromatography (silica gel) to obtain 42.6 g of a compound represented by the formula (I-1-2).

  To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 37.2 g of the compound represented by the formula (I-1-2), 54.4 g of triethylamine, 2.0 g of dimethylaminopyridine, and 680 mL of dichloromethane were added. While cooling with ice, 40.8 g of methanesulfonyl chloride was added dropwise and reacted at room temperature. After the reaction, the mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and purified by column chromatography (silica gel) to obtain 48.0 g of a compound represented by the formula (I-1-3).

  In a reaction vessel equipped with a thermometer and a condenser and purged with nitrogen, 44.8 g of the compound represented by the formula (I-1-3), diethyl malonate 24.0 g, cesium carbonate 149.6 g, tetrabutylammonium bromide 2.0 g Then, 480 mL of acetonitrile was added and heated to reflux. After the reaction, acetonitrile is distilled off, redissolved in dichloromethane, washed successively with water and saturated brine, purified by column chromatography (silica gel) and distillation, and a compound represented by the formula (I-1-4) 34.4 g was obtained.

  7.6 g of lithium aluminum hydride and 100 mL of tetrahydrofuran were added to a reaction vessel equipped with a thermometer, a cooler, and a dropping funnel and purged with nitrogen. While cooling with ice, 34.4 g of the compound represented by the formula (I-1-4) and 200 mL of tetrahydrofuran were added dropwise and heated to reflux. After the reaction, appropriate amounts of ethyl acetate and an aqueous sulfuric acid solution were added dropwise, followed by celite filtration, and the filtrate was diluted with ethyl acetate. The mixture was washed successively with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and purified by recrystallization to obtain 20.0 g of a compound represented by the formula (I-1-5).

  A reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen was charged with 55.1 g of the compound represented by formula (I-1-6), 50.0 g of 2,3-difluorophenol, 121.0 g of triphenylphosphine, and 500 mL of tetrahydrofuran. added. While cooling with ice, 85.5 g of diisopropyl azodicarboxylate was added dropwise and reacted at room temperature. After the reaction, the reaction mixture was diluted with ethyl acetate, washed successively with water and saturated brine, and purified by column chromatography (silica gel) to obtain 58.7 g of a compound represented by the formula (I-1-7).

  Into a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 58.7 g of the compound represented by the formula (I-1-7) and 500 mL of tetrahydrofuran were added. While cooling to −50 ° C., 315 mL of 1.0 mol / L sec-butyllithium was added dropwise and reacted at the same temperature. Further, 35.4 g of dimethylformamide and 100 mL of tetrahydrofuran were added dropwise at the same temperature and reacted at room temperature. After the reaction, an appropriate amount of 10% hydrochloric acid was added dropwise, diluted with hexane, washed successively with water and saturated brine, isolated and purified by column chromatography (silica gel), and represented by the formula (I-1-8). 26.8 g of the compound obtained are obtained.

  16.3 g of the compound represented by the formula (I-1-5) and 15.0 g of the compound represented by the formula (I-1-8) in a reaction vessel equipped with a thermometer, a condenser and a Dean-Stark tube and purged with nitrogen. P-Toluenesulfonic acid monohydrate (1.1 g), cyclohexane (140 mL), and diiropropyl ether (35 mL) were added and heated to reflux. After the reaction, the mixture is diluted with toluene, washed successively with a saturated aqueous sodium hydrogen carbonate solution, water, and saturated brine, purified by column chromatography (alumina), and the compound represented by formula (I-1-9) 22. 2 g (cis / trans = 22/78) were obtained.

  To the autoclave container, 22.2 g of the compound represented by the formula (I-1-9), 2.2 g of 5% palladium carbon (50% Wet) and 220 mL of tetrahydrofuran were added, and the reaction was performed at 50 ° C. in a hydrogen atmosphere of 0.4 MPa. . The reaction solution was filtered and isolated and purified by column chromatography (silica gel) to obtain 9.9 g (cis / trans = 3/97) of the compound represented by the formula (I-1-10).

