WO2017090384A1

WO2017090384A1 - Liquid crystal compound, liquid crystal composition, and display element

Info

Publication number: WO2017090384A1
Application number: PCT/JP2016/082404
Authority: WO
Inventors: 清香野瀬; 須藤　豪; 翔太小坂; 楠本　哲生; 宗矩櫻井
Original assignee: Dic株式会社
Priority date: 2015-11-24
Filing date: 2016-11-01
Publication date: 2017-06-01
Also published as: JPWO2017090384A1

Abstract

The present invention addresses the problem of providing: a liquid crystal compound which has a large negative Δε, a high Tni, a small η, and a large Δn, and can be easily synthesized; a liquid crystal composition which has a large refractive-index anisotropy (Δn), and a negative dielectric-constant anisotropy (Δε) having a large absolute value, is applicable to a narrow-gap LCD, and can be driven by a low voltage; and a liquid crystal display element of VA type, PSA type, PSVA type, or the like. The present invention provides a compound represented by general formula (i), a liquid crystal composition using the same, and a liquid crystal display element using the same.

Description

Liquid crystal compound, liquid crystal composition and display element

The present invention relates to a liquid crystal compound.

Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical alignment) type using TFT (thin film transistor), and IPS (in-plane Switching) type or FFS (fringe field switching) type. The main characteristics required for the liquid crystal composition are (1) being stable against external stimuli such as moisture, air, heat, light, etc. There are four examples: (3) low viscosity, and (4) low driving voltage. For each display element, dielectric anisotropy (Δε) and refractive index anisotropy (Δn) In general, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to obtain an optimal value.

Among the characteristics of the liquid crystal composition described above, for Δε, a positive value composition and a negative value composition are used separately. Among these, examples of a display method using a liquid crystal material in which Δε has a negative value include ECB type, VA type, and further FFS type. Among these, the VA display system is used for applications such as televisions, and is required to have a high speed and a wide viewing angle. At this time, the liquid crystal composition is required to have low voltage driving, high-speed response, and a wide operating temperature range. That is, Δε is negative, the absolute value is large, the viscosity (η) is low, and a high nematic phase-isotropic liquid phase transition temperature (T _ni ) is required. Further, from the setting of Δn × d, which is the product of refractive index anisotropy (Δn) and cell gap (d), Δn of the liquid crystal composition needs to be adjusted to an appropriate range according to d. In order to cope with high-speed response, the cell gap tends to be designed to be small, and in this case, it is required to increase Δn of the liquid crystal composition.

Also, PSA (Polymer Sustained Alignment) type liquid crystal display devices and PSVA (Polymer Stabilized Vertical Alignment) type liquid crystal display devices have been developed as liquid crystal display elements that can obtain high-speed response and high contrast. A PSA or PSVA type liquid crystal display element is a liquid crystal molecule in which a polymerizable compound-containing liquid crystal composition comprising a non-polymerizable liquid crystal composition and a polymerizable compound is arranged between substrates, and a voltage is applied between the substrates in some cases. The polymerized compound is polymerized by irradiating ultraviolet rays or the like in the aligned state, and the alignment state of the liquid crystal is stored in the cured product. Moreover, when applying to an IPS (in-plane switching) type | mold liquid crystal display element, it can produce by hardening in a no-application state. When applied to such a liquid crystal display element, a composition resistant to ultraviolet rays is required.

In order to satisfy the above requirements, various liquid crystal compounds have been developed so far. As a liquid crystal material having a negative Δε, a liquid crystal compound having the following 2,3-difluorophenylene skeleton has been proposed (see Patent Document 1).

However, such a compound has a relatively large absolute value of Δε (| Δε |), but since Δn is small, it is not effective for realizing a high-speed response by reducing d, and Tni is low. When these compounds are added to the liquid crystal composition, there is a problem that Tni of the liquid crystal composition is lowered.

Further, as compounds having a high Tni and a large Δn, the following compounds having a tolan skeleton are known, but they have a high viscosity (η) and are insufficient for the demand for a high-speed response (non- (See Patent Documents 1 and 2).

From the above, a liquid crystal compound having a large | Δε |, a small η, and a large Δn is desired. Moreover, since it is used for the liquid crystal composition for TFT, development of the manufacturing method and manufacturing intermediate which can manufacture at low cost with few trace impurities was calculated | required.

Japanese Patent Application No. 1-565666

The problem to be solved by the present invention is to provide a liquid crystal compound having a large negative Δε, a high Tni, a small η, a large Δn, and a compound that can be easily synthesized, together with a refractive index anisotropy (Δn). Liquid crystal composition having a large negative value and a negative dielectric anisotropy (Δε) having a large absolute value, compatible with a narrow gap LCD, and capable of driving at a low voltage, and a liquid crystal such as a VA type, a PSA type, and a PSVA type It is to provide a display element.

The inventor of the present application has intensively studied to solve the above problems, and as a result, the present invention has been completed.
That is, the present invention relates to the general formula (i)

(Wherein R ⁱ¹ represents an alkenyl group having 3 to 15 carbon atoms, and one —CH ₂ — present in the alkenyl group or two or more non-adjacent —CH ₂ — represents —O— , —S—, —COO—, —OCO—, —CO—, —CH═CH—, —C≡C— or a ring structure,
R ⁱ² represents an alkyl group having from 1 to 15 carbon atoms, one -CH ₂ present in the alkyl group - or nonadjacent two or more -CH ₂ - is -O -, - S- , —COO—, —OCO—, —CO—, —CH═CH—, —C≡C— or a ring structure,
n ⁱ¹ represents 1, 2 or 3,
X ⁱ¹ and X ⁱ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethoxy group. And a liquid crystal composition containing the compound and a display element.

The liquid crystal compound according to the present invention has a low viscosity, a high isotropic transition temperature, a high compatibility, a high refractive index anisotropy, and is hardly deteriorated by heat or light. When the liquid crystal composition using the liquid crystal compound according to the present invention is used, a high-speed response liquid crystal display element can be provided.

In general formula (i), R ⁱ¹ is preferably an alkenyl group having 3 to 8 carbon atoms, and particularly preferably an alkenyl group having 3 to 5 carbon atoms, in order to reduce the viscosity. Moreover, it is preferable that it is linear.

R ⁱ² is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms in order to reduce the viscosity, and an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. Particularly preferred is an alkenyl group of ˜5. Moreover, it is preferable that it is linear. In order to increase miscibility with other liquid crystal components, it is preferable that R ⁱ¹ and R ⁱ² are different, and it is preferable that the number of carbon atoms is different.

n ⁱ¹ is preferably 1 or 2.

X ⁱ¹ and X ⁱ² are preferably both a hydrogen atom, a fluorine atom, or one is a hydrogen atom and the other is a fluorine atom.

The number of fluorine atoms in the molecule is preferably 0 to 2, preferably 2 as a compound with a negative Δε, and 0 or 1 as a neutral compound with a Δε of about −1 to 1. It is preferable that

In general formula (i), n ⁱ¹ is 1 or 2, and X ⁱ¹ and X ⁱ² are each independently preferably a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethoxy group. In (i), it is more preferable that n ⁱ¹ is 2, and X ⁱ¹ and X ⁱ² are each independently a fluorine atom, a chlorine atom, a trifluoromethyl group, or a trifluoromethoxy group. In particular, it is particularly preferable that n ⁱ¹ is 2 and that X ⁱ¹ and X ⁱ² are both fluorine atoms.

In order to exhibit negative Δε and increase | Δε |, it is preferable that X ⁱ¹ and X ⁱ² are each independently a fluorine atom, a chlorine atom, a trifluoromethyl group, or a trifluoromethoxy group. In order to increase Tni, n ⁱ¹ is preferably 2 or 3. In order to reduce the viscosity, n ⁱ¹ is preferably 1 or 2, and X ⁱ¹ and X ⁱ² are each independently a hydrogen atom or a fluorine atom. In order to increase Δn, n ⁱ¹ is preferably 2 or 3.

Specific examples of preferable compounds of the compound represented by the general formula (i) of the present invention are shown below, but the present invention is not limited thereto.

The compound represented by general formula (i) is preferably a compound represented by general formula (i-1) to (i-2).

^{^{^{(Wherein, R i1, R i2, X}}} i1 and ^{X i2} in the general formula (i) represents the same meaning as ^R ^{^i1,} ^R ^i2, ^X i1 and ^{X i2.)}
R ⁱ¹ is preferably an alkenyl group having 3 to 8 carbon atoms, particularly preferably an alkenyl group having 3 to 5 carbon atoms, in order to reduce the viscosity. Moreover, it is preferable that it is linear.

