JP2017210409A - Polymerizable compound and optical anisotropic body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition that causes few orientation defects when added to a polymerizable composition and making a film-like polymer, and is resistant to discoloration when put in a high temperature condition.SOLUTION: The present invention provides a compound illustrated by the formula (I-6), a polymerizable composition containing the compound, a polymer obtained by the polymerization of the composition, and an optical anisotropic body prepared with the polymer.SELECTED DRAWING: None

Description

  The present invention relates to a compound having a polymerizable group, a polymerizable composition containing the compound, a polymerizable liquid crystal composition, and an optical anisotropic body using the polymerizable liquid crystal composition.

  Polymerizable compounds are used in various films. For example, it is possible to produce a film having a uniform orientation by aligning a polymerizable compound in a liquid crystal state and then polymerizing it. Thus, the produced film can be used for a polarizing plate, a phase difference plate, etc. which are required for a liquid crystal display. The polymerizable compound can also be used to produce a film having a cholesteric structure. In many cases, two or more types of polymerizability are required to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, film transparency, mechanical strength, surface hardness, heat resistance and light resistance. Compositions consisting of compounds are used. At that time, the polymerizable compound to be used is required to bring good physical properties to the composition without adversely affecting other properties. In particular, when the purpose is to produce a film having a cholesteric structure, a polymerizable compound that can exist as a nematic phase or a cholesteric phase in a wide temperature range and has a high nematic phase or cholesteric phase liquid crystal orientation is required. In addition, when a polymerizable liquid crystal composition is used industrially, high storage stability is required so that a polymerizable compound in the polymerizable liquid crystal composition does not precipitate even when stored for a long time.

  Furthermore, when used as an optical film for a display or the like, it is preferable that the produced film has few orientation defects, and discoloration hardly occurs when placed in a high temperature state. However, conventionally known compounds have a problem that alignment defects are likely to occur when a film-like polymer is produced, and a problem that discoloration is likely to occur when a film-like polymer is heated ( Patent Documents 1 to 4). When a film having such a problem is used for, for example, a display, the color of the screen becomes unnatural due to long-term use and the desired optical characteristics cannot be obtained. There was a problem that would decrease. Therefore, development of a highly versatile polymerizable compound that can solve such a problem has been demanded.

JP 2010-270108 A JP 2011-246365 A Japanese Patent Laid-Open No. 10-87565 US2011 / 0147657A1

  The problem to be solved by the present invention is to provide a polymerizable composition that has few orientation defects when added to the polymerizable composition to produce a film-like polymer, and hardly undergoes discoloration when placed in a high temperature state. Is to provide. Furthermore, it is providing the polymer obtained by polymerizing the said polymeric composition, and the optical anisotropic body using the said polymer.

  As a result of intensive studies to solve the above problems, the present inventors have developed a polymerizable compound having a mesogenic group or a mesogenic supporting group containing a specific partial structure. That is, the present invention provides a compound represented by the general formula (I), and also a polymerizable composition containing the compound, a resin, a resin additive, an oil, a filter, an adhesive, and a pressure-sensitive adhesive using the compound. , Oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals And a food, a product using the same, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optical anisotropic body using the polymer.

  The compound of the present invention is useful as a constituent member of the polymerizable composition. In addition, the optical anisotropic body using the polymerizable liquid crystal composition containing the compound of the present invention has few alignment defects and is unlikely to discolor when placed in a high temperature state. Therefore, a retardation film and a selective reflection film It is useful for the use of optical materials such as.

  The present invention provides a compound having a specific structure, a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, a pressure-sensitive adhesive, an oil and fat, an ink, Pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals and foodstuffs and the like Provided are a product used, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optical anisotropic body using the polymer.

  The compound of the present invention is represented by the following general formula (I).

(Wherein P ¹ represents a group that is polymerized by radical polymerization, cationic polymerization or anionic polymerization;
Sp ¹ represents a spacer group, and when a plurality of Sp ¹ are present, they may be the same or different,
X ¹ represents —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 represents a single bond, ^{X 1} is more present They may be different even in the same case that,
k1 represents an integer of 0 to 10,
A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1 , 3-dioxane-2,5-diyl groups, these groups may be unsubstituted or substituted by one or more substituents L, and when there are multiple A ¹ they are the same Or a plurality of A ² may be the same or different.
B ¹ represents expression from the following formula (B-1) (B- 3)

(Wherein these groups are unsubstituted or may be substituted by one or more of the following substituents L),
L is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, 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 carbon atom optionally substituted by —C≡C— Number 1 20 represents a linear or branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is P ^L- (Sp ^L -X ^L ) _kL-. However, when a plurality of Ls are present in the compound, they may be the same or different, and P ^L , Sp ^L , X ^L and kL are respectively P ¹ , Represents the same as Sp ¹ , X ¹ and k ¹ ,
One of Y ¹ and Y ² represents a group selected from the following group (Y-A), and the other represents a group selected from the following group (Y-B):
(YA) group: * -CO-, * -COO-, -OCO- *, * -CO-S-, -S-CO- *, * -CO-NH-, -NH-CO- *, * —COO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —OCO— *, * —COO—CH ₂ —, —CH ₂ —OCO— *, * —CH═N—, —N═CH— *, And * —CH═N—N═CH— (* means a site directly bonded to the group represented by B ¹ ).
(YB) group: —OCH ₂ — *, * —CH ₂ O—, —SCH ₂ — *, * —CH ₂ S—, * —CF ₂ O—, —OCF ₂ — *, * —CF ₂ S—, —SCF ₂ — *, —NHCH ₂ — *, * —CH ₂ NH—, —COO—CH ₂ — *, and * —CH ₂ —OCO— (* represents a group represented by B ¹ It means the site that binds directly.)
Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH 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 2 -, - CH 2 -COO -, - CH -OCO -, - CH = CH - , - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, they if Z ¹ there are a plurality may be the same or different and although they may be the same or different if Z ² there are a plurality, is Z ¹ when present represents Z ¹ is a single bond attached directly to Y ^1, Z ² directly attached to Y ² when the Z ² there is a single bond,
m1 and m2 each independently represents an integer from 0 to 6, while m1 + m2 represents an integer from 0 to 6,
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one —CH ₂ — or adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. A straight chain of 1 to 20 carbon atoms which may be substituted by -O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is a group represented by — (X ² -Sp ² ) _k2 -P ² ( wherein the heavy P ² is a radical polymerization, by cationic polymerization or anionic polymerization Represents radicals, Sp ² each represents a spacer group, they if Sp ² there are a plurality may be different even in the same, ^{X 2} is -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 represents a single bond, the same those ^{if X 2} there are a plurality may be different even, k2 represents an represents.) an integer from 0 to 10, X ¹ directly bonded to Y ¹ if m1 is and there is X ¹ represents 0 represents a single bond m2 Although but the X ² bound directly to Y ² if and X ² are present represents 0 represents a single bond, the formula does not contain -O-O- bond. )
In the general formula (I), P ¹ and P ² present each independently represent a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and each independently represents the following formula (P-1) to formula (P-20)

It is preferable to represent a group selected from: 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 the general formula (I), Sp ¹ and existing Sp ² each independently represent a spacer group, but when there are a plurality of Sp ^1, they may be the same or different, and there are a plurality of Sp ² They may be the same or different. From the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis, when there are a plurality of Sp ¹ and Sp ² present, they may be the same or different from each other, and each independently represents one − CH ₂ — or two or more non-adjacent —CH 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— or —C≡C— is preferably an alkylene group having 1 to 20 carbon atoms, and when there are a plurality of Sp ¹ and Sp ² present, They may be the same or different, and each independently represents one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O—, —COO—, —OCO. Represents an alkylene group having 1 to 20 carbon atoms which may be replaced by-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or -C≡C-. more preferably, each identical if Sp ² that Sp ¹ and there are plurality of It may be different even, each independently one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO- or More preferably, it represents a linear alkylene group having 1 to 20 carbon atoms which may be replaced by -OCO-O-, and when there are a plurality of Sp ¹ and Sp ² present, they may be the same or different. even if well, each independently one -CH 2 _- or nonadjacent two or more -CH 2 _- from a good 1 -C be replaced by the each independently -O- 12 of It is even more preferred that it represents a linear alkylene group, and when there are a plurality of Sp ¹ and Sp ² present, they may be the same or different and each independently represents a straight chain having 1 to 12 carbon atoms. Especially represents a chain alkylene group preferable.

