JP2016017053A - Antioxidant, liquid crystal composition, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound and a composition giving such properties to a liquid crystal display element that when the liquid crystal display element is irradiated with UV rays, a voltage holding ratio of the display element hardly decreases and that when the display element is heated, the display element hardly causes discoloration.SOLUTION: The present invention provides a compound represented by, for example, formula I-4 below, and a composition and a product comprising the above compound.EFFECT: The compound is added to a liquid crystal composition, from which a PSA type liquid crystal display element is fabricated. When the display element is irradiated with UV rays, the voltage holding ratio of the display element hardly decreases; and when the display element is heated, the display element hardly shows discoloration. Thereby, the above compound is useful as a constituent of a liquid crystal composition and a display element.SELECTED DRAWING: None

Description

  The present invention is a compound having an antioxidant action and a resin, pigment, dye, resin additive, oil, filter, adhesive, adhesive, oil, ink, printed matter, pharmaceutical, cosmetics, detergent, building material containing the compound, The present invention relates to a packaging material, a liquid crystal material, an organic EL material, an organic semiconductor material, an optical anisotropic body, a display element, an electronic material, an automobile part, an aircraft part, a machine part, an agricultural chemical, a food, and a product using them.

  A PSA (Polymer Sustained Alignment) type liquid crystal display element, which is one of the types of TFT liquid crystal display elements, has a polymer structure for controlling the pretilt angle in the cell, enabling high-contrast display and high-speed response. is there. This device is produced by injecting a liquid crystal composition to which a polymerizable compound is added into a cell, and performing UV irradiation in a state where a voltage is applied to polymerize the polymerizable compound. Therefore, the liquid crystal compounds and additives used in this device are required not to have an adverse effect such as image sticking on the panel by UV irradiation. There are various causes for image sticking. One of them is a decrease in voltage holding ratio caused by deterioration of the liquid crystal composition by light or heat. Usually, an antioxidant is added to the liquid crystal composition for the purpose of suppressing such deterioration of the liquid crystal composition.

  Various hindered phenols are known as antioxidants added to the liquid crystal composition. However, when UV irradiation is performed on a PSA type liquid crystal display device prepared by adding these antioxidants, the voltage holding ratio decreases. There was a problem (Patent Documents 1 and 2). In addition, other hindered phenols known as antioxidants decrease the voltage holding ratio when UV irradiation is applied to a PSA type liquid crystal display element prepared by adding an antioxidant, or discolor the display element when heated. There is a problem that occurs (Patent Documents 3 and 4, Non-Patent Document 1).

JP-A-49-3887 German Patent Application Publication No. 19539141 German Patent Application No. 2432098 US Patent Application Publication No. 2011/0306668 Journal of Organic Chemistry, 1994, 59 (16), 4482-4489

  The problem to be solved by the present invention is that a PSA type liquid crystal display element is prepared by adding to a liquid crystal composition, and when the display element is irradiated with UV, it is difficult to lower the voltage holding ratio of the display element and heating is performed. It is to provide a compound that hardly causes discoloration in the display element. Furthermore, it is providing the liquid crystal composition and display element containing the said compound.

  The present invention relates to the general formula (I)

(In the formula, S represents a spacer group, and when a plurality of S are present, they may be the same or different, and X represents —O—, —S—, —OCH ₂ —, —CH ₂ O. -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _{2- , -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond, but when there are a plurality of X, they may be the same or different ( However,-(X-S) _k -does not include -O-O-, -O-S-, and -S-O-), k represents an integer of 1 to 8, and A ¹ and A ² Are each independently 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, decahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, or tetrahydropyran-2,5-diyl group Wherein these groups may be unsubstituted or substituted by one or more L A plurality of A ² may be the same or different, and Z ¹ represents —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—, —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, a respectively identical ^{if Z 1} appears more M represents an integer of 2 to 6, and R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, Chioisoshiano group or represents an alkyl group having 1 to 20 carbon atoms, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = H—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, the alkyl chain may be linear or branched, L is a fluorine atom, Chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, represents an alkyl group having from 1 to 12 carbon atoms, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH -CO- By —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. The alkyl chain may be linear or branched, and when a plurality of Ls are present, they may be the same or different. And a liquid crystal composition containing the compound and a display element.

  The compound of the present invention is added to a liquid crystal composition to produce a PSA type liquid crystal display element, and when the display element is irradiated with UV, it is difficult to lower the voltage holding ratio of the display element and is displayed when heated. Since it is difficult to cause discoloration in the element, it is useful as a constituent member of a liquid crystal composition and a display element.

In general formula (I), S represents a spacer group, and when a plurality of S are present, they may be the same or different. In the present invention, the spacer group means a spacer described in Pure and Applied Chemistry, 2001, Vol. 73, No. 5, pages 845-895. From the viewpoints of compatibility with other components, availability of raw materials, and ease of synthesis, when a plurality of them appear, they may be the same or different from each other, and each independently represents one —CH ₂ — or Two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO—, —OCO—O—, —CO—NH—, —NH—CO—, —N═. It preferably represents an alkylene group having 1 to 20 carbon atoms which may be replaced by CH—, —CH═N—, —CH═CH— or —C≡C—, one —CH ₂ — or adjacent one It is more preferable that two or more —CH ₂ — that are not represented each independently represent an alkylene group having 1 to 20 carbon atoms that may be independently replaced by —O—, —COO—, or —OCO—. It is particularly preferred to represent an alkylene group having 1 to 8 atoms.

X represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—. _{O -, - CO-NH -} , - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, -N = N-, -CH = N-N = CH-, -CH = N-, -CH = N-, -CF = CF-, -C≡C- or a single bond In the case where a plurality of Xs are present, they may be the same or different (provided _that- (X-S) ₁ -represents -O-O-, -O-S- and -S- . free O- a), from the standpoint of ease of raw material availability and _{synthesis, -O -, - OCH 2 -} , - CH 2 O -, - COO -, - OCO -, - 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, -O -, - COO -, - OCO- Or it is more preferable to represent a single bond, and it is especially preferable to represent -O- or a single bond.

  k represents an integer of 1 to 8, and preferably represents an integer of 1 to 4 from the viewpoint of compatibility with other components, availability of raw materials, and ease of synthesis, and represents 1 or 2. Particularly preferred.

A ¹ and A ² are each independently 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, decahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, or tetrahydropyran-2 , 5-diyl group, these groups may be unsubstituted or substituted by one or more L, and a plurality of A ² may be the same or different, but other components From the viewpoints of compatibility, availability of raw materials and ease of synthesis, and antioxidant performance, A ² is independently represented by the following formulas (a-1) to (a-8):

It is preferable to represent a group selected from Formula (a-1) to Formula (a-7), more preferably a group selected from Formula (a-1) to Formula (a-4) or Formula ( It is more preferable to represent a group selected from a-7), and it is particularly preferable to represent a group selected from Formula (a-1) to Formula (a-4).