As the compound represented by the general formula (i-1) (synonymous with the general formula (ia)), the following general formulas (ia-1) to (ia-5) are particularly preferable.

As the compound represented by the general formula (i-2) (synonymous with the general formula (ib)), the following general formulas (ib-1) to (ib-5) are particularly preferable.

In the present invention, the compound represented by the general formula (i) can be produced as follows. Of course, the spirit and scope of the present invention are not limited by these production examples.
(Production Method 1) Synthesis Method (1) of Compound Represented by General Formula (i)

^{^{^{(Wherein, R i1, R i2, X}}} i1, X i2 and ^{n i1} are as defined ^{^{^{R i1, R i2, X i1}}} , X i2 and ^{n i1} in formula ^{(i), R i3} and R ⁱ⁴ independently represents a methyl group, an ethyl group, or a propyl group, or R ⁱ³ and R ⁱ⁴ have a cyclic structure, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, or —CH ₂ C (CH ₃ ) represents ₂ CH ₂ —)
The compound represented by the general formula (S-3) is obtained by reacting the compound represented by the general formula (S-1) with the compound represented by the general formula (S-2). Several reactions can be used depending on the choice of X ⁱ³ substituent in -1).

When a compound in which ^Xi3 represents chlorine, bromine, iodine, benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyloxy group is used, the hydroxyl group of the general formula (S-2) is A method of reacting with the general formula (S-1) as a phenolate with a base can be used. Examples of the base used in this case include metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred. Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.

Any reaction solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether.Examples of chlorine solvents include dichloromethane, 1,2-dichloroethane, and carbon tetrachloride. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane, aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, and polar solvents include N, N-dimethylformamide, Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. Among these, ether solvents such as tetrahydrofuran and diethyl ether and polar solvents such as N, N-dimethylformamide are more preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

The reaction temperature can be from the freezing point of the solvent to the reflux temperature range, but is preferably 0 ° C to 150 ° C, more preferably 30 ° C to 120 ° C. The generated phenolate may be isolated once and then reacted with the compound represented by the general formula (S-5), or may be reacted without isolation, but it is not isolated for ease of work. It is better to react.

When a compound in which ^Xi3 represents a hydroxyl group is used, Mitsunobu reaction can be used. The Mitsunobu reaction is a reaction in which alcohol and a wide variety of nucleophiles having active protons are dehydrated, and uses a combination of triphenylphosphine and an azodicarboxylic acid derivative or maleic acid derivative. Specifically, the compound represented by the general formula (S-2) and the alcohol derivative represented by the general formula (S-1) are reacted in the presence of a trisubstituted phosphine derivative and an azodicarboxylic acid derivative. A compound represented by (S-3) is obtained.

Examples of the trisubstituted phosphine derivative include trialkylphosphine and triphenylphosphine, but triphenylphosphine is preferable. Various compounds are used as azodicarboxylic acid derivatives, and it is possible to use maleic acid derivatives instead of azodicarboxylic acid derivatives, but the combination of triphenylphosphine and azodicarboxylic acid derivatives is easier to handle. Is desirable. Examples of the azodicarboxylic acid derivative include diethyl azodicarboxylate, diisopropyl azodicarboxylate, tetramethyl azodicarboxamide, tetrapropyl azodicarboxyamide, 1,1 '-(azodicarbonyl) dipiperidine. Diethyl azodicarboxylate and diisopropyl azodicarboxylate are preferred for ease of handling, and diisopropyl azodicarboxylate is more preferred for ease of handling.

Any reaction solvent may be used as long as it allows the reaction to proceed appropriately, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, and the like can be preferably used. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether. Examples of chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride. Preferable examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane and octane, and examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. Of these, ether solvents such as tetrahydrofuran and aromatic solvents such as toluene are more preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

The reaction temperature can be from the freezing point of the solvent to the reflux temperature range, but is preferably 0 ° C to 150 ° C, more preferably 0 ° C to 30 ° C.

A compound represented by the general formula (S-4) can be obtained by oxidizing the compound represented by the general formula (S-3). This oxidation can be carried out by deprotonation with an organometallic reagent, reaction with a trialkyl borate to form a boron compound, and subsequent action of an oxidizing agent. Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred. Examples of organometallic reagents include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide, lithium 2,2,4,4-tetramerpiperidide, etc. N-Butyllithium, sec-butyllithium and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide which can be efficiently deprotonated are more preferable. In the deprotonation, a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent. The reaction temperature at the time of deprotonation is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.

As the trialkyl borate, trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate are preferably used, but trimethyl borate and triisopropyl borate are more preferred from the viewpoint of availability and handling. As the combination of trialkyl borate and organometallic reagent, any of the above-mentioned combinations can be used, but the combination of sec-butyl lithium and trimethyl borate, and the combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl A combination of amide and triisopropyl borate is more preferred. The reaction temperature during boriding is preferably from -100 ° C to -20 ° C, more preferably from -78 ° C to -40 ° C. The obtained boron compound may be isolated once or may be reacted with an oxidizing agent without isolation. Further, the obtained boron compound may be hydrolyzed and converted into a boric acid compound and then reacted with an oxidizing agent.

As the oxidizing agent, hydrogen peroxide water, peracetic acid or performic acid is preferably used. The reaction temperature is preferably -78 ° C to 70 ° C, more preferably 0 ° C to 50 ° C. Moreover, water may be contained in the solvent at the time of reaction with an oxidizing agent.

The compound represented by the general formula (S-6) is obtained by reacting the compound represented by the general formula (S-4) with the compound represented by the general formula (S-5). Several reactions can be used depending on the choice of X ⁱ⁴ substituent in -5).

When a compound in which ^Xi3 represents chlorine, bromine, iodine, benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyloxy group is used, the hydroxyl group of the general formula (S-4) is A method of reacting with the general formula (S-5) as a phenolate with a base can be used. Examples of the base used in this case include metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred. Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.

When a compound in which ^Xi4 represents a hydroxyl group is used, Mitsunobu reaction can be used. The Mitsunobu reaction is a reaction in which an alcohol and a wide variety of nucleophiles having active protons are dehydrated and used in combination with triphenylphosphine and an azodicarboxylic acid derivative or maleic acid derivative. Specifically, the compound represented by the general formula (S-4) and the alcohol derivative represented by the general formula (S-5) are reacted in the presence of a trisubstituted phosphine derivative and an azodicarboxylic acid derivative. A compound represented by (S-6) is obtained.

Examples of the trisubstituted phosphine derivative include trialkylphosphine and triphenylphosphine, but triphenylphosphine is preferable. Various compounds are used as azodicarboxylic acid derivatives, and it is possible to use maleic acid derivatives instead of azodicarboxylic acid derivatives, but the combination of triphenylphosphine and azodicarboxylic acid derivatives is easier to handle. Is desirable. Examples of azodicarboxylic acid derivatives include diethyl azodicarboxylate, diisopropyl azodicarboxylate, tetramethyl azodicarboxyamide, tetrapropyl azodicarboxyamide, 1,1 '-(azodicarbonyl) dipiperidine, Diethyl azodicarboxylate and diisopropyl azodicarboxylate are preferred for ease of handling, and diisopropyl azodicarboxylate is more preferred for ease of handling.

The deprotection of the compound represented by the general formula (S-6) is preferably performed under acidic conditions. Examples of the acid used include protonic acids such as formic acid, acetic acid, trifluoroacetic acid, oxalic acid, and p-toluenesulfonic acid, and Lewis acids such as boron trifluoride. Formic acid is preferably used.

Any reaction solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, ketone solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like are preferably used. And may be reacted without solvent. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of chlorine solvents include dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride. Acetone, 2-butanone and the like as ketone solvents, pentane, hexane, cyclohexane, heptane and octane as hydrocarbon solvents, and benzene, toluene, xylene, mesitylene, chlorobenzene and dibenzene as aromatic solvents. Preferable examples include chlorobenzene and acetonitrile, dimethyl sulfoxide and the like as polar solvents. Of these, hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane and octane, and aromatic solvents such as benzene, toluene and xylene are more preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

The reaction temperature can be from the freezing point of the solvent to the reflux temperature range, but is preferably 0 ° C to 100 ° C, more preferably 30 ° C to 60 ° C.