In general formula (I), X ¹ and X ² present 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 = C -, - C≡C- or represents a single bond, they if X ¹ there are a plurality may be the same or different and they if X ² there are a plurality or different may be the same May be. In view of the availability of raw materials and the ease of synthesis, when there are a plurality of X ¹ and X ² present, they may be the same or different, and each independently represents —O— or —S—. , —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO _{-, - COO-CH 2 CH} 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - it is preferable to represent a _CH 2 CH 2 -OCO- or a single bond, each independently _{-O -, - OCH 2 -,} - CH 2 O -, - COO -, - OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO-, more preferably represents a -CH ₂ CH ₂ -OCO- or a single bond, each independently - -, - COO -, - OCO- or more preferably a single bond, even more preferably represent each independently -O- or a single bond, and particularly preferably a -O-.

  In general formula (I), k1 and existing k2 each independently represent an integer of 0 to 10, but from the viewpoint of ease of synthesis and liquid crystallinity, k1 and existing k2 are each independently 0 to 5 It is preferable that k1 and existing k2 each independently represent an integer of 0 to 2, more preferably k1 and existing k2 each independently represent 0 or 1, From the viewpoint of low curing shrinkage when formed into a film, it is particularly preferable to represent 1 for each.

In the general formula (I), A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine. -2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group or 1,3-dioxane-2,5-diyl group, these groups may be unsubstituted or substituted by one or more substituents L described below, ¹ they If there are multiple may be different even in the same, a ² may be those when there are multiple different be the same. In view of ease of synthesis, availability of raw materials, and liquid crystallinity, A ¹ and A ² are each independently unsubstituted or may be substituted with one or more substituents L -Preferably represents a phenylene group, a 1,4-cyclohexylene group or a naphthalene-2,6-diyl group, and each independently represents the following formulas (A-1) to (A-11):

It is even more preferable that each group independently represents a group selected from formula (A-1) to (A-8), and each group independently represents formula (A-1). It is particularly preferable to represent a group selected from formula (A-4).

In the general formula (I), B ¹ represents the following formulas (B-1) to (B-3):

(Wherein these groups are unsubstituted or may be substituted by one or more substituents L described below). From the viewpoint of ease of synthesis and availability of raw materials, fewer orientation defects when formed into a film, and less discoloration when placed in a high temperature state, B ¹ is unsubstituted or one or more It is preferable to represent a group selected from the above formula (B-1) or formula (B-2) which may be substituted by the above-described substituent L, and B ¹ represents an unsubstituted formula (B- It is more preferable to represent a group selected from 1) or formula (B-2), and B ¹ particularly preferably represents a group represented by the above-described formula (B-1).

In General Formula (I), ^one of Y ¹ and Y ² represents a group selected from the following (Y-A) group, and the other represents a group selected from the following (Y-B) group.
(YA) group: * -CO-, -CO- *, * -COO-, -OCO- *, * -CO-S-, -S-CO- *, * -CO-NH-, -NH _{-CO - *, * - COO-} CH 2 CH 2 -, - CH 2 CH 2 -OCO - *, * - COO-CH 2 -, - CH 2 -OCO - *, * - CH = N -, - N ═CH— * and * —CH═N—N═CH— (* means a site directly bonded to the group represented by B ¹ , for example, * —CO— means Y ² is —CO— It indicates that, -CO- * represents that ^{Y 1} is -CO-.)
(YB) group: —OCH ₂ — *, * —CH ₂ O—, —SCH ₂ — *, * —CH ₂ S—, * —CF ₂ O—, —OCF ₂ — *, * —CF ₂ S—, —SCF ₂ — *, —NHCH ₂ — *, * —CH ₂ NH—, —COO—CH ₂ — *, and * —CH ₂ —OCO— (* represents a group represented by B ¹ (This means a direct bonding site, for example, * —CH ₂ O— represents that Y ² is —CH ₂ O—, and —OCH ₂ — * represents that Y ¹ is —OCH ₂ —.)
From the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis, in the above (YA) group, * —COO—, —OCO— *, * —CO—S—, —S—CO— * , * —CO—NH—, —NH—CO— *, * —COO—CH ₂ CH ₂ — or —CH ₂ CH ₂ —OCO— * are preferred, and * —COO—, —OCO— A group represented by *, * —CO—NH—, —NH—CO— *, * —COO—CH ₂ CH ₂ — or —CH ₂ CH ₂ —OCO— * is more preferred, * —COO—, — A group represented by OCO— *, * —COO—CH ₂ CH ₂ — or —CH ₂ CH ₂ —OCO— * is more preferred, and a group represented by * —COO— or —OCO— * is particularly preferred.

Further, from the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis, in the above (Y-B) group, —OCH ₂ — *, * —CH ₂ O—, —SCH ₂ — *, * — _{CH 2 S -, - NHCH 2} - *, * - CH 2 NH -, * - CF 2 O -, - OCF 2 - *, * - CF 2 S- or -SCF ₂ - preferably a group represented by * , —OCH ₂ — *, * —CH ₂ O—, —SCH ₂ — *, * —CH ₂ S—, —NHCH ₂ — * or * —CH ₂ NH— are more preferred, and —OCH ₂ - * or * a group represented by _-CH 2 O-is particularly preferred.

In general formula (I), the group represented by —Y ¹ —B ¹ —Y ² — is derived from the following formula (YBY-1) from the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis. Formula (YBY-24)

It is preferable to represent a group selected from formula (YBY-1) to formula (YBY-10), formula (YBY-13) to formula (YBY-16), formula (YBY-19) to formula (YBY-22). It is more preferable to represent a group selected from formula (YBY-1), formula (YBY-2), formula (YBY-9), formula (YBY-10), formula (YBY-13), or formula (YBY). -14) represents a group selected from formula (YBY-1), formula (YBY-2), formula (YBY-13) or formula (YBY-14). It is even more preferable that a group selected from the formula (YBY-1) or the formula (YBY-2) is particularly preferable.

In the general formula (I), there is ^{-X 1 -A 1 -Z 1 -,} - X 1 -A 1 -Y 1 -, - Z 1 -A 1 -Z 1 -, - Z 1 -A 1 -Y ^{1 -, - Z 2 -A 2} -X 2 -, - Y 2 -A 2 -X 2 -, - Z 2 -A 2 -Z 2 - and / or ^{-Y 2 -A} 2 -Z 2 - are each Independently composed of a combination of groups selected from the groups defined by X ¹ , X ² , A ¹ , A ² , Z ¹ and Z ² , the above formula (YBY-1) to formula (YBY- The group selected from 24) may be represented, and other groups may be represented. When a group selected from the above formulas (YBY-1) to (YBY-24) is represented, the preferred structures of these groups are the same as described above.

In the general formula (I), Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH 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 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, when a plurality of Z ¹ are present, they may be the same or different, and when a plurality of Z ² are present, they are the same or different. and it may be but, Z ^{when one} is present Z ¹ directly bonded to Y ¹ represents a single bond, Z ² is attached directly to Y ² when the Z ² present represents a single bond. Z ¹ and Z ² are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O from the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis. _{-, - OCF 2 -, -} CH 2 CH 2 -, - CF 2 CF 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 -, - CH = CH -, - CF = CF- , —C≡C— or a single bond is preferred, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH _{2 -, - COO-CH 2 CH} 2 -, - OCO-CH 2 CH 2 -, - CH 2 C _{2 -COO -, - CH 2 CH} 2 -OCO -, - CH = CH -, - C≡C- or is more preferably a single _{bond, -OCH 2 -, - CH 2} O -, - COO-, More preferably, it represents —OCO—, —CF ₂ O—, —OCF ₂ — or a single bond, and further represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— or a single bond. More preferably, it represents -COO- or -OCO-.

  In general formula (I), m1 and m2 each independently represent an integer of 0 to 6, while m1 + m2 represents an integer of 0 to 6. From the viewpoints of solubility in a solvent and liquid crystallinity, m1 and m2 preferably each independently represent an integer of 0 to 3, and particularly preferably each independently represent 0, 1 or 2.

