TW201806942A - Piperidine derivatives, liquid-crystal composition, and liquid-crystal display element - Google Patents

Abstract

The present invention addresses the problem of providing a liquid crystal composition that satisfies at least one characteristic from among such characteristics as a high upper limit temperature, a low lower limit temperature, low viscosity, appropriate optical anisotropy, a large negative dielectric anisotropy, a high specific electrical resistance, high stability against ultraviolet rays, and high stability against heat, or that has a suitable balance of at least two such characteristics. A liquid crystal composition with negative dielectric anisotropy that has the advantage of including, as a first additive, a compound that is highly soluble in the liquid crystal composition and has the effect of suppressing display defects in a liquid crystal display element.

Description

Piperidine derivative, liquid crystal composition, and liquid crystal display element

The present invention relates to a piperidine derivative, a liquid crystal composition containing the compound, a liquid crystal display element containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and an element containing the composition and having a mode such as IPS, VA, FFS, and FPA. The invention also relates to a polymer stable alignment type device.

In liquid crystal display elements, the operation modes based on liquid crystal molecules are classified into phase change (PC), twisted nematic (TN), super twisted nematic (STN), and electrically controlled birefringence ( electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and other modes. The component-based driving methods are classified into a passive matrix (PM) and an active matrix (AM). PM is classified as static, multiplex, etc. AM is classified as thin film transistor (TFT), metal-insulator-metal (MIM), and the like. TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to manufacturing steps. The classification based on the light source is a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation among these characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferable upper limit temperature of the nematic phase is about 70 ° C or higher, and the preferable lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of a composition is related to the response time of the element. In order to display a moving image with a component, it is preferable that the response time is short. Ideally a response time shorter than 1 millisecond. Therefore, the viscosity of the composition is preferably small. Especially preferred is low viscosity at low temperatures.

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy is required, that is, an appropriate optical anisotropy. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The value of the appropriate product depends on the type of operation mode. In the VA mode device, the value ranges from about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode devices, the value ranges from about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is preferred for a device having a small cell gap. The large dielectric anisotropy of the composition contributes to low threshold voltage, small power consumption, and large contrast in the device. Therefore, a large dielectric anisotropy is preferred. The large specific resistance of the composition contributes to the large voltage holding ratio and large contrast of the device. Therefore, a composition having a large specific resistance in the initial stage is preferred. A composition having a large specific resistance after long-term use is preferred. The stability of the composition to ultraviolet rays or heat is related to the life of the device. When the stability is high, the life of the device is long. Such characteristics are preferred for AM elements used in liquid crystal projectors and liquid crystal televisions.

In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules can be achieved by using a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display device, a polymer and an alignment film are combined. First, a composition to which a small amount of a polymerizable compound is added is injected into a device. Next, a voltage is applied between the substrates facing the element, and the composition is irradiated with ultraviolet rays. The polymerizable compound is polymerized to form a polymer network structure in the composition. In this composition, a polymer can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened, and the afterimage of the image is improved. Such an effect of a polymer can be expected in a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having a positive dielectric anisotropy is used for an AM device having a TN mode. A composition having a negative dielectric anisotropy is used for an AM device having a VA mode. A composition having a positive or negative dielectric anisotropy is used for an AM device having an IPS mode or an FFS mode. A polymer stabilized alignment type AM device uses a composition having a positive or negative dielectric anisotropy.

The following compound (A-1) is a kind of hindered amine light stabilizer (HALS). This compound has a polar group> N-CH ₃ . In this compound, the two polar groups are the same. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/76105 [Patent Document 2] Japanese Patent Laid-Open No. 2014-84460

[Problems to be Solved by the Invention] An object of the present invention is to provide a compound which has high solubility with respect to a liquid crystal composition and has an effect of suppressing display defects of a liquid crystal display element. Another object is to provide a liquid crystal composition which satisfies a high upper temperature of the nematic phase, a low lower temperature of the nematic phase, a low viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, At least one of the characteristics of high stability to ultraviolet light and high stability to heat. Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another object is to provide a liquid crystal display element containing such a composition. Still another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast, and long life. [Means for solving problems]

The present invention relates to a compound, a liquid crystal composition containing the compound and having a negative dielectric anisotropy, and a liquid crystal display element containing the composition. The compound has at least two formulas (S) divalent group, the plurality monovalent group, represented by R ¹ group is represented by the other group represented by R ¹ are different. In the formula (S), R ¹ is hydrogen, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons; R is an alkyl group having 1 to 12 carbons. [Effect of the invention]

An advantage of the present invention is to provide a compound which has high solubility with respect to a liquid crystal composition and has an effect of suppressing display failure of a liquid crystal display element. Another object is to provide a liquid crystal composition which satisfies a high upper temperature of the nematic phase, a low lower temperature of the nematic phase, a low viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, At least one of the characteristics of high stability to ultraviolet light and high stability to heat. Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another object is to provide a liquid crystal display element containing such a composition. Still another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast, and long life.

The terms used in this specification are described below. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. A "liquid crystal compound" is a compound having a nematic phase, a smectic phase, and a liquid crystal phase, and is mixed for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of a nematic phase, although it does not have a liquid crystal phase Generic term for compounds in a composition. The compound has a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystal compound which has an alkenyl group is not polymerizable in the meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. To this liquid crystal composition, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are added as necessary. That is, when it is convenient to add an additive, the proportion of the liquid crystal compound is expressed by a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. The ratio of the additive is expressed by a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Sometimes parts per million by weight (ppm) is used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as the "lower limit temperature". "High specific resistance" means that the composition has a large specific resistance in the initial stage, and also has a large specific resistance after long-term use. "Large voltage holding rate" means that the element has a large voltage holding rate not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and not only at room temperature after long-term use, but also It also has a large voltage holding ratio at a temperature close to the upper limit temperature. The characteristics of a composition or an element are sometimes studied by a change over time test. The expression "improving dielectric anisotropy" refers to a composition with a positive dielectric anisotropy, which means that its value increases positively, and a composition with a negative dielectric anisotropy means a negative value. Increase to the ground.

The expression "at least one -CH ₂ -may be substituted with -O-" is used in this specification. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by non-adjacent -CH ₂ -substituted with -O-. However, adjacent -CH ₂ -will not be replaced by -O-. This is because -OO-CH _2- (peroxide) is formed during the substitution. That is, the expression refers to both "one -CH ₂ -may be substituted with -O-" and "at least two non-adjacent -CH ₂ -may be substituted with -O-". This rule applies not only to the case of substitution with -O-, but also to the case of substitution with a divalent group like -CH = CH- or -COO-.

In the chemical formula of the component compound, the symbol of the terminal group R ³ is used for various compounds. In these compounds, two groups represented by any two R ³ may be the same or different. For example, there may be a case where R ³ of the compound (2-1) is an ethyl group and R ³ of the compound (2-2) is an ethyl group. In some cases, R ³ of the compound (2-1) is ethyl, and R ³ of the compound (2-2) is propyl. This rule also applies to other tokens. In formula (2), when the subscript 'b' is 2, there are two rings B. In this compound, the two rings represented by the two rings B may be the same or different. This rule also applies to any two rings B with subscript 'b' greater than 2. This rule also applies to other tokens. This rule also applies when the compound has a substituent represented by the same symbol.

Symbols A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings. In compound (4), a diagonal line crossing one side of the hexagon indicates that any hydrogen on the ring may be substituted with a group such as -Sp ¹ -P ¹ . Subscripts such as 'f' indicate the number of substituted groups. When the subscript 'f' is 0 (zero), there is no such substitution. When the subscript 'f' is 2 or more, there are multiple -Sp ¹ -P ¹ on the ring G. The multiple radicals represented by -Sp ¹ -P ¹ may be the same or different. In the expression "ring A and ring B are independently X, Y, or Z", since there are multiple subjects, "independently" is used. When the subject is "ring A", "independently" is not used because the subject is singular.

2-Fluoro-1,4-phenylene refers to two types of divalent groups described below. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to left-right asymmetric divalent radicals like tetrahydropyran-2,5-diyl, which are generated by removing two hydrogens from the ring. This rule also applies to divalent bonding groups like carbonyloxy (-COO- or -OCO-).

The alkyl group of the liquid crystal compound is linear or branched, and does not include a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. In order to raise the upper limit temperature, the stereo configuration associated with 1,4-cyclohexyl is a trans configuration that is better than a cis configuration.

The present invention includes the following items.

Item 1. A compound having a divalent group represented by at least two of formula (S), the plurality monovalent group, the other group with a group represented by R ¹ is represented by R ¹ by a different, In the formula (S), R ¹ is hydrogen, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons; R is an alkyl group having 1 to 12 carbons.

Item 2. The compound according to Item 1, wherein in the monovalent group represented by formula (S) according to Item 1, R is a methyl group.

Item 3. The compound according to item 1 or item 2, which is represented by formula (1), In Formula (1) and Formula (S-1), R ¹ is hydrogen, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons. Here, the group represented by R ¹ and Other R ¹ groups are different; ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenyl, naphthalene-1,2-diyl, naphthalene-1 , 3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl Naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2, 5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, carbon 1 Alkoxy to 12, at least one hydrogen substituted with fluorine or chlorine, an alkyl group having 1 to 12 carbons, or a group represented by formula (S-1); Z ¹ and Z ^{2 are} independently a single bond or carbon 1 to 20 alkylene groups, at least one of which is -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and among these groups, at least one hydrogen may be Substituted by fluorine, chlorine, or a group represented by formula (S-1); Z ³ is a single bond or an alkylene group having 1 to 20 carbon atoms, and at least one -CH of the alkylene group ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, in which at least one hydrogen may be substituted with fluorine or chlorine; a is 0, 1, 2, or 3.

Item 4. The compound according to any one of Items 1 to 3, which is represented by any one of Formulas (1-1) to (1-9), In formulas (1-1) to (1-9), R ² is an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons; Z ⁴ is an alkylene group having 1 to 15 carbons; Z ⁵ and Z ^{6 are} independently an alkylene group having 1 to 5 carbon atoms; Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 20 carbon atoms, and at least one of the alkylene groups is -CH ₂ -May be substituted with -O-, -COO-, -OCO-, or -OCOO-, in which at least one hydrogen may be substituted with fluorine or chlorine; X ¹ is hydrogen or fluorine.

Item 5. A liquid crystal composition containing at least one compound according to any one of Items 1 to 4 as a first additive, and having a negative dielectric anisotropy.

Item 6. The liquid crystal composition according to Item 5, wherein the ratio of the first additive is in a range of 0.005% to 1% by weight.

Item 7. The liquid crystal composition according to Item 5 or 6, which contains, as a first component, at least one compound selected from the group of compounds represented by formula (2), In formula (2), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an olefin having 2 to 12 carbons Oxygen; ring B and ring D are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least 1,4-phenylene substituted with fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, chromogen-2,6 -Diyl, or chromogen-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; ring C is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro -1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8 -Difluorochroman-2,6-diyl; Z ⁹ and Z ^{10 are} independently a single bond, ethylene, carbonyloxy, or methyleneoxy; b is 1, 2, or 3, and c is 0 or 1, and the sum of b and c is 3 or less.

Item 8. The liquid crystal composition according to any one of Items 5 to 7, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-22) as First ingredient, In the formulae (2-1) to (2-22), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyloxy group having 2 to 12 carbon atoms.