L is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, Represents a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 12 carbon atoms, and one —CH ₂ — in the alkyl group or two or more —CH that are not adjacent to each other. _2- are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—. NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═ CF -Or -C≡C- may be substituted, and the alkyl chain may be linear or branched. When a plurality of L are present, they may be the same or different. good. From the viewpoint of compatibility with other components, ease of synthesis and availability of raw materials, and antioxidant performance, L represents a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 12 carbon atoms. It said alkyl 1 -CH ₂ in the radical - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - may be replaced by OCO-, the alkyl The chain may be linear or branched, and represents a fluorine atom or an alkyl group having 1 to 8 carbon atoms, and one —CH ₂ — or adjacent group in the alkyl group. Two or more —CH ₂ — that are not present may be each independently substituted by —O—, and the alkyl chain is more preferably linear, and represents a fluorine atom, a methyl group, or a methoxy group. Is more preferable and represents a fluorine atom. Preferred.

Z ¹ represents —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 -, - 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 = NN-CH-, -CF = CF , -C≡C- or a single bond, and when they appear multiple times, they may be the same or different, but compatibility with other components, availability of raw materials and ease of synthesis, antioxidant from a performance _{standpoint, -OCH 2 -, - CH 2} O -, - CH 2 CH 2 -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or preferably a single bond, and particularly preferably a single bond.

  m represents an integer of 2 to 6, preferably 2, 3, or 4 from the viewpoint of ease of synthesis and antioxidant performance, more preferably 2 or 3, particularly preferably 3. preferable.

R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO- It may be substituted by CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—, and the alkyl chain may be linear or branched. May be, but compatible with other components, ease of synthesis, and availability of raw materials From the viewpoint of antioxidant performance, it represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 20 carbon atoms, and one —CH ₂ — in the alkyl group or adjacent to each other. Two or more —CH ₂ — may be independently substituted with —O—, —COO—, —OCO—, and the alkyl chain may be linear or branched. is preferably a hydrogen atom, represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently it may be substituted by a by -O-, and the alkyl chain is a straight a chain more preferably which may be branched, of one -CH 2 _- or two or more nonadjacent -CH ₂ - is replaced each by independently -O- More preferably also represents an straight-chain alkyl group having 1 to 8 carbon atoms, and particularly preferably a straight-chain alkyl group having from 1 to 8 carbon atoms.

In the group represented by — (X—S) _k —, X that is directly bonded to A ² is —O— or —OCO— from the viewpoint of ease of synthesis, availability of raw materials, and antioxidant performance. , —OCH ₂ — or a single bond is preferable, —O—, —OCH ₂ — or a single bond is more preferable, and a group represented by — (X—S) _k — is represented by the following formula (k -1) to formula (k-7)

(Wherein k1 represents an integer of 2 to 20, k2 represents an integer of 1 to 20, and n1 represents 0 or 1), and preferably represents a group consisting of a combination thereof. It is particularly preferable to represent a group selected from formulas (k-1) to (k-4).

In addition, groups represented by -A ^1- (Z ¹ -A ² ) _m -are represented by the following formulas (b-1) to (b-20).

(In the formula, La represents ^a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms, and one —CH ₂ — in the alkyl group or two or more —CH ₂ — not adjacent to each other) Each independently may be substituted by -O-, preferably represents a fluorine atom, a methyl group or a methoxy group, particularly preferably represents a fluorine atom, and when ^a plurality of ^La are present, each is the same. Or r may be different, and r represents an integer of 0 to 4, preferably 0, 1 or 2, and Z ^1a represents —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —. _{, -COO -, - OCO -,} - CF 2 O -, - OCF 2 -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO- or -CH ₂ CH ₂ —OCO— represents —OCH ₂ —, —C It is preferable to represent a group selected from H ₂ O—, —CH ₂ CH ₂ —, —CF ₂ O—, or —OCF ₂ —), and from formula (b-1) to formula (b— It is more preferable to represent a group selected from 12), and it is more preferable to represent a group selected from Formula (b-1) to Formula (b-5), and Formula (b-1) or Formula (b-2) Is particularly preferred.

  The compound represented by the general formula (I) is preferably a compound represented by the following general formulas (Ia) to (Is).

(In the formula, La represents ^a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms, and one —CH ₂ — in the alkyl group or two or more —CH ₂ — not adjacent to each other) Each independently may be substituted by -O-, preferably represents a fluorine atom, a methyl group or a methoxy group, particularly preferably represents a fluorine atom, and when ^a plurality of ^La are present, each is the same. Or r may be different, and r represents an integer of 0 to 4, preferably 0, 1 or 2, and Z ^1b , Z ^1c , Z ^1d and Z ^1e are each independently —OCH ₂ —. _{, -CH 2 O -, - CH} 2 CH 2 -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 - _{, -CH 2 CH 2 -COO -,} - CH 2 C ₂ -OCO- or represents a single _{bond, -OCH 2 -, - CH 2} O -, - CH 2 CH 2 -, - COO -, - OCO -, - CF 2 O -, - OCF 2 - or a single bond And w ₁ and w ₂ each independently represent —CH ₂ — or —O—, and R, X, S and k are the same as R, X, S and k in the general formula (I). It represents the same meaning.)
The compound of this invention can be manufactured with the following manufacturing methods.
(Manufacturing method 1) Manufacture of the compound represented by a following formula (S-8)

(Wherein R and L each independently represent the same as defined in formula (I), r each independently represents an integer of 0 to 4, and halogen each independently represents halogen. Represents an atomic or halogen equivalent.)
The compound represented by general formula (S-3) can be obtained by reacting the compound represented by general formula (S-1) with the compound represented by general formula (S-2). Examples of the reaction include a method of cross-coupling in the presence of a metal catalyst and a base. Specific examples of the metal catalyst include [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, palladium (II) acetate, tetrakis (triphenylphosphine) palladium (0) and the like. Specific examples of the base include potassium carbonate, potassium phosphate, cesium carbonate and the like. Reaction conditions include, for example, Metal-Catalyzed Cross-Coupling Reactions (Co-authored by Armin de Meijer, Francois Diedrich, Wiley-VCH), Palladium Reagents and Catalysts: New Perspectives: New Perspective. Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry) (SL Buchwald, K. Fugami, T. Hiyama, M. Kourai, M. Miura, M. Miura, M. Miura, M. Miura, M. Miura, N. Mura. a, E. Shiragawa, K. Tamao, Springer) and the like.

  The compound represented by the general formula (S-4) is obtained by boring the compound represented by the general formula (S-3). Examples of the borated method include a method in which a proton on the aromatic ring of the compound represented by the general formula (S-3) is extracted with a strong base, reacted with a boric acid ester, and then hydrolyzed. Examples of the strong base include butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide and the like. Tetramethylethylenediamine or the like may be added as necessary. Examples of the boric acid ester include those described above. Further, after halogenating the compound represented by the general formula (S-3), derivatization into a Grignard reagent, reaction with a boric acid ester, and subsequent hydrolysis, or lithiation by a halogen lithium exchange reaction, A method of hydrolyzing after reacting with boric acid ester is mentioned. Specific examples of the boric acid ester include trimethyl borate and triisopropyl borate. Specific examples of the lithiating agent include butyl lithium, sec-butyl lithium, tert-butyl lithium and the like.

  The compound represented by general formula (S-6) can be obtained by reacting the compound represented by general formula (S-4) with the compound represented by general formula (S-5). Examples of the reaction include a method of cross coupling in the presence of a metal catalyst and a base. Examples of the metal catalyst, base and reaction conditions include those described above.

  The compound represented by the general formula (S-8) is obtained by reacting the compound represented by the general formula (S-6) with the compound represented by the formula (S-7). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-7) is converted to an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then represented by the general formula (S-6). And a method of reacting the compound 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, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the like. Examples of the base include N, N-dimethylaminopyridine.