The compound represented by the formula (S-7) thus obtained may be obtained as a mixture of a cis isomer and a trans isomer relating to the cyclohexane ring, but must be a trans isomer for use as an intermediate of a liquid crystal compound. Is preferred. With respect to the cyclohexane ring of the compound represented by the formula (S-7), cis-trans isomerization can be performed by allowing a base to act as necessary, and an excess of trans isomer can be obtained. The base used at this time is preferably sodium hydroxide, potassium hydroxide or the like, the reaction solvent is preferably methanol, ethanol or tetrahydrofuran, the reaction temperature is preferably -40 ° C to 20 ° C, more preferably -20 ° C to 10 ° C. preferable.

A compound represented by the general formula (i) can be obtained by reacting an alkyl phosphorus ylide with the compound represented by the formula (S-7). The phosphorus ylide can be adjusted from a phosphonium salt, a phosphonic acid ester or the like, but is preferably adjusted from an alkyltriphenylphosphonium salt.

When adjusting an ylide using an alkyltriphenylphosphonium salt, a base is allowed to act. As the base to be used, potassium-t-butoxide, n-butyllithium, phenyllithium, sodium hydride and the like are preferable, and potassium-t -Butoxide is more preferred. As the reaction solvent, ether solvents, aromatic solvents, polar solvents and the like can be preferably used. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of aromatic solvents include benzene, toluene, xylene, mesitylene, and the like as polar solvents. A good example is N, N-dimethylformamide. Tetrahydrofuran and toluene are more preferred. Each of the above solvents may be used alone, or two or more solvents may be mixed and used. The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably -40 ° C to 30 ° C, more preferably -20 ° C to 20 ° C. The obtained ylide is preferably reacted with the compound represented by the formula (5) without isolation. Further, a base may be added to the mixture of the alkyltriphenylphosphonium salt and the compound represented by the formula (5). As the alkyltriphenylphosphonium salt, methyltriphenylphosphonium salt is preferable.

In the present invention, a compound represented by general formula (S-1) is used as a starting material, and general formula (S-3), general formula (S-4), general formula (S-6) and general formula (S— 7) The compound represented by the general formula (i) is produced via the compound represented by the formula (S), and the compound represented by the general formula (S-3) is used as a starting material. -4), it is also preferable to produce the compound represented by the general formula (i) via the compound represented by the general formula (S-6) and (S-7). 4) Starting from the compound represented by 4), the compound represented by general formula (i) is produced via the compound represented by general formula (S-6) and (S-7). It is also preferable that the compound represented by the general formula (S-6) is used as a starting material and the compound represented by the general formula (i) via the compound represented by the general formula (S-7). It is also preferred to produce a compound represented by the compound represented by formula (S-7) as a starting material, it is also preferable to produce a compound represented by the general formula (i).
(Production Method 2) Method for Synthesizing Compound Represented by General Formula (i) (2)

^{^{^{(Wherein, R i1, R i2, X}}} i1, X i2 and ^{n i1} are as defined ^{^{^{R i1, R i2, X i1}}} , X i2 and ^{n i1} in formula ^{(i), R i3} and R ⁱ⁴ independently represents a methyl group, an ethyl group, or a propyl group, or R ⁱ³ and R ⁱ⁴ have a cyclic structure, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, or —CH ₂ C (CH ₃ ) represents ₂ CH ₂ —)
The compound represented by the general formula (S-6) is obtained by reacting the compound represented by the general formula (S-1) with the compound represented by the general formula (S-8). Several reactions can be used depending on the choice of X ⁱ³ substituent in -1).

When a compound in which ^Xi3 represents chlorine, bromine, iodine, benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyloxy group is used, the hydroxyl group of the general formula (S-8) is A method of reacting with the general formula (S-1) as a phenolate with a base can be used. Examples of the base used in this case include metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred. Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.

When a compound in which ^Xi3 represents a hydroxyl group is used, Mitsunobu reaction can be used. The Mitsunobu reaction is a reaction in which an alcohol and a wide variety of nucleophiles having active protons are dehydrated and used in combination with triphenylphosphine and an azodicarboxylic acid derivative or maleic acid derivative. Specifically, the compound represented by the general formula (S-8) and the alcohol derivative represented by the general formula (S-1) are reacted in the presence of a trisubstituted phosphine derivative and an azodicarboxylic acid derivative. A compound represented by (S-6) is obtained.

The present invention provides a compound represented by general formula (i) via a compound represented by general formula (S-6) and (S-7) using a compound represented by general formula (S-1) as a starting material. The compound represented by the general formula (i) is produced from the compound represented by the general formula (S-6) as a starting material via the compound represented by the general formula (S-7). It is also preferable to produce a compound represented by general formula (i) using a compound represented by general formula (S-7) as a starting material.

The composition of the present invention preferably contains one or more compounds represented by the general formula (N-1) together with the compound represented by the general formula (i). Represented by the general formula (N-1) is a dielectrically negative compound (the sign of Δε is negative and its absolute value is greater than 2).

(Wherein R ^N11 and R ^N12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently Optionally substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
Independently A ^N11 and ^{A N12,} respectively (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is -O And (b) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ are replaced with —N =). May be.)
(C) (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6- One —CH═ present in a diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ are replaced by —N═. Is also good.)
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^N11 and Z ^N12 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —OCF ₂ -, -CF ₂ O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
Although n ^N11 and ^{n N12} each represent independently an integer of ^{^{0 ~ 3, n N11 + n}} N12 is 1, 2 or ^3, if ^{^{A N11 ~ A N12, Z N11}} ~ Z N12 there is a plurality, They may be the same or different. )
The compound represented by the general formula (N-1) is preferably a compound having a negative Δε and an absolute value larger than 3.

In general formula (N-1), R ^N11 and R ^N12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or An alkenyloxy group having 2 to 8 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 2 to 5 carbon atoms. An alkenyloxy group is preferred, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferred, and an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is further preferred. An alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

Further, when the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms and carbon An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain A straight-chain alkoxy group having 1 to 4 carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

A ^N11 and A ^N12 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic for improving the response speed, and trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

More preferably, it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ^N11 and ^{Z N12} are each _{independently} _{-CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CH 2 O-, —CH ₂ CH ₂ — or a single bond is more preferable, —CH ₂ O— or a single bond is particularly preferable.

n ^N11 + n ^N12 is preferably 1 or 2, a combination in which n ^N11 is 1 and n ^N12 is 0, a combination in which n ^N11 is 2 and n ^N12 is 0, n ^N11 is 1 and n ^N12 is 1 A certain combination is preferred in which n ^N11 is 2 and n ^N12 is 1.

The lower limit of the preferable content of the compound represented by the formula (N-1) with respect to the total amount of the composition of the present invention is 1%, 10%, 20%, 30% , 40%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

In particular, the compounds represented by the following general formulas (N-1a) to (N-1d) can be exemplified as preferred compounds when combined with the compound represented by the general formula (i).

^{(Wherein, R N11} and ^{R N12} are as defined ^{R N11} and ^{R N12} in the general formula ^{(N-1), n Na11} represents 0 or ^{1, n NB11} represents 0 or ^{1, n NC11} is Represents 0 or 1, and n ^Nd11 represents 0 or 1)
In the case where a composition having a low response speed and a high response speed is required, the lower limit value is preferably low and the upper limit value is preferably low. Furthermore, when the composition of the present invention keeps Tni high and a composition having good temperature stability is required, the above lower limit value is preferably low and the upper limit value is preferably low. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is increased and the upper limit value is high.

More specifically, the compound represented by the general formula (N-1) is a compound selected from the group of compounds represented by the general formulas (N-1-1) to (N-1-21). preferable.

The compound represented by the general formula (N-1-1) is the following compound.

(In the formula, R ^N111 and R ^N112 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group or a pentyl group. ^RN112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group or a butoxy group.

The compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

Further, the compound represented by the general formula (N-1-1) is a compound selected from the group of compounds represented by the formula (N-1-1.1) to the formula (N-1-1.14). Preferably, it is a compound represented by the formulas (N-1-1.1) to (N-1-1.4), and the formula (N-1-1.1) and the formula (N The compound represented by -1-1.3) is preferable.

The compounds represented by the formulas (N-1-1.1) to (N-1-1.4) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, 20%, 23% 25% 27% 30% 33% 35% The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

The compound represented by the general formula (N-1-2) is the following compound.

(In the formula, R ^N121 and R ^N122 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group or a pentyl group. ^RN122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and includes a methyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group. preferable.