In the general formula (I), R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano 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—. 1 carbon atom which may be substituted by CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- To 20 straight-chain or branched alkyl groups, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² represents — (X ² —Sp ² ) _k2 —P. ² represents a group represented by ² ; When importance is attached to the flexibility when the film is formed, R ² preferably represents a group other than the group represented by-(X ² -Sp ² ) _k2 -P ² , and the mechanical strength when the film is formed is determined. In the case of emphasis, R ² preferably represents a group represented by — (X ² —Sp ² ) _k2 —P ² .
When R ² represents a group other than the group represented by — (X ² —Sp ² ) _k ² —P ² , R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, from the viewpoint of liquid crystallinity and ease of synthesis. A cyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, —O—CO. Linear or branched having 1 to 12 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C— Preferably, it represents an alkyl group, and R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. , -CO-, -COO-, -OCO- or -O-CO-O- More preferably represents a straight-chain or branched alkyl group of atoms from 1 to 12, R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or a straight-chain alkyl group or straight chain alkoxy group having 1 to 12 carbon atoms It is more preferable that R ² represents a linear alkyl group having 1 to 12 carbon atoms or a linear alkoxy group, and it is particularly preferable.

When R ² represents a group represented by — (X ² —Sp ² ) _k2 —P ² , preferred structures of P ² , Sp ² , X ² and k ² are P ¹ , Sp ¹ and X, respectively. It is the same as the preferable structure which ¹ and k1 employ | adopt.

In the general formula (I), L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a 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-, By —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. Replaced Represents a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L represents P ^L- (Sp ^L -X ^L ) _kL- may be represented, but when a plurality of L are present in the compound, they may be the same or different. From the viewpoint of liquid crystallinity and ease of synthesis, L is a fluorine atom, chlorine atom, pentafluorosulfuranyl group, nitro group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, or any hydrogen atom May be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently —O—, —S—, —CO—, —COO—. A straight chain having 1 to 20 carbon atoms which may be substituted by a group selected from: —OCO—, —O—CO—O—, —CH═CH—, —CF═CF— or —C≡C— And a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent ones may be substituted. -CH ₂ - are each independently - More preferably, it represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with a group selected from-, -COO- or -OCO-, and is a fluorine atom, a chlorine atom, or More preferably, the arbitrary hydrogen atom represents a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched alkoxy group having 1 to 12 carbon atoms, which may be substituted with a fluorine atom. , A fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 8 carbon atoms or a linear alkoxy group having 1 to 8 carbon atoms is particularly preferable. Further, L is _{^{P L - (Sp L -X L}} ) kL - group may represent represented by ^but, P ^L, Sp L, preferred structure of ^{X L} and kL, respectively ^P 1, ^Sp 1, it is the same as the preferred structure employed in X ¹ and k1.

  As the compound represented by the general formula (I), the following general formula (I-B1-A) to general formula (I-B3-B)

(Wherein P ¹ , Sp ¹ , X ¹ , k ¹ , A ¹ , A ² , Z ¹ , Z ² , R ² , m 1 and m ² are P ¹ , Sp ¹ , X ¹ in the general formula (I), respectively. , K1, A ¹ , A ² , Z ¹ , Z ² , R ² , m1 and m2 have the same meanings, but in the above general formula (I-B1-A) to general formula (I-B3-B) A group represented by Z ¹ directly bonded to —OCO— or —OCH ₂ — represents a single bond, and a group represented by Z ² directly bonded to —COO— or —CH ₂ O— represents a single bond. .) Is preferred.

  Examples of the compounds represented by the above general formula (I-B1-A) to general formula (I-B3-B) include the following general formula (I-B1-A-1) to general formula (I-B2- B-4)

(In the formula, P ¹ , Sp ¹ , X ¹ , k ¹ , A ² , Z ² and R ² are respectively P ¹ , Sp ¹ , X ¹ , k ¹ , A ² , Z ² and R in the general formula (I). ² , A ¹¹ , A ¹² and A ¹³ each have the same meaning as A ¹ in formula (I), and Z ¹¹ and Z ¹² each have the same meaning as Z ¹ in formula (I). And m21 represents an integer of 0 to 5).

  Examples of the compound represented by the general formula (I-B1-A-1) to the general formula (I-B2-B-4) include the following general formula (I-B1-A-1-1) to the general formula. Formula (I-B2-B-4-1)

^{(Wherein, P 1, Sp 1, X 1} , k1 and ^{R 2} each represent the same meaning as ^{P 1, Sp 1, X 1} , k1 and ^{R 2} in the general formula ^{(I), A 11, A} 12 , A ¹³ , A ²¹ , A ²² , A ²³ and A ²⁴ represent the same meaning as A ¹ and A ² in the general formula (I), and Z ¹¹ , Z ¹² , Z ²¹ , Z ²² and Z ²³ represent the general formula The compound represented by the same meaning as Z ¹ and Z ² in (I) is more preferable.

R ² is ^- if ^{(X ₂} -Sp _²⁾ represents a k2 -P ² represented by groups other than groups of the general formula from the above general formula (I-B1-A-1-1 ) (I-B2- As the compound represented by B-4-1), the following general formula (I-B1-A-1-1-1) to general formula (I-B2-B-2-2-1)

(Wherein P ¹ , Sp ¹ , X ¹ , k ¹ and L represent the same meaning as P ¹ , Sp ¹ , X ¹ , k ¹ and L in the general formula (I), respectively, A ¹¹¹ , A ²¹¹ , A ²²¹ And A ²³¹ each independently represents an unsubstituted or 1,4-phenylene group or a 1,4-cyclohexylene group which may be substituted by one or more substituents L, and Z ²¹¹ and Z ²²¹ are Each independently represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— or a single bond, and R ²¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or 1 or more carbon atoms in which two or more non-adjacent —CH ₂ — may be each independently substituted by —O—, —CO—, —COO—, —OCO— or —O—CO—O— To 12 straight or branched alkyl groups, and s represents each The compound represented independently from 0.) Representing the integer 4 is more preferred.

When R ² represents a group represented by — (X ² —Sp ² ) _k2 —P ² , the above general formula (I-B1-A-1-1) to general formula (I-B2-B) are used. -4-1) As a compound represented by the following general formula (I-B1-A-1-1-2) to general formula (I-B2-A-3-2-2)

(Wherein P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k ¹ , k ² and L are respectively P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k1, k2 and L have the same meaning, and A ¹¹¹ , A ¹²¹ , A ¹³¹ , A ²²¹ , A ²³¹ and A ²⁴¹ are each independently unsubstituted or substituted by one or more substituents L Represents an optionally substituted 1,4-phenylene group or 1,4-cyclohexylene group, and Z ¹¹¹ , Z ¹²¹ , Z ²¹¹ , Z ²²¹ and Z ²³¹ are each independently —OCH ₂ —, —CH ₂ O; -, -COO-, -OCO- or a single bond, wherein each s independently represents an integer of 0 to 4, is more preferred, and the following general formula (I-B1-A- 1-1-2-1) to general formula (I-B2-A-2-) 2-2-2)

(Wherein P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k ¹ , k ² and L are respectively P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k 1, k ² and L have the same meaning, Z ²¹¹ and Z ²²¹ each independently represent —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— or a single bond, and s represents Each independently represents an integer of 0 to 4.).

  In addition, the 1,4-cyclohexylene group, decahydronaphthalene-2,6-diyl group and 1,3-dioxane-2,5-diyl group present in the compound represented by the general formula (I) are: Only the trans isomer, only the cis isomer, or a mixture of the trans isomer and the cis isomer may be used. From the viewpoint of liquid crystallinity, the trans isomer is preferably excessive, and the trans isomer is more preferably excessive. It is particularly preferable that only the trans form is present.

  Specifically, compounds represented by the following formulas (I-1) to (I-70) are preferable as the compounds represented by the general formula (I).

The compound of this invention can be manufactured with the following manufacturing methods.
(Manufacturing method 1) Manufacture of the compound represented by a following formula (S-9)

(In the formula, P ¹ , Sp ¹ and L each represent the same meaning as P ¹ , Sp ¹ and L in the general formula (I), and R ²¹ represents the above general formula (I-B1-A-1-1-1). 1) to R ²¹ in formula (I-B2-B-2-2-1), each s independently represents an integer of 0 to 4, PG represents a protecting group, and halogen is Represents a halogen atom or a halogen equivalent.)
The carboxyl group of the compound represented by the formula (S-1) is protected with a protecting group (PG). The protecting group (PG) is not particularly limited as long as it can be stably protected until the deprotection step. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM. Protecting groups (PG) mentioned in WUTS, THEODORA W. GREENE, John Wiley & Sons, Inc., Publication) and the like are preferred. Specific examples of the protecting group include a tetrahydropyranyl group, a tert-butyl group, a methoxymethyl group, an ethoxymethyl group, a methyl group, an ethyl group, and a benzyl group.

  The protecting group (PG) of the compound represented by the formula (S-2) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-3), but those listed in the above-mentioned literature are preferable. It is also possible to obtain a compound represented by the formula (S-3) by protecting only one carboxyl group of the compound represented by the formula (S-1) with a protecting group (PG).