  Examples of reaction conditions other than those described in each of the above steps include, for example, an experimental chemistry course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), and Bilstein Handbook of Organic Chemistry (Chemical Chemistry). -Described in Institute for Literacy der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH, Co. K, Fiesers' Reagents for Organic Science. mical Abstracts Service, American Chemical Society), include those listed in databases such as Reaxys (Elsevier Ltd.).

  In each step, a reaction solvent can be appropriately used. Specific examples of the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Specific examples of the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.

In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. Specific examples of the purification agent include silica gel, alumina, activated carbon and the like.
(Production method 2) Production of a compound represented by the following formula (S-15)

(Wherein R and L each independently represent the same as defined in formula (I), r each independently represents an integer of 0 to 4, and halogen each independently represents halogen. Represents an atom or a halogen equivalent, and k1 represents an integer of 2 to 18.)
The compound represented by the general formula (S-11) can be obtained by reacting the compound represented by the formula (S-9) with a compound represented by the general formula (S-10). Examples of the reaction include Friedel-Crafts reaction. Examples of Lewis acids include aluminum chloride.

  The compound represented by the general formula (S-13) can be obtained by reacting the compound represented by the general formula (S-12) with the compound represented by the general formula (S-4). Examples of the reaction include a method of cross coupling in the presence of a metal catalyst and a base. Examples of the metal catalyst, the base, and the reaction conditions include those described in production method 1.

  The compound represented by the general formula (S-14) can be obtained by reacting the compound represented by the general formula (S-13) with the compound represented by the general formula (S-11). Examples of the reaction include Friedel-Crafts reaction. Examples of Lewis acids include aluminum chloride.

  The compound represented by the general formula (S-15) can be obtained by reducing the carbonyl group of the compound represented by the general formula (S-14). Examples of the reaction include reduction using a hydride reagent or catalytic hydrogenation reduction using a metal catalyst. An example of the hydride reagent is lithium aluminum hydride. Examples of the metal catalyst include palladium on carbon.

  Examples of reaction conditions other than those described in the respective steps include those described in the literature described in production method 1 or those listed in the database. Further, a reaction solvent can be appropriately used in each step as in Production Method 1. As in production method 1, purification can be performed as necessary in each step.

  The compound of the present invention can be used in various liquid crystal compositions. When used in a liquid crystal composition having a negative dielectric anisotropy, the following general formula (II-1) is used as a compound having a negative dielectric anisotropy.

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- and may be substituted with one or more hydrogen atoms in the alkyl group May be optionally substituted with a halogen atom, and A ³ and A ⁴ are each independently any one of the following structures:

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). Z ² and Z ³ are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH. _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, L ¹ and L ² each independently represent a fluorine atom, a chlorine atom or a trifluoromethyl group, m ¹ and m ² each independently represent ^{0~3, m} 1 + m ² is 1, 2 or ^{3, a 3,} a ⁴ If Z ² and Z ³ there are multiple, they may be the same or different. )
It is preferable to use the compound represented by these.

  As a compound represented by general formula (II-1), as a preferable component, general formula (II-1a)

Wherein R ^1a and R ^2a are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CH═CH— or — Represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by CF═CF—, and A ^3a and A ^4a are each independently represented by the following formulas (II-a-1) to (II-a- 4)

In the case where a plurality of A ^4a are present, they may be the same or different, and Z ^2a and Z ^3a are each independently —OCH ₂ —, —CH ₂ O—, — CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or a single bond is represented, but when a plurality of Z ^2a appear, they may be the same or different, and L ^1a and L ^2a are each independent. Represents a fluorine atom, a chlorine atom or a trifluoromethyl group, and m1a represents 0 or 1. It is preferable to use a compound represented by

  Specifically, as the compound represented by the general formula (II-1a), one or more compounds represented by the formulas (II-1a-1) to (II-1a-12) are used. Is preferred.

^{(Wherein, R 1a} and ^{R 2a} represent the same meaning as ^{R 1a} and ^{R 2a} in formula (II-1a).)
Moreover, as a compound represented by general formula (II-1), as a preferable component, general formula (II-1b)

Wherein R ^1b and R ^2b are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CH═CH— or — Represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by CF═CF—, and A ^3b , A ^4b and R ^5b are each independently represented by the following formulas (II-b-1) to (II) -B-4)

In which at least one of A ^3b , A ^4b or A ^5b represents the formula (II-b-4). It is preferable to use a compound represented by

  Specifically, as the compound represented by the general formula (II-1b), it is preferable to use one or more of the formulas (II-1b-1) to (II-1b-5).

^{(Wherein, R 1b} and ^{R 2b} represent the same meaning as ^{R 1b} and ^{R 2b} in formula (II-1b).)
Further, as a liquid crystal compound having a negative dielectric anisotropy, a compound represented by the general formula (II-2)

Wherein R ³ and R ⁴ are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CH═CH— or — Represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by CF = CF-, and A ⁶ and A ⁷ are each independently represented by the following formulas (II-a-1) to (II-a- 4)

In the case where a plurality of A ⁷ are present, they may be the same or different, and each A ⁸ independently represents the following formula (II-c-1) or formula (II-c): -2)

(Wherein L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ and L ⁸ represent a hydrogen atom or a fluorine atom, but at least one of L ³ , L ⁴ or L ⁵ or L ⁶ , L ⁷ Or at least one of L ⁸ represents a fluorine atom), and Z ⁴ and Z ⁵ are each independently —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or a single bond is represented, but when a plurality of Z ⁴ are present, they may be the same or different, and m3 represents 0 or 1. It is preferable to use a compound represented by

  Specifically, as the compound represented by the general formula (II-2), it is preferable to use one or more of formulas (II-2-1) to (II-2-9).

(Representing the same meaning as ^{R 3} and ^{R 4} in the formula, ^{R 3} and ^{R 4} are the general formula (II-2).) Dielectric anisotropy is approximately zero, as a so-called non-polar compounds, the following Formula (II-3)

(In the formula, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- and may be substituted with one or more hydrogen atoms in the alkyl group May be optionally halogen-substituted, A ⁹ and A ¹⁰ are each independently

(In the structure, one or more —CH ₂ CH ₂ — in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —. -In the phenylene group, one or two or more CH groups may be substituted with a nitrogen atom.), Z ⁶ is a single bond, —CH═CH—, —C≡C—, — CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and m ⁴ represents 0 to 4. . )
It is preferable to use the compound represented by these.

  As a compound represented by general formula (II-3), general formula (II-3a)

Wherein R ^5a and R ^6a are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CH═CH— or — Represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by CF═CF—, and A ^9a and A ^10a are each independently represented by the following formulas (II-a-1) to (II-a- 4)

In the case where a plurality of A ^10a are present, they may be the same or different, and Z ^6a each independently represents —OCH ₂ —, —CH ₂ O—, —CH ₂ CH. ₂ —, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ — or a single bond, but when a plurality of Z ^6a appear, they may be the same or different. , M4a represents 1 or 2. It is preferable to use a compound represented by

  Specifically, as the compound represented by the general formula (II-3a), one or more compounds represented by the formulas (II-3a-1) to (II-3a-7) are used. Is preferred.

