JP6772549B2 - Polymerizable compounds and optical anisotropics - Google Patents

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 variant using the polymerizable liquid crystal composition.

Polymerizable compounds are used in various films. For example, it is possible to prepare a film having a uniform orientation by arranging the polymerizable compounds in a liquid crystal state and then polymerizing them. The film thus produced can be used for a polarizing plate, a retardation plate, etc. required for a liquid crystal display. The polymerizable compound can also be used to prepare a film having a cholesteric structure. In many cases, two or more types of polymerizable properties 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. A composition consisting of a compound is used. At that time, the polymerizable compound 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 a cholesteric phase liquid crystal orientation is required. Further, when the polymerizable liquid crystal composition is industrially used, high storage stability is required so that the polymerizable compound in the polymerizable liquid crystal composition does not precipitate even if it is stored for a long time.

Further, when used as an optical film for a display or the like, it is preferable that the produced film has few orientation defects and is less likely to discolor when placed in a high temperature state. However, conventionally known compounds have a problem that orientation 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 a display, for example, the color of the screen becomes unnatural due to long-term use, and the desired optical characteristics cannot be obtained. Therefore, the quality of the display product is greatly improved. There was a problem of lowering it. Therefore, there has been a demand for the development of a highly versatile polymerizable compound capable of solving such a problem.

Japanese Unexamined Patent Publication No. 2010-270108 Japanese Unexamined Patent Publication No. 2011-246365 Japanese Unexamined Patent Publication No. 10-87565 US2011 / 0147657A1

The problem to be solved by the present invention is to obtain a polymerizable composition that has few orientation defects and is less likely to be discolored when placed in a high temperature state when a film-like polymer is produced by adding it to the polymerizable composition. Is to provide. Further, it is to provide a polymer obtained by polymerizing the polymerizable composition and an optically anisotropic substance using the polymer.

As a result of diligent research to solve the above problems, the present inventors have developed a polymerizable compound having a mesogen group or a mesogen support group containing a specific partial structure. That is, the present invention provides a compound represented by the general formula (I), and a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, and a pressure-sensitive adhesive. , Oils, 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, mechanical parts, pesticides And foods and products using them, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optical variant using the polymer.

The compound of the present invention is useful as a constituent member of a polymerizable composition. Further, since the optically anisotropic substance using the polymerizable liquid crystal composition containing the compound of the present invention has few orientation defects and is less likely to cause discoloration when placed in a high temperature state, it is a retardation film or a selective reflection film. It is useful for applications such as optical materials.

The present invention provides a compound having a specific structure, and a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, an adhesive, an oil, an ink, and the like. 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, mechanical parts, pesticides and foods, and their products. Provided are a product used, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optical variant using the polymer.

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

(In the formula, P ¹ represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization.
Sp ¹ represents a spacer group, but when there are a plurality of Sp ^1, they may be the same or different.
X ¹ 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 a single bond, but if there are multiple X ¹ , they are different even if they are the same. May be
k1 represents an integer from 0 to 10
A ¹ and A ² are independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine-2,5-diyl group, respectively. , 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 represents a dioxane-2,5-diyl group, these groups may be substituted by unsubstituted or substituted with one or more substituents L, the same those if a ¹ there are multiple may be different even, they if a ² there are a plurality may be the same or different and
B ¹ is from the following equation (B-1) to equation (B-3)

Represents a group selected from (in the formula, these groups may be unsubstituted or substituted with one or more of the following substituents L).
L is 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 thioisocyanogroup, or one −CH ₂ − or two or more non-adjacent −CH ₂₋ are 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- may be substituted carbon atoms. Although a few 1 represents a linear or branched alkyl group of 20, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, L represents ^{P L - (Sp L -X L} ) _{kL -} group may represent represented by, but if L is more present in the compounds they may be different even in the same, P ^L, Sp ^L, X ^L and kL, each P Represents the same as ¹ , Sp ¹ , X ¹ and k ¹ .
Of Y ¹ and Y ² , one represents a group selected from the following (YA) group, and the other represents a group selected from the following (YB) group.
Group (YA): * -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 - (* denotes a site which binds directly to the group represented by ^{B 1.)}
Group (Y-B): -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- (* is the group represented by B ^1). It means the part that directly binds.)
Z ¹ and Z ² are 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 represents a single bond, ^{if Z 1} there are a plurality of they may be different even in the same, Z ¹ Z ² are those when there are a plurality may be the same or different, but which binds directly when Y ¹ where Z ¹ is present single It represents a bond, Z ² is attached directly to Y ² when the Z ² there is a single bond,
m1 and m2 independently represent integers from 0 to 6, while m1 + m2 represent integers 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 to it. No two or more -CH ₂ -are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO Linear or linear with 1 to 20 carbon atoms which may be substituted by -O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- It represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, ^{R 2} is ^{- (X ₂} -Sp _²⁾ a group represented by k2 -P ² ( In the formula, P ² represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ² represents a spacer group, but when there are a plurality of Sp ^2, they may be the same or different. 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, they ^{if X 2} there are a plurality be the same or different K2 represents an integer from 0 to 10), but when m1 represents 0 and X ¹ is present, X ^{1 which} is directly bonded to Y ¹ represents a single bond and m 2 represents 0. and although the X ² directly bonded to Y ² if X ² is present represents a single bond, the formula does not contain -O-O- bond. )
In the general formula (I), P ¹ and the existing P ² each independently represent a group that is polymerized by radical polymerization, cationic polymerization or anionic polymerization, and each of them is independently formulated from the following formula (P-1). (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), the formula (P-2), the formula (P-3), the formula (P-4), the formula (P-5), and the formula (P) -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) is preferable, and formula (P-1), formula (P-2), formula (P-2) P-3), formula (P-7), formula (P-11) or formula (P-13) is more preferable, and formula (P-1), formula (P-2) or formula (P-3) is Further preferred, formula (P-1) or formula (P-2) is particularly preferred.