The compound represented by the general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, it is more effective to set the content lower. When emphasizing T _NI , the content is preferable. Setting a large number of is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-2) with respect to the total amount of the composition of the present invention is 5%, 7%, 10%, 13% 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37% 40% and 42%. The upper limit of the preferable content is 50%, 48%, 45%, 43%, 40%, 38%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% %, 8%, 7%, 6%, 5%.

Further, the compound represented by the general formula (N-1-2) is a compound selected from the group of compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13). Preferably, the formula (N-1-2.3) to the formula (N-1-2.7), the formula (N-1-2.10), the formula (N-1-2.11) and the formula The compound represented by (N-1-2.13) is preferable, and when importance is placed on the improvement of Δε, the formula (N-1-2.3) to the formula (N-1-2.7) in the compounds _represented, when emphasizing improvements in _{T NI} formula (N-1-2.10), formula (N-1-2.11) and formula (N-1-2.13) It is preferable that it is a compound represented by these.

The compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount of is 5%, 10%, 13%, 15%, 17%, 20%, 23 %, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

The compound represented by the general formula (N-1-3) is the following compound.

(In the formula, R ^N131 and R ^N132 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-3) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-3) is a compound selected from the group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.11). Preferably, it is a compound represented by the formulas (N-1-3.1) to (N-1-3.7), and the formula (N-1-3.1) and the formula (N -1-3.2), formula (N-1-3.3), formula (N-1-3.4) and compounds represented by formula (N-1-3.6) are preferred.

The compounds represented by formula (N-1-3.1) to formula (N-1-3.4) and formula (N-1-3.6) may be used alone or in combination. Is possible, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) ) And a combination of two or three selected from formula (N-1-3.6) are preferred. The lower limit of the preferred content of these compounds alone or with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15%, 17%, 20% %. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-4) is the following compound.

^{(Wherein, R N141} and ^{R N142} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N).)
R ^N141 and ^{R N142} are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5 preferably a methyl group, a propyl group, an ethoxy Group or butoxy group is preferred.

The compound represented by the general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-4) with respect to the total amount of the composition of the present invention is 3%, 5%, 7%, 10% 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.

Further, the compound represented by the general formula (N-1-4) is a compound selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14). Preferably, it is a compound represented by the formulas (N-1-4.1) to (N-1-4.4), and the formula (N-1-4.1) and the formula (N The compound represented by -1-4.2) is preferable.

The compounds represented by formulas (N-1-4.1) to (N-1-4.4) can be used singly or in combination, but the compounds of the present invention The lower limit of the preferable content of these compounds alone or with respect to the total amount is 3%, 5%, 7%, 10%, 13%, 15%, 17% And 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.

The compound represented by the general formula (N-1-5) is the following compound.

(In the formula, R ^N151 and R ^N152 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N151 and R ^N152 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethyl group, a propyl group, or a butyl group. Is preferred.

The compound represented by the general formula (N-1-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-5) with respect to the total amount of the composition of the present invention is 5%, 8%, 10%, 13% 15%, 17%, 20%. The upper limit of the preferable content is 35%, 33%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the composition of the present invention. %, 18%, 15% and 13%.

Further, the compound represented by the general formula (N-1-5) is a compound selected from the group of compounds represented by the formula (N-1-5.1) to the formula (N-1-5.6). It is preferable that a compound represented by the formula (N-1-3.2 and the formula (N-1-3.4) is preferable.

The compounds represented by formula (N-1-3.2) and formula (N-1-3.4) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 8%, 10%, 13%, 15%, 17%, 20% The upper limit of the preferred content is 35%, 33%, 30%, 28%, 25%, and 23% with respect to the total amount of the composition of the present invention. Yes, 20%, 18%, 15%, 13%.

The compound represented by the general formula (N-1-10) is the following compound.

(In the formula, R ^N1101 and R ^N1102 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-10) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-10) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-10) is a compound selected from the group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.11). Preferably, it is a compound represented by the formulas (N-1-10.1) to (N-1-10.5), and the formula (N-1-10.1) and the formula (N The compound represented by (1-10.2) is preferable.

The compounds represented by the formula (N-1-10.1) and the formula (N-1-10.2) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-11) is the following compound.

(In the formula, R ^N1111 and R ^N1112 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

The compound represented by the general formula (N-1-11) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-11) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-11) is a compound selected from the group of compounds represented by the formula (N-1-11.1) to the formula (N-1-11.15). Preferably, it is a compound represented by the formulas (N-1-11.1) to (N-1-11.15), and is preferably a compound represented by the formula (N-1-11.2) or the formula (N-- The compound represented by 1-11.4) is preferable.

The compounds represented by the formula (N-1-11.2 and the formula (N-1-11.4) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the amount is 35%, 30%, 28%, 25%, 23%, 20%, 18% with respect to the total amount of the composition of the present invention. Yes, 15%, 13%.

The compound represented by the general formula (N-1-12) is the following compound.

(In the formula, R ^N1121 and R ^N1122 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. ^RN1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-12) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-12) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-13) is the following compound.

(In the formula, R ^N1131 and R ^N1132 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-13) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-13) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-14) is the following compound.

(In the formula, R ^N1141 and R ^N1142 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N).)
R ^N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-14) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-14) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-15) is the following compound.

(In the formula, R ^N1151 and R ^N1152 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1152 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-15) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-15) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-16) is the following compound.

(In the formula, R ^N1161 and R ^N1162 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-16) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-16) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-17) is the following compound.

(In the formula, R ^N1171 and R ^N1172 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N)).
^RN1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1172 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-17) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-17) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-18) is the following compound.

( ^Wherein , R ^N1181 and R ^N1182 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N)).
^RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-18) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-18) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-20) is the following compound.

(In the formula, R ^N1201 and R ^N1202 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N)).
R ^N1201 and R ^N1202 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.

The compound represented by the general formula (N-1-20) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-20) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-21) is the following compound.

(In the formula, R ^N1211 and R ^N1212 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1211 and R ^N1212 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.

The compound represented by the general formula (N-1-21) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-21) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

It is preferable that the composition of this invention contains 1 type, or 2 or more types of compounds represented by general formula (L). The compound represented by the general formula (L) corresponds to a dielectrically neutral compound (Δε value is −2 to 2).

(Wherein R ^L1 and R ^L2 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently Optionally substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^L1 represents 0, 1, 2 or 3,
A ^L1 , A ^L2 and A ^L3 each independently represent (a) a 1,4-cyclohexylene group (one —CH ₂ — present in the group or two or more —CH ₂ — not adjacent to each other). May be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ not adjacent to each other —N May be replaced by =.)
(C) (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6- One —CH═ present in a diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ are replaced by —N═. Is also good.)
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —OCF ₂ -, -CF ₂ O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
When n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different, and when n ^L1 is 2 or 3, and a plurality of Z ^L3 are present, May be the same or different, but excludes compounds represented by general formula (i) and general formula (N-1). )
Although the compound represented by general formula (L) may be used independently, it can also be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention. Alternatively, in another embodiment of the present invention, there are two types, three types, four types, five types, six types, seven types, eight types, nine types, 10 types, More than types.

In the composition of the present invention, the content of the compound represented by the general formula (L) is low-temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, It is necessary to appropriately adjust according to required performance such as dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the composition of the present invention is 1%, 10%, 20%, 30%, 40 %, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, and 25%.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when the composition of the present invention maintains a high Tni and requires a composition having good temperature stability, the above lower limit value is preferably high and the upper limit value is preferably high. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is lowered and the upper limit value is low.

When importance is attached to reliability, R ^L1 and R ^L2 are preferably both alkyl groups, and when importance is placed on reducing the volatility of the compound, it is preferably an alkoxy group, and importance is placed on viscosity reduction. In this case, at least one is preferably an alkenyl group.

The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3, preferably 0 or 1, and 1 is preferred when importance is attached to compatibility with other liquid crystal molecules.

R ^L1 and R ^L2 are each a linear alkyl group having 1 to 5 carbon atoms or a linear alkyl group having 1 to 4 carbon atoms when the ring structure to which R ^L1 is bonded is a phenyl group (aromatic). When the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a straight-chain C 1-5 carbon atom is preferred. Alkyl groups, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

n ^L1 is preferably 0 when importance is attached to the response speed, 2 or 3 is preferred for improving the upper limit temperature of the nematic phase, and 1 is preferred for balancing these. In order to satisfy the properties required for the composition, it is preferable to combine compounds having different values.

A ^L1 , A ^L2, and A ^L3 are preferably aromatic when it is required to increase Δn, and are preferably aliphatic for improving the response speed, and are each independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -It preferably represents a diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

Z ^L1 and Z ^L2 are preferably single bonds when the response speed is important.