^{(Wherein, R 5a} and ^{R 6a} represents the same meaning as ^{R 5a} and ^{R 6a} of the general formula (II-2a).)
Moreover, as a compound represented by general formula (II-3), general formula (II-3b)

Wherein R ^5b and R ^6b are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CH═CH— or — Represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by CF═CF—, and A ^9b , A ^10b and A ^11b are each independently represented by the following formulas (II-b-1) to (II) -B-3)

^Wherein at least one of A ^9b , A ^10b or A ^11b represents a group selected from the formula (II-b-2) or the formula (II-b-4). It is preferable to use a compound represented by

  Specifically, as the compound represented by the general formula (II-3b), one or more compounds represented by the formulas (II-3b-1) to (II-3b-2) are used. Is preferred.

^{(Wherein, R 5b} and ^{R 6b} denote the same meaning as ^{R 5b} and ^{R 6b} of Formula (II-3b).)
When used in a liquid crystal composition having a positive dielectric anisotropy, a preferred component as a compound having a positive dielectric anisotropy is represented by formula (II-4).

(Wherein R ⁶ is each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CH═CH— or —CF═CF -Represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by-, and A ¹² and A ¹³ are each independently represented by the following formulas (II-d-1) to (II-d-6):

In the case where a plurality of A ¹³ are present, they may be the same or different, and Z ⁶ and Z ⁷ are each independently —OCH ₂ —, —CH ₂ O—, — CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or a single bond is represented, but when a plurality of Z ⁶ appear, they may be the same or different, and L ⁹ and L ¹⁰ are independent of each other. Y ¹ represents a hydrogen atom or a fluorine atom, and Y ¹ represents a fluorine atom, a chlorine atom, and one or two or more hydrogen atoms each independently may be substituted with a fluorine atom. —CH ₂ — or two or more non-adjacent —CH ₂ — each independently represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by —O— or —CH═CH—. , M4 represents 0, 1 or 2. It is preferable to use a compound represented by

  Specifically, as the compound represented by the general formula (II-4), one or more compounds represented by the formulas (II-4-1) to (II-4-37) are used. Is preferred.

(Wherein, it represents the same meaning as ^{R 6} and ^{Y 1 R 6,} and ^{Y 1} is the general formula (II-5).)
Further, as a liquid crystal compound having a positive dielectric anisotropy, a compound represented by the general formula (II-5)

(Wherein R ⁷ is each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CH═CH— or —CF═CF - represents a linear alkyl group having 10 good 1 -C be replaced ^{by, a 14} and ^{a 15} are each independently formula (II-d-1) from the formula (II-d-6)

In the case where a plurality of A ¹⁵ are present, they may be the same or different, and Z ⁸ and Z ⁹ are each independently —OCH ₂ —, —CH ₂ O—, — CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or a single bond is represented, but when a plurality of Z ⁸ appear, they may be the same or different, and L ¹¹ , L ¹² and L ¹³ Each independently represents a hydrogen atom or a fluorine atom, Y ² is a fluorine atom, a chlorine atom, each independently one or two or more hydrogen atoms may be substituted with a fluorine atom, and each independently Straight chain alkyl having 1 to 10 carbon atoms in which one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently substituted by —O— or —CH═CH— Represents a group, m5 represents 0, 1 or 2; It is preferable to use a compound represented by

  Specifically, as the compound represented by the general formula (II-5), one or more compounds represented by the formulas (II-5-1) to (II-5-6) are used. Is preferred.

  In addition, when the compound of the present invention is used for a liquid crystal display element whose orientation is stabilized by a polymer, for example, a material for a liquid crystal display element such as PS-VA, PS-IPS, PS-OCB, etc., any polymerizable compound is used. Can be used. The polymerizable compound is not particularly limited as long as it is a compound having at least one polymerizable group. For example, the compound represented by the general formula (II-6)

And / or general formula (II-7)

(In the formula, P ¹ , P ² and P ³ each independently represent a polymerizable group, and S ¹ , S ² and S ³ each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms. represents but one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced ^{by, S} 1, S ^{When two} or more S ³ appear, they may be the same or different, and X ¹ , X ² and X ³ are each independently —O—, —S—, —OCH ₂ —, —CH _2. O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _{2 -, - CH 2 S -,} - CF 2 O -, - OCF 2 -, - CF 2 S -, - 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— or —C≡ C- represents that when a plurality of X ¹ , X ² and X ³ appear, they may be the same or different, and k 2, k 3 and k 4 each independently represent an integer of 0 to 10; ¹⁰ and Z ¹¹ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, —CO—S—, —S—CO. -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 _{S -, - CF 2 O -} , - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF _{2 -, - CH = CH-} COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH _{2 -, - CH 2 CH 2} -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH—, —CF═CF—, —C≡C— or a single bond is represented, but when a plurality of Z ¹⁰ and Z ¹¹ appear, they may be the same or different. A ¹⁶ , A ¹⁷ , ^{A 18} and ^{A 19} are each independently, 1,4-phenylene group, 1,4-sheet Lohexylene 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 ¹⁶ , A ¹⁷ , A ¹⁸ and A ¹⁹ may be unsubstituted or substituted by one or more L ¹¹ , but A ¹⁷ and A ¹⁹ are When multiple occurrences may be the same or different, R ¹⁰ is a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, Chioisoshiano group, or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO-, CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO- A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. L ¹¹ represents fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, Diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—. , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH- COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted. A linear or branched alkyl group having 1 to 12 carbon atoms is represented, and m6 and m7 represent 0, 1, 2, or 3. ) Is preferred, and the case where P ¹ , P ² and P ³ are acrylic or methacrylic groups is particularly preferred. Specific examples of the compound represented by the general formula (II-6) include formulas (II-6-1) to (II-6-18).

(Wherein, ^{W 1} and ^{W 2} represents a hydrogen atom or a methyl group each independently, represent the same meaning as ^{S 1} and ^{S 2} of ^{S 1} and ^{S 2} is the general formula (II-6), respectively Independently, it is preferably an alkylene group having 1 to 8 carbon atoms. Specific examples of the compound represented by the general formula (II-7) include formulas (II-7-1) to (II-7-15).

Wherein W ³ represents a hydrogen atom or a methyl group, and S ³ represents the same meaning as S ^{3 in} formula (II-7), but preferably represents an alkylene group having 1 to 8 carbon atoms. , R ¹⁰ represents the same meaning as R ^{10 in} formula (II-7), but a hydrogen atom, a fluorine atom, a cyano group, or one —CH ₂ — or two or more — that are not adjacent to each other. It is particularly preferred that the compound represented by (CH _2- represents a linear alkyl group having 1 to 8 carbon atoms which may be independently substituted with -O-).

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

  Moreover, you may add a photoinitiator to the liquid-crystal composition containing the compound of this invention according to the objective. In that case, the concentration of the photopolymerization initiator is preferably 0.0001% by mass to 10% by mass and more preferably 0.001% by mass to 8% by mass with respect to the liquid crystal composition. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Specific examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907), benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene]. Amino (IRGACURE OXE 01) etc. are mentioned. Examples of the thermal polymerization initiator include azo compounds and peroxides. Specific examples of the thermal polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile) and the like. One type of polymerization initiator may be used, or two or more types of polymerization initiators may be used in combination.