In the general formula (I), represents a Sp ² are each independently a spacer group Sp ¹ and present, they if Sp ¹ there are a plurality may be different even in the same, Sp ² is plurality of If they do, they may be the same or different. From the viewpoint of liquidity, availability of raw materials, and ease of synthesis, Sp ¹ and existing Sp ² may be the same or different when there are a plurality of them, and each of them is independently one-. CH ₂ - or nonadjacent two or more -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- in replaced It is preferable to represent an alkylene group having 1 to 20 carbon atoms, and Sp ¹ and Sp ² existing may be the same or different when a plurality of Sp ¹ are present, and each of them is independently one-. CH ₂ − or two or more non-adjacent −CH ₂ − are independently −O−, −COO−, −OCO−, −OCO—O−, −CO-NH−, −NH-CO− , -CH = CH- or -C≡C- may be replaced by representing an alkylene group having 1 to 20 carbon atoms, and Sp ¹ and Sp ² present are the same when a plurality of Sp ² are present. It may be present or different, and each independently has one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -COO-, -OCO- or. It is more preferable to represent a linear alkylene group having 1 to 20 carbon atoms which may be replaced with −OCO—O−, and Sp ¹ and Sp ² present may be the same or different when a plurality of Sp ² are present. 1-CH ₂ − or two or more non-adjacent −CH ₂ − may be independently replaced by −O− each of 1 to 12 carbon atoms. It is even more preferable to represent a linear alkylene group, and Sp ¹ and Sp ² present may be the same when a plurality of Sp ¹ are present. It may be different, and it is particularly preferable that each of them independently represents a linear alkylene group having 1 to 12 carbon atoms.

In the general formula (I), X ¹ and the existing X ² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, respectively. -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-,- OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO- CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond , When there are a plurality of X ^1, they may be the same or different, and when there are a plurality of X ^2, they may be the same or different. From the viewpoint of availability of raw materials and ease of synthesis, X ¹ and existing X ² may be the same or different when they exist, and they are independently -O- and -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-, -CH ₂ It is more preferable to represent CH _2- OCO- or a single bond, and it is further preferable to represent -O-, -COO-, -OCO- or a single bond independently, and each independently represents -O-. Alternatively, it is even more preferable to represent a single bond, and it is particularly preferable to represent −O−.

In the 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 liquidity, k1 and existing k2 independently represent 0 to 5, respectively. It is more preferable that k1 and existing k2 each independently represent an integer of 0 to 2, and it is further preferable that k1 and existing k2 each independently represent 0 or 1. From the viewpoint of less 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 independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, and 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 with one or more of the above-mentioned substituents L, A. ^When there are a plurality of ^1's, they may be the same or different, and when there are a plurality of A ^2, they may be the same or different. From the viewpoint of ease of synthesis, availability of raw materials, and liquid crystallinity, A ¹ and A ² may be independently unsubstituted or substituted with one or more substituents L 1,4. It is more preferable to represent a −phenylene group, a 1,4-cyclohexylene group, and a naphthalene-2,6-diyl group, and each of them independently represents the following formulas (A-1) to (A-11).

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

In the general formula (I), B ¹ is expressed by the following formulas (B-1) to (B-3).

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

In the general formula (I), of the Y ¹ and Y ^2, one representing a group selected from (Y-A) the following group, the other represents a group selected from (Y-B) the following group.
Group (YA): * -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 = NN = CH- (* means a site that directly binds to the group represented by B ¹ , for example, * -CO- has Y ² of -CO-. This means that -CO- * means that Y ¹ is -CO-.)
Group (Y-B): -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- (* is the group represented by B ^1). It means a site that directly binds, for example, * -CH ₂ O- means that Y ² is -CH ₂ O-, and -OCH _2- * means that Y ¹ is -OCH _2- ).
In the above (YA) group, * -COO-, -OCO- *, * -CO-S-, -S-CO- * from the viewpoint of liquidity, availability of raw materials, and ease of synthesis. , * -CO-NH-, -NH-CO- *, * -COO-CH ₂ CH _2- or -CH ₂ CH _2- OCO- *, preferably groups * -COO-, -OCO- Groups represented by *, * -CO-NH-, -NH-CO- *, * -COO-CH ₂ CH _2- or -CH ₂ CH _2- OCO- * are more preferred, and * -COO-,- Groups represented by OCO- *, * -COO-CH ₂ CH _2- or -CH ₂ CH _2- OCO- * are more preferred, and groups represented by * -COO- or -OCO- * are 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 the 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. Equation (YBY-24)

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

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 It is composed of a combination of groups independently selected from the groups defined by X ¹ , X ² , A ¹ , A ² , Z ¹ and Z ² , but from the above formula (YBY-1) to formula (YBY-). The group selected from 24) may be represented, or other groups may be represented. When representing a group selected from the above formula (YBY-1) to the formula (YBY-24), the preferred structure of these groups is the same as above.

In the general formula (I), Z ¹ and Z ² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, respectively. , -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, If there are multiple Z ^1, they may be the same or different, and if there are multiple Z ^2, they may be the same or different, but if Z ¹ is present, they may be in Y ¹ . direct bond to Z ¹ represents a single bond, Z ² is attached directly to Y ² when the Z ² present represents a single bond. From the viewpoint of liquidity, availability of raw materials, and ease of synthesis, Z ¹ and Z ² are independently -OCH _2- , -CH ₂ O-, -COO-, -OCO-, and -CF ₂ O, respectively. -, -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, preferably -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 CH _2- COO-, -CH ₂ CH _2- OCO-, -CH = CH-, -C≡C- or It is more preferred to represent a single bond, more preferably -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- or a single bond, and -OCH. _{2 -, - CH 2 O -} , - COO -, - OCO- or even more preferably a single bond, and particularly preferably a -COO- or -OCO-.