  The carboxyl group of the compound represented by formula (S-3) is reduced. The conditions for the reduction reaction are not particularly limited as long as they give the compound represented by the formula (S-4), and examples thereof include borane-tetrahydrofuran complex.

  The compound represented by the formula (S-6) can be obtained by reacting the compound represented by the formula (S-4) with the compound represented by the formula (S-5). Examples of the reaction conditions include Mitsunobu reaction. Alternatively, the hydroxyl group of the compound represented by the formula (S-4) is changed to a methanesulfoxy group or p-toluenesulfoxy group, and then reacted with the compound represented by the formula (S-5) in the presence of a base. It is also possible to make it. Examples of the base include potassium carbonate, cesium carbonate, potassium phosphate and the like.

  The protecting group (PG) of the compound represented by the formula (S-6) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by the formula (S-7), but those listed in the above-mentioned literature are preferable.

The compound represented by the formula (S-9) can be obtained by reacting the compound represented by the formula (S-7) with the compound represented by the formula (S-8) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.
(Production method 2) Production of a compound represented by the following formula (S-15)

^(Wherein, from ^{P 1, Sp 1, X 1} , k1 and L each represents the same meaning as ^{P 1, Sp 1, X 1} , k1 and L in the general formula (I), s each independently is 0 Represents an integer of 4, and PG represents a protecting group.)
The compound represented by the formula (S-12) can be obtained by reacting the compound represented by the formula (S-10) with the compound represented by the formula (S-11). Examples of the reaction conditions include Mitsunobu reaction. Alternatively, the hydroxyl group of the compound represented by the formula (S-10) is changed to a methanesulfoxy group or p-toluenesulfoxy group, and then reacted with the compound represented by the formula (S-11) in the presence of a base. It is also possible to make it. Examples of the base include potassium carbonate, cesium carbonate, potassium phosphate and the like.

  The protecting group (PG) of the compound represented by the formula (S-12) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by the formula (S-13), but those listed in the above-mentioned literature are preferable.

  The compound represented by the formula (S-15) can be obtained by reacting the compound represented by the formula (S-13) with a compound represented by the formula (S-14). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-13) is converted to an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then represented by the general formula (S-14). The method of making it react with a compound in base presence is mentioned. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the base include triethylamine and diisopropylethylamine.

  Examples of reaction conditions other than those described in each step of production method 1 and production method 2 include, for example, an experimental chemistry course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (John Wiley & Sons, Inc., Publication), and Bilstein Handbook of. Organic Chemistry (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) conditions or SciFind described in the literature such as r (Chemical Abstracts Service, American Chemical Society) or Reaxys conditions provided from the online search services (Elsevier Ltd.) and the like.

  In each step, a reaction solvent can be appropriately used. The solvent is not particularly limited as long as it gives the target compound. For example, isopropyl alcohol, ethylene glycol, methanol, ethanol, chloroform, dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether, xylene, ethyl acetate, 1,4-dioxane, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, toluene, hexane, cyclohexane, heptane, methyl Examples include isobutyl ketone, tert-butyl methyl ether, and methyl ethyl ketone. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, polyoxyethylene (20) sorbitan monolaurate [Tween 20], sorbitan monooleate [Span 80], and the like.

  In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel.

  The compound of the present invention is preferably used in a nematic liquid crystal composition, a smectic liquid crystal composition, a chiral smectic liquid crystal composition, and a cholesteric liquid crystal composition. In the liquid crystal composition using the reactive compound of the present invention, a compound other than the present invention may be added.

  Specifically, the other polymerizable compound used by mixing with the polymerizable compound of the present invention is represented by the general formula (X-11).

And / or general formula (X-12)

(In the formula, P ¹¹ , P ¹² and P ¹³ each independently represent a group which is polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ¹¹ , Sp ¹² and Sp ¹³ are each independently a single bond or a carbon atom. Represents an alkylene group of 1 to 20, but one —CH ₂ — or two or more non-adjacent —CH ₂ — is replaced by —O—, —COO—, —OCO—, —OCOO—. X ¹¹ , X ¹² and X ¹³ 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—, —CF═CF—, —C≡ C— or a single bond, and Z ¹¹ and Z ¹² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, — 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 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 - , —CF ₂ CF 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 a single bond, and A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are each independently a 1,4-phenylene group 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2, 6-diyl group or 1,3-dioxane-2, A 5-diyl group, wherein A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen atom, cyano Or a nitro group, R ¹¹ may be a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano 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- represents a linear or branched alkyl group having 1 to 20 carbon atoms, and m11 and m12 are 0, 1, 2, or 3 and m11 and / or m12 represents 2 or 3, two or three A ¹¹ , A ¹³ , Z ¹¹ and / or Z ¹² may be the same or different. ) Is preferred, and the case where P ¹¹ , P ¹² and P ¹³ are acrylic groups or methacrylic groups is particularly preferred. Specifically, the compound represented by the general formula (X-11) is represented by the general formula (X-11a).

Wherein W ¹¹ and W ¹² each independently represent a hydrogen atom or a methyl group, Sp ¹⁴ and Sp ¹⁵ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ¹⁴ and X ¹⁵ each independently to -O -, - COO -, - OCO- or a single ^{bond, Z 13} and ^{Z 14} are each independently represents a -COO- or ^{-OCO-, a 15,} a ¹⁶ and ^{a 17} are each independently And may be unsubstituted or substituted by a fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. , A 4-phenylene group) is preferable, and the following formulas (X-11a-1) to (X-11a-4)

(Wherein, W ¹¹ , W ¹² , Sp ¹⁴ and Sp ¹⁵ represent the same meaning as in the general formula (X-11a)) are particularly preferable. In the above formulas (X-11a-1) to (X-11a-4), compounds in which Sp ¹⁴ and Sp ¹⁵ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

  In addition, preferable bifunctional polymerizable compounds include those represented by the following general formulas (X-11b-1) to (X-11b-3):

(Wherein W ¹³ and W ¹⁴ each independently represent a hydrogen atom or a methyl group, and Sp ¹⁶ and Sp ¹⁷ each independently represent an alkylene group having 2 to 18 carbon atoms). Is mentioned. In the above formulas (X-11b-1) to (X-11b-3), compounds in which Sp ¹⁶ and Sp ¹⁷ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

  Specific examples of the compound represented by the general formula (X-12) include the following general formula (X-12-1) to formula (X-12-7).

(In the formula, P ¹⁴ represents an acrylic group or a methacryl group, and Sp ¹⁸ represents a single bond or an alkylene group having 1 to 20 carbon atoms, but one —CH ₂ — or two or more not adjacent to each other. —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —O—CO—O—, and X ¹⁶ represents a single bond, —O—, —COO—, or —OCO—. Z ¹⁵ represents a single bond, —COO— or —OCO—, and L ¹¹ represents a fluorine atom, a chlorine atom, one —CH ₂ —, or two or more non-adjacent —CH ₂ —. ¹² represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be independently replaced by -O-, -COO-, or -OCO-, s11 represents an integer of 0 to 4, and R ¹² Is a hydrogen atom, fluorine atom, chlorine atom, cyano group, nitro group, one -C ₂ - or nonadjacent two or more -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— represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted. Compounds.

  A polymerizable compound that does not exhibit liquid crystallinity can be added to the polymerizable liquid crystal composition containing the compound of the present invention to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound that is recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples include those described in “Photocuring Technology Data Book, Materials (Monomer, Oligomer, Photopolymerization Initiator)” (supervised by Kunihiro Ichimura, Kiyosuke Kato, Technonet).

  The compound of the present invention can be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added depending on the purpose. In this case, the concentration of the photopolymerization initiator is preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, and 0.4% by mass to 8% by mass with respect to the compound of the present invention. % Is more preferable. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Specific examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907), benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene]. Amino (IRGACURE OXE 01) etc. are mentioned. Examples of the thermal polymerization initiator include azo compounds and peroxides. Specific examples of the thermal polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile) and the like. One type of polymerization initiator may be used, or two or more types of polymerization initiators may be used in combination.

  In addition, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5% by mass is more preferable. One kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specifically, as the stabilizer, the formula (X-13-1) to the formula (X-13-35)

(Wherein n represents an integer of 0 to 20) is preferred.