Item 9. The liquid crystal composition according to Item 7 or Item 8, wherein the ratio of the first component is in a range of 10% by weight to 90% by weight.

Item 10. The liquid crystal composition according to any one of Items 5 to 9, comprising at least one compound selected from the group of compounds represented by formula (3) as a second component, In formula (3), R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least one hydrogen is substituted with fluorine or chlorine Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring E and ring F are independently 1,4-cyclohexyl, 1,4-cyclohexyl Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ¹¹ is a single bond, ethylene, carbonyloxy, or methyleneoxy ; D is 1, 2, or 3.

Item 11. The liquid crystal composition according to any one of Items 5 to 10, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as The second component, In the formulae (3-1) to (3-13), R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , At least one hydrogen having 1 to 12 carbons substituted with fluorine or chlorine, or at least one hydrogen having 2 to 12 carbons substituted with fluorine or chlorine.

Item 12. The liquid crystal composition according to Item 10 or Item 11, wherein the ratio of the second component is in a range of 10% by weight to 90% by weight.

Item 13. The liquid crystal composition according to any one of Items 5 to 12, comprising at least one compound selected from the group of polymerizable compounds represented by Formula (4) as a second additive, In formula (4), ring G and ring J are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Or at least one hydrogen substituted with fluorine or chlorine and 1 to 12 carbon alkyl groups; ring I is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be passed through fluorine, chlorine , An alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Z ¹² and Z ^{13 are} independently a single bond Or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, at least one -CH ₂ CH ₂ -can be replaced by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, these In the group, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ^{3 are} independently polymerizable groups; Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or a carbon number of 1 to 10 Alkenyl, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be -CH = CH -Or -C≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; e is 0, 1, or 2; f, g, and h are independently 0, 1, 2, 3, Or 4, and the sum of f, g, and h is 1 or more.

Item 14. The liquid crystal composition according to Item 13, wherein in the formula (4), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of the formulae (P-1) to (P-5) Groups in a group of polymerizable groups, In the formulae (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkyl having 1 to 5 carbons.

Item 15. The liquid crystal composition according to item 13 or item 14, which contains at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27) as the second Additives, In Formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ^{6 are} independently selected from the group consisting of polymerizable groups represented by Formulas (P-1) to (P-3) Base in group, Here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. At least one -CH ₂ -in this alkylene group may be passed through -O-, -COO-, -OCO-, or- OCOO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Item 16. The liquid crystal composition according to any one of Items 13 to 15, wherein the ratio of the second additive is in a range of 0.03% by weight to 10% by weight.

Item 17. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 5 to 16.

Item 18. The liquid crystal display element according to item 17, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 19. A polymer stabilized alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 13 to 16, and a second additive contained in the liquid crystal composition is polymerized.

Item 20. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 5 to 16, and is used in a liquid crystal display element.

Item 21. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 5 to 16, and is used in a polymer-stable alignment type liquid crystal display element.

The present invention also includes the following items. (A) The composition further contains at least one of an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and an additive such as a polar compound . (B) An AM device containing the composition. (C) A polymer stabilized alignment (PSA) type AM device comprising the composition, and the composition further includes a polymerizable compound. (D) A polymer stabilized alignment (PSA) type AM device comprising the composition and polymerizing a polymerizable compound in the composition. (E) An element containing the composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive element containing the composition. (G) Use of the composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the composition.

The liquid crystal composition of the present invention contains a compound having at least two monovalent groups represented by formula (S). In formula (S), R ¹ is hydrogen, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons. The four radicals R are independently alkyl groups having 1 to 12 carbons.

The compound of the present invention has at least two monovalent groups represented by formula (S). The plurality monovalent group, represented by R ¹ group is represented by the other group represented by R ¹ are different. When the compound has two groups represented by formula (S), the two groups represented by R ¹ are different from each other. That is, when it is convenient for the compound to have three groups represented by formula (S), the two groups represented by R ¹ are also different from each other. An example is a case where three groups R ¹ are hydrogen, hydrogen, and methyl. Another example is a combination of hydrogen, methyl, and ethyl. That is, all the groups represented by R ¹ are not the same.

As shown in Comparative Example 1, Comparative Example 2, and Comparative Example 3, this compound is effective for suppressing display failure of an element. However, the cause of the poor display is complicated and cannot be fully elucidated. Furthermore, the effect of this compound on poor display is unknown at this stage. Although this is the case, the descriptions described in the following paragraphs can be made.

When the device is used for a long time, the brightness may be partially reduced. One example is a line afterimage, and a phenomenon in which the brightness between electrodes decreases in a striped manner by repeatedly applying different voltages to two adjacent electrodes. This phenomenon is caused by the accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrode. Therefore, in order to suppress the line afterimage, it is effective to prevent the ionic impurities from locally existing on the alignment film. For this purpose, the surface of the alignment film is covered with an additive such as a polar compound, and ionic impurities are adsorbed to the additive. In order to obtain a desired effect, it is important for these additives to have high solubility with respect to the liquid crystal composition.

The liquid crystal composition is injected into the device from the injection port under reduced pressure. Generally, a composition is filled in a device without changing the ratio of its components. However, additives like polar compounds are sometimes adsorbed on the alignment film. When the adsorption speed is high, the additive may not reach the inside of the device. Additives remain because the adsorption rate is greater than the injection rate. In order to prevent this phenomenon, an additive having an appropriate adsorption property with respect to the alignment film is preferred. Therefore, it is also important to select an additive having an appropriate polarity. The compound described in item 1, especially compound (1) is suitable for this purpose. The compound (1) has at least two groups R ¹ . Since the groups represented by at least two groups R ¹ are different from each other, the compound (1) is asymmetric. This asymmetry may contribute to proper polarity. Please refer to the comparative example. The composition of the present invention contains the compound (1) as a first additive.

The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or device will be described. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, preferred embodiments of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. This composition may contain additives. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. From the viewpoint of a liquid crystal compound, the composition is classified into a composition A and a composition B. The composition A may contain a liquid crystal compound selected from the compound (2) and the compound (3), and may further contain other liquid crystal compounds, additives, and the like. The "other liquid crystal compound" is a liquid crystal compound different from the compound (2) and the compound (3). Such a compound is mixed in the composition for the purpose of further adjusting the characteristics.

The composition B contains substantially only a liquid crystal compound selected from the compound (2) and the compound (3). "Substantially" means that although the composition B may contain additives, it does not contain other liquid crystal compounds. Compared with the composition A, the number of components of the composition B is small. From the viewpoint of cost reduction, the composition B is superior to the composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is superior to the composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or device will be described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L is large or high, M is medium, and S is small or low. Symbols L, M, and S are classifications based on a qualitative comparison between component compounds, and 0 (zero) means extremely small.

The main effects of the component compounds are as follows. The compound (1) helps suppress poor display. Since the amount of the compound (1) to be added is extremely small, it has no effect on characteristics such as the upper limit temperature, optical anisotropy, and dielectric anisotropy in many cases. Compound (2) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (3) reduces the viscosity or raises the upper limit temperature. Since the compound (4) is polymerizable, a polymer is formed by polymerization. Since this polymer stabilizes the alignment of liquid crystal molecules, it shortens the response time of the device and improves the afterimage of the image.

Third, the combination of components in the composition, the preferred ratio of the component compounds, and the basis thereof will be described. A preferred combination of the components in the composition is compound (1) + compound (2), compound (1) + compound (3), compound (1) + compound (2) + compound (3), compound (1) + Compound (2) + compound (4), compound (1) + compound (3) + compound (4), or compound (1) + compound (2) + compound (3) + compound (4). A particularly preferred combination is compound (1) + compound (2) + compound (3) or compound (1) + compound (2) + compound (3) + compound (4).

In order to suppress display defects, a preferred ratio of the compound (1) is about 0.005% by weight or more. In order to lower the lower limit temperature, a preferred ratio of the compound (1) is about 1% by weight or less. A particularly preferred ratio is in the range of about 0.02% by weight to about 0.5% by weight. A particularly preferred ratio is in the range of about 0.1% by weight to about 0.3% by weight.

In order to improve the dielectric anisotropy, the preferred ratio of the compound (2) is about 10% by weight or more, and to lower the lower limit temperature, the preferred ratio of the compound (2) is about 90% by weight or less. A particularly preferred ratio is in the range of about 20% by weight to about 85% by weight. A particularly preferred ratio is in the range of about 30% by weight to about 85% by weight.

In order to increase the upper limit temperature or to reduce the viscosity, the preferred ratio of the compound (3) is about 10% by weight or more. In order to improve the dielectric anisotropy, the preferred ratio of the compound (3) is about 90% by weight or less. A particularly preferred ratio is in the range of about 20% by weight to about 80% by weight. A particularly preferred ratio is in the range of about 30% by weight to about 70% by weight.

The compound (4) is added to the composition for the purpose of being suitable for a polymer-stable alignment device. In order to align the liquid crystal molecules, the preferred ratio of the compound (4) is about 0.03% by weight or more. In order to prevent display failure of the device, the preferred ratio of the compound (4) is about 10% by weight or less. A particularly preferred ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight.

Fourth, preferred embodiments of the component compounds will be described. In the formula (S), R ¹ is hydrogen, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons. Here, a group represented by R ¹ and a group represented by another R ¹ different. R is an alkyl group having 1 to 12 carbons.

In formula (1) and formula (S-1), Z ¹ and Z ^{2 are} independently a single bond or an alkylene group having 1 to 20 carbon atoms. At least one of the alkylene groups may be -CH ₂ -via -O. -, -COO-, -OCO-, or -OCOO-. At least one of these groups may be substituted with fluorine, chlorine, or a group represented by formula (S-1). Preferred Z ¹ or Z ² are single bonds or at least one alkylene group having 1 to 20 carbon atoms substituted with -CH ₂ -by -COO- or -OCO-. Z ³ is a single bond or an alkylene group having 1 to 20 carbon atoms. At least one -CH ₂ -in the alkylene group may be substituted with -O-, -COO-, -OCO-, or -OCOO-. These In the radical, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ³ is a single bond or at least one -CH ₂ -alkylene having 1 to 20 carbon atoms substituted with -COO- or -OCO-.

Ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 , 4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl Naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, at least one Hydrogen is substituted by a C1-C12 alkyl group substituted by fluorine or chlorine, or a group represented by formula (S-1). Preferred ring A is 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, Naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, or naphthalene-2, 7-diyl.

a is 0, 1, 2, or 3. The preferred a is 0 or 1. A particularly preferred a is 0.

In the formulae (1-1) to (1-9), R ² is an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons. Preferred R ² is an alkyl group having 1 to 12 carbons.

Z ⁴ is an alkylene group having 1 to 15 carbon atoms. Preferred Z ⁴ is an alkylene group having 6 to 10 carbon atoms. Particularly preferred Z ⁴ is an alkylene group having 8 carbon atoms. Z ⁵ and Z ^{6 are} independently an alkylene group having 1 to 5 carbon atoms. Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 20 carbon atoms, at least one of -CH ₂ -may pass through -O-, -COO-, -OCO-, or -OCOO -Substitution, in which at least one hydrogen may be substituted with fluorine or chlorine. The preferred Z ⁷ or Z ⁸ is a single bond.

X ¹ is hydrogen or fluorine. A preferred X ¹ is hydrogen.