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

In the general formula (I), 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 two or more non-adjacent −CH ₂ − are independently −O−, −S−, −CO−, −COO−, −OCO−, −CO−S−, −S− Number of carbon atoms 1 which may be substituted by CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- Although from a linear or branched alkyl group of 20, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, R ² is _{^{- (X 2 -Sp 2) k2}} -P Represents a group represented by ² . When importance is attached to flexibility when made into film, R ² is - (X ² -Sp ²⁾ preferably represents a group other than a group represented by the in _k2 -P ^2, the mechanical strength when formed into a film when importance is attached, ^{R 2} is ^{- (X ₂} -Sp _²⁾ preferably represents a group represented by k2 -P ^2.
When R ² represents a group other than the group represented by − (X ^2- Sp ² ) _k2- P ² , R ² is a hydrogen atom, a fluorine atom, a chlorine atom, from the viewpoint of liquidity and ease of synthesis. A cyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -CO-, -COO-, -OCO-, -O-CO Linear or branched with 1 to 12 carbon atoms which may be substituted by -O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- It preferably represents an alkyl group, where R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or one −CH ₂ − or two or more non-adjacent −CH ₂ − independently of −O−. , -CO-, -COO-, -OCO- or -O-CO-O- may more preferably represent a linear or branched alkyl group having 1 to 12 carbon atoms, where R ² is hydrogen. It is more preferable to represent an atom, a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms, and R ² is a linear alkyl group or a linear chain having 1 to 12 carbon atoms. It is particularly preferable to represent an alkoxy group.

Further, when R ² represents a group represented by − (X ^2- Sp ² ) _k2- P ² , the preferable structures of P ² , Sp ² , X ² and k ² are P ¹ , Sp ¹ , X, respectively. It is the same as the preferable structure adopted by ¹ and k1.

In the general formula (I), L is 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 thioisocyanogroup, or one -CH _2- or two or more non-adjacent -CH ₂ --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- Although substituted from a good 1 -C be a straight or branched alkyl group of 20, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, L represents P ^L - (Sp L ^{-X L)} kL _- group may represent represented by, but they may be the same or different if L is more present in the compound. From the viewpoint of liquidity 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 replaced by a fluorine atom, and one −CH ₂ − or two or more non-adjacent −CH ₂ − are independently −O−, −S−, −CO−, −COO− , -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- may be substituted with a group having 1 to 20 carbon atoms. It preferably represents a state or branched alkyl group, and a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted with a fluorine atom, and one −CH ₂ − or two or more non-adjacent ones. −CH ₂₋ may represent a linear or branched alkyl group having 1 to 12 carbon atoms, each of which may be independently substituted with a group selected from −O−, −COO− or −OCO−. More preferably, the fluorine atom, the chlorine atom, or any hydrogen atom may be replaced with a fluorine atom. A linear or branched alkyl group having 1 to 12 carbon atoms or a linear chain having 1 to 12 carbon atoms. Alternatively, it is more preferable to represent a branched alkoxy group, and it is particularly preferable to represent a fluorine atom, a chlorine atom, a linear alkyl group having 1 to 8 carbon atoms, or a linear alkoxy group having 1 to 8 carbon atoms. 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.

The compounds represented by the general formula (I) include the following general formulas (IB1-A) to general formulas (IB3-B).

(In the formula, P ¹ , Sp ¹ , X ¹ , k1, 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, represents the same meaning as m1 and m2, in the general formula (I-B3-B) from the above general formula (I-B1-a) The group represented by Z ¹ that directly binds to −OCO − or −OCH ₂ − represents a single bond, and the group represented by Z ² that directly binds to −COO − or −CH ₂ O− represents a single bond. The compound represented by.) Is preferable.

The compounds represented by the above general formulas (IB1-A) to the general formula (IB3-B) include the following general formulas (IB1-A-1) to the general formula (IB2-). B-4)

^{(Wherein, P 1, Sp 1, X} 1, k1, A 2, Z 2 and ^{R 2, P} 1 respectively in the general formula ^{(I), Sp 1, X} 1, k1, A 2, Z 2 and R represents the same meaning as ^2, each a ^{11, a 12} and ^{a 13} are as defined ^{a 1} in the general formula ^(I), the same meanings as ^{Z 1} each ^{Z 11} and ^{Z 12} in the general formula (I) The compound represented by (m21) represents an integer from 0 to 5) is more preferable.

The compounds represented by the above general formulas (I-B1-A-1) to (IB2-B-4) are generally classified from the following general formulas (IB1-A-1-1). Formula (IB2-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 have 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 have the same general formula. The compound represented by (I) has the same meaning as Z ¹ and Z ² ) is more preferable.

When R ² represents a group other than the group represented by − (X ^2- Sp ² ) _k2- P ² , the above general formula (IB1-A-1-1) to the general formula (IB2- Examples of the compound represented by B-4-1) include the following general formulas (IB1-A-1-1-1) to general formulas (I-B2-B-2-2-1).

^{(Wherein, 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), A 111, A} 211, A 221 And A ²³¹ each represent a 1,4-phenylene group or a 1,4-cyclohexylene group which is independently unsubstituted or may be substituted with one or more substituents L, where Z ²¹¹ and Z ²²¹ are Each independently represents -OCH _2- , -CH ₂ O-, -COO-, -OCO- or a single bond, where R ²¹ is a hydrogen atom, a fluorine atom, a chlorine atom, or a single -CH ₂ -or. nonadjacent two or more -CH ₂ - -O are each independently -, - CO -, - COO -, - OCO- or -O-CO-O-carbon atoms which may be substituted by 1 A compound represented by 12 to 12 linear or branched alkyl groups, where s independently represents an integer of 0 to 4) is more preferred.

Further, ^{R 2} is ^{- (X ₂} -Sp _²⁾ If a group represented by k2 -P ^2, the general formula from the above general formula (I-B1-A-1-1 ) (I-B2-B Examples of the compound represented by -4-1) include the following general formulas (IB1-A-1-1-2) to general formulas (IB2-A-3-2-2).