To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 9.9 g of the compound represented by the formula (I-1-10), 4.5 g of diisopropylethylamine, and 150 mL of dichloromethane were added. While cooling with ice, 2.7 g of acryloyl chloride was added dropwise and reacted at room temperature. After the reaction, it was washed successively with 10% hydrochloric acid and saturated saline, and purified by column chromatography (silica gel) and recrystallization to obtain 8.0 g of compound represented by the formula (I-1) (trans isomer only). It was.
MS 483 (M + H ⁺ )
Example 2 Production of Compound Represented by Formula (I-19)

  40.0 g of a compound represented by (I-1-2) in a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen; , 3-Difluorophenol 22.8 g, triphenylphosphine 55.1 g, and tetrahydrofuran 230 mL were added. While cooling with ice, 39.1 g of diisopropyl azodicarboxylate was added dropwise and reacted at room temperature. After the reaction, the reaction mixture was diluted with ethyl acetate, washed successively with water and saturated brine, and purified by column chromatography (silica gel) to obtain 30.4 g of a compound represented by the formula (I-19-1).

  To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 30.4 g of the compound represented by the formula (I-19-1) and 250 mL of tetrahydrofuran were added. While cooling to −50 ° C., 150 mL of 1.0 mol / L sec-butyllithium was added dropwise and reacted at the same temperature. Further, 13.9 g of dimethylformamide and 40 mL of tetrahydrofuran were added dropwise at the same temperature and reacted at room temperature. After the reaction, an appropriate amount of 10% hydrochloric acid was added dropwise, diluted with hexane, washed successively with water and saturated brine, isolated and purified by column chromatography (silica gel), and represented by the formula (I-19-2). 6.9 g of the compound obtained are obtained.

  6.1 g of the compound represented by the formula (I-1-5) and 6.9 g of the compound represented by the formula (I-19-2) in a reaction vessel equipped with a thermometer, a condenser and a Dean-Stark tube and purged with nitrogen Then, 0.4 g of p-toluenesulfonic acid monohydrate, 60 mL of cyclohexane, and 15 mL of diisopropyl ether were added and heated to reflux. After the reaction, the reaction mixture is diluted with toluene, washed successively with a saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, purified by column chromatography (alumina), and the compound represented by formula (I-19-3) 9. 1 g (cis / trans = 26/74) was obtained.

  To the autoclave container, 9.1 g of the compound represented by the formula (I-19-3), 1.1 g of 5% palladium carbon (50% Wet) and 80 mL of tetrahydrofuran were added and reacted at 50 ° C. in a hydrogen atmosphere of 0.4 MPa. . The reaction solution was filtered and isolated and purified by column chromatography (silica gel) to obtain 3.0 g (cis / trans = 4/96) of the compound represented by the formula (I-19-4).

To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 3.0 g of the compound represented by the formula (I-19-4), 3.0 g of diisopropylethylamine, and 60 mL of dichloromethane were added. While cooling with ice, 1.9 g of acryloyl chloride was added dropwise and reacted at room temperature. After the reaction, it was washed successively with 10% hydrochloric acid and saturated brine, and purified by column chromatography (silica gel) and recrystallization to obtain 1.1 g of compound represented by the formula (I-19) (trans isomer only). It was.
MS 525 (M + H ⁺ )
Example 3 Production of Compound Represented by Formula (I-38)

  To the autoclave container was added 15.0 g of the compound represented by the formula (I-1-5), 1.5 g of 5% palladium carbon (50% Wet) and 90 mL of tetrahydrofuran, and the mixture was reacted at 35 ° C. in a hydrogen atmosphere of 0.5 MPa. . The reaction solution was filtered and concentrated to obtain 10.0 g of a compound represented by the formula (I-38-1).

  In a reaction vessel equipped with a thermometer, a condenser and a Dean-Stark tube, 9.0 g of the compound represented by the formula (I-38-1), 3.1 g of terephthalaldehyde, 0.2 g of p-toluenesulfonic acid monohydrate Toluene 55 mL was added and heated to reflux. After the reaction, the reaction mixture was diluted with tetrahydrofuran, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and purified by recrystallization to obtain 8.7 g of a compound represented by the formula (I-38-2).

To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 8.4 g of the compound represented by the formula (I-38-2), 7.2 g of diisopropylethylamine, and 120 mL of dichloromethane were added. While cooling with ice, 4.4 g of acryloyl chloride was added dropwise and reacted at room temperature. After the reaction, the mixture was washed successively with 10% hydrochloric acid and saturated brine, and purified by column chromatography (silica gel) and recrystallization to obtain 5.5 g of a compound represented by the formula (I-38).
MS 595 (M + H ⁺ )
Example 4 Production of Compound Represented by Formula (I-26)

  To a reaction vessel equipped with a thermometer, a condenser, and a dropping funnel and purged with nitrogen, 31.5 g of sodium hydride (60% oily) and 420 mL of tetrahydrofuran were added. While cooling with ice, 50.0 g of a compound represented by the formula (I-26-1) and 420 mL of tetrahydrofuran were added dropwise. Further, 53.0 g of tetrabutylammonium bromide was added, and 134.8 g of benzyl bromide was added dropwise while cooling with ice, followed by heating to reflux. After the reaction, the reaction mixture was diluted with toluene, washed successively with water and saturated brine, and purified by column chromatography (silica gel) to obtain 45.9 g of a compound represented by the formula (I-26-2).