The number of halogen atoms in the molecule is preferably 0 or 1.

The compound represented by the general formula (L) is preferably a compound selected from the group of compounds represented by the general formulas (L-1) to (L-7).

The compound represented by the general formula (L-1) is the following compound.

(In the formula, R ^L11 and R ^L12 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L11 and R ^L12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The compound represented by the general formula (L-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content is 1%, 2%, 3%, 5%, 7%, 10%, and 15% with respect to the total amount of the composition of the present invention. %, 20%, 25%, 30%, 35%, 40%, 45%, 50%, and 55%. The upper limit of the preferable content is 95%, 90%, 85%, 80%, 75%, 70%, 65%, based on the total amount of the composition of the present invention. %, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when the composition of the present invention requires a high Tni and a composition having good temperature stability, it is preferable that the lower limit value is moderate and the upper limit value is moderate. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value is low and the upper limit value is low.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-1).

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The compound represented by the general formula (L-1-1) is a compound selected from the group of compounds represented by the formula (L-1-1.1) to the formula (L-1-1.3). And is preferably a compound represented by formula (L-1-1.2) or formula (L-1-1.3), and particularly represented by formula (L-1-1.3). It is preferable that it is a compound.

The lower limit of the preferable content of the compound represented by the formula (L-1-1.3) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%, and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7%, and 6% with respect to the total amount of the composition of the present invention. %, 5%, 3%.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-2).

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The lower limit of the preferable content of the compound represented by the formula (L-1-2) with respect to the total amount of the composition of the present invention is 1%, 5%, 10%, 15% 17%, 20%, 23%, 25%, 27%, 30%, 35%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 42%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 33%, and 30%.

Further, the compound represented by the general formula (L-1-2) is a compound selected from the group of compounds represented by the formula (L-1-2.1) to the formula (L-1-2.4). Preferably, it is a compound represented by the formula (L-1-2.2) to the formula (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because the response speed of the composition of the present invention is particularly improved. When obtaining Tni higher than the response speed, it is preferable to use a compound represented by the formula (L-1-2.3) or the formula (L-1-2.4). The content of the compounds represented by formula (L-1-2.3) and formula (L-1-2.4) is not preferably 30% or more in order to improve the solubility at low temperatures.

The lower limit of the preferable content of the compound represented by the formula (L-1-2.2) with respect to the total amount of the composition of the present invention is 10%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38%, and 40%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 43%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, and 22%.

The lower limit of the preferable total content of the compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) with respect to the total amount of the composition of the present invention The values are 10%, 15%, 20%, 25%, 27%, 30%, 35% and 40%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 43%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, and 22%.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-3).

(Wherein R ^L13 and R ^L14 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L13 and R ^L14 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (L-1-3) with respect to the total amount of the composition of the present invention is 1%, 5%, 10%, 13% 15%, 17%, 20%, 23%, 25%, 30%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 40%, 37%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 27%, 25%, 23%, 23%, 20%, 17%, 15%, 13%, 10% %.
Further, the compound represented by the general formula (L-1-3) is a compound selected from the group of compounds represented by the formula (L-1-3.1) to the formula (L-1-3.12). Preferably, it is a compound represented by formula (L-1-3.1), formula (L-1-3.3) or formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferable because the response speed of the composition of the present invention is particularly improved. Further, when obtaining Tni higher than the response speed, the equation (L-1-3.3), the equation (L-1-3.4), the equation (L-1-3.11), and the equation (L− It is preferable to use a compound represented by 1-3.12). Sum of compounds represented by formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12) The content of is not preferably 20% or more in order to improve the solubility at low temperatures.

The lower limit of the preferable content of the compound represented by the formula (L-1-3.1) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, 10%, 8%, and 7% with respect to the total amount of the composition of the present invention. % And 6%.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-4) and / or (L-1-5).

(In the formula, R ^L15 and R ^L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L15 and R ^L16 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (L-1-4) with respect to the total amount of the composition of the present invention is 1%, 5%, 10%, 13% 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition of the present invention. %.

The lower limit of the preferable content of the compound represented by the formula (L-1-5) with respect to the total amount of the composition of the present invention is 1%, 5%, 10%, 13% 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition of the present invention. %.

Furthermore, the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-4.1) to (L-1-5.3). And a compound represented by the formula (L-1-4.2) or the formula (L-1-5.2) is preferable.

The lower limit of the preferable content of the compound represented by the formula (L-1-4.2) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, 10%, 8%, and 7% with respect to the total amount of the composition of the present invention. % And 6%.

Formula (L-1-1.3), Formula (L-1-2.2), Formula (L-1-3.1), Formula (L-1-3.3), Formula (L-1- 3.4), it is preferable to combine two or more compounds selected from the compounds represented by formula (L-1-3.11) and formula (L-1-3.12). -1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by formula (L-1-4.2), and the lower limit of the preferable content of the total content of these compounds is the composition of the present invention. 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18% of the total amount 20% and 23% 25%, 27%, 30%, 33%, 35%, and the upper limit is 80% and 70% with respect to the total amount of the composition of the present invention, 60%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 28%, 25%, 23% and 20%. When emphasizing the reliability of the composition, compounds represented by formula (L-1-3.1), formula (L-1-3.3) and formula (L-1-3.4)) It is preferable to combine two or more compounds selected from the group consisting of formulas (L-1-1.3) and (L-1-2.2) when the response speed of the composition is important. It is preferable to combine two or more compounds selected from the following compounds.

The compound represented by the general formula (L-2) is the following compound.

(In the formula, R ^L21 and R ^L22 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable.

When emphasizing solubility at low temperatures, it is highly effective to set a large amount of content. Conversely, when emphasizing response speed, setting a small amount of content is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (L-2) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7% and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7%, and 6% with respect to the total amount of the composition of the present invention. %, 5%, 3%.

Further, the compound represented by the general formula (L-2) is preferably a compound selected from the group of compounds represented by the formulas (L-2.1) to (L-2.6). A compound represented by formula (L-2.1), formula (L-2.3), formula (L-2.4) and formula (L-2.6) is preferred.

The compound represented by the general formula (L-3) is the following compound.

(In the formula, R ^L31 and R ^L32 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L31 and R ^L32 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the general formula (L-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (L-3) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7% and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7%, and 6% with respect to the total amount of the composition of the present invention. %, 5%, 3%.

When a high birefringence is obtained, the effect is high when the content is set to be large. On the other hand, when high Tni is emphasized, the effect is high when the content is set low. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

Further, the compound represented by the general formula (L-3) is preferably a compound selected from the group of compounds represented by the formulas (L-3.1) to (L-3.4). A compound represented by the formula (L-3.7) from (L-3.2) is preferable.

The compound represented by the general formula (L-4) is the following compound.

(In the formula, R ^L41 and R ^L42 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable. )
The compound represented by the general formula (L-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

In the composition of the present invention, the content of the compound represented by the general formula (L-4) is low-temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, and 30%. 20%, 15%, 10%, 5%.

The compound represented by general formula (L-4) is preferably a compound represented by formula (L-4.1) to formula (L-4.3), for example.

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence, even if the compound represented by the formula (L-4.1) is contained, the formula (L -4.2) Even if it contains a compound represented by formula (L-4.1), it contains both a compound represented by formula (L-4.1) and a compound represented by formula (L-4.2). Or all of the compounds represented by formulas (L-4.1) to (L-4.3) may be included. The lower limit of the preferable content of the compound represented by formula (L-4.1) or formula (L-4.2) with respect to the total amount of the composition of the present invention is 3%, Yes, 7%, 9%, 11%, 12%, 13%, 18%, 21%, and the preferred upper limit is 45, 40% , 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% .

When both the compound represented by formula (L-4.1) and the compound represented by formula (L-4.2) are contained, the amount of both compounds relative to the total amount of the composition of the present invention is The lower limit of the preferred content is 15%, 19%, 24%, and 30%, and the preferred upper limit is 45, 40%, 35%, and 30%. Yes, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (L-4) is preferably, for example, a compound represented by the formula (L-4.4) to the formula (L-4.6). It is preferable that it is a compound represented by this.

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like, even if the compound represented by the formula (L-4.4) is contained, the formula (L -4.5) contains both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5). May be.

The lower limit of the preferable content of the compound represented by the formula (L-4.4) or the formula (L-4.5) with respect to the total amount of the composition of the present invention is 3%, Yes, 7%, 9%, 11%, 12%, 13%, 18%, 21%. Preferred upper limit values are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13% %, 10%, and 8%.