(In the formula, P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k ¹ , k ² and L are P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , respectively in the general formula (I). X ^2, the same meanings as k1, k2 and ^L, the ^{a 111, a 121, a 131} , a 221, or ^{a 231} and ^{a 241} are each independently unsubstituted or 1 or more substituents L It represents a 1,4-phenylene group or a 1,4-cyclohexylene group which may be substituted, and Z ¹¹¹ , Z ¹²¹ , Z ²¹¹ , Z ²²¹ and Z ²³¹ are independently −OCH _2- , −CH ₂ O, respectively. A compound represented by −, −COO−, −OCO− or a single bond, in which s independently represents an integer of 0 to 4) is more preferable, and the following general formula (IB1-A−) is more preferable. From 1-1-2-1) to the general formula (IB2-A-2-2-2-2)

(In the formula, P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k ¹ , k ² and L are P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , respectively in the general formula (I). It has the same meaning as X ² , k1, k2 and L, where Z ²¹¹ and Z ²²¹ independently represent -OCH _2- , -CH ₂ O-, -COO-, -OCO- or a single bond, where s is. Compounds represented by (), each independently representing an integer from 0 to 4, are even more preferred.

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

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

The compound of the present invention can be produced by the following production method.
(Manufacturing method 1) Production of a compound represented by the following formula (S-9)

(In the formula, P ¹ , Sp ¹ and L have the same meanings as P ¹ , Sp ¹ and L in the general formula (I), respectively, and R ²¹ has the same meaning as the above general formula (I-B1-A-1-1-). 1) to the same meaning as R ²¹ in the general formula (I-B2-B-2-2-1), s independently represents an integer from 0 to 4, PG represents a protecting group, and halogen Represents a halogen atom or halogen equivalent.)
The carboxyl group of the compound represented by the formula (S-1) is protected by a protecting group (PG). The protecting group (PG) is not particularly limited as long as it can stably protect up to the deprotection step. Protecting groups (PGs) listed 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, a benzyl group and the like.

The protecting group (PG) of the compound represented by the formula (S-2) is deprotected. The deprotection reaction conditions are not particularly limited as long as they give a compound represented by the formula (S-3), but those listed in the above literature are preferable. It is also possible to obtain the 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 the formula (S-3) is reduced. The conditions for the reduction reaction are not particularly limited as long as they give a compound represented by the formula (S-4), and examples thereof include a borane-tetrahydrofuran complex.

By reacting the compound represented by the formula (S-4) with the compound represented by the formula (S-5), the compound represented by the formula (S-6) can be obtained. Examples of the reaction conditions include the Mitsunobu reaction. Alternatively, the hydroxyl group of the compound represented by the formula (S-4) is changed to a methanesulfoxi group, a p-toluenesulfoxi group, or the like, 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 deprotection reaction conditions are not particularly limited as long as they give a compound represented by the formula (S-7), but those listed in the above literature are preferable.

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, the compound represented by the formula (S-9) can be obtained. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.
(Manufacturing 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 It represents an integer of 4, and PG represents a protecting group.)
By reacting the compound represented by the formula (S-10) with the compound represented by the formula (S-11), the compound represented by the formula (S-12) can be obtained. Examples of the reaction conditions include the Mitsunobu reaction. Alternatively, the hydroxyl group of the compound represented by the formula (S-10) is changed to a methanesulfoxi group, a p-toluenesulfoxi group, or the like, 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 deprotection reaction conditions are not particularly limited as long as they give a compound represented by the formula (S-13), but those listed in the above literature are preferable.

By reacting the compound represented by the formula (S-13) with the compound represented by the formula (S-14), the compound represented by the formula (S-15) can be obtained. As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-13) is represented by an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride, and then represented by the general formula (S-14). Examples thereof include a method of reacting with a compound in the presence of a base. 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.

Reaction conditions other than those described in each step of manufacturing method 1 and manufacturing method 2 include, for example, Experimental Chemistry Course (edited by the Japan Chemistry Society, published by Maruzen Co., Ltd.), Organic Syntheses (John Wiley & Sons, Inc., Publication), Belstein 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 described in the literature such as SciFinder ( Conditions provided by online search services such as Chemical Abstracts Service, American Chemical Society) or Reaxys (Elsevier Ltd.) can be mentioned.

In addition, a reaction solvent can be appropriately used in each step. The solvent is not limited as long as it gives the desired compound, but 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 thereof include isobutyl ketone, tert-butyl methyl ether and methyl ethyl ketone. When the reaction is carried out in a two-phase system of an organic solvent and water, it is also possible to add a phase transfer catalyst. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, polyoxyethylene (20) sorbitan monolaurate [Tween 20], sorbitan monooleate [Span 80] and the like.

In addition, purification can be performed as needed in each step. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purifying agent, silica gel, alumina, activated charcoal, activated clay, Celite, zeolite, mesoporous silica, carbon nanotubes, carbon nanohorns, Bicho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples thereof include pearlite, cellulose, organic polymers, porous gels and the like.

The compounds of the present invention are preferably used in nematic liquid crystal compositions, smectic liquid crystal compositions, chiral smectic liquid crystal compositions and cholesteric liquid crystal compositions. A compound other than the present invention may be added to the liquid crystal composition using the reactive compound of the present invention.