In formulas (2) and (3), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon number 2 to 12 alkenyloxy. For increasing the stability to ultraviolet light or heat, preferably R ³ or R ⁴ is alkyl having 1 to 12, for increasing the dielectric anisotropy, preferred R ³ or R ⁴ is from 1 to 12 carbon atoms, Alkoxy. R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least one hydrogen having 1 to 12 carbon atoms substituted with fluorine or chlorine Alkyl, or at least one hydrogen alkenyl having 2 to 12 carbons substituted with fluorine or chlorine. In order to reduce the viscosity, preferred R ⁵ or R ⁶ is an alkenyl group having 2 to 12 carbons. In order to improve the stability to ultraviolet rays or heat, preferred R ⁵ or R ⁶ is an alkyl group having 1 to 12 carbon numbers.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. To reduce viscosity, particularly preferred alkyl groups are methyl, ethyl, propyl, butyl, or pentyl.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, or heptyloxy. To reduce viscosity, a particularly preferred alkoxy group is methoxy or ethoxy.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3 -Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. To reduce viscosity, particularly preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred stereo configuration of -CH = CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity, etc., among 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl-like alkenyl groups are preferred. Style configuration. Among 2-butenyl, 2-pentenyl, and 2-hexenyl-like alkenyl groups, the cis configuration is preferred.

The preferred alkenyloxy group is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to reduce viscosity, particularly preferred allyloxy is allyloxy or 3-butenyloxy.

Preferred examples of the alkyl group in which at least one hydrogen is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7 -Fluoroheptyl, or 8-fluorooctyl. In order to increase the dielectric anisotropy, particularly preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.

Preferred examples of the alkenyl group in which at least one hydrogen is substituted with fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5, 5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, a particularly preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring B and Ring D are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen atom Fluorine or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine naphthalene-2,6-diyl, chromogen-2,6-diyl , Or at least one chromogen-2,6-diyl substituted with fluorine or chlorine. In order to reduce the viscosity, the preferred ring B or ring D is 1,4-cyclohexyl. In order to improve the dielectric anisotropy, the preferred ring B or ring D is tetrahydropyran-2,5-diyl. In order to improve optical anisotropy, the preferred ring B or ring D is 1,4-phenylene. Ring C is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromogen-2,6-diyl. To reduce viscosity, the preferred ring C is 2,3-difluoro-1,4-phenylene. To reduce the optical anisotropy, the preferred ring C is 2-chloro-3-fluoro-1,4- In order to increase the dielectric anisotropy of phenylene, the preferred ring C is 7,8-difluorochroman-2,6-diyl. Tetrahydropyran-2,5-diyl is or , Preferably .

Ring E and Ring F are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene base. In order to reduce the viscosity or to increase the upper limit temperature, the preferred ring E or ring F is 1,4-cyclohexyl, and in order to lower the lower limit temperature, the preferred ring E or ring F is 1,4-phenylene.

Z ⁹ and Z ^{10 are} independently a single bond, ethylene, carbonyloxy, or methyleneoxy. In order to reduce the viscosity, the preferred Z ⁹ or Z ¹⁰ is a single bond, in order to reduce the lower limit temperature, the preferred Z ⁹ or Z ¹⁰ is ethylene, and to improve the dielectric anisotropy, the preferred Z ⁹ or Z ¹⁰ Is methyleneoxy. Z ¹¹ is a single bond, ethylene, carbonyloxy, or methyleneoxy. In order to improve the stability to ultraviolet rays or heat, the preferred Z ¹¹ is a single bond.

b is 1, 2, or 3, c is 0 or 1, and the sum of b and c is 3 or less. In order to reduce the viscosity, the preferred b is 1, and in order to increase the upper limit temperature, the preferred b is 2 or 3. In order to reduce the viscosity, the preferred c is 0, and to lower the lower limit temperature, the preferred c is 1. d is 1, 2, or 3. In order to reduce the viscosity, the preferred d is 1, and in order to increase the upper limit temperature, the preferred d is 2 or 3.

In formula (4), P ¹ , P ² , and P ^{3 are} independently a polymerizable group. Preferably, P ¹ , P ² , or P ³ is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). Particularly preferred P ¹ , P ² , or P ³ is a radical (P-1) or a radical (P-2). A particularly preferred group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy lines from the base (P-1) to the base (P-5) indicate the bonding sites.

In the groups (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is substituted with fluorine or chlorine. Alkyl having 1 to 5 carbons. In order to improve reactivity, preferred M ¹ , M ² , or M ³ is hydrogen or methyl. Particularly preferred M ¹ is methyl, and particularly preferred M ² or M ³ is hydrogen.

In the formulae (4-1) to (4-27), P ⁴ , P ⁵ , and P ^{6 are} independently the groups represented by the formulae (P-1) to (P-3). Preferably, P ⁴ , P ⁵ , or P ⁶ is a radical (P-1) or a radical (P-2). A particularly preferred group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy lines from the base (P-1) to the base (P-3) indicate the bonding sites.

In formula (4), Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. At least one of the alkylene groups may be -CH ₂ -via -O-,- COO-, -OCO-, or -OCOO- substitution, at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-, and among these groups, at least one hydrogen may be substituted by fluorine or chlorine . Preferably, Sp ¹ , Sp ² , or Sp ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, Or -CH = CH-CO-. Particularly preferred Sp ¹ , Sp ² , or Sp ³ are single bonds.

Ring G and ring J are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen C1-C12 alkyl substituted with fluorine or chlorine. Preferred ring G or ring J is phenyl. Ring I is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 , 4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl Naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen is substituted by a C1-C12 alkyl group substituted by fluorine or chlorine. Preferred ring I is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹² and Z ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -can pass through -O-, -CO-, -COO-, or -OCO. -Substitution, at least one -CH ₂ CH ₂ -may be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ ) -Substituting, in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferably, Z ¹² or Z ¹³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. A particularly preferred Z ¹² or Z ¹³ is a single bond.

e is 0, 1, or 2. The preferred e is 0 or 1. f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 1 or more. Preferably, f, g, or h is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to compound (1-9) according to item 4. Particularly preferred compound (1) is compound (1-1) to compound (1-3). Particularly preferred compound (1) is compound (1-1).

Preferred compound (2) is the compound (2-1) to compound (2-22) according to item 8. Among these compounds, it is preferred that at least one of the first components is compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8), Or compound (2-10). It is preferable that at least two of the first components are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2- 6) Compound (2-3) and compound (2-10), compound (2-4) and compound (2-6), or a combination of compound (2-4) and compound (2-8).

Preferred compound (3) is the compound (3-1) to compound (3-13) according to item 11. Among these compounds, it is preferred that at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8), Or compound (3-9). It is preferable that at least two of the second component are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3 -6).

Preferred compound (4) is the compound (4-1) to compound (4-27) according to item 15. Among these compounds, it is preferred that at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26) , Or compound (4-27). It is preferred that at least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4 -24), compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4 -18) and compound (4-24). Among the groups (P-1) to (P-3), preferred M ¹ , M ² , or M ³ is hydrogen or methyl. Preferably, Sp ¹ , Sp ² , or Sp ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, Or -CH = CH-CO-.

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of giving a torsion angle to the helical structure of the liquid crystal. Examples of such compounds are compound (5-1) to compound (5-5). A preferred ratio of the optically active compound is about 5 wt% or less. A particularly preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

In order to prevent the decrease in specific resistance caused by heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, An antioxidant is added to the composition. Preferable examples of the antioxidant are a compound (6) in which n is an integer of 1 to 9, and the like.

In the compound (6), preferred n is 1, 3, 5, 7, or 9. A particularly preferred n is 7. The compound (6) in which n is 7 is small in volatility, and is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after a long-term use of the device. In order to obtain the effect, a preferred ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature, or not to raise the lower limit temperature, the preferred ratio of the antioxidant is about 600 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. In addition, an amine-like light stabilizer having a steric hindrance is also preferred. In order to obtain the effect, the preferred ratio of these absorbers or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature, or to not raise the lower limit temperature, the preferred ratio of these absorbers or stabilizers is about 10,000 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

A dichroic dye such as an azo-based pigment, an anthraquinone-based pigment, or the like is added to the composition in order to be suitable for an element in a guest host (GH) mode. A preferred ratio of the pigment is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition. In order to obtain the effect, the preferred ratio of the defoaming agent is about 1 ppm or more, and in order to prevent poor display, the preferred ratio of the defoaming agent is about 1000 ppm or less. A particularly preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for a polymer stabilized alignment (PSA) type device, a polymerizable compound is used. Compound (4) is suitable for this purpose. The compound (4) and a polymerizable compound different from the compound (4) may be added to the composition together. Instead of the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Preferred examples of such polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane, oxetane), and vinyl ketones. And other compounds. A particularly preferred example is a derivative of acrylate or methacrylate. By changing the type of the compound (4), or by combining a polymerizable compound different from the compound (4) with the compound (4) at an appropriate ratio, the reactivity of polymerization or the pretilt angle of the liquid crystal molecules can be adjusted. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio or a long life can be achieved.

The polymerizable compound is polymerized by irradiation with ultraviolet rays. Polymerization can also be performed in the presence of an initiator such as a photopolymerization initiator. Suitable conditions for carrying out the polymerization, or suitable types and amounts of initiators are known to those skilled in the art and are described in the literature. Examples include photopolymerization initiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (Registered trademark; BASF) is suitable for free radical polymerization. The preferred ratio of the photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight based on the weight of the polymerizable compound. A particularly preferred ratio is in the range of about 1% to about 3% by weight.

When storing a polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, methylhydroquinone-like hydroquinone derivatives, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.

A polar compound is a polar organic compound. Here, a compound having an ionic bond is not included. Oxygen, sulfur, and nitrogen-like atoms are electrically negative and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partially positive charge. Polarity is caused by the uneven distribution of partial charges among different kinds of atoms in a compound. For example, the polar compound has at least one of -OH, -COOH, -SH, -NH ₂ ,> NH, and> N-like partial structures.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Illustrative synthesis methods. The synthesis method of the compound (1-1-1) and the compound (1-1-2) is described in the item of an Example. Reference may also be made to the synthesis method described in Japanese Patent Laid-Open No. 2016-037605. The compound (2-6) is synthesized by a method described in Japanese Patent Laid-Open No. 2000-53602. Compound (3-1) is synthesized by the method described in Japanese Patent Laid-Open No. 59-176221. Compound (4-18) is synthesized by a method described in Japanese Patent Laid-Open No. 7-101900. The compound of formula (6) where n is 1 is available from Sigma-Aldrich Corporation. Compound (6) and the like in which n is 7 are synthesized by a method described in US Pat. No. 3,660,505.

Compounds without a synthetic method can be synthesized by the methods described in the following books: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" Reactions, John Willie & Sons Publishing Company), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Lecture (Maruzen), etc. The composition is prepared from a compound obtained in the above-mentioned manner by a known method. For example, the component compounds are mixed and then dissolved in each other by heating.

Finally, the use of the composition will be described. Most compositions have a lower limit temperature of about -10 ° C or lower, an upper limit temperature of about 70 ° C or higher, and optical anisotropy in a range of about 0.07 to about 0.20. A composition having an optical anisotropy in a range of about 0.08 to about 0.25 can be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in a range of about 0.10 to about 0.30 can be prepared by trial and error. The device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.