When both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) are contained, the amount of both compounds relative to the total amount of the composition of the present invention is The lower limit of the preferred content is 15%, 19%, 24%, and 30%, and the preferred upper limit is 45, 40%, 35%, and 30%. Yes, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (L-4) is preferably a compound represented by the formula (L-4.7) to the formula (L-4.10), and particularly the formula (L-4. The compound represented by 9) is preferred.

The compound represented by the general formula (L-5) is the following compound.

(In the formula, R ^L51 and R ^L52 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L52 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable.

The compound represented by the general formula (L-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

In the composition of the present invention, the content of the compound represented by the general formula (L-5) includes solubility at low temperature, transition temperature, electrical reliability, birefringence index, process suitability, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, and 30%. , 20%, 15%, 10%, 5% The compound represented by the general formula (L-5) is represented by the formula (L-5.1) or the formula (L-5.2). The compound represented by formula (L-5.1) is particularly desirable.

The lower limit of the preferable content of these compounds with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, and 7%. The upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.

The compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.3) or the formula (L-5.4).

The compound represented by the general formula (L-5) is preferably a compound selected from the group of compounds represented by the formulas (L-5.5) to (L-5.7). The compound represented by L-5.7) is preferred.

The compound represented by the general formula (L-6) is the following compound.

(In the formula, R ^L61 and R ^L62 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L), and X ^L61 and X ^L62 each independently represent a hydrogen atom or a fluorine atom. )
R ^L61 and R ^L62 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one of X ^L61 and X ^L62 is a fluorine atom and the other is a hydrogen atom. Is preferred.

The compound represented by the general formula (L-6) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, and 30%. 20%, 15%, 10%, 5%. When emphasizing to increase Δn, it is preferable to increase the content, and when emphasizing the precipitation at low temperature, it is preferable to decrease the content.

The compound represented by the general formula (L-6) is preferably a compound represented by the formula (L-6.1) to the formula (L-6.9).

There are no particular restrictions on the types of compounds that can be combined, but 1 to 3 types of these compounds are preferably contained, more preferably 1 to 4 types. Further, since the wide molecular weight distribution of the selected compound is also effective for the solubility, for example, one type of the compound represented by the formula (L-6.1) or (L-6.2), the formula (L- 6.4) or one type from the compound represented by (L-6.5), one type from the compound represented by formula (L-6.6) or formula (L-6.7), It is preferable to select one compound from the compounds represented by -6.8) or (L-6.9) and combine them as appropriate. Among them, represented by formula (L-6.1), formula (L-6.3), formula (L-6.4), formula (L-6.6) and formula (L-6.9). It is preferable to include a compound.

Further, the compound represented by the general formula (L-6) is preferably, for example, a compound represented by the formula (L-6.10) to the formula (L-6.17). A compound represented by L-6.11) is preferable.

The compound represented by the general formula (L-7) is the following compound.

^{(Wherein, R L71} and ^{R L72} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), A L71} and ^{A L72} is ^{A L2} and in the general formula (L) independently A ^L3 represents the same meaning, but the hydrogen atoms on A ^L71 and A ^L72 may be each independently substituted with a fluorine atom, Z ^L71 represents the same meaning as Z ^L2 in formula (L), X ^L71 and X ^L72 each independently represent a fluorine atom or a hydrogen atom.)
In the formula, R ^L71 and R ^L72 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and A ^L71 and A ^L72 Are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, the hydrogen atoms on A ^L71 and A ^L72 may be each independently substituted with a fluorine atom, and Z ^L71 is a single group. A bond or COO- is preferable, a single bond is preferable, and X ^L71 and X ^L72 are preferably a hydrogen atom.

There are no particular restrictions on the types of compounds that can be combined, but they are combined according to the required performance, such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, and four kinds.

In the composition of the present invention, the content of the compound represented by the general formula (L-7) includes solubility at low temperature, transition temperature, electrical reliability, birefringence index, process suitability, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5% 7%, 10%, 14%, 16%, 20%. The upper limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present invention is 30%, 25%, 23%, and 20%. 18%, 15%, 10%, 5%.

When an embodiment with high Tni is desired for the composition of the present invention, the content of the compound represented by formula (L-7) is preferably increased, and when an embodiment with low viscosity is desired, the content is It is preferable to reduce the amount.

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.1) to the formula (L-7.4), and the formula (L-7. It is preferable that it is a compound represented by 2).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.11) to the formula (L-7.13). It is preferable that it is a compound represented by 11).

Furthermore, the compound represented by the general formula (L-7) is a compound represented by the formula (L-7.21) to the formula (L-7.23). A compound represented by formula (L-7.21) is preferable.

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.31) to the formula (L-7.34), and the formula (L-7. 31) or / and a compound represented by the formula (L-7.32).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.41) to the formula (L-7.44), and the formula (L-7. 41) or / and a compound represented by formula (L-7.42).

The lower limit of the preferable total content of the compounds represented by the general formulas (i), (L) and (N) with respect to the total amount of the composition of the present invention is 80% and 85%. Yes, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% Yes, 100%. The upper limit of the preferable content is 100%, 99%, 98%, and 95%.

The total of the compounds represented by general formula (i), general formula (L-1) to (L-7) and (M-1) to (M-8) with respect to the total amount of the composition of the present invention The lower limit of the preferable content is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96% 97%, 98%, 99%, 100%. The upper limit of the preferable content is 100%, 99%, 98%, and 95%.

The composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms such as a peracid (—CO—OO—) structure are bonded in the molecule.

When emphasizing the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less with respect to the total mass of the composition. Preferably, it is more preferably 1% or less, and most preferably not substantially contained.

When importance is attached to the stability by UV irradiation, the content of the compound substituted with chlorine atoms is preferably 15% or less, preferably 10% or less, based on the total mass of the composition. % Or less, preferably 5% or less, more preferably 3% or less, and still more preferably substantially not contained.

It is preferable to increase the content of a compound in which all the ring structures in the molecule are 6-membered rings, and the content of the compound in which all the ring structures in the molecule are 6-membered rings is 80% relative to the total mass of the composition. % Or more, more preferably 90% or more, still more preferably 95% or more, and the composition is composed only of a compound in which all of the ring structures in the molecule are all 6-membered rings. Most preferably.

In order to suppress deterioration due to oxidation of the composition, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group as the total mass of the composition. On the other hand, it is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and still more preferably not contained.

When importance is attached to improvement of viscosity and improvement of Tni, the content of a compound having a 2-methylbenzene-1,4-diyl group in the molecule, in which a hydrogen atom may be substituted with a halogen, may be reduced. Preferably, the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, more preferably 8% or less, based on the total mass of the composition. It is more preferably 5% or less, further preferably 3% or less, and still more preferably substantially not contained.

“Substantially not contained” in the present application means that it is not contained except for an unintentionally contained product.

When the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, when the alkenyl group is bonded to cyclohexane, the alkenyl group has 2 to 5 carbon atoms. When the alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are directly bonded. Preferably not.

The composition of the present invention may contain a polymerizable compound in order to produce a liquid crystal display element such as a PS mode, a transverse electric field type PSA mode, or a transverse electric field type PSVA mode. Examples of the polymerizable compound that can be used include a photopolymerizable monomer that undergoes polymerization by energy rays such as light. The structure has, for example, a liquid crystal skeleton in which a plurality of six-membered rings such as biphenyl derivatives and terphenyl derivatives are connected. Examples thereof include a polymerizable compound. More specifically, the general formula (XX)

(Wherein, X ²⁰¹ and X ²⁰² each independently represent a hydrogen atom or a methyl group,
Sp ²⁰¹ and Sp ²⁰² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7, Preferably bonded to an aromatic ring)
Z ²⁰¹ represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —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—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CY ¹ ═CY ² — (Wherein Y ¹ and Y ² each independently represents a fluorine atom or a hydrogen atom), —C≡C— or a single bond;
M ²⁰¹ represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and all 1,4-phenylene groups in the formula have an arbitrary hydrogen atom substituted with a fluorine atom. Also good. ) Is preferred.

X ²⁰¹ and X ²⁰² are each preferably a diacrylate derivative that represents a hydrogen atom, or a dimethacrylate derivative that has a methyl group, and a compound in which one represents a hydrogen atom and the other represents a methyl group. As for the polymerization rate of these compounds, diacrylate derivatives are the fastest, dimethacrylate derivatives are slow, asymmetric compounds are in the middle, and a preferred embodiment can be used depending on the application. In the PSA display element, a dimethacrylate derivative is particularly preferable.