Specific examples of other polymerizable compounds used in combination with the polymerizable compound of the present invention include 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 that is polymerized by radical polymerization, cationic polymerization or anion polymerization, and Sp ¹¹ , Sp ¹² and Sp ¹³ are independent single bonds or carbon atoms, respectively. Represents the number 1 to 20 alkylene groups, but replaces one -CH _2- or two or more non-adjacent -CH _2- with -O-, -COO-, -OCO-, -OCOO- X ¹¹ , X ¹² and X ¹³ may be independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-,-, respectively. 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 single bond, Z ¹¹ and Z ¹² 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 -,- Represents CH _2- COO-, -CH _2- OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond, where A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are independent. Then, 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-2,5-diyl group. , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are each independently unsubstituted or alkyl group, alkyl halide group, alkoxy group, alkoxy halide group, halogen atom, cyano group or nitro group. R ¹¹ may be substituted with hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, thioisocyano group, or one. -CH ₂ − or two or more non-adjacent −CH ₂ − are 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 Represents a linear or branched alkyl group with 1 to 20 carbon atoms which may be substituted by −CH = CH−, −CH = CH−, −CF = CF− or −C≡C−, where m11 and m12 are 0. 1, 2 or 3, but if m11 and / or m12 represents 2 or 3, the two or three A ¹¹ , A ¹³ , Z ¹¹ and / or Z ¹² are different even if they are the same. You may be. ) Is preferable, and it is particularly preferable that P ¹¹ , P ¹² and P ¹³ are acrylic or methacrylic groups. Specifically, as the compound represented by the general formula (X-11), the general formula (X-11a)

(In the formula, W ¹¹ and W ¹² each independently represent a hydrogen atom or a methyl group, Sp ¹⁴ and Sp ¹⁵ are independent alkylene groups having 2 to 18 carbon atoms, and X ¹⁴ and X ¹⁵ are independent, respectively. Then -O-, -COO-, -OCO- or a single bond, Z ¹³ and Z ¹⁴ independently represent -COO- or -OCO-, and A ¹⁵ , A ¹⁶ and A ¹⁷ are independent, respectively. It may be substituted with an unsubstituted or fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched alkoxy group having 1 to 4 carbon atoms1. , 4-Representing a phenylene group) is preferable, and the following formulas (X-11a-1) to (X-11a-4) are preferable.

(In the formula, W ¹¹ , W ¹² , Sp ¹⁴ and Sp ¹⁵ have the same meanings as those in the general formula (X-11a)), and the compound represented by the general formula (X-11a) is particularly preferable. In the above formulas (X-11a-1) to (X-11a-4), compounds in which Sp ¹⁴ and Sp ¹⁵ are independently alkylene groups having 2 to 8 carbon atoms are particularly preferable.

In addition, preferred bifunctional polymerizable compounds include the following general formulas (X-11b-1) to formulas (X-11b-3).

(In the formula, 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). Can be mentioned. In the above formulas (X-11b-1) to (X-11b-3), compounds in which Sp ¹⁶ and Sp ¹⁷ are independently alkylene groups having 2 to 8 carbon atoms are particularly preferable.

Further, as the compound represented by the general formula (X-12), specifically, the following general formulas (X-12-1) to formulas (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 with -O-, -COO-, -OCO-, -O-CO-O-, and X ¹⁶ is a single bond, -O-, -COO-, or -OCO-. , Z ¹⁵ represents a single bond, -COO- or -OCO-, and L ¹¹ is a fluorine atom, a chlorine atom, one -CH _2- or two or more non-adjacent -CH _2- , respectively. Represents a linear or branched alkyl group with 1 to 10 carbon atoms that may be independently replaced by -O-, -COO-, -OCO-, s11 represents an integer from 0 to 4, R ¹² Is a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, one −CH ₂ − or two or more non-adjacent −CH ₂ − independently of −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-. Examples thereof include compounds represented by the numbers 1 to 20 representing a linear or branched alkyl group).

It is also possible to add a polymerizable compound that does not exhibit liquid crystallinity to the polymerizable liquid crystal composition containing the compound of the present invention to the extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples include those described in "Photocuring Technology Data Book, Materials (Monomers, Oligomers, Photopolymerization Initiators)" (supervised by Kunihiro Ichimura and Kiyomi Kato, Technonet Co., Ltd.).

Further, the compound of the present invention can be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added for the purpose. In that 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, acylphosphine oxides and the like. Specific examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (IRGACURE 907) and benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene]. Amino (IRGACURE OXE 01) and the like can be 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. Further, one kind of polymerization initiator may be used, or two or more kinds 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 stabilizers that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like. Be done. When a stabilizer is used, the amount added 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. From 0.5% by mass is more preferable. Further, one kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specific examples of the stabilizer include formulas (X-13-1) to (X-13-35).

(In the formula, n represents an integer from 0 to 20.) The compound represented by is preferable.

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 and the like, Metals, metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixo agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, depending on the purpose. , Ion exchange resin, metal oxides such as titanium oxide, etc. can also be added.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used for various purposes. 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. Further, the polymer obtained by polymerizing after orientation has optical anisotropy and is useful. Such an optically anisotropic substance is, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth or the like, a substrate on which an organic thin film is formed, or an alignment film obtained by obliquely vapor-depositing SiO _2. It can be produced by carrying it on a substrate having it or sandwiching it between substrates, and then polymerizing the polymerizable liquid crystal composition.

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, printing method and the like. .. Further, at the time of coating, an organic solvent may be added to the polymerizable liquid crystal composition. As the organic solvent, a hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an alcohol solvent, a ketone solvent, an ester solvent, an aproton solvent and the like can be used. For example, a hydrocarbon solvent 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, and dimethylformamide or acetonitrile as the aproton solvent. Can be done. 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, vacuum drying, and vacuum heating drying can be used. In order to further improve the coatability 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 the substrate is effective for improving the adhesion between the polymer obtained by polymerizing the polymerizable liquid crystal material and the substrate.

Examples of the orientation treatment other than the above include the use of flow orientation of the liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Further, a photo-alignment method can be used as an orientation treatment method instead of rubbing. As the shape of the substrate, a curved surface may be provided as a constituent portion in addition to the flat plate. The material constituting the substrate can be used regardless of whether it is an organic material or an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethylmethacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Examples thereof include cellulose, cellulose, polyetheretherketone, and the like, and examples of the inorganic material include silicon, glass, and polysulfone.