This composition can be used for an AM device. It can also be used for PM devices. This composition can be used for AM devices and PM devices with PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. Particularly preferred is for AM devices with VA, OCB, IPS mode or FFS mode. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the arrangement of the liquid crystal molecules may be parallel to the glass substrate, or may be vertical. These elements can be reflective, transmissive, or transflective. It is preferably used for a transmissive element. It can also be used for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements. The composition can also be used in a nematic curvilinear aligned phase (NCAP) device made by microencapsulation or a polymer formed by forming a three-dimensional network polymer in the composition. A polymer dispersed (PD) type device.

An example of a method of manufacturing a polymer-stabilized alignment element is described below. Assemble an element that includes two substrates, which are called an array substrate and a color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additives can be added if necessary. This composition is injected into a device. Light irradiation is performed in a state where a voltage is applied to the element. Preferred is ultraviolet light. The polymerizable compound is polymerized by light irradiation. A polymer-containing composition is produced by this polymerization. The polymer stabilized alignment type element is manufactured in the order described above.

In this sequence, when a voltage is applied, the liquid crystal molecules are aligned by the action of an alignment film and an electric field. According to this alignment, the molecules of the polymerizable compound are also aligned. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. The effect of this polymer shortens the response time of the device. Since the residual image of the image is a poor operation of the liquid crystal molecules, the effect of the polymer also improves the residual image. In addition, the polymerizable compound in the composition may be polymerized in advance, and the composition may be disposed between the substrates of the liquid crystal display element. [Example]

The present invention will be further described in detail through examples. The invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture obtained by mixing at least two of the compositions of the composition examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of compounds, compositions, and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for measurement. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under the conditions of 500 MHz and a cumulative number of 16 times. Tetramethylsilane was used as the internal standard. ^{In the 19} F-NMR measurement, CFCl _{3 was} used as an internal standard, and the total number of measurements was performed 24 times. In the description of nuclear magnetic resonance spectrum, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet. (Quintet), sex means sixt (sextet), m means multiplet, and br means broad.

Gas chromatographic analysis: The GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas was helium (2 mL / min). The sample gasification chamber was set to 280 ° C, and the detector (flame ionization detector (FID)) was set to 300 ° C. For separation of constituent compounds, a capillary column DB-1 (30 m in length, 0.32 mm in inner diameter, and 0.25 μm in thickness) manufactured by Agilent Technologies Inc. was used; the fixed liquid phase was dimethylpolysiloxane ; Non-polar). After the column was held at 200 ° C for 2 minutes, the temperature was raised to 280 ° C at a rate of 5 ° C / min. After the sample was prepared as an acetone solution (0.1% by weight), 1 μL of the sample was injected into the sample gasification chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed the retention time of the peak corresponding to the component compounds and the area of the peak.

As a solvent for diluting the sample, chloroform, hexane, or the like can be used. To separate the component compounds, the following capillary columns can be used. HP-1 (30 m in length, 0.32 mm ID, film thickness of 0.25 μm) manufactured by Agilent Technologies, Rtx-1 (30 m in length, 0.32 mm ID, film thickness) manufactured by Restek Corporation 0.25 μm), BP-1 manufactured by Australia SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). To prevent compound peaks from overlapping, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, and film thickness 0.25 μm) manufactured by Shimadzu Corporation can be used.

The ratio of the liquid crystal compound contained in the composition can be calculated by the method described below. Gas chromatography (FID) was used to analyze a mixture of liquid crystal compounds. The area ratio of the peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of various liquid crystal compounds can be regarded as one. Therefore, the ratio (% by weight) of the liquid crystalline compound can be calculated from the peak area ratio.

Measurement sample: When measuring the characteristics of a composition or an element, the composition is directly used as a sample. When measuring the characteristics of a compound, a sample for measurement was prepared by mixing the compound (15% by weight) with a mother liquid crystal (85% by weight). From the values obtained by the measurement, the characteristic values of the compounds were calculated by extrapolation. (Extrapolated value) = ｛(measured value of the sample)-0.85 × (measured value of the mother liquid crystal)｝ /0.15. When the smectic phase (or crystal) is precipitated at 25 ° C at this ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, and 1% by weight: 99% % Order change. This extrapolation method was used to determine the values of the compound-dependent upper temperature, optical anisotropy, viscosity, and dielectric anisotropy.

The following mother liquid crystals were used. The proportion of the component compounds is expressed in% by weight.

Measurement method: The characteristics were measured by the following method. Most of these methods are methods described or modified from the JEITA standard (JEITA · ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (referred to as JEITA). The thin-film transistor (TFT) was not mounted on the TN element used for the measurement.

(1) Upper limit temperature of the nematic phase (NI; ° C): A sample is placed on a hot plate of a melting point measuring device equipped with a polarizing microscope, and heated at a rate of 1 ° C / min. The temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was measured. The upper limit temperature of the nematic phase may be simply referred to as the "upper limit temperature".

(2) Lower limit temperature (T _C ; ℃) of nematic phase: Put the sample with nematic phase into the glass bottle at 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ After storing in a freezer for 10 days, the liquid crystal phase was observed. For example, when the sample maintains a nematic phase state at -20 ° C and changes to a crystal or a smectic phase at -30 ° C, the T _{C is} described as <-20 ° C. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

(3) Viscosity (volume viscosity; η; measured at 20 ° C; mPa · s): For measurement, an E-type rotary viscometer manufactured by Tokyo Keiki Co., Ltd. was used.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s): According to "Molecular Crystals and Liquid Crystals" by M. Imai et al. The measurement is described in the method described on page 37 (1995). A sample was placed in a VA device with a gap (cell gap) between two glass substrates of 20 μm. A voltage is applied to the device in a range of 39 volts to 50 volts in steps of 1 volt. After 0.2 seconds without applying voltage, the voltage was repeatedly applied under the conditions of applying only 1 rectangular wave (rectangular pulse; 0.2 seconds) and not applying (2 seconds). The peak current and peak time of the transient current generated by the application were measured. From these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al., The value of the rotational viscosity is obtained. The dielectric anisotropy required for this calculation is measured by the item (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C): The light was measured at 589 nm using an Abbe refractometer with a polarizing plate mounted on the eyepiece. After rubbing the surface of the main shaft in one direction, the sample was dropped onto the main shaft. The refractive index n∥ is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index n⊥ is measured when the direction of polarized light is perpendicular to the direction of rubbing. The value of optical anisotropy is calculated from the formula of Δn = n∥-n⊥.

(6) Dielectric anisotropy (Δε; measured at 25 ° C): The value of the dielectric anisotropy is calculated according to the formula of Δε = ε∥-ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows. 1) Measurement of dielectric constant (ε∥): Apply a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) on a sufficiently cleaned glass substrate. After the glass substrate was rotated by a spinner, it was heated at 150 ° C for 1 hour. A sample was placed in a VA device having a distance (cell gap) between two glass substrates of 4 μm, and the device was sealed with an adhesive hardened with ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant ε (∥) in the major axis direction of the liquid crystal molecules was measured after 2 seconds.

2) Measurement of dielectric constant (ε⊥): A polyimide solution is coated on a sufficiently cleaned glass substrate. After the glass substrate is fired, the obtained alignment film is subjected to a rubbing treatment. A sample was placed in a TN device having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured after 2 seconds.

(7) Threshold voltage (Vth; measured at 25 ° C; V): The LCD5100 brightness meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample was placed in a normally black mode VA device with a gap (cell gap) of two glass substrates of 4 μm and a rubbing direction in antiparallel, and the adhesive was cured with an ultraviolet curing adhesive. Component sealed. The voltage (60 Hz, rectangular wave) applied to the device was increased stepwise from 0 V to 20 V in units of 0.02 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve having a transmittance of 100% when the amount of light reaches the maximum and a transmittance of 0% when the amount of light reaches the minimum is made. The threshold voltage is expressed as a voltage when the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-1; measured at 25 ° C;%): The TN device used for the measurement has a polyimide alignment film, and the distance (cell gap) between two glass substrates is 5 μm. This device was sealed with an adhesive hardened with ultraviolet rays after the sample was put in the sample. A pulse voltage (5 V, 60 microseconds) was applied to the TN device to charge it. The decaying voltage was measured with a high-speed voltmeter over a period of 16.7 milliseconds, and the area A between the voltage curve per unit cycle and the horizontal axis was obtained. Area B is the area when the voltage is not attenuated. The voltage holding ratio is expressed as a percentage of the area A to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80 ° C;%): The voltage holding ratio was measured in the same procedure as described above, except that the measurement was performed at 80 ° C instead of 25 ° C. The obtained value is represented by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25 ° C;%): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate the stability to ultraviolet rays. The TN device used for the measurement has a polyimide alignment film, and the cell gap is 5 μm. A sample was injected into the device, and the device was irradiated with light for 20 minutes. The light source is an ultra-high-pressure mercury lamp USH-500D (made by Ushio Motor), and the distance between the component and the light source is 20 cm. In the measurement of VHR-3, the attenuated voltage was measured over a period of 16.7 milliseconds. A composition having a large VHR-3 has a large stability to ultraviolet rays. VHR-3 is preferably 90% or more, particularly preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25 ° C;%): After heating the TN element filled with the sample in a constant temperature bath at 80 ° C for 500 hours, measure the voltage holding ratio and evaluate the stability against heat Sex. In the measurement of VHR-4, the attenuated voltage was measured over a period of 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

(12) Response time (τ; measured at 25 ° C; ms): LCD5100 type brightness meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally black mode VA device in which the distance (cell gap) between two glass substrates was 4 μm and the rubbing direction was antiparallel. This element was sealed with an adhesive hardened with ultraviolet rays. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to the device. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. When the amount of light reaches the maximum, the transmittance is considered to be 100%, and when the amount of light is the smallest, the transmittance is considered to be 0%. Response time is expressed as the time (fall time; milliseconds) required for the transmittance to change from 90% to 10%.

(13) Specific resistance (ρ; measured at 25 ° C; Ωcm): Inject 1.0 mL of a sample into a container provided with an electrode. A DC voltage (10 V) was applied to the container, and a DC current after 10 seconds was measured. The specific resistance is calculated based on the following formula. (Specific resistance) = ｛(voltage) × (capacitance of the container)｝ / ｛(DC current) × (dielectric constant of the vacuum)｝.

(14) Line image sticking parameter (LISP;%): A line afterimage is generated by applying electrical stress to a liquid crystal display element. The brightness of the area where the line afterimage is present and the brightness of the remaining areas are measured. Calculate the ratio of the brightness reduction caused by the line afterimage, and use this ratio to indicate the size of the line afterimage.

14a) Measurement of brightness: An imaging color brightness meter (manufactured by Radiant Zemax, manufactured by PM-1433F-0) was used to take an image of the element. The brightness of each region of the element was calculated by analyzing the image using software (Prometric 9.1, manufactured by Radiant Imaging).

14b) Setting of stress voltage: Put a sample in an FFS device with a cell gap of 3.5 μm and a matrix structure (16 cells in 4 cells x 4 cells in 4 cells), and use an adhesive hardened with ultraviolet rays to make the device seal. A polarizing plate is arranged above and below the element so that the polarization axes are orthogonal to each other. This element was irradiated with light and a voltage was applied (rectangular wave, 60 Hz). The voltage was gradually increased in the range of 0 V to 7.5 V in units of 0.1 V, and the brightness of transmitted light at each voltage was measured. The voltage when the brightness reaches the maximum is referred to as V255. The voltage when the brightness reaches 21.6% of V255 (ie, 127 gray levels) is referred to as V127 for short.