  Further, when the polymerizable liquid crystal composition containing the compound of the present invention is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins, Depending on the purpose, metals, metal complexes, dyes, pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants Further, metal oxides such as ion exchange resin and titanium oxide can be added.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used for various applications. For example, a polymer obtained by polymerizing a polymerizable liquid crystal composition containing the compound of the present invention without orientation can be used as a light scattering plate, a depolarizing plate, and a moire fringe prevention plate. Moreover, the polymer obtained by superposing | polymerizing after orientating has optical anisotropy, and is useful. Such an optical anisotropic body includes, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth, a substrate on which an organic thin film is formed, or an alignment film on which SiO ₂ is obliquely deposited. It can be produced by polymerizing the polymerizable liquid crystal composition after it is supported on a substrate having it or sandwiched between substrates.

  Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. . Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. As the organic solvent, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, aprotic solvents and the like can be used. The solvent is toluene or hexane, the halogenated hydrocarbon solvent is methylene chloride, the ether solvent is tetrahydrofuran, acetoxy-2-ethoxyethane or propylene glycol monomethyl ether acetate, and the alcohol solvent is methanol, ethanol or Isopropanol, acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone or N-methylpyrrolidinone as the ketone solvent, ethyl acetate or cellosolve as the ester solvent, dimethyl as the aprotic solvent It can be mentioned formamide or acetonitrile. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide thin film on a substrate is effective for improving the adhesion between a polymer obtained by polymerizing a polymerizable liquid crystal material and the substrate.

  Examples of the alignment treatment other than the above include use of fluid alignment of a liquid crystal material, use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

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

  The optical anisotropic body obtained by polymerization can be subjected to a heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

  The optical anisotropic body manufactured by such a method may be peeled off from the substrate and used alone or without being peeled off. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”. When handling a substance unstable to oxygen and / or moisture in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. In addition to the operations specifically described below, as necessary, operations such as quenching, separation / extraction, neutralization, washing, separation, purification, drying, concentration, etc. that are commonly performed among those skilled in the art May be performed.
Example 1 Production of Compound Represented by Formula (I-1)

  Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (I-1-1), 6.0 g of triethylamine, and 40 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 6.4 g of ethyl chloroformate was added dropwise and stirred at room temperature for 1 hour. The precipitate was removed by filtration. Under a nitrogen atmosphere, 2.2 g of sodium borohydride and 10 mL of tetrahydrofuran were added to another reaction vessel. The filtrate was added dropwise while cooling with ice. A mixed solution of 40 mL of methanol and 10 mL of water was added dropwise and stirred at room temperature for 3 hours. After adding 20 mL of 10% hydrochloric acid, the mixture was extracted with ethyl acetate. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 7.4 g of a compound represented by the formula (I-1-2).

  Under a nitrogen atmosphere, 7.4 g of the compound represented by the formula (I-1-2), 4.1 g of pyridine, and 35 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 5.4 g of methanesulfonyl chloride was added dropwise and stirred at room temperature for 3 hours. Poured into water and washed sequentially with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) and recrystallization (acetone / hexane) to obtain 7.5 g of a compound represented by the formula (I-1-3).

  In a reaction vessel, 3.0 g of the compound represented by the formula (I-1-3), 0.7 g of the compound represented by the formula (I-1-4), 2.5 g of potassium carbonate, 30 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 20 hours. The mixture was poured into water, extracted with toluene, and washed with brine. Purification was performed by column chromatography (silica gel, toluene) and recrystallization (toluene / hexane) to obtain 2.0 g of a compound represented by the formula (I-1-5).

  Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (I-1-5), 20 mL of tetrahydrofuran, 20 mL of methanol, and 10 mL of 25% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was heated and stirred at 60 ° C. for 2 hours. The solvent was distilled off and redissolved in a mixed solvent of tetrahydrofuran and water. 10% hydrochloric acid was added to bring the pH of the solution to 2. The solvent was distilled off, water was added, and the precipitated solid was filtered. The obtained solid was washed with water and dried to obtain 1.7 g of a compound represented by the formula (I-1-6).

In a reaction vessel, 1.7 g of the compound represented by the formula (I-1-6), 1.6 g of the compound represented by the formula (I-1-7), 1.8 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 20 hours. It was poured into water and the precipitated solid was filtered. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol) to obtain 2.4 g of a compound represented by the formula (I-1).
LCMS: 699 [M + 1]
Example 2 Production of Compound Represented by Formula (I-2)

  Under a nitrogen atmosphere, 20.0 g of the compound represented by the formula (I-2-1), 8.8 g of tert-butyl alcohol, 1.3 g of N, N-dimethylaminopyridine, and 100 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 16.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 20.8 g of a compound represented by the formula (I-2-2).

  To the reaction vessel, 20.8 g of the compound represented by the formula (I-2-2), 200 mL of methanol, and 30 mL of 25% aqueous sodium hydroxide solution were added, and the mixture was heated and stirred at 60 ° C. Cool and add chloroform. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, followed by liquid separation treatment. The organic layer was washed with brine and dried over sodium sulfate. The insoluble material was filtered through Celite, and the solvent was evaporated and dried to obtain 17.7 g of a compound represented by the formula (I-2-3).

  Under a nitrogen atmosphere, 17.7 g of the compound represented by the formula (I-2-3) and 100 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 103 mL of 0.9 mol / L borane-tetrahydrofuran complex was added dropwise and stirred for 1 hour. After 5% hydrochloric acid was added dropwise, the mixture was extracted with ethyl acetate and washed with brine. By drying with sodium sulfate and distilling off the solvent, 14.9 g of a compound represented by the formula (I-2-4) was obtained.

  Under a nitrogen atmosphere, 14.9 g of the compound represented by the formula (I-2-4), 7.2 g of pyridine, and 150 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 8.8 g of methanesulfonyl chloride was added dropwise and stirred at room temperature for 3 hours. Poured into water and washed sequentially with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) and recrystallization (acetone / hexane) to obtain 16.3 g of a compound represented by the formula (I-2-5).

  In a reaction vessel, 5.0 g of the compound represented by the formula (I-2-5), 1.1 g of the compound represented by the formula (I-2-6), 3.5 g of potassium carbonate, 70 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 15 hours. It was poured into water, extracted with toluene, and washed with brine. Purification was performed by column chromatography (silica gel, toluene) and recrystallization (acetone / methanol) to obtain 3.5 g of a compound represented by the formula (I-2-7).

  To the reaction vessel, 3.5 g of the compound represented by the formula (I-2-7), 15 mL of dichloromethane, and 10 mL of formic acid were added and heated at 40 ° C. for 8 hours. After distilling off the solvent, the obtained solid was washed with water and dried to obtain 2.5 g of a compound represented by the formula (I-2-8).

In a reaction vessel, 2.5 g of the compound represented by the formula (I-2-8), 2.3 g of the compound represented by the formula (I-2-9), 2.6 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 20 hours. It was poured into water and the precipitated solid was filtered. Purification by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol) gave 3.5 g of a compound represented by the formula (I-2).
Phase transition temperature (heating rate: 5 ° C./min) C 62 I ¹ H NMR (CDCl ₃ ) δ 1.10 (m, 4H), 1.38-1.46 (m, 12H), 1.60- 1.84 (m, 10H), 1.96-2.05 (m, 8H), 2.20 (s, 3H), 2.27 (m, 2H), 3.71 (t, 4H), 4 .07 (t, 4H), 4.16 (t, 4H), 5.82 (dd, 2H), 6.12 (dd, 2H), 6.40 (dd, 2H), 6.61-6. 73 (m, 3H) ppm.
LCMS: 713 [M + 1]
Example 3 Production of Compound Represented by Formula (I-3)

Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (I-3-1), 2.6 g of the compound represented by the formula (I-3-2), N, N-dimethylaminopyridine 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.4 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.2 g of the compound represented by formula (I-3). .
Phase transition temperature (heating rate: 5 ° C./min) C 99 X 195 N 200 I
¹ H NMR (CDCl ₃ ) δ 1.21 (m, 4H), 1.45-1.83 (m, 22H), 2.04 (m, 4H), 2.19-2.22 (m, 7H) ), 2.52 (m, 2H), 3.74 (t, 4H), 3.94 (t, 4H), 4.17 (t, 4H), 5.82 (dd, 2H), 6.12 (Dd, 2H), 6.40 (dd, 2H), 6.64-6.75 (m, 3H), 6.87 (d, 4H), 6.97 (d, 4H) ppm.
LCMS: 897 [M + 1]
Example 4 Production of Compound Represented by Formula (I-4)

  In a reaction vessel, 5.0 g of the compound represented by formula (I-4-1), 3.7 g of the compound represented by formula (I-4-2), 3.5 g of potassium carbonate, 50 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 9 hours. It was poured into water, extracted with toluene, and washed with brine. Purification was performed by column chromatography (silica gel, toluene) and recrystallization (acetone / methanol) to obtain 5.7 g of a compound represented by the formula (I-4-3).