  In addition, a stabilizer other than the compound of the present invention may be added to the liquid crystal composition containing the compound of the present invention in order to improve the storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the liquid crystal composition. % To 0.5% by mass is more preferable. One kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specifically, as the stabilizer, the formula (III-1) to the formula (III-36)

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

  The two substrates used for the display element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

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

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate via a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant. As a method for sandwiching a liquid crystal composition for a PS (polymer stabilization) type or PSA (polymer sustaining alignment) type liquid crystal display element between two substrates, a vacuum injection method, a liquid crystal dropping (ODF) method, or the like is used. Can do.

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

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Most preferably, the polymerization is carried out at a temperature close to room temperature, that is, typically at a temperature of 15 ° C to 60 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultrahigh-pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is preferably 100W / cm ² from 0.1 mW / cm ^2, and more preferably 80W / cm ² from 2 mW / cm ^2. Energy of ultraviolet light irradiation, can be appropriately adjusted, is preferably 10000 mJ / cm ² from 10 mJ / cm ^2, from 100mJ / cm ² 7000mJ / cm ² is more preferable. When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays, but is preferably 10 seconds to 600 seconds.

  Further, the liquid crystal display element of the present invention obtained by polymerization can be subjected to heat treatment for the purpose of reducing the initial characteristic change and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 ° C. to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
Example 1 Production of Compound Represented by Formula (I-1)

  To the reaction vessel was added 20.0 g of the compound represented by formula (I-1-1), 21.3 g of the compound represented by formula (I-1-2), 25.3 g of potassium carbonate, 100 mL of tetrahydrofuran, and 100 mL of water. It was. After substituting the system with nitrogen, 1.41 g of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 7 hours. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) to obtain 22.2 g of a compound represented by the formula (I-1-3).

  To a reaction vessel equipped with a dropping funnel, 22.2 g of the compound represented by the formula (I-1-3) and 150 mL of tetrahydrofuran were added. 124 mL of a sec-butyllithium solution (1.0 mol / L) was added dropwise at -70 ° C. After stirring for 2 hours, 25.3 g of triisopropyl borate was added dropwise. After stirring for 2 hours, 10% hydrochloric acid was added dropwise. The mixture was stirred at room temperature for 1 hour and washed with brine. By concentrating and drying, 25.7 g of a compound represented by the formula (I-1-4) was obtained.

  To the reaction vessel, 25.7 g of the compound represented by the formula (I-1-4), 25.0 g of the compound represented by the formula (I-1-5), 20.6 g of potassium carbonate, 150 mL of tetrahydrofuran, and 150 mL of water were added. It was. After substituting the system with nitrogen, 1.15 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 10 hours. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 31.2 g of a compound represented by the formula (I-1-6).

  2.25 g of aluminum chloride and 10 mL of dichloromethane were added to a reaction vessel equipped with a dropping funnel. While cooling with ice, a dichloromethane solution of 3.49 g of the compound represented by the formula (I-1-7) was added dropwise. After stirring for 1 hour, a dichloromethane solution of 5.00 g of the compound represented by the formula (I-1-6) was added dropwise while cooling with ice. After stirring at room temperature for 5 hours, it was poured into water. Diluted with dichloromethane and washed with brine. Purification was performed by column chromatography to obtain 5.05 g of a compound represented by the formula (I-1-8).

  To the autoclave, 5.05 g of the compound represented by the formula (I-1-8), 50 mL of tetrahydrofuran, 25 mL of acetic acid, and 1.00 g of palladium carbon were added. The mixture was heated and stirred at a hydrogen pressure of 0.5 MPa and 50 ° C. for 5 hours. The catalyst was filtered and the solvent was distilled off. Redissolved in tetrahydrofuran, 25% aqueous sodium hydroxide solution was added, and the mixture was stirred with heating. After 10% hydrochloric acid was added dropwise for neutralization, the mixture was extracted and washed with ethyl acetate. By distilling off the solvent, 3.84 g of a compound represented by the formula (I-1-10) was obtained.

  To the reaction vessel, 3.84 g of the compound represented by the formula (I-1-10), 1.50 g of the compound represented by the formula (I-1-11), and 30 mL of dichloromethane were added. While cooling with ice, 1.68 g of trifluoroacetic anhydride was added dropwise. After stirring, the mixture was poured into water and the organic layer was washed with brine. Purification by column chromatography (silica gel) and recrystallization gave 3.65 g of a compound represented by the formula (I-1-12).

To the autoclave, 3.00 g of a compound represented by the formula (I-1-12), 50 mL of tetrahydrofuran, 3 mL of concentrated sulfuric acid, and 0.30 g of palladium carbon were added. After stirring at a hydrogen pressure of 0.2 MPa, the solvent was distilled off. After being dispersed and washed with methanol, purification was performed by column chromatography (silica gel) and recrystallization to obtain 1.76 g of a compound represented by the formula (I-1).
¹ H NMR (CDCl ₃ ) δ 0.99 (t, 3H), 1.45 (s, 18H), 1.65-1.76 (m, 14H), 2.59-2.72 (m, 6H) ), 5.12 (s, 1H), 7.08 (s, 2H), 7.13 (d, 2H), 7.29 (d, 2H), 7.40-7.62 (m, 10H) ppm.
Example 2 Production of Compound Represented by Formula (I-2)

  Add 5.00 g of the compound represented by the formula (I-1-4), 5.17 g of the compound represented by the formula (I-2-1), 4.02 g of potassium carbonate, 100 mL of tetrahydrofuran and 100 mL of water to the reaction vessel. It was. After the inside of the system was replaced with nitrogen, 1.12 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 7 hours. Dilute with dichloromethane and wash with hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 5.43 g of a compound represented by the formula (I-2-2).

  To the reaction vessel, 5.43 g of the compound represented by the formula (I-2-2), 1.39 g of pyridine, and 80 mL of dichloromethane were added. While cooling with ice, 4.97 g of trifluoroacetic anhydride was added dropwise. After stirring for 5 hours, the mixture was washed with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) to obtain 6.86 g of a compound represented by the formula (I-2-3).

  6.86 g of a compound represented by the formula (I-2-3), 1.81 g of 3-butyn-1-ol, 0.05 g of copper (I) iodide, 50 mL of triethylamine, N, N-dimethylformamide in a reaction vessel 150 mL was added. After substituting the system with nitrogen, 0.15 g of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred for 5 hours. Dilute with ethyl acetate and wash with hydrochloric acid, water and brine. Purification by column chromatography (alumina) gave 3.50 g of a compound represented by the formula (I-2-4).

  To the autoclave, 3.50 g of a compound represented by the formula (I-2-4), 50 mL of tetrahydrofuran, 0.35 g of concentrated sulfuric acid, and 1.00 g of palladium carbon were added. The mixture was stirred at a hydrogen pressure of 0.2 MPa for 5 hours. The catalyst was filtered and the solvent was distilled off. Redissolved in ethyl acetate and washed with brine. Purification by column chromatography (alumina) gave 2.82 g of a compound represented by the formula (I-2-5).