14c) Stress conditions: V255 (rectangular wave, 30 Hz) and 0.5 V (rectangular wave, 30 Hz) are applied to the element at 60 ° C for 23 hours, and a checkerboard pattern is displayed. Next, V127 (rectangular wave, 0.25 Hz) was applied, and the brightness was measured under an exposure time of 4000 milliseconds.

14d) Calculation of line residual image: In the calculation, 4 units (2 units vertically × 2 units horizontally) of the central portion of the 16 units are used. The 4 cells are divided into 25 regions (5 cells in a vertical direction and 5 cells in a horizontal direction). The average brightness of four areas (2 units by 2 units) at the four corners is referred to as brightness A for short. The area formed by excluding the four corner areas from the 25 areas is cross-shaped. Of the four areas obtained by excluding the central intersection area from the cross-shaped area, the minimum value of the brightness is simply referred to as the brightness B. The line residual image is calculated based on the following formula. (Line afterimage) = (Brightness A-Brightness B) / Brightness A × 100.

(15) Expandability: The expandability of the additive is qualitatively evaluated by applying a voltage to the element and measuring the brightness. The measurement of the brightness is performed in the same manner as in the item 14a. The setting of the voltage (V127) is performed in the same manner as in the item 14b. Among them, a VA element is used instead of the FFS element. The brightness was measured as follows. First, a DC voltage (2 V) was applied to the element for 2 minutes. Next, V127 (rectangular wave, 0.05 Hz) was applied, and the brightness was measured under an exposure time of 4000 milliseconds. Based on the results, scalability was evaluated.

Figures 1 to 3 are photos of the elements, showing the state of brightness. In FIG. 1 and FIG. 2, the brightness is different from each other, but the brightness is uniform as a whole. These indicate good scalability. A convex curve is observed above in FIG. 3. This means that the liquid crystal composition was injected into the entire device from the injection port located on the lower side of the photograph, but the additives contained in the composition did not reach the upper end of the device.

Synthesis Example 1 Compound (1-1-1) was synthesized by the following route.

Step 1: Under a nitrogen environment, place sebacin chloride (532.0 g, 2.225 mol) and diethyl ether (1500 ml) into the reactor, and cool to -70 ° C. Over 1.5 hours, benzyl alcohol (158.8 g, 1.468 mol) was added dropwise thereto, and then triethylamine (225.1 g, 2.225 mol) was added dropwise over 1 hour. Warm to room temperature and stir for 18 hours. The reaction mixture was cooled to 0 ° C, and 1 N hydrochloric acid (500 ml) was added dropwise. The organic layer was separated, and the aqueous layer was extracted with diethyl ether. The organic layers generated together were washed with saturated saline and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography. In the developing solvent, toluene was used first, and a mixed solvent of toluene / ethyl acetate = 9/1 (volume ratio) was used next. Recrystallization was performed from a mixed solvent of heptane / toluene = 1/1 (volume ratio) to obtain compound (T-1) (206.5 g, yield 31.7%).

Step 2: Under a nitrogen atmosphere, compound (T-1) (60.00 g, 204.8 mmol), 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (36.83 g, 215.1 mmol) And dichloromethane (600 ml) were put into the reactor and cooled to 0 ° C. To this was added 4-dimethylaminopyridine (DMAP) (7.51 g, 61.44 mmol), followed by N, N'-dicyclohexylcarbodiimide (DCC) (46.48 g, 225.3 mmol). Warm to room temperature and stir for 24 hours. The precipitated colorless solid was removed, and the filtrate was sequentially washed with a saturated sodium bicarbonate aqueous solution and water, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (toluene / ethyl acetate = 8/2 to 0/10 (volume ratio)) to obtain a compound (T-2) (69.44 g, yield 75.9%).

Step 3: Put compound (T-2) (69.44 g, 155.5 mmol), 20% palladium hydroxide carbon (3.47 g), 2-propanol (IPA) (700 ml) into the reactor, and Stir under a hydrogen atmosphere at room temperature for 18 hours. The 20% palladium hydroxide carbon was removed, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (acetone) to obtain compound (T-3) (55.01 g, yield 99.5%).

Step 4: Under a nitrogen atmosphere, compound (T-3) (56.43 g, 158.7 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (26.21 g, 166.7 mmol), and Dichloromethane (600 ml) was placed in the reactor and cooled to 0 ° C. To this was added DMAP (5.82 g, 47.62 mmol), followed by DCC (36.03 g, 174.6 mmol). Warm to room temperature and stir for 16 hours. The precipitated colorless solid was removed, and the filtrate was sequentially washed with a saturated sodium bicarbonate aqueous solution and water, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (acetone). Recrystallization was performed from heptane to obtain compound (1-1-1) (25.51 g, yield 32.4%).

¹ H-NMR (ppm; CDCl ₃ ): δ5.19 (tt, J = 11.5 Hz, J = 4.2 Hz, 1H), 5.09 (tt, J = 11.7 Hz, J = 4.2 Hz, 1H), 2.27 (t , J = 7.5 Hz, 2H), 2.26 (t, J = 7.4 Hz, 2H), 2.24 (s, 3H), 1.91 (ddd, J = 10.9 Hz, J = 4.2 Hz, J = 1.4 Hz, 2H), 1.83 (ddd, J = 11.0 Hz, J = 4.2 Hz, J = 1.4 Hz, 2H), 1.59 (quin, J = 6.9 Hz, 4H), 1.47 (dd, J = 11.6 Hz, J = 11.6 Hz, 2H) , 1.36-1.28 (m, 8H), 1.24 (s, 6H), 1.16 (s, 6H), 1.15 (s, 6H), 1.13 (dd, J = 11.7 Hz, J = 11.7 Hz, 2H), 1.07 ( s, 6H), 0.88-0.50 (br, 1H).

Synthesis Example 2 Compound (1-1-2) was synthesized by the following route.

Step 1: Add 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical (25.00 g, 145.1 mmol) and tertiary butanol (50 ml) / water (25 ml) Put into the reactor, and add nonanal (72.26 g, 508.0 mmol) and copper (I) chloride (0.36 g, 3.63 mmol) to the reactor. Furthermore, hydrogen peroxide (30% aqueous solution; 49.37 g, 435.4 mmol) was added dropwise over 1.5 hours, followed by stirring at room temperature for 18 hours. The reaction mixture was extracted with heptane, and the extract was sequentially washed with 10% ascorbic acid aqueous solution, 10% sodium bisulfite aqueous solution, 1 N sodium hydroxide aqueous solution, water, and saturated brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (heptane / acetone = 8/1 (volume ratio)) to obtain compound (T-4) (25.00 g, product Rate 60.3%).

Step 2: Under a nitrogen atmosphere, compound (T-4) (2.56 g, 8.98 mmol), compound (T-1) obtained in Synthesis Example 1 (2.63 g, 8.98 mmol), and dichloromethane (250 ml) into the reactor and cooled to 0 ° C. To this was added DMAP (0.33 g, 2.69 mmol), followed by DCC (2.04 g, 9.88 mmol). Warm to room temperature and stir for 22 hours. The precipitated colorless solid was removed, and the filtrate was sequentially washed with a saturated sodium bicarbonate aqueous solution and water, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (heptane / ethyl acetate = 4/1 (volume ratio)) to obtain compound (T-5) (3.64 g , Yield 72.4%).

Step 3: Put compound (T-5) (3.64 g, 6.50 mmol), 20% palladium hydroxide carbon (0.18 g), and toluene (35 ml) / IPA (35 ml) into the reactor, and Stir under a hydrogen atmosphere at room temperature for 18 hours. The 20% palladium hydroxide carbon was removed, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (heptane / ethyl acetate = 4/1 (volume ratio)) to obtain a compound (T- 6) (2.40 g, 78.6% yield).

Step 4: Under a nitrogen atmosphere, compound (T-6) (2.83 g, 6.03 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (0.99 g, 6.33 mmol), and Dichloromethane (50 ml) was placed in the reactor and cooled to 0 ° C. To this was added DMAP (0.22 g, 1.81 mmol), followed by DCC (1.37 g, 6.63 mmol). Warm to room temperature and stir for 24 hours. The precipitated colorless solid was removed, and the filtrate was sequentially washed with a saturated sodium bicarbonate aqueous solution and water, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate) to obtain compound (1-1-2) (1.62 g, yield 44.2%).

¹ H-NMR (ppm; CDCl ₃ ): δ5.19 (tt, J = 11.4 Hz, J = 4.2 Hz, 1H), 5.01 (tt, J = 11.5 Hz, J = 4.4 Hz, 1H), 3.72 (t , J = 6.7 Hz, 2H), 2.27 (t, J = 7.5 Hz, 2H), 2.25 (t, J = 7.7 Hz, 2H), 1.91 (dd, J = 12.5 Hz, J = 4.2 Hz, 2H), 1.80 (dd, J = 11.1 Hz, J = 3.7 Hz, 2H), 1.61 (quin, J = 7.2 Hz, 4H), 1.56-1.48 (m, 4H), 1.37-1.28 (m, 18H), 1.24 (s , 6H), 1.18 (s, 12H), 1.15 (s, 6H), 1.14 (dd, J = 11.9 Hz, J = 11.9 Hz, 2H), 0.88 (t, J = 6.9 Hz, 3H), 0.85-0.65 (br, 1H).

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is a trans configuration. The number in parentheses after the marked compound indicates the chemical formula to which the compound belongs. The symbol (-) means another liquid crystal compound. The ratio (percentage) of the liquid crystalline compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized.

[Example 1] V-HB (2F, 3F) -O2 (2-1) 7% V2-BB (2F, 3F) -O2 (2-4) 10% V-HHB (2F, 3F) -O1 ( 2-6) 7% V-HHB (2F, 3F) -O2 (2-6) 9% V2-HHB (2F, 3F) -O2 (2-6) 8% 3-HH2B (2F, 3F) -O2 (2-7) 9% V-HBB (2F, 3F) -O2 (2-10) 8% V-HBB (2F, 3F) -O4 (2-10) 6% 3-HH-V (3-1 ) 15% 3-HH-V1 (3-1) 6% 2-HH-3 (3-1) 9% 3-HH-5 (3-1) 3% 1V2-HH-3 (3-1) 3 % The composition (1) was prepared. Compound (1-1-1) was added to the composition in a proportion of 0.15% by weight. The linear afterimage (LISP) was measured according to the method described in Measurement (14), and it was 2.2%. NI = 87.5 ℃; Tc <-20 ℃; Δn = 0.100; Δε = -3.4; Vth = 2.02 V; η = 18.9 mPa ･ s.

[Comparative Example 1] A comparative compound (A-1) was added to the composition (1) described in Example 1 at a ratio of 0.15% by weight. The linear afterimage (LISP) was 4.4%. It is summarized in Table 4 together with the results of Example 1. As can be seen from Table 4, the compound (1-1-1) is more excellent than the comparative compound.

[Example 2] The compound (1-1-2) was added to the composition (1) described in Example 1 at a ratio of 0.15% by weight. The lower limit temperature (Tc) is <-20 ° C. This result is the same as in the case of Example 1.

[Comparative Example 2] The following comparative compound (A-2) was added to the composition (1) described in Example 1 at a ratio of 0.15% by weight. The lower limit temperature (Tc) is <0 ° C. The results of Example 1 and Example 2 are summarized in Table 5. When the solubility of the additive with respect to the composition is good, it is easy to maintain the nematic phase. In the case of poor solubility, it is easy to transfer to crystals (or smectic phases). This method can be used to compare solubility at low temperatures. From Table 5, it turns out that the compound (1) is excellent in solubility compared with a comparative compound.