  To the reaction vessel, 5.7 g of the compound represented by the formula (I-4-3), 20 mL of dichloromethane, and 10 mL of formic acid were added and heated at 40 ° C. for 8 hours. After distilling off the solvent, the obtained solid was washed with water and dried to obtain 4.4 g of a compound represented by the formula (I-4-4).

In a reaction vessel, 4.4 g of the compound represented by the formula (I-4-4), 2.3 g of the compound represented by the formula (I-4-5), 2.6 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. It was poured into water and the precipitated solid was filtered. Purification by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol) gave 4.4 g of the compound represented by formula (I-4).
LCMS: 513 [M + 1]
Example 5 Production of Compound Represented by Formula (I-5)

  Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-5-1), 3.9 g of diisopropylethylamine, and 50 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 2.3 g of acryloyl chloride was added dropwise and stirred at room temperature for 8 hours. The product was washed successively with 1% hydrochloric acid and brine, and purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 5.0 g of a compound represented by the formula (I-5-2).

  To the reaction vessel, 5.0 g of the compound represented by the formula (I-5-2), 50 mL of dichloromethane, and 25 mL of formic acid were added and heated to reflux for 5 hours. After the solvent was distilled off, purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 3.6 g of a compound represented by the formula (I-5-3).

Under a nitrogen atmosphere, 3.6 g of the compound represented by the formula (I-5-3), 1.0 g of the compound represented by the formula (I-5-4), N, N-dimethylaminopyridine 2 g, 50 mL dichloromethane was added. While cooling with ice, 2.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.0 g of the compound represented by the formula (I-5). .
Phase transition temperature (heating rate: 5 ° C./min) C 103 N 107 I
¹ H NMR (CDCl ₃ ) δ 1.09-1.19 (m, 4H), 1.59 (m, 4H), 1.75 (m, 2H), 1.94 (d, 4H), 2. 15-2.23 (m, 7H), 2.46-2.57 (m, 2H), 4.03 (d, 4H), 5.85 (dd, 2H), 6.14 (dd, 2H) , 6.42 (dd, 2H), 6.88-6.99 (m, 3H) ppm.
LCMS: 513 [M + 1]
Example 6 Production of Compound Represented by Formula (I-6)

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-6-1), 2.2 g of the compound represented by the formula (I-6-2), N, N-dimethylaminopyridine,. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.5 g of a compound represented by the formula (I-6). .
LCMS: 605 [M + 1]
Example 7 Production of Compound Represented by Formula (I-7)

  Under a nitrogen atmosphere, 0.9 g of sodium hydride and 5 mL of tetrahydrofuran were added to the reaction vessel. A solution prepared by dissolving 2.0 g of the compound represented by the formula (I-7-2) in 5 mL of tetrahydrofuran was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 2 hours. A solution prepared by dissolving 10.1 g of the compound represented by the formula (I-7-1) in 30 mL of tetrahydrofuran was dropped, and the mixture was heated to reflux for 6 hours. The reaction solution was poured into water and extracted with toluene. After washing with brine, purification was performed by column chromatography (silica gel, toluene) and recrystallization (toluene / ethanol) to obtain 5.3 g of a compound represented by the formula (I-7-3).

  To the reaction vessel, 5.3 g of the compound represented by the formula (I-7-3), 20 mL of dichloromethane, and 10 mL of formic acid were added and heated at 40 ° C. for 8 hours. After distilling off the solvent, the obtained solid was washed with water and dried to obtain 3.7 g of a compound represented by the formula (I-7-4).

In a reaction vessel, 3.7 g of the compound represented by the formula (I-7-4), 4.1 g of the compound represented by the formula (I-7-5), 3.9 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. It was poured into water and the precipitated solid was filtered. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.2 g of a compound represented by the formula (I-7).
LCMS: 649 [M + 1]
Example 8 Production of Compound Represented by Formula (I-8)

  In a reaction vessel, 5.0 g of the compound represented by the formula (I-8-1), 4.7 g of the compound represented by the formula (I-8-2), 4.1 g of potassium carbonate, 50 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 9 hours. It was poured into water, extracted with toluene, and washed with brine. Purification was performed by column chromatography (silica gel, toluene / hexane) and recrystallization (acetone / methanol) to obtain 6.2 g of a compound represented by the formula (I-8-3).

  To the reaction vessel, 6.2 g of the compound represented by the formula (I-8-3), 60 mL of methanol, and 30 mL of 25% aqueous sodium hydroxide solution were added, and the mixture was heated and stirred at 60 ° C. Cool and add ethyl acetate. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, followed by liquid separation treatment. The organic layer was washed with brine and dried over sodium sulfate. The solvent was distilled off and dried to obtain 5.4 g of a compound represented by the formula (I-8-4).

  In a reaction vessel, 5.4 g of the compound represented by formula (I-8-4), 3.5 g of the compound represented by formula (I-8-5), 3.0 g of potassium carbonate, 50 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 6 hours. Poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 6.2 g of a compound represented by the formula (I-8-6).

  To the reaction vessel, 6.2 g of a compound represented by the formula (I-8-6) and 50 mL of dichloromethane were added. While cooling with ice, 20 mL of trifluoroacetic acid was added dropwise and stirred for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. After washing with brine, purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 5.0 g of a compound represented by the formula (I-8-7).

  Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-8-8) and 30 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 29 mL of 0.9 mol / L borane-tetrahydrofuran complex was added dropwise and stirred for 1 hour. After 5% hydrochloric acid was added dropwise, the mixture was extracted with ethyl acetate and washed with brine. By drying with sodium sulfate and distilling off the solvent, 4.2 g of a compound represented by the formula (I-8-9) was obtained.

  Under a nitrogen atmosphere, 4.2 g of the compound represented by the formula (I-8-9), 2.0 g of pyridine, and 40 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 2.6 g of methanesulfonyl chloride was added dropwise and stirred at room temperature for 3 hours. Poured into water and washed sequentially with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 5.3 g of a compound represented by the formula (I-8-10).

Under a nitrogen atmosphere, 2.9 g of the compound represented by the formula (I-8-10), 5.0 g of the compound represented by the formula (I-8-7), 5.0 g of cesium carbonate, and 50 mL of dimethyl sulfoxide in a reaction vessel. And heated and stirred at 80 ° C. for 5 hours. Poured into water, extracted with dichloromethane and washed with brine. Purification was carried out by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.8 g of a compound represented by the formula (I-8).
LCMS: 669 [M + 1]
Example 9 Production of Compound Represented by Formula (I-9)

  A compound represented by the formula (I-9-2) was produced by the method described in Macromolecular Chemistry and Physics, 2009, Vol. 210, No. 7, pages 531-541. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-9-1), 7.1 g of the compound represented by the formula (I-9-2), 11.2 g of triphenylphosphine, and 30 mL of tetrahydrofuran were added. . While cooling with ice, 8.0 g of diisopropyl azodicarboxylate was added and stirred at room temperature for 3 hours. After adding water, the mixture was extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 8.1 g of a compound represented by the formula (I-9-3).

  To the reaction vessel was added 8.1 g of the compound represented by the formula (I-9-3), 5.5 g of sodium dihydrogen phosphate dihydrate, 100 mL of methanol, 50 mL of water, and 5.0 mL of 35% hydrogen peroxide solution. It was. A solution prepared by dissolving 4.7 g of sodium chlorite in 20 mL of water was added dropwise, and the mixture was stirred with heating at 60 ° C. for 2 hours. Water was added and cooled, and the precipitate was filtered. The obtained solid was dried to obtain 6.7 g of a compound represented by the formula (I-9-4).

  Under a nitrogen atmosphere, 6.7 g of a compound represented by the formula (I-9-4), 2.7 g of a compound represented by the formula (I-9-5), N, N-dimethylaminopyridine 1 g and 40 mL of dichloromethane were added. While cooling with ice, 2.8 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 3.6 g of a compound represented by the formula (I-9-6).

  In a reaction vessel, 7.0 g of the compound represented by the formula (I-9-7), 3.6 g of the compound represented by the formula (I-9-8), 5.0 g of potassium carbonate, 50 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 6 hours. It was poured into water, extracted with toluene, and washed with brine. Purification was performed by column chromatography (silica gel, toluene / hexane) to obtain 6.6 g of a compound represented by the formula (I-9-9).