Sp ²⁰¹ and Sp ²⁰² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s —, but at least one of them is a single bond in a PSA display element. A compound in which both represent a single bond or one in which one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) _s — is preferable. In this case, 1 to 4 alkyl groups are preferable, and s is preferably 1 to 4.

Z ²⁰¹ represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond Are preferred, —COO—, —OCO— or a single bond is more preferred, and a single bond is particularly preferred.

M ²⁰¹ represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted by a fluorine atom, but the 1,4-phenylene group or the single bond is preferable. When C represents a ring structure other than a single bond, Z ²⁰¹ is preferably a linking group other than a single bond. When M ²⁰¹ is a single bond, Z ²⁰¹ is preferably a single bond.

From these points, in the general formula ^(XX), the ring structure between ^{Sp 201} and ^{Sp 202} is specifically structured as described next are preferred.

In the general formula (XX), when M ²⁰¹ represents a single bond and the ring structure is formed of two rings, the following formulas (XXa-1) to (XXa-5) are preferably represented, It is more preferable to represent the formula (XXa-3) from (XXa-1), and it is particularly preferable to represent the formula (XXa-1).

(In the formula, both ends shall be bonded to Sp ²⁰¹ or Sp ^202. )
The polymerizable compounds containing these skeletons are optimal for PSA-type liquid crystal display elements because of the alignment regulating power after polymerization, and a good alignment state can be obtained, so that display unevenness is suppressed or does not occur at all.

From the above, as the polymerizable monomer, general formula (XX-1) to general formula (XX-4) are particularly preferable, and among them, general formula (XX-2) is most preferable.

(In the formula, Sp ²⁰ represents an alkylene group having 2 to 5 carbon atoms.)
In the case of adding a monomer to the composition of the present invention, the polymerization proceeds even when no polymerization initiator is present, but may contain a polymerization initiator in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.

The composition in the present invention can further contain a compound represented by the general formula (Q).

(Wherein, R ^Q represents a straight-chain alkyl group or branched alkyl group having from 1 22 carbon atoms, one or two or more CH ₂ groups in the alkyl group, so that the oxygen atoms are not directly adjacent a, -O -, - CH = CH -, - CO -, - OCO -, - COO -, - C≡C -, - CF 2 O -, - OCF 2 - may be replaced by, ^{M Q} is trans Represents a 1,4-cyclohexylene group, a 1,4-phenylene group or a single bond.)
^RQ represents a straight-chain alkyl group or a branched-chain alkyl group having 1 to 22 carbon atoms, and one or more CH ₂ groups in the alkyl group are —O—so that oxygen atoms are not directly adjacent to each other. —, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF ₂ — may be substituted. Linear alkyl group, linear alkoxy group, linear alkyl group in which one CH ₂ group is substituted with —OCO— or —COO—, branched alkyl group, branched alkoxy group, one CH ₂ group is —OCO— Or a branched alkyl group substituted with —COO—, a linear alkyl group having 1 to 20 carbon atoms, a linear alkyl group in which one CH ₂ group is substituted with —OCO— or —COO—, branched Chain alkyl group, branched alkoxy group, one CH ₂ group Is more preferably a branched alkyl group substituted with —OCO— or —COO—. ^MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond, and a trans-1,4-cyclohexylene group or a 1,4-phenylene group is preferred.

More specifically, the compound represented by the general formula (Q) is preferably a compound represented by the following general formula (Qa) to general formula (Qd).

In the formula, R ^Q1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, R ^Q2 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and R ^Q3 is A straight-chain alkyl group having 1 to 8 carbon atoms, a branched-chain alkyl group, a straight-chain alkoxy group or a branched-chain alkoxy group is preferred, and L ^Q is preferably a straight-chain alkylene group or branched-chain alkylene group having 1 to 8 carbon atoms. . Of the compounds represented by general formula (Qa) to general formula (Qd), compounds represented by general formula (Qc) and general formula (Qd) are more preferable.

In the composition of the present invention, the compound represented by the general formula (Q) preferably contains one or two kinds, more preferably contains 1 to 5 kinds, and the content thereof is from 0.001. It is preferably 1%, more preferably 0.001 to 0.1%, and particularly preferably 0.001 to 0.05%.

In the composition containing the polymerizable compound of the present invention, the polymerizable compound contained therein is polymerized by ultraviolet irradiation to impart liquid crystal alignment ability, and the amount of transmitted light is controlled using the birefringence of the composition. Used for liquid crystal display elements. As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (in-plane switching liquid crystal display element) However, it is particularly useful for AM-LCDs and can be used for transmissive or reflective liquid crystal display elements.

The two substrates of the liquid crystal cell used in the liquid crystal 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 of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

The substrate is opposed so that the transparent electrode layer is on the inside. In that case, you may adjust the space | interval of a board | substrate through a spacer. In this case, it is preferable to adjust so that the thickness of the obtained light control layer is 1 to 100 μm. 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 columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

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

As a method for polymerizing a polymerizable compound, an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, active energy rays such as ultraviolet rays or electron beams are irradiated singly or in combination or sequentially. The method of polymerizing by is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out in a state where the polymerizable compound-containing composition is sandwiched between two substrates, at least the substrate on the irradiated surface side must be given adequate transparency to the active energy rays. Don't be. 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 electric field to the polymerizable compound-containing composition. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 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 a horizontal electric field type MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-ray to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a composition, and it is preferable to cut and use an ultraviolet-ray as needed. The intensity of the irradiated ultraviolet light is preferably 0.1 mW / cm 2 to 100 W / cm 2, more preferably 2 mW / cm 2 to 50 W / cm 2. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm 2 to 500 J / cm 2, and more preferably 100 mJ / cm 2 to 200 J / cm 2. When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays.

The liquid crystal display device using the composition of the present invention is useful for achieving both high-speed response and suppression of display failure, and is particularly useful for a liquid crystal display device for active matrix driving. VA mode, PSVA mode, PSA It can be applied to a mode, IPS mode or ECB mode liquid crystal display element.

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. “%” In the compositions of the following examples and comparative examples means “% by mass”. The purity of the compound was analyzed by GC or UPLC. Abbreviations of compounds and reaction solvents are as follows: tetrahydrofuran (THF), lithium diisopropylamide (LDA)
EXAMPLES The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
The following abbreviations are used for the description of compounds in the examples.
(Side chain and linking structure)
-n: -C _n H _{2n + 1} linear alkyl group having n carbon atoms n-: C _n H _{2n + 1-} linear alkyl group having n carbon atoms -On: -OC _n H _{2n +1} linear alkoxyl group of carbon atoms _{_{n nO-: C n H 2n +}} 1 O- carbon atom number n of the linear alkoxyl groups -V: -CH = CH ₂
V-: CH ₂ = CH-
-V1: -CH = CH-CH ₃
1V-: CH ₃ -CH = CH-
-On-: -OCH _n- linear alkoxyl linking group having n carbon atoms -nO-: -CH _n O- linear alkoxyl linking group having n carbon atoms (ring structure)

In the examples, the measured characteristics are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
T _cn : Solid phase (smectic phase) -nematic phase transition temperature (° C)
Δn: Refractive index anisotropy at 20 ° C. Δε: Dielectric anisotropy at 20 ° C. γ ₁ : Rotational viscosity at 20 ° C. (mPa · s)
Example 1 Production of Compound (ia1-301)

(Synthesis of Compound (a1-2)) Under a nitrogen atmosphere, 65.3 g of diisopropylamine and 500 ml of THF were added to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and cooled to −10 ° C. 374 ml of 1.6 M butyllithium / hexane solution was added dropwise at −10 ° C., stirred for 1 hour, and then 137.5 g of compound (a1-1) previously dissolved in 500 ml of THF and 130.0 g of triisopropyl borate. Were simultaneously added dropwise at −10 ° C. and stirred for 1 hour. The temperature of the reaction mixture was raised to 0 ° C., 700 ml of 10% aqueous ammonium chloride solution was added and stirred, the organic layer was separated, and the aqueous layer was further extracted with 200 ml of THF. The obtained organic layers were combined, washed with 10% aqueous ammonium chloride solution (500 ml) and saturated brine (500 ml), dried over anhydrous sodium sulfate. The obtained solution was cooled to 0 ° C., a mixture of 71 g of 30% aqueous hydrogen peroxide and 210 ml of water was added, the temperature was raised to room temperature, and the mixture was stirred for 2.5 hours. After adding 700 ml of aqueous sodium sulfite solution to this reaction mixture, the organic layer was separated, and the aqueous layer was further extracted with 300 ml of THF / toluene (volume ratio 1/2). The obtained organic layers were combined, washed with 500 ml of water and 500 ml of saturated brine, and dried by adding anhydrous sodium sulfate. The obtained solution was concentrated to obtain 189.4 g of a crude product of compound (a1-2).