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 with active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source may be used, or a non-polarized light source may be used. Further, when the liquid crystal composition is sandwiched between two substrates for polymerization, at least the substrate on the irradiation surface side must have appropriate transparency with respect to active energy rays. In addition, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as electric field, magnetic field, or temperature, and further irradiation with active energy rays. You may use the means of polymerizing. Further, the temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention is maintained. In particular, when an optically anisotropic substance is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible, that is, typically at a temperature of 25 ° C. in order to avoid inducing unintended thermal polymerization. It is preferable to let 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 large amount of time is required to complete the photopolymerization and the productivity deteriorates. When the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal There is a risk that the composition will deteriorate.

The optically anisotropic substance obtained by polymerization can also be heat-treated for the purpose of reducing the initial characteristic change and achieving stable characteristic development. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

The optically anisotropic substance produced by such a method may be peeled off from the substrate and used alone, or may be used without peeling off. Further, the obtained optically anisotropic bodies may be laminated or bonded to another substrate for use.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following Examples and Comparative Examples means "mass%". When handling substances that are 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, operations such as quenching, separation / extraction, neutralization, washing, separation, purification, drying, and concentration of reactions usually performed among those skilled in the art are performed as necessary. May be done.
(Example 1) Production of a compound represented by the 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 the mixture was 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 mixture of 40 mL of methanol and 10 mL of water was added dropwise, and the mixture was 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 the 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 the mixture was stirred at room temperature for 3 hours. It was poured into water and washed successively 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 the compound represented by the formula (I-1-3).

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 in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 20 hours. It 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 the 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 a 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 adjust 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 the compound represented by the formula (I-1-6).

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 in the reaction vessel. Was added, and the mixture was 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 the compound represented by the formula (I-1).
LCMS: 699 [M + 1]
(Example 2) Production of a compound represented by the 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. 16.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was 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 the 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 a 25% aqueous sodium hydroxide solution were added, and the mixture was heated and stirred at 60 ° C. After cooling, chloroform was added. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, and liquid separation treatment was performed. The organic layer was washed with brine and dried over sodium sulfate. The insoluble material was filtered through Celite, and then the solvent was distilled off and dried to obtain 17.7 g of the 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 the mixture was stirred for 1 hour. After dropping 5% hydrochloric acid, the mixture was extracted with ethyl acetate and washed with brine. The compound was dried over sodium sulfate and the solvent was distilled off to obtain 14.9 g of the compound represented by the formula (I-2-4).

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. 8.8 g of methanesulfonyl chloride was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 3 hours. It was poured into water and washed successively 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 the compound represented by the formula (I-2-5).

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 in the reaction vessel. Was added, and the mixture was 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 the compound represented by the formula (I-2-7).

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 to the reaction vessel, and the mixture was 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 the compound represented by the formula (I-2-8).

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 in the reaction vessel. Was added, and the mixture was 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 3.5 g of the compound represented by the formula (I-2).
Phase transition temperature (heating rate: 5 ° C./min) C 62 I ^{1 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 a compound represented by the 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 0. 1 g and 40 mL of dichloromethane were added. 1.4 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, 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 the formula (I-3). ..
Phase transition temperature (heating rate: 5 ° C / min) C 99 X 195 N 200 I
^{1 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 a compound represented by the formula (I-4)

5.0 g of the compound represented by the formula (I-4-1), 3.7 g of the compound represented by the formula (I-4-2), 3.5 g of potassium carbonate, 50 mL of N, N-dimethylformamide in the reaction vessel. Was added, and the mixture was 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 the 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 the mixture was 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 the compound represented by the formula (I-4-4).

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 in the reaction vessel. Was added, and the mixture was 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 / hexane) and recrystallization (dichloromethane / methanol) to obtain 4.4 g of the compound represented by the formula (I-4).
LCMS: 513 [M + 1]
(Example 5) Production of a compound represented by the 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. 2.3 g of acryloyl chloride was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 8 hours. The mixture was washed successively with 1% hydrochloric acid and brine, and purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 5.0 g of the compound represented by the formula (I-5-2).

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 to the reaction vessel, and the mixture was heated under reflux for 5 hours. After distilling off the solvent, purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 3.6 g of the compound represented by the formula (I-5-3).

In 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 0. 2 g and 50 mL of dichloromethane were added. 2.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, 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 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 a compound represented by the 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 0. 1 g and 40 mL of dichloromethane were added. 1.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 7 hours. After removing the precipitate by filtration, 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 the compound represented by the formula (I-6). ..
LCMS: 605 [M + 1]
(Example 7) Production of a compound represented by the 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 added dropwise, and the mixture was heated under reflux for 6 hours. The reaction solution was poured into water and extracted with toluene. After washing with a saline solution, purification was performed by column chromatography (silica gel, toluene) and recrystallization (toluene / ethanol) to obtain 5.3 g of the compound represented by the formula (I-7-3).

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 to the reaction vessel, and the mixture was 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 the compound represented by the formula (I-7-4).

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 in the reaction vessel. Was added, and the mixture was 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 the compound represented by the formula (I-7).
LCMS: 649 [M + 1]
(Example 8) Production of a compound represented by the formula (I-8)

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 in the reaction vessel. Was added, and the mixture was 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 the compound represented by the formula (I-8-3).

6.2 g of the compound represented by the formula (I-8-3), 60 mL of methanol and 30 mL of a 25% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was heated and stirred at 60 ° C. After cooling, ethyl acetate was added. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, and liquid separation treatment was performed. 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 the compound represented by the formula (I-8-4).

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

6.2 g of the compound represented by the formula (I-8-6) and 50 mL of dichloromethane were added to the reaction vessel. 20 mL of trifluoroacetic acid was added dropwise while cooling with ice, and the mixture was stirred for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. After washing with a saline solution, purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 5.0 g of the 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 the mixture was stirred for 1 hour. After dropping 5% hydrochloric acid, the mixture was extracted with ethyl acetate and washed with brine. The mixture was dried over sodium sulfate and the solvent was distilled off to obtain 4.2 g of the compound represented by the formula (I-8-9).