[Example 3] 3-HB (2F, 3F) -O2 (2-1) 7% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 4% 5-HHB (2F, 3F) -O2 (2-6) 5% 3-HH1OB (2F, 3F) -O2 (2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 33% V-HHB-1 (3-5) 3% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 76.4 ℃; Tc <-20 ℃; Δn = 0.104; Δε = -3.2; Vth = 2.06 V; η = 15.6 mPa ･ s; LISP = 2.4%.

[Example 4] 2-H1OB (2F, 3F) -O2 (2-3) 6% 3-H1OB (2F, 3F) -O2 (2-3) 4% 3-BB (2F, 3F) -O2 ( 2-4) 3% 2-HH1OB (2F, 3F) -O2 (2-8) 14% 2-HBB (2F, 3F) -O2 (2-10) 7% 3-HBB (2F, 3F) -O2 (2-10) 11% 5-HBB (2F, 3F) -O2 (2-10) 9% 2-HH-3 (3-1) 5% 3-HH-VFF (3-1) 30% 1- BB-3 (3-3) 5% 3-HHB-1 (3-5) 3% 3-HBB-2 (3-6) 3% Compound (1-1-1) is added in a proportion of 0.10% by weight In the composition. NI = 78.3 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -3.2; Vth = 2.17 V; η = 17.7 mPa ･ s; LISP = 2.2%.

[Example 5] 3-HB (2F, 3F) -O2 (2-1) 5% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 5% 5-HHB (2F, 3F) -O2 (2-6) 4% 3-HH1OB (2F, 3F) -O2 (2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 9% 4-HBB (2F, 3F) -O2 (2-10) 4% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 (3-5) 5% Compound (1-1-2) is added to the composition at a ratio of 0.10% by weight . NI = 81.2 ℃; Tc <-20 ℃; Δn = 0.107; Δε = -3.2; Vth = 2.11 V; η = 15.5 mPa ･ s.

[Example 6] 3-H2B (2F, 3F) -O2 (2-2) 7% 3-HHB (2F, 3F) -O2 (2-6) 8% 3-HH1OB (2F, 3F) -O2 ( 2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 7% 2-BB (2F, 3F) B-4 (2-9) 7% 3-HDhB (2F, 3F) -O2 (2-16) 3% 5-HDhB (2F, 3F) -O2 (2-16) 4% 2-HchB (2F, 3F) -O2 (2-19) 8% 4-HH-V (3 -1) 15% 3-HH-V1 (3-1) 6% 1-HH-2V1 (3-1) 6% 3-HH-2V1 (3-1) 4% V2-BB-1 (3-3 ) 5% 1V2-BB-1 (3-3) 5% 3-HHB-1 (3-5) 6% 3-HB (F) BH-3 (3-12) 4% Compound (1-1-1) is added to the composition. NI = 88.7 ℃; Tc <-20 ℃; Δn = 0.115; Δε = -1.9; Vth = 2.82 V; η = 17.3 mPa ･ s; LISP = 2.1%.

[Example 7] V2-H2B (2F, 3F) -O2 (2-2) 8% V2-H1OB (2F, 3F) -O4 (2-3) 4% 3-BB (2F, 3F) -O2 ( 2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH2B (2F, 3F) -O2 (2-7) 7% 5-HH2B (2F, 3F) -O2 (2-7) 4% V-HH2B (2F, 3F) -O2 (2-7) 6% V2-HBB (2F, 3F)- O2 (2-10) 5% V-HBB (2F, 3F) -O2 (2-10) 5% V-HBB (2F, 3F) -O4 (2-10) 6% 2-HH-3 (3- 1) 12% 1-BB-5 (3-3) 12% 3-HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 3% 3-HBB-2 (3-6) 3% Compound (1-1-1) was added to the composition at a ratio of 0.10% by weight. NI = 89.9 ℃; Tc <-20 ℃; Δn = 0.122; Δε = -4.2; Vth = 2.16 V; η = 23.4 mPa ･ s; LISP = 2.3%.

[Example 8] 3-HB (2F, 3F) -O2 (2-1) 3% V-HB (2F, 3F) -O2 (2-1) 3% V2-HB (2F, 3F) -O2 ( 2-1) 5% 5-H2B (2F, 3F) -O2 (2-2) 5% V2-BB (2F, 3F) -O2 (2-4) 3% 1V2-BB (2F, 3F) -O2 (2-4) 3% 3-HHB (2F, 3F) -O2 (2-6) 6% V-HHB (2F, 3F) -O2 (2-6) 6% V-HHB (2F, 3F)- O4 (2-6) 5% V2-HHB (2F, 3F) -O2 (2-6) 4% V2-BB (2F, 3F) B-1 (2-9) 4% V2-HBB (2F, 3F ) -O2 (2-10) 5% V-HBB (2F, 3F) -O2 (2-10) 4% V-HBB (2F, 3F) -O4 (2-10) 5% V-HHB (2F, 3Cl) -O2 (2-12) 3% 3-HH-V (3-1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 (3-5) 3% by weight of 0.10 Compound (1-1-1) is added to the composition at a ratio of%. NI = 77.1 ℃; Tc <-20 ℃; Δn = 0.101; Δε = -3.0; Vth = 2.04 V; η = 13.9 mPa ･ s; LISP = 2.2%.

[Example 9] V-HB (2F, 3F) -O2 (2-1) 10% V2-HB (2F, 3F) -O2 (2-1) 10% 2-H1OB (2F, 3F) -O2 ( 2-3) 3% 3-H1OB (2F, 3F) -O2 (2-3) 3% 2O-BB (2F, 3F) -O2 (2-4) 3% V2-BB (2F, 3F) -O2 (2-4) 8% V2-HHB (2F, 3F) -O2 (2-6) 5% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F)- O2 (2-10) 3% V-HBB (2F, 3F) -O2 (2-10) 6% V-HBB (2F, 3F) -O4 (2-10) 8% V-HHB (2F, 3Cl) -O2 (2-12) 7% 3-HH-4 (3-1) 14% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 7% to 0.10% by weight Compound (1-1-2) is added to this composition in proportion. NI = 75.9 ℃; Tc <-20 ℃; Δn = 0.114; Δε = -3.9; Vth = 2.20 V; η = 24.7 mPa ･ s.

[Example 10] 3-HB (2F, 3F) -O2 (2-1) 10% 5-HB (2F, 3F) -O2 (2-1) 7% 2-BB (2F, 3F) -O2 ( 2-4) 7% 3-BB (2F, 3F) -O2 (2-4) 7% 3-B (2F, 3F) B (2F, 3F) -O2 (2-5) 3% 2-HHB ( 2F, 3F) -O2 (2-6) 5% 3-HHB (2F, 3F) -O2 (2-6) 10% 2-HBB (2F, 3F) -O2 (2-10) 8% 3-HBB (2F, 3F) -O2 (2-10) 10% 2-HH-3 (3-1) 14% 3-HB-O1 (3-2) 5% 3-HHB-1 (3-5) 3% 3-HHB-O1 (3-5) 3% 3-HHB-3 (3-5) 4% 2-BB (F) B-3 (3-8) 4% The compound (1 -1-1) is added to the composition. NI = 73.2 ℃; Tc <-20 ℃; Δn = 0.113; Δε = -4.0; Vth = 2.18 V; η = 22.6 mPa ･ s; LISP = 2.1%.

[Example 11] 3-HB (2F, 3F) -O4 (2-1) 6% 3-H2B (2F, 3F) -O2 (2-2) 8% 3-H1OB (2F, 3F) -O2 ( 2-3) 4% 3-BB (2F, 3F) -O2 (2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH2B (2F, 3F) -O2 (2-7) 7% 5-HH2B (2F, 3F) -O2 (2-7) 4% 2-HBB (2F, 3F)- O2 (2-10) 5% 3-HBB (2F, 3F) -O2 (2-10) 5% 4-HBB (2F, 3F) -O2 (2-10) 6% 2-HH-3 (3- 1) 12% 1-BB-5 (3-3) 12% 3-HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 3% 3-HBB-2 (3-6) 3% Compound (1-1-1) was added to the composition at a ratio of 0.10% by weight. NI = 82.8 ℃; Tc <-20 ℃; Δn = 0.118; Δε = -4.4; Vth = 2.13 V; η = 22.5 mPa ･ s; LISP = 2.0%.

[Example 12] 3-HB (2F, 3F) -O2 (2-1) 7% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 5% 5-HHB (2F, 3F) -O2 (2-6) 4% 3-HH1OB (2F, 3F) -O2 (2-8) 4% 2-BB (2F, 3F) B-3 (2-9) 5% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 (3-5) 3% Compound (1-1-1) is added to the composition in a proportion of 0.15% by weight . NI = 78.1 ℃; Tc <-20 ℃; Δn = 0.107; Δε = -3.2; Vth = 2.02 V; η = 15.9 mPa ･ s; LISP = 2.2%.

[Example 13] 3-HB (2F, 3F) -O2 (2-1) 10% 5-HB (2F, 3F) -O2 (2-1) 10% 3-H2B (2F, 3F) -O2 ( 2-2) 8% 5-H2B (2F, 3F) -O2 (2-2) 8% 2-HBB (2F, 3F) -O2 (2-10) 6% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 7% 3-HDhB (2F, 3F)- O2 (2-16) 5% 3-HH-4 (3-1) 14% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 7% at a ratio of 0.10% by weight Compound (1-1-1) is added to the composition. NI = 88.5 ℃; Tc <-20 ℃; Δn = 0.108; Δε = -3.8; Vth = 2.25 V; η = 24.6 mPa ･ s; LISP = 2.1%.

[Example 14] 3-HB (2F, 3F) -O2 (2-1) 7% 3-HB (2F, 3F) -O4 (2-1) 8% 3-H2B (2F, 3F) -O2 ( 2-2) 8% 3-BB (2F, 3F) -O2 (2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 4% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -1 (2-6) 6% 2-HBB (2F, 3F) -O2 (2-10) 6% 3-HBB (2F, 3F)- O2 (2-10) 6% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 4% 3-HEB (2F, 3F) B (2F, 3F) -O2 (2-11) 3% 3-H1OCro (7F, 8F) -5 (2-14) 3% 3-HDhB (2F, 3F) -O2 (2-16) 5% 3 -HH-O1 (3-1) 5% 1-BB-5 (3-3) 4% V-HHB-1 (3-5) 4% 5-HB (F) BH-3 (3-12) 5 % Compound (1-1-1) is added to the composition in a proportion of 0.15% by weight. NI = 81.1 ℃; Tc <-20 ℃; Δn = 0.119; Δε = -4.5; Vth = 1.69 V; η = 31.4 mPa ･ s; LISP = 2.4%.

[Example 15] 3-HB (2F, 3F) -O4 (2-1) 15% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 ( 2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 7% 3-dhBB (2F, 3F) -O2 (2-17) 5% 3-chB (2F, 3F) -O2 (2-18) 7% 2-HchB (2F, 3F) -O2 (2-19) 8% 5-HH-V (3-1) 18% 7-HB-1 (3-2) 5% V- HHB-1 (3-5) 7% V2-HHB-1 (3-5) 7% 3-HBB (F) B-3 (3-13) 8% Compound (1-1 -1) Added to this composition. NI = 98.8 ℃; Tc <-20 ℃; Δn = 0.111; Δε = -3.2; Vth = 2.47 V; η = 23.9 mPa ･ s; LISP = 2.1%.