In a reaction vessel, 2.82 g of the compound represented by formula (I-2-5), 1.72 g of the compound represented by formula (I-2-6), 0.08 g of N, N-dimethylaminopyridine, and 50 mL of dichloromethane. Was added. After adding dropwise 0.94 g of diisopropylcarbodiimide, the mixture was stirred. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 3.10 g of a compound represented by the formula (I-2).
Transition temperature (temperature rise, 5 ° C./min): C 128 N 136 I
¹ H NMR (CDCl ₃ ) δ 0.99 (t, 3H), 1.43 (s, 18H), 1.65-1.76 (m, 6H), 2.59-2.72 (m, 6H) ), 2.88 (t, 2H), 4.13 (t, 2H), 5.07 (s, 1H), 7.00 (s, 2H), 7.29 (dd, 4H), 7.40. -7.56 (m, 10H) ppm.
Example 3 Production of Compound Represented by Formula (I-3)

  To the reaction vessel, 5.00 g of the compound represented by the formula (I-2-2), 1.77 g of 3-chloropropanol, 6.10 g of cesium carbonate, and 80 mL of dimethyl sulfoxide were added. After stirring with heating, the mixture was diluted with dichloromethane and washed with brine. Purification was performed by column chromatography (alumina) to obtain 4.58 g of a compound represented by the formula (I-3-1).

In a reaction vessel, 4.58 g of the compound represented by formula (I-3-1), 2.78 g of the compound represented by formula (I-2-6), 0.12 g of N, N-dimethylaminopyridine, 80 mL of dichloromethane Was added. After 1.51 g of diisopropylcarbodiimide was added dropwise, the mixture was stirred. Purification was performed by column chromatography and recrystallization to obtain 5.02 g of a compound represented by the formula (I-3).
Transition temperature (temperature rise, 5 ° C./min): C 125 N 158 I
¹ H NMR (CDCl ₃ ) δ 0.98 (t, 3H), 1.43 (s, 18H), 1.70 (sex, 2H), 2.14 (quin, 2H), 2.64 (m, 4H), 2.88 (t, 2H), 4.08 (t, 2H), 4.31 (t, 2H), 5.07 (s, 1H), 6.99 (m, 4H), 7. 29 (d, 2H), 7.39-7.56 (m, 10H) ppm.
Example 4 Production of Compound Represented by Formula (I-4)

In a reaction vessel, 3.00 g of a compound represented by formula (I-2-2), 2.09 g of a compound represented by formula (I-2-6), 0.09 g of N, N-dimethylaminopyridine, 60 mL of dichloromethane Was added. 1.13 g of diisopropylcarbodiimide was added dropwise and stirred. Purification was performed by column chromatography and recrystallization to obtain 3.46 g of a compound represented by the formula (I-4).
Transition temperature (temperature rise, 5 ° C./min): C 170 N 174 I
¹ H NMR (CDCl ₃ ) δ 0.99 (t, 3H), 1.45 (s, 18H), 1.70 (sext, 2H), 2.65 (t, 2H), 2.90 (t, 2H), 3.03 (t, 2H), 5.12 (s, 1H), 7.08 (s, 2H), 7.13 (d, 2H), 7.29 (d, 2H), 7. 40-7.62 (m, 10H) ppm.
Example 5 Production of Compound Represented by Formula (I-5)

  Formula (I-5-1) was obtained in the same manner as in Example 1. To the reaction vessel was added 3.00 g of the compound represented by the formula (I-5-1), 1.81 g of the compound represented by the formula (I-5-2), 2.17 g of potassium carbonate, 60 mL of ethanol, and 30 mL of water. It was. After replacing the system with nitrogen, 0.12 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Dilute with ethyl acetate and wash with 5% hydrochloric acid, water, and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 2.45 g of a compound represented by the formula (I-5-3).

In a reaction vessel, 2.45 g of the compound represented by the formula (I-5-3), 2.04 g of the compound represented by the formula (I-2-6), 0.09 g of N, N-dimethylaminopyridine, 50 mL of dichloromethane Was added. 1.13 g of diisopropylcarbodiimide was added dropwise and stirred. Purification was performed by column chromatography and recrystallization to obtain 2.62 g of a compound represented by the formula (I-5).
m / z = 594
Example 6 Production of Compound Represented by Formula (I-6)

  To the reaction vessel, 5.00 g of the compound represented by the formula (I-6-1), 5.30 g of the compound represented by the formula (I-6-2), 5.70 g of potassium carbonate, and 50 mL of tetrahydrofuran were added. After replacing the inside of the system with nitrogen, 0.32 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 4.81 g of a compound represented by the formula (I-6-3).

  To the reaction vessel, 4.81 g of the compound represented by the formula (I-6-3) and 25 mL of tetrahydrofuran were added. The solution was cooled to −70 ° C., and a secBuLi solution was added dropwise. After stirring for 30 minutes, a solution prepared by dissolving 5.37 g of iodine in 20 mL of tetrahydrofuran was added dropwise. After stirring for 1 hour, an aqueous sodium thiosulfate solution was added dropwise. Diluted with toluene and washed with water and brine. Purification by column chromatography (silica gel) gave 5.79 g of a compound represented by the formula (I-6-4).

  To the reaction vessel, 5.79 g of the compound represented by the formula (I-6-4), 2.31 g of the compound represented by the formula (I-6-5), 3.19 g of potassium carbonate, and 50 mL of tetrahydrofuran were added. After substituting the system with nitrogen, 0.18 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 2.73 g of a compound represented by the formula (I-6-6).

  To the reaction vessel, 5.00 g of a compound represented by the formula (I-6-7), 4.73 g of triphenylphosphine, and 50 mL of toluene were added. After stirring with heating, the precipitate was filtered and washed to obtain 7.79 g of a compound represented by the formula (I-6-8).

  To the reaction vessel, 4.57 g of a compound represented by the formula (I-6-8) and 25 mL of tetrahydrofuran were added. At −20 ° C., 0.95 g of potassium tert-butoxide was added. After stirring at −20 ° C., a tetrahydrofuran solution of 2.73 g of the compound represented by the formula (I-6-6) was added dropwise. After further stirring, water was added. Diluted with toluene, washed with methanol / water and brine. Purification was performed by column chromatography (silica gel) to obtain 3.29 g of a compound represented by the formula (I-6-9).

  To the autoclave, 3.29 g of a compound represented by the formula (I-6-9), 50 mL of tetrahydrofuran, and 0.33 g of palladium carbon were added. After stirring with heating at 50 ° C. and a hydrogen pressure of 0.5 MPa, the catalyst was filtered. The solvent was distilled off, and purification was performed by column chromatography (silica gel) and recrystallization to obtain 1.93 g of a compound represented by the formula (I-6-10).

To the reaction vessel, 1.93 g of a compound represented by the formula (I-6-10), 1.02 g of a compound represented by the formula (I-6-11), 1.47 g of triphenylphosphine, and 30 mL of tetrahydrofuran were added. While cooling with ice, 1.13 g of diisopropyl azodicarboxylate was added dropwise. After stirring, water was added. Diluted with toluene, washed with methanol / water and brine. By performing purification by column chromatography (silica gel) and recrystallization, 2.01 g of a compound represented by the formula (I-6) was obtained.
m / z = 664
Example 7 Production of Compound Represented by Formula (I-7)

  To the reaction vessel, 5.00 g of a compound represented by the formula (I-7-1), 2.79 g of 3-chloropropanol, 11.1 g of cesium carbonate, and 50 mL of dimethyl sulfoxide were added. The mixture was heated and stirred for 5 hours, diluted with dichloromethane, and washed with brine. Purification was performed by column chromatography (alumina) to obtain 5.69 g of a compound represented by the formula (I-7-2).