(Synthesis of Compound (a1-3)) In a reaction vessel equipped with a stirrer, a thermometer and a condenser under a nitrogen atmosphere, 189.4 g of the crude product of Compound (a1-2) obtained as described above, iodinated 72.0 g of methyl, 95.6 g of potassium carbonate and 500 ml of DMF were added, and the mixture was stirred at 80 ° C. for 1.5 hours. After cooling the reaction mixture to room temperature, 1000 ml of THF / toluene (volume ratio 1/1) and 1000 ml of water were added to separate the organic layer, and the aqueous layer was further extracted with 300 ml of toluene. The obtained organic layers were combined, washed with 500 ml of water and 500 ml of saturated brine, and dried by adding anhydrous sodium sulfate. The obtained solution was concentrated to obtain 192.9 g of a crude product of compound (a1-3).

(Synthesis of Compound (a1-4)) Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer and a thermometer, 192.9 g of the crude product of Compound (a1-3) obtained as described above, 800 ml of toluene and formic acid ( 51.3 ml) was added, and the mixture was stirred at 50 ° C. for 3 hours, then cooled to room temperature, and 500 ml of water was added. After extraction with 200 ml of toluene from the aqueous layer, the obtained organic layers were combined and washed with 300 ml of water, 300 ml of saturated aqueous sodium bicarbonate, and 300 ml of saturated brine. The obtained organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 164.3 g of a crude product of compound (a1-4).

(Synthesis of Compound (ia1-301)) 222.5 g of ethyltriphenylphosphonium bromide was dispersed in 500 ml of THF, and 64.7 g of potassium tert-butoxide was added at −20 ° C., followed by stirring for 30 minutes. Thereafter, a solution of 192.9 g of the crude product (a1-4) obtained as described above in 500 ml of toluene was added dropwise and stirred for 1 hour. After adding 30 ml of water, the solvent was distilled off under reduced pressure. To the residue, 600 ml of hexane, 200 ml of toluene, 50 ml of aqueous sodium hypochlorite solution, 450 ml of water and 1000 ml of methanol were added to separate the organic layer, and the aqueous layer was further separated into hexane / toluene ( Extraction was performed at a volume ratio of 3/1) 400 ml. The obtained organic layers were combined, washed twice with 450 ml of water / methanol (volume ratio 2/1), dried over anhydrous sodium sulfate. The obtained solution was concentrated to obtain 193.2 g of a crude product of compound (ia1-301). A crude product previously dissolved in 400 ml of hexane / toluene (volume ratio 4/1) was passed through column chromatography (silica gel 200 g), and further eluted with 1200 ml of hexane / toluene (volume ratio 4/1). The obtained solution was concentrated to obtain 184.0 g of a crude product of compound (ia1-301). Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 184.0 g of a crude product of the obtained compound (ia1-301), 3.8 g of sodium benzenesulfinate, 16.8 g of 10% hydrochloric acid and After adding 400 ml of toluene and stirring for 3 hours while heating at 85 ° C., the mixture was cooled to room temperature, and 400 ml of saturated aqueous sodium bicarbonate was added. After extraction with 200 ml of toluene from the aqueous layer, the obtained organic layers were combined and washed with 300 ml of water and 300 ml of saturated brine. The obtained organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 145.3 g of a crude product of compound (ia1-301). A crude product previously dissolved in 300 ml of hexane / toluene (volume ratio 4/1) was passed through column chromatography (silica gel 200 g), and further eluted with 1200 ml of hexane / toluene (volume ratio 4/1). The obtained solution was concentrated to obtain 114.4 g of a crude product of compound (ia1-301). By repeating recrystallization using an acetone / methanol mixed solvent, 55.5 g of compound (ia-1-302) was obtained. The transition point is C68I.
GC-MS: m / z [M ⁺ ]
Using the same reaction as in Example 1, and if necessary, a method based on a known method, Example 2 (Compound (ia-1-201)) to Example 28 (Compound (ia-2-802)) ) Was synthesized.

Example 2 Production of Compound (ia-2-301)

In Example 1, Example 30 (Compound (ia-1-203)) was used except that the compound represented by the formula (a2-1) was used in place of the compound represented by the formula (a1-1). ) To Example 56 (compound (ia-2-804)) was synthesized.

(Example 3, Example 4, Comparative Example 1 and Comparative Example 2)
LC-1 (Example 3), LC-2 (Example 4), LC-A (Comparative Example 1) and LC-B (Comparative Example 2) liquid crystal compositions were prepared and their physical properties were measured. The composition of the liquid crystal composition and the results of its physical properties were as shown in the following table.

The liquid crystal composition LC-1 of the present invention showed large Δn and Δε absolute values. In contrast, 1V-Cy-1O-Ph5-O1 which is a compound represented by the general formula (i) of the present application is replaced with 3-Cy-1O-Ph5-O2 having a common skeleton, and LC- As for A, although Tni raised, (DELTA) (epsilon) fell. Compared to LC-A, while maintaining Δn and γ1, Tni is adjusted to be about the same as LC-1, LC-B, but Δε can be increased to the same level as LC-1. could not.

From the above, the liquid crystal composition of the present invention has a large refractive index anisotropy (Δn) and a large absolute value and a negative dielectric anisotropy (Δε). It was confirmed that the liquid crystal display elements such as the type and the PSVA type are excellent in low-voltage driving and can sufficiently cope with the narrow gap LCD.

Claims

The compound represented by general formula (i).

(Wherein R i1 represents an alkenyl group having 3 to 15 carbon atoms, and one —CH 2 — present in the alkenyl group or two or more non-adjacent —CH 2 — represents —O— , —S—, —COO—, —OCO—, —CO—, —CH═CH—, —C≡C— or a ring structure,
R i2 represents an alkyl group having from 1 to 15 carbon atoms, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O -, - S- , —COO—, —OCO—, —CO—, —CH═CH—, —C≡C— or a ring structure,
n i1 represents 1, 2 or 3,
X i1 and X i2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethoxy group. )
2. The compound according to claim 1, wherein in general formula (i), n i1 is 1, and X i1 and X i2 are each independently a fluorine atom, a chlorine atom, a trifluoromethyl group, or a trifluoromethoxy group.
The compound according to claim 1, wherein in general formula (i), n i1 is 2, and X i1 and X i2 are each independently a fluorine atom, a chlorine atom, a trifluoromethyl group, or a trifluoromethoxy group.
The compound according to claim 1, wherein in formula (i), R i2 is a methyl group.
A composition containing one or more compounds according to any one of claims 1 to 3.
The composition according to claim 5, further comprising a compound represented by the general formula (N-1).

(Wherein R N11 and R N12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH 2 — in the alkyl group are each independently Optionally substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
Independently A N11 and A N12, respectively (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O And (b) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ are replaced with —N =). May be.)
(C) (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6- One —CH═ present in a diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ are replaced by —N═. Is also good.)
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z N11 and Z N12 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —OCF 2 -, -CF 2 O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
Although n N11 and n N12 each represent independently an integer of 0 ~ 3, n N11 + n N12 is 1, 2 or 3, if A N11 ~ A N12, Z N11 ~ Z N12 there is a plurality, They may be the same or different. )
Furthermore, the composition of Claim 5 or 6 containing the compound represented by general formula (L).

(Wherein R L1 and R L2 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH 2 — in the alkyl group are each independently Optionally substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n L1 represents 0, 1, 2 or 3,
A L1 , A L2 and A L3 each independently represent (a) a 1,4-cyclohexylene group (one —CH 2 — present in the group or two or more —CH 2 — not adjacent to each other). May be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ not adjacent to each other —N May be replaced by =.)
(C) (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6- One —CH═ present in a diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ are replaced by —N═. Is also good.)
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z L1 and Z L2 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —OCF 2 -, -CF 2 O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
When n L1 is 2 or 3, and a plurality of A L2 are present, they may be the same or different, and when n L1 is 2 or 3, and a plurality of Z L3 are present, May be the same or different, but excludes compounds represented by general formula (i) and general formula (N-1). )
The composition according to any one of claims 5 to 7, which has a liquid crystal phase at room temperature.
A display device using the composition according to any one of claims 5 to 8.