[Example 16] 3-H2B (2F, 3F) -O2 (2-2) 18% 5-H2B (2F, 3F) -O2 (2-2) 17% 3-HHB (2F, 3Cl) -O2 ( 2-12) 5% 3-HBB (2F, 3Cl) -O2 (2-13) 8% 5-HBB (2F, 3Cl) -O2 (2-13) 7% 3-HDhB (2F, 3F) -O2 (2-16) 5% 3-HH-V (3-1) 11% 3-HH-VFF (3-1) 7% F3-HH-V (3-1) 10% 3-HHEH-3 (3 -4) 4% 3-HB (F) HH-2 (3-10) 4% 3-HHEBH-3 (3-11) 4% Compound (1-1-1) is added to 0.15 wt% This composition. NI = 77.5 ℃; Tc <-20 ℃; Δn = 0.084; Δε = -2.6; Vth = 2.43 V; η = 22.8 mPa ･ s; LISP = 2.5%.

[Example 17] 3-HB (2F, 3F) -O2 (2-1) 8% 3-H2B (2F, 3F) -O2 (2-2) 10% 3-BB (2F, 3F) -O2 ( 2-4) 10% 2O-BB (2F, 3F) -O2 (2-4) 3% 2-HHB (2F, 3F) -O2 (2-6) 4% 3-HHB (2F, 3F) -O2 (2-6) 7% 2-HHB (2F, 3F) -1 (2-6) 5% 2-BB (2F, 3F) B-3 (2-9) 6% 2-BB (2F, 3F) B-4 (2-9) 6% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F) -O2 (2-10) 7% 3-HH1OCro (7F, 8F) -5 (2-15) 4% 3-HDhB (2F, 3F) -O2 (2-16) 6% 3-dhBB (2F, 3F) -O2 (2-17) 4% 3-HH-V (3-1) 11% 1-BB-5 (3-3) 5% Compound (1-1-2) is added to the composition at a ratio of 0.10% by weight. NI = 70.6 ℃; Tc <-20 ℃; Δn = 0.129; Δε = -4.3; Vth = 1.69 V; η = 27.0 mPa ･ s.

[Example 18] 3-HB (2F, 3F) -O4 (2-1) 14% 3-H1OB (2F, 3F) -O2 (2-3) 3% 3-BB (2F, 3F) -O2 ( 2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH1OB (2F, 3F) -O2 (2-8) 6% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F) -O2 (2-10) 6% 4-HBB (2F, 3F)- O2 (2-10) 4% 3-HH-V (3-1) 14% 1-BB-3 (3-3) 3% 3-HHB-1 (3-5) 4% 3-HHB-O1 ( 3-5) 4% V-HBB-2 (3-6) 4% 1-BB (F) B-2V (3-8) 6% 5-HBBH-1O1 (-) 4% at a ratio of 0.12% by weight Compound (1-1-1) is added to the composition. NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.123; Δε = -4.0; Vth = 2.27 V; η = 29.6 mPa ･ s; LISP = 2.2%.

[Example 19] 3-HB (2F, 3F) -O4 (2-1) 6% 3-H2B (2F, 3F) -O2 (2-2) 8% 3-H1OB (2F, 3F) -O2 ( 2-3) 5% 3-BB (2F, 3F) -O2 (2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 5-HHB (2F, 3F) -O2 (2-6) 7% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F)- O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 6% 3-HH-V (3-1) 11% 1-BB-3 (3-3) 6% 3 -HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 4% 3-B (F) BB-2 (3-7) 4 % Compound (1-1-1) is added to the composition in a proportion of 0.15% by weight. NI = 87.6 ℃; Tc <-20 ℃; Δn = 0.126; Δε = -4.5; Vth = 2.21 V; η = 25.3 mPa ･ s; LISP = 2.3%.

[Example 20] 3-HB (2F, 3F) -O4 (2-1) 6% 3-H2B (2F, 3F) -O2 (2-2) 8% 3-H1OB (2F, 3F) -O2 ( 2-3) 4% 3-BB (2F, 3F) -O2 (2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 6% 3-HHB (2F, 3F) -O2 (2-6) 10% 5-HHB (2F, 3F) -O2 (2-6) 8% 2-HBB (2F, 3F) -O2 (2-10) 5% 3-HBB (2F, 3F)- O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 5% 2-HH-3 (3-1) 12% 1-BB-3 (3-3) 6% 3 -HHB-1 (3-5) 3% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 6% 3-B (F) BB-2 (3-7) 3 % Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.124; Δε = -4.5; Vth = 2.22 V; η = 25.0 mPa ･ s; LISP = 2.2%.

[Example 21] 3-H2B (2F, 3F) -O2 (2-2) 10% 3-BB (2F, 3F) -O2 (2-4) 10% 5-BB (2F, 3F) -O2 ( 2-4) 5% V-HHB (2F, 3F) -O1 (2-6) 5% V-HHB (2F, 3F) -O2 (2-6) 12% V-HHB (2F, 3F) -O4 (2-6) 8% 3-HDhB (2F, 3F) -O2 (2-16) 8% 3-HH-V (3-1) 23% 3-HH-4 (3-1) 11% 3- HHB-1 (3-5) 4% 3-HHB-3 (3-5) 2% 3-HHB-O1 (3-5) 2% Compound (1-1-1) is added in a proportion of 0.10% by weight In the composition. NI = 74.7 ℃; Tc <-20 ℃; Δn = 0.089; Δε = -3.3; Vth = 2.14 V; η = 16.3 mPa ･ s; LISP = 2.4%.

[Example 22] 3-BB (2F, 3F) -O2 (2-4) 13% 5-BB (2F, 3F) -O2 (2-4) 12% V-HHB (2F, 3F) -O1 ( 2-6) 5% V-HHB (2F, 3F) -O2 (2-6) 12% V-HHB (2F, 3F) -O4 (2-6) 14% 3-HH-V (3-1) 16% 3-HH-4 (3-1) 11% 1-BB-3 (3-3) 4% 3-HHB-O1 (3-5) 2% 3-HHB-1 (3-5) 7% 3-HHB-3 (3-5) 4% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 76.3 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -2.9; Vth = 2.24 V; η = 16.4 mPa ･ s; LISP = 2.1%.

[Example 23] 3-H2B (2F, 3F) -O2 (2-2) 13% 5-H2B (2F, 3F) -O2 (2-2) 14% V-HHB (2F, 3F) -O1 ( 2-6) 5% V-HHB (2F, 3F) -O2 (2-6) 12% V-HHB (2F, 3F) -O4 (2-6) 14% 3-HH2B (2F, 3F) -O2 (2-7) 4% 3-HH-V (3-1) 16% 1-BB-3 (3-3) 4% 1-BB-5 (3-3) 4.5% 3-HHB-1 (3 -5) 1.5% 3-HBB-2 (3-6) 12% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 75.6 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -3.1; Vth = 2.30 V; η = 18.1 mPa ･ s; LISP = 2.0%.

[Example 24] 3-HB (2F, 3F) -O2 (2-1) 6% 3-H1OB (2F, 3F) -O2 (2-3) 11% 2-HH1OB (2F, 3F) -O2 ( 2-8) 13% 3-HH1OB (2F, 3F) -O2 (2-8) 8% 3-HH-5 (3-1) 5% 2-HH-3 (3-1) 11% 3-HH -4 (3-1) 11% 3-HB-O2 (3-2) 3% 1-BB-3 (3-3) 4% 1-BB-5 (3-3) 4% 3-HHB-1 (3-5) 5.5% 3-HBB-2 (3-6) 6.5% 5-B (F) BB-2 (3-7) 12% Compound (1-1-1) at a ratio of 0.10% by weight Added to this composition. NI = 75.3 ℃; Tc <-20 ℃; Δn = 0.105; Δε = -2.4; Vth = 2.43 V; η = 16.7 mPa ･ s; LISP = 2.3%.

[Example 25] 2-H1OB (2F, 3F) -O2 (2-3) 7% 3-H1OB (2F, 3F) -O2 (2-3) 7% 2-HHB (2F, 3F) -O2 ( 2-6) 3% 3-HHB (2F, 3F) -O2 (2-6) 4% 5-HHB (2F, 3F) -O2 (2-6) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 3% 5-HBB (2F, 3F)- O2 (2-10) 4% 3-HDhB (2F, 3F) -O2 (2-16) 6% 2-HH-3 (3-1) 18% 2-HH-5 (3-1) 3% 3 -HH-4 (3-1) 4% 3-HH-5 (3-1) 3% 3-HB-O2 (3-2) 17.5% 3-HHB-3 (3-5) 3.5% 3-HHB -O1 (3-5) 2% Compound (1-1-1) is added at a ratio of 0.10% by weight, and compound (4-25-1) is added at a ratio of 0.43% by weight. NI = 75.2 ℃; Δn = 0.089; Δε = -3.0; Vth = 2.24 V; LISP = 2.2%.

[Example 26] 2-H1OB (2F, 3F) -O2 (2-3) 7% 3-H1OB (2F, 3F) -O2 (2-3) 7% 2-HHB (2F, 3F) -O2 ( 2-6) 3% 3-HHB (2F, 3F) -O2 (2-6) 4% 5-HHB (2F, 3F) -O2 (2-6) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 3% 5-HBB (2F, 3F)- O2 (2-10) 4% 3-HDhB (2F, 3F) -O2 (2-16) 6% 2-HH-3 (3-1) 18% 2-HH-5 (3-1) 3% 3 -HH-4 (3-1) 4% 3-HH-5 (3-1) 3% 3-HB-O2 (3-2) 17.5% 3-HHB-3 (3-5) 3.5% 3-HHB -O1 (3-5) 2% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight, and compound (4-25-1) is added at a ratio of 0.80% by weight. NI = 74.9 ℃; Δn = 0.089; Δε = -3.3; Vth = 2.24 V; LISP = 2.1%.

[Example 27] V-HB (2F, 3F) -O2 (2-1) 7% V2-BB (2F, 3F) -O2 (2-4) 10% V-HHB (2F, 3F) -O1 ( 2-6) 7% V-HHB (2F, 3F) -O2 (2-6) 9% V2-HHB (2F, 3F) -O2 (2-6) 8% 3-HH2B (2F, 3F) -O2 (2-7) 9% V-HBB (2F, 3F) -O2 (2-10) 7% V-HBB (2F, 3F) -O4 (2-10) 7% 3-HH-V (3-1 ) 15% 3-HH-V1 (3-1) 6% 2-HH-3 (3-1) 9% 3-HH-4 (3-1) 3% 1V2-HH-3 (3-1) 3 % Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 87.5 ℃; Δn = 0.100; Δε = -3.4; Vth = 2.25 V; LISP = 2.2%.

[Example 28] 3-H1OB (2F, 3F) -O2 (2-3) 10% 2-BB (2F, 3F) -O2 (2-4) 5% V2-BB (2F, 3F) -O2 ( 2-4) 11% 2-HH1OB (2F, 3F) -O2 (2-8) 6% 3-HH1OB (2F, 3F) -O2 (2-8) 18% 3-HH-VFF (3-1) 30% 1-BB-3 (3-3) 2.5% 3-HHB-1 (3-5) 5% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 8.5% Compound (1-1-1) was added to the composition at a ratio of 0.10% by weight. NI = 75.7 ℃; Δn = 0.101; Δε = -3.3; Vth = 2.22 V; η = 15.8 mPa ･ s; LISP = 2.4%.