  To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 45.9 g of the compound represented by the formula (I-26-2), 83.7 g of triethylamine, 3.4 g of dimethylaminopyridine, and 840 mL of dichloromethane were added. While cooling with ice, 63.2 g of methanesulfonyl chloride was added dropwise and reacted at room temperature. After the reaction, it was washed with a saturated aqueous sodium hydrogen carbonate solution and purified by column chromatography (silica gel) to obtain 64.7 g of a compound represented by the formula (I-26-3).

  In a reaction vessel equipped with a thermometer and a condenser and purged with nitrogen, 64.7 g of the compound represented by the formula (I-26-3), 38.2 g of diethyl malonate, 237.3 g of cesium carbonate, 3.4 g of tetrabutylammonium bromide 650 mL of acetonitrile was added and heated to reflux. After the reaction, acetonitrile is distilled off, redissolved in dichloromethane, washed successively with water and saturated brine, purified by column chromatography (silica gel) and distillation, and represented by the formula (I-26-4) 41.2 g was obtained.

  10.1 g of lithium aluminum hydride and 240 mL of tetrahydrofuran were added to a reaction vessel equipped with a thermometer, a cooler, and a dropping funnel and purged with nitrogen. While cooling with ice, 41.2 g of a compound represented by the formula (I-26-4) and 120 mL of tetrahydrofuran were added dropwise and heated to reflux. After the reaction, appropriate amounts of ethyl acetate and an aqueous sulfuric acid solution were added dropwise, followed by celite filtration, and the filtrate was diluted with ethyl acetate. The mixture was washed successively with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and purified by recrystallization to obtain 22.4 g of a compound represented by the formula (I-26-5).

  A reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen was charged with 35.1 g of the compound represented by formula (I-26-2), 25.0 g of 2,3-difluorophenol, 60.5 g of triphenylphosphine, and 250 mL of tetrahydrofuran. added. While cooling with ice, 42.7 g of diisopropyl azodicarboxylate was added dropwise and reacted at room temperature. After the reaction, the reaction mixture was diluted with ethyl acetate, washed successively with water and saturated brine, and purified by column chromatography (silica gel) to obtain 30.5 g of a compound represented by the formula (I-26-6).

  To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 30.5 g of the compound represented by the formula (I-26-6) and 250 mL of tetrahydrofuran were added. While cooling to −50 ° C., 142 mL of 1.0 mol / Lsec butyl lithium was added dropwise and reacted at the same temperature. Further, 16.0 g of dimethylformamide and 40 mL of tetrahydrofuran were added dropwise at the same temperature and reacted at room temperature. After the reaction, an appropriate amount of 10% hydrochloric acid was added dropwise, diluted with hexane, washed successively with water and saturated brine, isolated and purified by column chromatography (silica gel), and represented by the formula (I-26-7). 10.7 g of the compound obtained are obtained.

  A reaction vessel equipped with a thermometer, a condenser, and a Dean-Stark tube and purged with nitrogen was 8.6 g of the compound represented by the formula (I-26-5), and 10.7 g of the compound represented by the formula (I-26-7). Then, 0.7 g of p-toluenesulfonic acid monohydrate, 100 mL of cyclohexane, and 25 mL of diisopropyl ether were added and heated to reflux. After the reaction, the mixture is diluted with toluene, washed successively with a saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, purified by column chromatography (alumina), and the compound represented by formula (I-26-8) 13. 8 g (cis / trans = 24/76) were obtained.

  To the autoclave container, 13.8 g of the compound represented by the formula (I-26-8), 1.4 g of 5% palladium carbon (50% Wet) and 120 mL of tetrahydrofuran were added and reacted at 50 ° C. in a hydrogen atmosphere of 0.4 MPa. . The reaction solution was filtered and isolated and purified by column chromatography (silica gel) to obtain 7.6 g (cis / trans = 3/97) of a compound represented by the formula (I-26-9).