  To the reaction vessel, 6.6 g of a compound represented by the formula (I-9-9), 40 mL of dichloromethane, and 20 mL of formic acid were added and heated at 40 ° C. for 6 hours. Poured into water and extracted with ethyl acetate. After washing with brine and drying over sodium sulfate, the solvent was distilled off to obtain 5.0 g of a compound represented by the formula (I-9-10).

Under a nitrogen atmosphere, 2.1 g of the compound represented by the formula (I-9-10), 3.6 g of the compound represented by the formula (I-9-6), N, N-dimethylaminopyridine,. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.1 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.9 g of a compound represented by the formula (I-9).
LCMS: 767 [M + 1]
Example 10 Production of Compound Represented by Formula (I-10)

  Under a nitrogen atmosphere, 5.0 g of a compound represented by formula (I-10-1), 3.6 g of a compound represented by formula (I-10-2), N, N-dimethylaminopyridine 3 g, 40 mL dichloromethane was added. While cooling with ice, 3.9 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 5 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (alumina, dichloromethane / hexane) to obtain 6.5 g of a compound represented by the formula (I-10-3).

  To the reaction vessel, 6.5 g of the compound represented by the formula (I-10-3), 40 mL of methanol, and 1 mL of concentrated hydrochloric acid were added and stirred at room temperature for 6 hours. Dilute with ethyl acetate and wash with brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 4.5 g of a compound represented by the formula (I-10-4).

  Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-5) and 40 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 24 mL of 0.9 mol / L borane-tetrahydrofuran complex was added dropwise and stirred for 1 hour. After 5% hydrochloric acid was added dropwise, the mixture was extracted with ethyl acetate and washed with brine. By drying with sodium sulfate and distilling off the solvent, 4.2 g of a compound represented by the formula (I-10-6) was obtained.

  Under a nitrogen atmosphere, 4.2 g of the compound represented by the formula (I-10-6), 4.5 g of the compound represented by the formula (I-10-4), 5.6 g of triphenylphosphine, and 40 mL of tetrahydrofuran were added. . While cooling with ice, 4.3 g of diisopropyl azodicarboxylate was added and stirred at room temperature for 3 hours. After adding water, the mixture was extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (alumina, dichloromethane / hexane) to obtain 5.9 g of a compound represented by the formula (I-10-7).

  To the reaction vessel, 5.9 g of the compound represented by the formula (I-10-7), 40 mL of tetrahydrofuran, 40 mL of methanol, and 1 mL of concentrated hydrochloric acid were added and stirred at room temperature for 8 hours. After the solvent was distilled off, the residue was diluted with ethyl acetate and washed successively with water and brine. After drying with sodium sulfate, the solvent was distilled off to obtain 4.6 g of a compound represented by the formula (I-10-8).

  Under a nitrogen atmosphere, 5.0 g of the compound represented by formula (I-10-9), 2.8 g of the compound represented by formula (I-10-10), 3.4 g of potassium carbonate, 30 mL of ethanol, Water (25 mL) and tetrakis (triphenylphosphine) palladium (0) (0.5 g) were added, and the mixture was heated to reflux for 6 hours. The mixture was poured into a saturated aqueous ammonium chloride solution, extracted with ethyl acetate, and washed successively with water and brine. Purification was performed by column chromatography (alumina, toluene / ethyl acetate) to obtain 4.0 g of a compound represented by the formula (I-10-11).

  Under a nitrogen atmosphere, 4.0 g of a compound represented by the formula (I-10-11), 4.2 g of a compound represented by the formula (I-10-8), N, N-dimethylaminopyridine 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.7 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 6 hours. After the precipitate was removed by filtration, reprecipitation (dichloromethane / methanol) was performed. Purification was performed by column chromatography (alumina, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 6.5 g of a compound represented by the formula (I-10-12).

  6.5 g of the compound represented by the formula (I-10-12), 40 mL of tetrahydrofuran, 40 mL of methanol, and 1 mL of concentrated hydrochloric acid were added to the reaction vessel, and the mixture was stirred at room temperature for 6 hours. Dilute with ethyl acetate and wash with brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 4.6 g of a compound represented by the formula (I-10-13).

  In a reaction vessel, 4.6 g of the compound represented by the formula (I-10-13), 1.4 g of the compound represented by the formula (I-10-14), 1.5 g of potassium carbonate, 50 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 6 hours. Poured into water and extracted with dichloromethane. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.4 g of a compound represented by the formula (I-10-15).

Under a nitrogen atmosphere, 4.4 g of the compound represented by the formula (I-10-15), 0.9 g of diisopropylethylamine, and 30 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 0.6 g of acryloyl chloride was added dropwise and stirred at room temperature for 8 hours. The product was washed successively with 1% hydrochloric acid and brine, and purified by column chromatography (silica gel, toluene) to obtain 3.3 g of a compound represented by the formula (I-10).
LCMS: 811 [M + 1]
Example 11 Production of Compound Represented by Formula (I-60)

  To the reaction vessel was added 3.0 g of the compound represented by the formula (I-60-1), 2.7 g of the compound represented by the formula (I-60-2), 5.0 g of cesium carbonate, and 50 mL of dimethyl sulfoxide, and the mixture was 80 ° C. And stirred for 8 hours. Poured into water, extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 3.8 g of a compound represented by the formula (I-60-3).

  To the reaction vessel, 3.8 g of the compound represented by the formula (I-60-3), 20 mL of dichloromethane, and 10 mL of formic acid were added and heated at 40 ° C. for 8 hours. After distilling off the solvent, the obtained solid was washed with water and dried to obtain 3.0 g of a compound represented by the formula (I-60-4).

In a reaction vessel, 3.0 g of the compound represented by the formula (I-60-4), 1.5 g of the compound represented by the formula (I-60-5), 1.5 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. It was poured into water and the precipitated solid was filtered. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.9 g of a compound represented by the formula (I-60).
Phase transition temperature (heating rate: 5 ° C./min) C 47 I
¹ H NMR (CDCl ₃ ) δ 1.09 (m, 2H), 1.40-1.80 (m, 19H), 2.00 (m, 4H), 2.28 (m, 1H), 3. 72 (d, 2H), 3.90 (t, 2H), 4.07 (t, 2H), 4.17 (td, 4H), 5.82 (dd, 2H), 6.12 (dd, 2H) ), 6.40 (dd, 2H), 6.81 (s, 4H) ppm.
LCMS: 559 [M + 1] (Example 12) Production of compound represented by formula (I-70)

  10.0 g of the compound represented by the formula (I-70-1), 100 mL of methanol, and 7.1 g of 25% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was stirred at 50 ° C. for 5 hours. Cool and add chloroform. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, followed by liquid separation treatment. The organic layer was washed with brine and dried over sodium sulfate. Purification was performed by column chromatography (hexane / ethyl acetate) to obtain 5.6 g of a compound represented by the formula (I-70-2).

  Under a nitrogen atmosphere, 5.6 g of a compound represented by the formula (I-70-2) and 50 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 32 mL of 0.9 mol / L borane-tetrahydrofuran complex was added dropwise and stirred for 1 hour. After 5% hydrochloric acid was added dropwise, the mixture was extracted with ethyl acetate and washed with brine. By drying with sodium sulfate and distilling off the solvent, 4.7 g of a compound represented by the formula (I-70-3) was obtained.

  Under a nitrogen atmosphere, 4.7 g of the compound represented by the formula (I-70-3), 2.5 g of pyridine, and 50 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 3.0 g of methanesulfonyl chloride was added dropwise and stirred at room temperature for 3 hours. Poured into water and washed sequentially with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 5.9 g of a compound represented by the formula (I-70-4).

  In a reaction vessel, 5.9 g of the compound represented by formula (I-70-4), 2.4 g of the compound represented by formula (I-70-5), 8.9 g of potassium carbonate, 70 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 15 hours. Poured into water, extracted with ethyl acetate and washed with brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (acetone / hexane) gave 4.4 g of a compound represented by the formula (I-70-6).

  The compound represented by formula (I-70-10) is represented by formula (I-70-10) in the same manner as described above except that the compound represented by formula (I-70-1) is replaced with the compound represented by formula (I-70-7). A compound was prepared. In a reaction vessel, 5.0 g of the compound represented by the formula (I-70-10), 4.4 g of the compound represented by the formula (I-70-6), 3.1 g of potassium carbonate, 70 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 15 hours. Poured into water, extracted with dichloromethane and washed with brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 6.3 g of a compound represented by the formula (I-70-11).