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. 2.6 g of methanesulfonyl chloride was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 3 hours. It was poured into water and washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 5.3 g of the 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 were placed in the reaction vessel. Was added, and the mixture was heated and stirred at 80 ° C. for 5 hours. It was poured into water, extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.8 g of the compound represented by the formula (I-8).
LCMS: 669 [M + 1]
(Example 9) Production of a compound represented by the formula (I-9)

The compound represented by the formula (I-9-2) was produced by the method described in Macropolymer Chemistry and Physics, 2009, Vol. 210, No. 7, pp. 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 the mixture was 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 the compound represented by the formula (I-9-3).

To the reaction vessel, add 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 heated and stirred 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 the compound represented by the formula (I-9-4).

Under a nitrogen atmosphere, 6.7 g of the compound represented by the formula (I-9-4), 2.7 g of the compound represented by the formula (I-9-5), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 2.8 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 6 hours. After removing the precipitate by filtration, 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 the compound represented by the formula (I-9-6).

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 in the reaction vessel. Was added, and the mixture was 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 the compound represented by the formula (I-9-9).

6.6 g of the compound represented by the formula (I-9-9), 40 mL of dichloromethane and 20 mL of formic acid were added to the reaction vessel, and the mixture was heated at 40 ° C. for 6 hours. It was 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 the 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 0. 1 g and 40 mL of dichloromethane were added. 1.1 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 6 hours. After removing the precipitate by filtration, 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 the compound represented by the formula (I-9).
LCMS: 767 [M + 1]
(Example 10) Production of a compound represented by the formula (I-10)

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-1), 3.6 g of the compound represented by the formula (I-10-2), N, N-dimethylaminopyridine 0. 3 g and 40 mL of dichloromethane were added. 3.9 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 5 hours. After removing the precipitate by filtration, 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 the compound represented by the formula (I-10-3).

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 to the reaction vessel, and the mixture was stirred at room temperature for 6 hours. It was diluted with ethyl acetate and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 4.5 g of the 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 the mixture was stirred for 1 hour. After dropping 5% hydrochloric acid, the mixture was extracted with ethyl acetate and washed with brine. The mixture was dried over sodium sulfate and the solvent was distilled off to obtain 4.2 g of the compound represented by the formula (I-10-6).

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 the mixture was 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 the 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 the mixture was stirred at room temperature for 8 hours. After distilling off the solvent, it was diluted with ethyl acetate and washed successively with water and brine. After drying over sodium sulfate, the solvent was distilled off to obtain 4.6 g of the compound represented by the formula (I-10-8).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-9), 2.8 g of the compound represented by the formula (I-10-10), 3.4 g of potassium carbonate, and 30 mL of ethanol were placed in the reaction vessel. 25 mL of water and 0.5 g of tetrakis (triphenylphosphine) palladium (0) were added, and the mixture was heated under reflux for 6 hours. After pouring into saturated aqueous ammonium chloride solution, the mixture was 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 the compound represented by the formula (I-10-11).

In a nitrogen atmosphere, 4.0 g of the compound represented by the formula (I-10-11), 4.2 g of the compound represented by the formula (I-10-8), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 1.7 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 6 hours. After removing the precipitate 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 the 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. It was diluted with ethyl acetate and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 4.6 g of the compound represented by the formula (I-10-13).

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 in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 6 hours. It was 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 the 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 the mixture was stirred at room temperature for 8 hours. The mixture was washed successively with 1% hydrochloric acid and brine, and purified by column chromatography (silica gel, toluene) to obtain 3.3 g of the compound represented by the formula (I-10).
LCMS: 811 [M + 1]
(Example 11) Production of a compound represented by the formula (I-60)

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 were added to the reaction vessel at 80 ° C. Was heated and stirred for 8 hours. It was 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 the compound represented by the formula (I-60-3).

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 to the reaction vessel, and the mixture was 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 the compound represented by the formula (I-60-4).

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 in the reaction vessel. Was added, and the mixture was 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 the compound represented by the formula (I-60).
Phase transition temperature (heating rate: 5 ° C / min) C 47 I
^{1 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: Preparation of compound represented by formula (I-70) of 559 [M + 1] (Example 12)

10.0 g of the compound represented by the formula (I-70-1), 100 mL of methanol and 7.1 g of a 25% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was stirred at 50 ° C. for 5 hours. After cooling, chloroform was added. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, and liquid separation treatment was performed. 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 the compound represented by the formula (I-70-2).

Under a nitrogen atmosphere, 5.6 g of the 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 the mixture was stirred for 1 hour. After dropping 5% hydrochloric acid, the mixture was extracted with ethyl acetate and washed with brine. The mixture was dried over sodium sulfate and the solvent was distilled off to obtain 4.7 g of the compound represented by the formula (I-70-3).

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. 3.0 g of methanesulfonyl chloride was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 3 hours. It was poured into water and washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 5.9 g of the compound represented by the formula (I-70-4).

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

It is represented by the formula (I-70-10) by the same method as described above except that the compound represented by the formula (I-70-1) is replaced with the compound represented by the formula (I-70-7). The compound was produced. 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 in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 15 hours. It was poured into water, extracted with dichloromethane and washed with brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 6.3 g of the compound represented by the formula (I-70-11).

6.3 g of the compound represented by the formula (I-70-11), 100 mL of methanol, and 30 mL g of a 25% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was 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 the compound represented by the formula (I-70-12).