To a reaction vessel equipped with a thermometer and a dropping funnel and purged with nitrogen, 7.6 g of the compound represented by the formula (I-26-9), 8.9 g of diisopropylethylamine, and 140 mL of dichloromethane were added. While cooling with ice, 6.2 g of methacryloyl chloride was added dropwise and reacted at room temperature. After the reaction, the product is washed successively with 10% hydrochloric acid and saturated brine, and purified by column chromatography (silica gel) and recrystallization to obtain 4.0 g of the compound represented by the formula (I-26) (trans isomer only). It was.
MS 469 (M + H ⁺ )
<Polymer stabilized liquid crystal display element>
(Example 5)
A composition (Δn0.102, viscosity η16.8, Δε-3.8) represented by the following (LCN-1) was prepared as an n-type liquid crystal. As the polymerizable compound, a compound represented by the following formula (I-1) and a compound represented by the following formula (A-1) were used.

  As an n-type liquid crystal composition (LCN-1; Δn0.102, viscosity η16.8, Δε-3.8) 90%, polymerizable compound (I-1) 8%, polymerizable compound (A-1) 2% And a polymerizable liquid crystal composition (LCM-1) containing 0.2% of the polymerization photoinitiator Irgacure 651 was prepared. After applying a polyimide alignment film with a cell gap of 3 μm so that liquid crystal vertical alignment (homeotropic alignment) can be obtained, rubbing alignment treatment is performed so that the pretilt angle is 1 ° to 2 ° with respect to the normal direction of the substrate surface. A parallel rubbing orientation cell with ITO was used. The polymerizable liquid crystal composition (LCM-1) was heated to 60 ° C. and injected into the glass cell by a vacuum injection method.

After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). Ultraviolet rays having an irradiation intensity of 15 mW / cm ² through an ultraviolet cut filter L-37 (manufactured by Hoya Candeo Optronics) were irradiated at 25 ° C. or −10 ° C. for 300 seconds. Thereby, the polymerizable compound of the polymerizable liquid crystal composition was polymerized to obtain a VA mode liquid crystal display element. When the cell prepared between two orthogonal polarizing plates is placed, it becomes black and the dark field does not change even if the cell is rotated in the azimuth direction, and the optical axis direction of the polymer network and the liquid crystal alignment easy axis direction are the same direction. It was confirmed.

  Table 1 below shows the results of measuring voltage-transmittance characteristics (V90: applied voltage at 90% transmittance) and response time (fall time, rise time) by applying a rectangular wave of 60 Hz.

(Example 6)
A VA mode liquid crystal display device was obtained in the same manner as in Example 5 except that the polymerizable compound used was changed to 5% polymerizable compound (I-19) and 5% polymerizable compound (A-1). It was.

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Example 7)
A VA mode liquid crystal display device was obtained in the same manner as in Example 5 except that the polymerizable compound used was changed to 10% of the polymerizable compound (I-38).

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Example 8)
A VA mode liquid crystal display device was obtained in the same manner as in Example 5 except that the polymerizable compound used was changed to 10% of the polymerizable compound (I-26).

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Comparative Example 1)
A VA mode liquid crystal display element was obtained in the same manner as in Example 5 except that the polymerizable compound was not used (that is, liquid crystal composition (LCN-1) 100%).

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Comparative Example 2)
A VA mode liquid crystal display device was obtained in the same manner as in Example 5 except that the polymerizable compound used was changed to 5% polymerizable compound (A-1) and 5% polymerizable compound (A-2). It was.

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
Example 9
The composition (Δn0.102, viscosity η16.8, Δε-3.8) represented by (LCN-1) as an n-type liquid crystal is changed to the composition (Δn0.12, viscosity η19 mPa · s) represented by (LCN-2) below. A VA mode liquid crystal display device was obtained in the same manner as in Example 5 except that it was changed to s, Δε-3.3).

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Example 10)
The composition (Δn0.102, viscosity η16.8, Δε-3.8) represented by (LCN-1) as an n-type liquid crystal is changed to the composition (Δn0.12, viscosity η19 mPa · s) represented by (LCN-2) below. s, Δε-3.3), and the polymerizable compound used was the same as in Example 6 except that the polymerizable compound (I-19) was changed to 7% and the polymerizable compound (A-1) 3%. By the method, a VA mode liquid crystal display element was obtained.

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Example 11)
The composition (Δn0.102, viscosity η16.8, Δε-3.8) represented by (LCN-1) as an n-type liquid crystal is changed to the composition (Δn0.12, viscosity η19 mPa · s) represented by (LCN-2) below. A VA mode liquid crystal display device was obtained in the same manner as in Example 7 except that it was changed to s, Δε-3.3).