  To the reaction vessel, 5.69 g of the compound represented by the formula (I-7-2), 6.75 g of bis (pinacolato) diboron, 4.01 g of potassium acetate, and 50 mL of dimethyl sulfoxide were added. After substituting the system with nitrogen, 0.75 g of 1,1′-bis (diphenylphosphino) ferrocenepalladium (II) dichloride was added and stirred with heating. After diluting with toluene and washing with brine, the solvent was distilled off to obtain 4.55 g of a compound represented by the formula (I-7-3).

  To the reaction vessel, 4.55 g of the compound represented by the formula (I-7-3), 4.38 g of the compound represented by the formula (I-7-4), 3.39 g of potassium carbonate, and 50 mL of tetrahydrofuran were added. After substituting the system with nitrogen, 0.19 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) to obtain 3.89 g of a compound represented by the formula (I-7-5).

  The compound represented by the formula (I-7-6) was produced by the method described in Journal of Materials Chemistry C: Materials for Optical and Electronic Devices, 2 (5), 891-900; 2014. To the reaction vessel, 3.89 g of a compound represented by the formula (I-7-5), 4.04 g of a compound represented by the formula (I-7-6), 5.60 g of cesium carbonate, and 50 mL of dimethyl sulfoxide were added. After stirring with heating, water was added and the precipitate was filtered. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 4.20 g of a compound represented by the formula (I-7-7).

In a reaction vessel, 4.20 g of a compound represented by the formula (I-7-7), 1.91 g of a compound represented by the formula (I-2-6), 0.09 g of N, N-dimethylaminopyridine, 50 mL of dichloromethane Was added. 1.13 g of diisopropylcarbodiimide was added dropwise and stirred. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 3.59 g of a compound represented by the formula (I-7).
m / z = 870
Example 8 Production of Compound Represented by Formula (I-8)

  To the reaction vessel, 5.00 g of the compound represented by the formula (I-8-1), 2.76 g of pyridine, and 50 mL of dichloromethane were added. While cooling with ice, 9.85 g of trifluoromethanesulfonic anhydride was added dropwise. After stirring, the mixture was washed with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) to obtain 7.69 g of a compound represented by the formula (I-8-2).

  To the reaction vessel, 7.69 g of a compound represented by the formula (I-8-2), 3.82 g of a compound represented by the formula (I-8-3), 5.01 g of potassium carbonate, and 80 mL of tetrahydrofuran were added. After substituting the system with nitrogen, 0.28 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 5.46 g of a compound represented by the formula (I-8-4).

  To the reaction vessel, 5.46 g of a compound represented by the formula (I-8-4) and 25 mL of tetrahydrofuran were added. The solution was cooled to −70 ° C., and a secBuLi solution was added dropwise. After stirring for 30 minutes, a solution in which 5.40 g of iodine was dissolved in 20 mL of tetrahydrofuran was added dropwise. After stirring for 1 hour, an aqueous sodium thiosulfate solution was added dropwise. Diluted with toluene and washed with water and brine. Purification by column chromatography (silica gel) gave 6.31 g of a compound represented by the formula (I-8-5).

  To the reaction vessel were added 6.31 g of the compound represented by the formula (I-8-5), 4.30 g of the compound represented by the formula (I-7-3), 3.21 g of potassium carbonate, and 70 mL of tetrahydrofuran. After substituting the system with nitrogen, 0.18 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Diluted with toluene and washed with brine. Purification was performed by column chromatography (silica gel) to obtain 4.68 g of a compound represented by the formula (I-8-6).

In a reaction vessel, 4.68 g of a compound represented by the formula (I-8-6), 3.01 g of a compound represented by the formula (I-2-6), 0.13 g of N, N-dimethylaminopyridine, 50 mL of dichloromethane Was added. 1.78 g of diisopropylcarbodiimide was added dropwise and stirred. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 5.24 g of a compound represented by the formula (I-8).
m / z = 692
Example 9 Production of Compound Represented by Formula (I-9)

  To the reaction vessel, 5.00 g of the compound represented by the formula (I-9-1), 10.4 g of the compound represented by the formula (I-9-2), 6.82 g of potassium carbonate, and 50 mL of tetrahydrofuran were added. After replacing the system with nitrogen, 0.38 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Dilute with toluene and wash with brine. Purification was performed by column chromatography (silica gel) to obtain 5.39 g of a compound represented by the formula (I-9-3).

  To the reaction vessel was added 5.39 g of the compound represented by formula (I-9-3), 4.53 g of the compound represented by formula (I-9-4), 3.75 g of potassium carbonate, 50 mL of ethanol, and 25 mL of water. It was. After substituting the system with nitrogen, 0.21 g of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. Dilute with ethyl acetate and wash with hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) to obtain 4.32 g of a compound represented by the formula (I-9-5).

In a reaction vessel, 4.32 g of the compound represented by the formula (I-9-5), 3.53 g of the compound represented by the formula (I-2-6), 0.15 g of N, N-dimethylaminopyridine, and 50 mL of dichloromethane. Was added. After adding 2.08 g of diisopropylcarbodiimide dropwise, the mixture was stirred. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 4.57 g of a compound represented by the formula (I-9).
m / z = 600
Example 10 Production of Compound Represented by Formula (I-10)

  To the reaction vessel, 5.00 g of a compound represented by the formula (I-10-1), 0.28 g of pyridinium p-toluenesulfonate, and 50 mL of dichloromethane were added. While cooling with ice, 2.21 g of 3,4-dihydro-2H-pyran was added dropwise. After stirring, the mixture was washed with saturated aqueous sodium hydrogen carbonate and brine. Purification by column chromatography (alumina) gave 6.16 g of a compound represented by the formula (I-10-2).

  To the reaction vessel, 6.16 g of the compound represented by the formula (I-10-2), 60 mL of tetrahydrofuran and 15% aqueous sodium hydroxide solution were added and stirred with heating. After neutralization with 5% hydrochloric acid, the crystals were filtered. By drying, 4.71 g of a compound represented by the formula (I-10-3) was obtained.

  The compound represented by the formula (I-10-4) was produced by the method described in Journal of Materials Chemistry C: Materials for Optical and Electronic Devices, 2 (5), 891-900; In a reaction vessel 4.71 g of the compound represented by the formula (I-10-3), 5.12 g of the compound represented by the formula (I-10-4), 0.19 g of N, N-dimethylaminopyridine, 50 mL of dichloromethane. Was added. After distilling 2.59 g of diisopropylcarbodiimide, the mixture was stirred. Purification was performed by column chromatography (alumina) to obtain 5.72 g of a compound represented by the formula (I-10-5).

  To the reaction vessel were added 5.72 g of the compound represented by the formula (I-10-5), 80 mL of tetrahydrofuran, and 1 mL of concentrated hydrochloric acid. After stirring, the solvent was distilled off and dispersed and washed. By drying, 3.94 g of a compound represented by the formula (I-10-6) was obtained.

In a reaction vessel, 3.94 g of the compound represented by formula (I-10-6), 2.11 g of the compound represented by formula (I-2-6), 0.09 g of N, N-dimethylaminopyridine, 50 mL of dichloromethane Was added. After adding 1.24 g of diisopropylcarbodiimide dropwise, the mixture was stirred. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 3.54 g of a compound represented by the formula (I-10).
m / z = 780
The compounds represented by the following formulas (I-11) to (I-106) were produced using the same method and a known method.