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 in the reaction vessel. Was added, and the mixture was 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 the compound represented by the formula (I-70).
LCMS: 807 [M + 1]
By combining the same method as described above and a known method, compounds represented by formulas (I-11) to (I-59) and formulas (I-61) to formula (I-69) were produced.
(Examples 13 to 24, Comparative Examples 1 to 4)
Compounds represented by formulas (I-1) to (I-10), formulas (I-60) and formulas (I-70) described in Examples 1 to 12 and compounds described in Patent Document 1 ( R-1), the compound described in Patent Document 2 (R-2), the compound described in Patent Document 3 (R-3), and the compound described in Patent Document 4 (R-4) were used as the compounds to be evaluated.

Further, the compound (X-1) described in JP-A-2005-015473, the compound (X-2) described in JP-A-10-87565, 20%, and the compound described in JP-A-2002-537280. A liquid crystal composition consisting of (X-3): 45% and LC-756 (manufactured by BASF): 5% as a chiral compound was designated as a parent liquid crystal (X).

A polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm by a spin coating method, dried at 100 ° C. for 10 minutes, and then fired 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 device.

11.87% of the parent liquid crystal (X), 7.91% of the compound to be evaluated, 0.20% of the photopolymerization initiator Irgacare907 (manufactured by BASF), 0.02% of 4-methoxyphenol and chloroform. A coating solution was prepared by mixing 80.00%. This coating liquid was applied to the rubbed glass substrate by the spin coating method. After drying at 80 ° C. for 1 minute, it was further dried at 120 ° C. for 1 minute. Then, using a high-pressure mercury lamp, ultraviolet rays were irradiated at an intensity of 40 mW / cm ² for 25 seconds to prepare a film to be evaluated. The correspondence between the film example numbers and the compounds to be evaluated is shown in Table 1 below.

Orientation defects were evaluated for the produced film. The film was divided into a total of 100 squares, 10 squares in length and 10 squares in width. By observing with a polarizing microscope, the number of squares with orientation defects was counted. The smaller the value, the less the orientation defect. 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 the 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 degree of yellowing (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 calculation formula is
YI = 100 (1.28X-1.06Z) / Y (JIS K7373)
Is. The smaller the value of the degree of yellowing (ΔYI), the less the discoloration after the heat treatment. The results are shown in Table 2 below.

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

Further, from Table 2, it can be seen that the films produced by using the compounds of the present invention of Examples 13 to 24 have little discoloration after the heat treatment.

From the above results, the compounds represented by the formulas (I-1) to (I-10), formula (I-60) and formula (I-70) of the present invention are all comparative compounds (R-1). Compared with the comparative compound (R-4), it can be seen that when a film is prepared by adding it to the polymerizable composition, there are few orientation defects and discoloration is less likely to occur when the film is placed in a high temperature state. Therefore, the compound of the present invention is useful as a constituent member of the polymerizable composition. Further, an optically anisotropic substance using a polymerizable liquid crystal composition containing the compound of the present invention is useful for applications such as optical films.

Claims (5)

The following general formula (I)

(In the formula, P ¹ and the existing P ² are independently the following formulas (P-1) to (P-3), formulas (P-7) to formulas (P-13), and formulas (P-13). Represents a group selected from -15) to formula (P-17),

Sp ¹ and existing Sp ² each have one -CH _2- or two or more non-adjacent -CH _2- independently -O-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -O-CO-O-, -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-, or -C≡C- from a good 1 -C be replaced by an alkylene group of 20,
X ¹ is _{-O-, -OCH 2 -, - CH} 2 O -, - CO -, - COO -, - OCO-, -O-CO-O-, -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-, or a single bond and tables,
k1 represents 0 or 1 and represents
A ¹ and A ² are independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine-2,5-diyl group, respectively. , 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 represents a dioxane-2,5-diyl group, these groups may be substituted by unsubstituted or substituted with one or more substituents L, the same those if a ¹ there are multiple may be different even, they if a ² there are a plurality may be the same or different and
L is 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 thioisocyanogroup, or one −CH ₂ − or two or more non-adjacent −CH ₂₋ are 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- may be substituted carbon atoms. Representing a linear or branched alkyl group of numbers 1 to 20, any hydrogen atom in the alkyl group may be substituted with a fluorine atom .
Z ¹ and Z ² are independently -O- , -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO- , -OCO- , -O-CO-O, respectively. - , -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-, represents a -C≡C- or a single bond, they if Z ¹ there are a plurality may be the same or different and even they are identical if the Z ² there are a plurality Although they may be different, Z ¹ that directly binds to Y ¹ in the presence of Z ¹ represents a single bond, and Z ² that directly binds to Y ² in the presence of Z ² represents a single bond.
m1 and m2 independently represent integers from 0 to 6, while m1 + m2 represent integers from 0 to 6.
The groups represented by Y ¹ −B ¹ −Y ² are the formula (YBY-1), the formula (YBY-2), the formula (YBY-13), the formula (YBY-14), the formula (YBY-19), Represents a group selected from the formula (YBY-20)

R ² is 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 not adjacent 2 A carbon atom in which more than one −CH ₂₋ may be independently substituted with −O− , −CO−, −COO− , −OCO− , −O—CO—O− , or −C≡C−. Although a few 1 represents a linear or branched alkyl group of 20, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, R ² is - (X ² -Sp ²⁾ _k2 Groups represented by −P ² (in the formula , X ² is −O− , −OCH ₂₋ , −CH ₂ O− , −CO− , −COO− , −OCO− , −O−CO−O− , -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 -., -C≡C- or a single bond was tables k2 represents an indicating) 0 or 1, ^{X 1} directly bonded to ^{Y 1} if m1 is and there is ^{X 1} represents 0 represents a single bond represents, ^{X 2} is directly bonded to ^{Y 2} if m2 is and is ^{X 2} exists represents 0 represents a single bond, the formula does not contain -O-O- bond. ). A composition containing the compound according to claim 1 . A liquid crystal composition containing the compound according to claim 1 . A polymer obtained by polymerizing the composition according to claim 2 or 3 . An optically anisotropic substance using the polymer according to claim 4 .