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Example 12)
A VA mode liquid crystal display device was obtained in the same manner as in Example 10, except that the polymerizable compound used was changed from (I-19) to (I-26).

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Comparative Example 3)
The composition (Δn0.102, viscosity η16.8, Δε-3.8) represented by (LCN-1) as an n-type liquid crystal is changed to the composition (Δn0.12, viscosity η19 mPa · s) represented by (LCN-2) below. A VA mode liquid crystal display device was obtained in the same manner as in Comparative Example 1 except that s, Δε-3.3).

The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.
(Comparative Example 4)
The composition (Δn0.102, viscosity η16.8, Δε-3.8) represented by (LCN-1) as an n-type liquid crystal is changed to the composition (Δn0.12, viscosity η19 mPa · s) represented by (LCN-2) below. A VA mode liquid crystal display element was obtained in the same manner as in Comparative Example 2 except that s, Δε-3.3).

  The results of measuring the voltage-transmittance characteristics and the response time by applying a 60 Hz rectangular wave are shown in Table 1 below.

As a result, the examples using the polymerizable compound represented by the general formula (I) of the present invention were compared with the results of Comparative Example 1 and Comparative Example 3 in which no polymerizable compound was used, and the falling time and the rising time. Was significantly shortened and improved responsiveness was observed. Further, Examples 5 to 12 using the polymerizable compound represented by the general formula (I) of the present invention are Comparative Examples 2 and 2 in which the polymerizable compound represented by the general formula (I) of the present invention is not used. Compared with Comparative Example 4, the value of V90 is lowered, and a liquid crystal display element in which an increase in driving voltage is suppressed can be obtained.
<Optical anisotropic body>
(Examples 13-16, Comparative Examples 5-6)
(Preparation of polymerizable liquid crystal composition (1))
As shown in the following table, 30 parts by mass of the compound represented by formula (I-1), 20 parts by mass of the compound represented by formula (X-1), and 20 parts by mass of the compound represented by formula (X-2) , 5 parts by mass of polymerization initiator Irgacure 907 (E-1), p-methoxyphenol (MEHQ) (F-1) with respect to 100 parts by mass of a total of 30 parts by mass of the compound represented by formula (X-3) ) Using 0.1 parts by mass and 0.1 part by mass of the surfactant Megafac F-554 (G-1), MEK which is an organic solvent so that the total amount of these compounds is 25% by mass (H-1) Using 75% by mass, using a stirring device having a stirring propeller, stirring for 1 hour under the conditions of a stirring speed of 500 rpm and a solution temperature of 60 ° C., and then filtering through a 0.2 μm membrane filter. A polymerizable liquid crystal composition (1) was obtained.
(Preparation of polymerizable liquid crystal compositions (2) to (4), comparative polymerizable liquid crystal compositions (5) and (6))
In the polymerizable liquid crystal composition (1) of the present invention, the compound represented by formula (I-1) is represented by formula (I-19), formula (I-38), formula (I-26), formula (R- 1) A polymerizable liquid crystal composition (2) as shown in Table 2 below under the same conditions as the preparation of the polymerizable liquid crystal composition (1) except that the compound represented by the formula (R-2) was changed. To (4), comparative polymerizable liquid crystal compositions (5) and (6) were obtained.

(Example 13)
<Preparation of thin film for evaluation such as adhesion>
As a base material, a silane coupling material (manufactured by JNC: DMOAP) for a vertical alignment film is applied on a COP (cycloolefin polymer) substrate by a spin coating method, and baked at 100 ° C. for 1 hour to obtain a base material. It was. The prepared polymerizable liquid crystal composition (1) was applied to the obtained substrate using a bar coater # 5 at room temperature and dried at 60 ° C. for 2 minutes. Then, after leaving at 25 ° C. for 1 minute, using a conveyor type high-pressure mercury lamp, the illuminance is set to 200 mJ / cm ² and irradiated with UV light to obtain the thin film of Example 13. It was.
<Evaluation of adhesion of coating film>
The thin film (coating film) obtained as described above is cut into a grid pattern with a cutter in accordance with JIS K5600-5-6, using a cross-cut method using a cutter, and a 2-mm square grid is formed. The adhesion of the film was measured.
Classification 0: No peeling on any base.
Classification 1: Small peeling of the coating film at the intersection of cuts is confirmed (less than 5%).
Classification 2: The coating film is peeled off at the intersection along the cut line (5% or more and less than 15%).
Classification 3: The coating film is partially or totally peeled along the cut line (15% or more and less than 35%).
Classification 4: The coating film is largely and completely peeled along the cut line (35% or more and less than 65%).
Classification 5: Classification 4 or more (65% or more).
<Haze evaluation of coating film>
The thin film obtained in the adhesion evaluation test was measured at three points using a turbidimeter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the average value was evaluated.
◎: Less than 0.1 ○: 0.1 or more and less than 0.2 Δ: 0.2 or more and less than 0.5 ×: 0.5 or more <Durability Evaluation of Coating Film>
The thin film obtained in the adhesion evaluation test was heated at 85 ° C. for 500 hours to obtain a thin film for durability measurement. Phase difference Re after incident heating θ = 50 ° before and after the heating test was measured with Otsuka Electronics RETS-100 (wavelength is 550 nm), and the phase difference after heating was set to 100% before heating. The rate of change was evaluated.
A: No change B: Decrease of less than 3% Δ: Decrease of 3% or more to less than 7% X: Decrease of 7% or more The results obtained are shown in Table 3 below.