  To the reaction vessel, 6.3 g of the compound represented by the formula (I-70-11), 100 mL of methanol, and 30 mL of 25% aqueous sodium hydroxide solution were added and stirred at 50 ° C. for 5 hours. After cooling, methanol, water and tetrahydrofuran were added. 10% hydrochloric acid was added to adjust the pH to 4-5. The precipitated solid was filtered and washed with water to obtain 4.8 g of a compound represented by the formula (I-70-12).

In a reaction vessel, 4.8 g of the compound represented by the formula (I-70-12), 3.7 g of the compound represented by the formula (I-70-13), 4.0 g of potassium carbonate, 60 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 20 hours. It was poured into water and the precipitated solid was filtered. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 5.4 g of a compound represented by the formula (I-70).
LCMS: 807 [M + 1]
The compounds represented by formula (I-11) to formula (I-59) and formula (I-61) to formula (I-69) were produced by combining the same method as described above and a known method.
(Examples 13-24, Comparative Examples 1-4)
Compounds represented by formula (I-1) to formula (I-10), formula (I-60) and formula (I-70) described in Example 1 to Example 12 and compounds described in Patent Document 1 ( R-1), compound (R-2) described in Patent Document 2, compound (R-3) described in Patent Document 3, and compound (R-4) described in Patent Document 4 were evaluated.

  Further, compound (X-1) described in JP-A No. 2005-015473: 30%, compound (X-2) described in JP-A No. 10-87565: 20%, compound described in JP-T-2002-537280 A liquid crystal composition composed of (X-3): 45% and LC-756 (manufactured by BASF): 5% as a chiral compound was used as a base liquid crystal (X).

  The polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus.

11.87% of the base liquid crystal (X), 7.91% of the compound to be evaluated, 0.20% of the photopolymerization initiator Irgacure 907 (BASF), 0.02% of 4-methoxyphenol and chloroform A coating solution was prepared by mixing 80.00%. This coating solution was applied to a rubbed glass substrate by a spin coating method. After drying at 80 ° C. for 1 minute, it was further dried at 120 ° C. for 1 minute. Then, the film of evaluation object was produced by irradiating an ultraviolet-ray with the intensity | strength of 40 mW / cm < ² > for 25 second using a high pressure mercury lamp. The correspondence between the film example numbers and the compounds to be evaluated is shown in Table 1 below.

  About the produced film, the orientation defect was evaluated. The film was divided into an area of 10 squares × 10 squares, for a total of 100 squares. The number of squares in which orientation defects occurred was counted by observation with a polarizing microscope. It means that there are few orientation defects, so that a value is small. The results are shown in Table 2 below.

Next, each newly prepared film to be evaluated was heat-treated at 180 ° C. for 30 minutes. The degree of discoloration before and after heat treatment was evaluated. The degree of discoloration was compared by the difference between the yellowness after heat treatment (YI ₁ ) and the yellowness before heat treatment (YI ₀ ), and the yellowing degree (ΔYI = YI ₁ −YI ₀ ). The yellowness (YI) was calculated by measuring the absorption spectrum of the film with UV / VIS Spectrophotometer V-560 (manufactured by JASCO Corporation) and using the attached color diagnostic program. The formula is
YI = 100 (1.28X-1.06Z) / Y (JIS K7373)
It is. It means that the smaller the value of yellowing degree (ΔYI), the less discoloration after the heat treatment. The results are shown in Table 2 below.

  From Table 2, it can be seen that any of the films produced using the compounds of the present invention of Examples 13 to 24 are less likely to cause orientation defects.

  In addition, Table 2 shows that any of the films produced using the compounds of the present invention of Examples 13 to 24 has little discoloration after the heat treatment.

  From the above results, the compounds represented by formula (I-1) to formula (I-10), formula (I-60) and formula (I-70) of the present invention are all comparative compounds (R-1). From the results, it can be seen that, when compared with the comparative compound (R-4), when a film is prepared by adding to the polymerizable composition, there are few orientation defects and discoloration hardly occurs when placed in a high temperature state. Therefore, the compound of the present invention is useful as a constituent member of the polymerizable composition. Moreover, the optical anisotropic body using the polymeric liquid crystal composition containing the compound of this invention is useful for uses, such as an optical film.

Claims (8)

The following general formula (I)

(Wherein P ¹ represents a group that is polymerized by radical polymerization, cationic polymerization or anionic polymerization;
Sp ¹ represents a spacer group, and when a plurality of Sp ¹ are present, they may be the same or different,
X ¹ represents —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 represents a single bond, ^{X 1} is more present They may be different even in the same case that,
k1 represents an integer of 0 to 10,
A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1 , 3-dioxane-2,5-diyl groups, these groups may be unsubstituted or substituted by one or more substituents L, and when there are multiple A ¹ they are the same Or a plurality of A ² may be the same or different.
B ¹ represents expression from the following formula (B-1) (B- 3)

(Wherein these groups are unsubstituted or may be substituted by one or more substituents L),
L is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, 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 carbon atom optionally substituted by —C≡C— Number 1 20 represents a linear or branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is P ^L- (Sp ^L -X ^L ) _kL-. However, when a plurality of Ls are present in the compound, they may be the same or different, and P ^L , Sp ^L , X ^L and kL are respectively P ¹ , Represents the same as Sp ¹ , X ¹ and k ¹ ,
One of Y ¹ and Y ² represents a group selected from the following group (Y-A), and the other represents a group selected from the following group (Y-B):
(YA) group: * -CO-, * -COO-, -OCO- *, * -CO-S-, -S-CO- *, * -CO-NH-, -NH-CO- *, * —COO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —OCO— *, * —COO—CH ₂ —, —CH ₂ —OCO— *, * —CH═N—, —N═CH— *, And * —CH═N—N═CH— (* means a site directly bonded to the group represented by B ¹ ).
(YB) group: —OCH ₂ — *, * —CH ₂ O—, —SCH ₂ — *, * —CH ₂ S—, * —CF ₂ O—, —OCF ₂ — *, * —CF ₂ S—, —SCF ₂ — *, —NHCH ₂ — *, * —CH ₂ NH—, —COO—CH ₂ — *, and * —CH ₂ —OCO— (* represents a group represented by B ¹ It means the site that binds directly.)
Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH 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 2 -, - CH 2 -COO -, - CH -OCO -, - CH = CH - , - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, they if Z ¹ there are a plurality may be the same or different and although they may be the same or different if Z ² there are a plurality, is Z ¹ when present represents Z ¹ is a single bond attached directly to Y ^1, Z ² directly attached to Y ² when the Z ² there is a single bond,
m1 and m2 each independently represents an integer from 0 to 6, while m1 + m2 represents an integer from 0 to 6,
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one —CH ₂ — or adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. A straight chain of 1 to 20 carbon atoms which may be substituted by -O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is a group represented by — (X ² -Sp ² ) _k2 -P ² ( wherein the heavy P ² is a radical polymerization, by cationic polymerization or anionic polymerization Represents radicals, Sp ² each represents a spacer group, they if Sp ² there are a plurality may be different even in the same, ^{X 2} is -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 represents a single bond, the same those ^{if X 2} there are a plurality may be different even, k2 represents an represents.) an integer from 0 to 10, X ¹ directly bonded to Y ¹ if m1 is and there is X ¹ represents 0 represents a single bond m2 Although but the X ² bound directly to Y ² if and X ² are present represents 0 represents a single bond, the formula does not contain -O-O- bond. ) A compound represented by In general formula (I), P ¹ and P ² present are each independently the following formulas (P-1) to (P-20):

The compound according to claim 1, which represents a group selected from: In the general formula (I), when there are a plurality of Sp ¹ and Sp ² present, they may be the same or different, and each independently represents one —CH ₂ — or _two not adjacent to each other. The above —CH ₂ — is 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- Or the compound of Claim 1 or Claim 2 which represents the C1-C20 alkylene group which may be substituted by -C≡C-.   The composition containing the compound as described in any one of Claims 1-3.   The liquid crystal composition containing the compound as described in any one of Claims 1-3.   A polymer obtained by polymerizing the composition according to claim 4.   An optical anisotropic body using the polymer according to claim 6.   A resin, a resin additive, an oil, a filter, an adhesive, an adhesive, a fat, an ink, a pharmaceutical, a cosmetic, a detergent, a building material, a packaging material using the compound according to any one of claims 1 to 3. , Liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals and foods, and products using them.