(Examples 11 to 30 and Comparative Examples 1 to 10)
Compounds represented by formula (I-1) to formula (I-10) described in Example 1 to Example 10, compound (R-1) described in Patent Document 1, compound (R-) described in Patent Document 2 2) The compound (R-3) described in Patent Document 3, the compound (R-4) described in Non-Patent Document 1, and the compound (R-5) described in Patent Document 5 were evaluated.

  A liquid crystal composition composed of compounds represented by the following compounds (X-1) to (X-4) was used as a base liquid crystal (X) for evaluation. Table 1 shows the composition of the base liquid crystal (X).

  In this base liquid crystal (X), 0.1 part by weight of the compound to be evaluated and the following polymerizable compound known in the art

Was added and dissolved to prepare a polymerizable liquid crystal composition to obtain a polymerizable liquid crystal composition to be evaluated. The polymerizable liquid crystal composition to be evaluated was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. While applying a rectangular wave of 1.8 V at a frequency of 1 kHz, using a high-pressure mercury lamp, irradiation with UV of 320 nm or more is performed at 10 mW / cm ² for 600 seconds to produce a vertical alignment liquid crystal display element (XI) to be evaluated. did.

  Each produced liquid crystal display element (XI) was subjected to UV irradiation for 60 minutes using an ultrahigh pressure mercury lamp USH-500D manufactured by USHIO INC., And then the voltage holding ratio VHR (UV) (%) was measured. A multi-channel liquid crystal display device Model 6254 (manufactured by Toyo Corporation) was used as the measuring device. A source voltage consisting of a square wave with a measurement temperature of 25 ° C. and ± 1 V is applied to the liquid crystal device for 64 microseconds and then cut off. The amount of voltage attenuation during 16.67 msec is measured. In this case, the area ratio relative to this was calculated as a voltage holding ratio (VHR (initial) (%)). The results are shown in Table 2.

  From the table, the compounds represented by the formulas (I-1) to (I-10) of the invention of the present application are all compared with the comparative compound (R-1) to the comparative compound (R-5). It can be seen that the voltage holding ratio of the display element is unlikely to decrease when UV irradiation is performed.

Further, after applying a voltage of 7.5 V to the display element and heating it at 80 ° C. for 240 hours, the degree of discoloration of the display element was evaluated using a spectrophotometer. About the vertical alignment liquid crystal display element (XI-0) produced using the polymerizable liquid crystal composition in which 0.3 part by weight of the polymerizable compound (X-5) is added to the base liquid crystal (X) and dissolved, heating is performed. The difference between the yellowness YI _{XI-0 (A) of the} previous display element and the yellowness YI _{XI-0 (B)} of the display element after heating ΔYI _XI-0 = YI _{XI-0 (B)} -YI _{XI-0 ( A)} was calculated. JASCO UV / VIS Spectrophotometer V-560 was used for the measurement of yellowness. The formula is
YI = 100 (1.28X-1.06Z) / Y
(In the formula, YI represents yellowness, and X, Y, and Z represent tristimulus values in the XYZ color system.) Also, changes in yellowness before and after heating of each display element to which the compound to be evaluated was added. The amount was similarly measured, and the degree of color change α was calculated according to the following formula.
α (%) = ΔYI _{(display element)} / ΔYI _XI-0 × 100
(In the formula, ΔYI _{(display element)} = YI _{(display element) (B)} −YI _{(display element) (A),} and the yellowness before heating of the display element to be evaluated is represented by YI _{(display element) (A)} The yellowness after heating represents YI _{(display element) (B)} . When α is 100%, it means that the degree of discoloration is equivalent to that of the display element (XI-0), and the value of α is The smaller the value, the smaller the degree of discoloration. The results are shown in Table 3.

  From the table, the compounds represented by the formulas (I-1) to (I-10) of the present invention are all compared with the comparative compound (R-1) to the comparative compound (R-5). It can be seen that discoloration hardly occurs in the display element when heated.

  From the above results, the compounds represented by the formulas (I-1) to (I-10) according to the present invention described in Examples 1 to 10 are added to the liquid crystal composition to obtain a PSA type liquid crystal display element. It was found that when the display element was manufactured and UV irradiation was performed, a decrease in voltage holding ratio could be suppressed, and the effect of suppressing discoloration due to heating was high.

Claims (7)

Formula (I)

(In the formula, S represents a spacer group, and when a plurality of S are present, they may be the same or different, and X represents —O—, —S—, —OCH ₂ —, —CH ₂ O. -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _{2- , -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond, but when there are a plurality of X, they may be the same or different ( However,-(X-S) _k -does not include -O-O-, -O-S-, and -S-O-), k represents an integer of 1 to 8, and A ¹ and A ² Are each independently 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, decahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, or tetrahydropyran-2,5-diyl group Wherein these groups may be unsubstituted or substituted by one or more L A plurality of A ² may be the same or different, and Z ¹ represents —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—, —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, a respectively identical ^{if Z 1} appears more M represents an integer of 2 to 6, and R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, Chioisoshiano group or represents an alkyl group having 1 to 20 carbon atoms, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = H—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, the alkyl chain may be linear or branched, L is a fluorine atom, Chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, represents an alkyl group of Chioisoshiano group or 1 to 12 carbon atoms, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH -CO , —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— The alkyl chain may be linear or branched, but when a plurality of L are present, they may be the same or different. ) A compound represented by In the general formula (I), S is one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO—, —OCO—O. -, -CO-NH-, -NH-CO-, -N = CH-, -CH = N-, -CH = CH- or -C≡C- The compound according to claim 1, which represents an alkylene group.   The composition containing the compound as described in any one of Claim 1 or Claim 2.   The liquid crystal composition containing the compound as described in any one of Claim 1 or Claim 2. One or more general formulas (II-1)

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- and may be substituted with one or more hydrogen atoms in the alkyl group May be optionally substituted with a halogen atom, and A ³ and A ⁴ are each independently any one of the following structures:

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). Z ² and Z ³ are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH. _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, L ¹ and L ² each independently represent a fluorine atom, a chlorine atom or a trifluoromethyl group, m ¹ and m ² each independently represent ^{0~3, m} 1 + m ² is 1, 2 or ^{3, a 3,} a ⁴ If Z ² and Z ³ there are multiple, they may be the same or different. The liquid crystal composition of Claim 4 which further contains the compound represented by this. The liquid crystal composition has the general formula (II-3)

(In the formula, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- and may be substituted with one or more hydrogen atoms in the alkyl group May be optionally halogen-substituted, A ⁹ and A ¹⁰ are each independently

(In the structure, one or more —CH ₂ CH ₂ — in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —. -In the phenylene group, one or two or more CH groups may be substituted with a nitrogen atom.), Z ⁶ is a single bond, —CH═CH—, —C≡C—, — CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, and m ⁴ represents 0 to 4. . 6. The liquid crystal composition according to claim 4 or 5, comprising one or more selected from the group consisting of compounds represented by:   Resins, pigments, dyes, resin additives, oils, filters, adhesives, adhesives, oils, fats, inks, printed matter, pharmaceuticals, cosmetics, detergents, architectures using the compound according to claim 1 or claim 2 Materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, optical anisotropic bodies, display elements, electronic materials, automobile parts, aircraft parts, machine parts, agricultural chemicals and foods, and products using them.