(Examples 14-16, Comparative Examples 5-6)
Using the polymerizable liquid crystal compositions (2) to (6), a thin film for adhesion evaluation was prepared in the same manner as in Example 13, and the adhesion, haze, and durability were measured. The results are shown in Table 3 above as Examples 14 to 16 and Comparative Examples 5 to 6, respectively.

  As a result, a polymerizable liquid crystal composition using the compound of the present invention represented by formula (I-1), formula (I-19), formula (I-38), or formula (I-26) (Example 13). ~ 16) can obtain an optically anisotropic body having better adhesion to the substrate as compared with Comparative Examples 5-6.

Claims (5)

Formula (I)

(Wherein P is the formula (P-1) to the formula (P-6), the formula (P-14) to the formula (P-18)

And Sp represents one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O—, —COO—, —OCO— or —OCO—O. -Represents an alkylene group having 1 to 20 carbon atoms which may be replaced by-or a single bond;
A ¹ and A ² are each independently unsubstituted or optionally substituted by one or two substituents L, 1,2-phenylene group, 1,4-phenylene group, naphthalene-1, 4-diyl group, naphthalene-2,6-diyl group, cyclohexane-1,4-diyl group, 1,4-cyclohexenylene group, bicyclo [2.2.2] octane-1,4-diyl group, spiro [3.3] Heptane-2,6-diyl group, 1,3-dioxane-2,5-diyl group, piperidine-2,5-diyl group, decahydronaphthalene-2,6-diyl group, 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, indane-2,5-diyl group, thiophene-2,5-diyl group or fluorene-2,7-diyl group, A ¹ and / or in each the same if A ² appears more Can be different or different,
Substituent L is P-Sp- group, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group , A dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- , —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— Replaced by Represents a linear or branched alkyl group having 1 to 20 carbon atoms, and when a plurality of substituents L are present, they may be the same or different,
Z ¹ represents —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CO. -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH —COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S _{-, - SCF 2 -, -} CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO _{-CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH _{-, - CH 2 -COO-, -} CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond and Table, ^{Z 2} is _{-O -, - S -, -} CH 2 -, - OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - CH 2 CF 2 _{-, - CF 2 CH 2 -} , - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH- CO—, —OCO—NH—, —NH—COO—, —NH—CO—NH—, —NH—O— , —O —NH—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O _{-, - OCF 2 -, -} CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- _{-COO-CH 2 CH 2 -,} - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - OCO-CH 2 -, - CH 2 -COO-, —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—, —N═CH—, —CH═N—N═CH—, —CF═CF—, —C≡. C- or represents a single bond, Z ² is attached directly to a ring having a B represents a single bond, rather it may also be different from each be the same if Z ¹ and / or Z ² appears more,
B represents —O— or —CH ₂ —;
m and n each independently represent an integer of 0 to 5, m + n represents an integer of 1 to 5,
R ¹ represents a P—Sp— group, and a plurality of P and Sp present in the formula may be the same or different, but at least one Sp is one —CH ₂ — or adjacent to each other. 2 or more —CH ₂ — not present each independently represents an alkylene group having 1 to 20 carbon atoms which may be replaced with —O—, —COO—, —OCO— or —OCO—O—. ) A polymerizable compound represented by:   The polymerizable compound according to claim 1, wherein B represents —O— in the general formula (I).   A composition containing the polymerizable compound according to claim 1.   A liquid crystal composition containing the polymerizable compound according to claim 1.   A polymer obtained by polymerizing the composition according to claim 3 or 4.