[Example 29] 3-H1OB (2F, 3F) -O2 (2-3) 11.5% 2-BB (2F, 3F) -O2 (2-4) 5% V2-BB (2F, 3F) -O2 ( 2-4) 11% V-HHB (2F, 3F) -O1 (2-6) 6% V-HHB (2F, 3F) -O2 (2-6) 10% 2-HH1OB (2F, 3F) -O2 (2-8) 6% 3-HH1OB (2F, 3F) -O2 (2-8) 3% 3-HH-VFF (3-1) 30% 3-HHB-1 (3-5) 5% 3- HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 8.5% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 76.4 ℃; Δn = 0.101; Δε = -3.3; Vth = 2.21 V; η = 15.9 mPa ･ s; LISP = 2.6%.

[Example 30] 3-H2B (2F, 3F) -O2 (2-2) 13% 2-BB (2F, 3F) -O2 (2-4) 3.5% 3-BB (2F, 3F) -O2 ( 2-4) 4% 3-HH2B (2F, 3F) -O2 (2-7) 11% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 9% 4-HBB (2F, 3F) -O2 (2-10) 2% V-HBB (2F, 3F) -O2 (2-10) 8% V-HBB (2F, 3F)- O4 (2-10) 4% 2-HH-3 (3-1) 21% 3-HH-VFF (3-1) 9% 3-HB-O2 (3-2) 2.5% 3-HHB-1 ( 3-5) 5% 3-HHB-3 (3-5) 5% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 80.2 ℃; Tc <-20 ℃; Δn = 0.102; Δε = -2.8; Vth = 2.43 V; η = 14.2 mPa ･ s; LISP = 2.1%.

[Example 31] 2-H1OB (2F, 3F) -O2 (2-3) 6% 3-H1OB (2F, 3F) -O2 (2-3) 7% V2-BB (2F, 3F) -O2 ( 2-4) 3% 2-BB (2F, 3F) -O2 (2-4) 4% 3-BB (2F, 3F) -O2 (2-4) 6% 3-HH2B (2F, 3F) -O2 (2-7) 7% 3-HH1OB (2F, 3F) -O2 (2-8) 5% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F)- O2 (2-10) 7% 4-HBB (2F, 3F) -O2 (2-10) 3% V-HBB (2F, 3F) -O2 (2-10) 7% V-HBB (2F, 3F) -O4 (2-10) 5% 2-HH-3 (3-1) 13% 3-HH-4 (3-1) 10% 3-HHB-1 (3-5) 4% 3-HHB-3 (3-5) 5% 3-HHB-O1 (3-5) 3% 3-HBB-2 (3-6) 2% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. In. NI = 85.7 ℃; Tc <-20 ℃; Δn = 0.111; Δε = -4.0; Vth = 2.08 V; η = 21.8 mPa ･ s; LISP = 2.2%.

[Example 32] 3-H2B (2F, 3F) -O2 (2-2) 17% 5-H2B (2F, 3F) -O2 (2-2) 12% 3-H1OB (2F, 3F) -O2 ( 2-3) 8% 3-HH1OB (2F, 3F) -O2 (2-8) 3% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 7% 4-HBB (2F, 3F) -O2 (2-10) 4% 5-HBB (2F, 3F) -O2 (2-10) 8% V-HBB (2F, 3F)- O2 (2-10) 4% V-HBB (2F, 3F) -O4 (2-10) 5% 3-HDhB (2F, 3F) -O2 (2-16) 8% 2-HH-3 (3- 1) 6% 3-HH-4 (3-1) 3% 3-HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 2% 3-HBB-2 (3-6) 6% Compound (1-1-1) was added to the composition at a ratio of 0.10% by weight. NI = 84.5 ℃; Tc <-20 ℃; Δn = 0.114; Δε = -5.5; Vth = 1.81 V; η = 29.4 mPa ･ s; LISP = 2.3%.

[Example 33] 3-BB (2F, 3F) -O2 (2-4) 10% V2-BB (2F, 3F) -O2 (2-4) 6% 2-HH1OB (2F, 3F) -O2 ( 2-8) 13% 3-HH1OB (2F, 3F) -O2 (2-8) 14% 2-HBB (2F, 3F) -O2 (2-10) 2% 3-HBB (2F, 3F) -O2 (2-10) 6% V-HBB (2F, 3F) -O2 (2-10) 6% V-HBB (2F, 3F) -O4 (2-10) 3% 2-HH-3 (3-1 ) 7% 3-HH-VFF (3-1) 25% 3-HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 2% 3-HBB-2 (3-6) 2 % Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 89.5 ℃; Tc <-20 ℃; Δn = 0.108; Δε = -3.8; Vth = 2.11 V; η = 20.2 mPa ･ s; LISP = 2.1%.

[Example 34] 3-H2B (2F, 3F) -O2 (2-2) 9% 3-BB (2F, 3F) -O2 (2-4) 9% V2-BB (2F, 3F) -O2 ( 2-4) 8% 3-HH2B (2F, 3F) -O2 (2-7) 15% 3-HDhB (2F, 3F) -O2 (2-16) 18% 3-HH-V (3-1) 29% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 2% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 74.6 ℃; Δn = 0.095; Δε = -3.5; Vth = 2.16 V; LISP = 2.2%.

[Example 35] 3-HB (2F, 3F) -O2 (2-1) 8% 5-HB (2F, 3F) -O2 (2-1) 3% 2-BB (2F, 3F) -O2 ( 2-4) 8% V2-BB (2F, 3F) -O2 (2-4) 7% 3-HHB (2F, 3F) -O2 (2-6) 10% V-HHB (2F, 3F) -O1 (2-6) 4% V-HHB (2F, 3F) -O2 (2-6) 10% 3-HDhB (2F, 3F) -O2 (2-16) 10% 3-HH-V (3-1 ) 29% V-HHB-1 (3-5) 11% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight. NI = 75.4 ℃; Δn = 0.094; Δε = -3.6; Vth = 2.05 V; LISP = 2.0%.

[Example 36] V-HB (2F, 3F) -O2 (2-1) 5% 2-BB (2F, 3F) -O2 (2-4) 6% 3-BB (2F, 3F) -O2 ( 2-4) 11% V-HHB (2F, 3F) -O1 (2-6) 6% V-HHB (2F, 3F) -O2 (2-6) 12% V-HHB (2F, 3F) -O4 (2-6) 6% V2-HHB (2F, 3F) -O2 (2-6) 10% V-HBB (2F, 3F) -O2 (2-10) 7% V-HBB (2F, 3F)- O4 (2-10) 7% 3-HH-V (3-1) 27.5% 3-HH-V1 (3-1) 2.5% Compound (1-1-1) is added to this in a proportion of 0.15% by weight组合 物。 Composition. NI = 79.6 ℃; Tc <-30 ℃; Δn = 0.107; Δε = -4.1; Vth = 1.94 V; LISP = 2.5%.

[Example 37] 2-H1OB (2F, 3F) -O2 (2-3) 10% 3-H1OB (2F, 3F) -O2 (2-3) 10% 2-HHB (2F, 3F) -O2 ( 2-6) 4% 3-HHB (2F, 3F) -O2 (2-6) 6% 5-HHB (2F, 3F) -O2 (2-6) 2% 2-HBB (2F, 3F) -O2 (2-10) 2% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 8% 5-HBB (2F, 3F)- O2 (2-10) 3% 2-HH-3 (3-1) 22% 3-HH-4 (3-1) 4% 3-HB-O2 (3-2) 10% 3-HBB-2 ( 3-6) 11% Compound (1-1-1) is added to the composition at a ratio of 0.10% by weight, and compound (4-25-1) is added at a ratio of 0.30% by weight. NI = 75.9 ℃; Δn = 0.098; Δε = -3.2; Vth = 2.09 V; LISP = 2.2%.

[Example 38] 3-BB (2F, 3F) -O2 (2-4) 13% 2-HH1OB (2F, 3F) -O2 (2-8) 20% 3-HH1OB (2F, 3F) -O2 ( 2-8) 14% 3-HH-V (3-1) 31% 1-BB-5 (3-3) 8% 3-HHB-1 (3-5) 4% 3-HHB-3 (3- 5) 3% 5-B (F) BB-2 (3-7) 7% Finally, evaluate scalability. The composition (38) is prepared. Compound (1-1-1) was added to the composition at a ratio of 0.01% by weight. Scalability was measured by the method described in Measurement (15), and qualitatively evaluated based on FIG. 1 (Table 6).

[Example 39] The compound (1-1-2) was added to the composition (38) described in Example 38 at a ratio of 0.01% by weight. The extensibility of the compound was evaluated according to FIG. 2 (Table 6).

[Comparative Example 3] A comparative compound (A-2) was added to the composition (38) described in Example 38 at a ratio of 0.01% by weight. The extensibility of the compound was evaluated according to FIG. 3. The results are summarized in Table 6 together with the results of Examples 38 and 39.

Figures 1 to 3 are photos of the components. The injection port is located on the lower side of the photo, from which the composition containing additives is injected. In FIG. 1 and FIG. 2, the brightness is different from each other, but the brightness is uniform as a whole. These indicate good scalability. In FIG. 3, a convex curve is observed from above. This means that although the device was filled with the liquid crystal composition, the additives contained in the composition did not reach the upper end of the device. From these results, it can be seen that in Examples 38 and 39, the scalability was good. On the other hand, in Comparative Example 3, the scalability was poor.

Comparative experiments on line afterimage, lower limit temperature (solubility at low temperature), and expandability were performed, and the results are summarized in Table 4, Table 5, and Table 6. In either case, the compound (1) achieved superior results compared to the comparative compound. Therefore, it can be concluded that the composition of the present invention has excellent characteristics. [Industrial availability]

The liquid crystal composition of the present invention can be used in a liquid crystal monitor, a liquid crystal television, and the like.

no

FIG. 1 is a photograph showing a device having good expandability. FIG. 2 is a photograph showing a device having good expandability. FIG. 3 is a photograph showing an element having poor scalability.

no

Claims (21)

A compound having the (S) a divalent group represented by the formula is at least two, the plurality monovalent group, the other group with a group represented by R ¹ is represented by R ¹ by a different, In the formula (S), R ¹ is hydrogen, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons; R is an alkyl group having 1 to 12 carbons. The compound according to item 1 of the scope of patent application, wherein in the monovalent group represented by the formula (S) described in item 1 of the scope of patent application, R is methyl. The compound as described in claim 1 or 2, which is represented by formula (1), In Formula (1) and Formula (S-1), R ¹ is hydrogen, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons. Here, the group represented by R ¹ and Other R ¹ groups are different; ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenyl, naphthalene-1,2-diyl, naphthalene-1 , 3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl Naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2, 5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, carbon 1 Alkoxy to 12, at least one hydrogen substituted with fluorine or chlorine, an alkyl group having 1 to 12 carbons, or a group represented by formula (S-1); Z ¹ and Z ^{2 are} independently a single bond or carbon 1 to 20 alkylene groups, at least one of which is -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and among these groups, at least one hydrogen group may be fluorine, chlorine, or formula (S-1) represented by substituent; Z ³ is a single bond or alkylene having a carbon number of 1 to 20, said alkylene, at least one -CH ₂ - may be -O - -OCOO- substituted OCO-, or, the plurality of groups, at least one hydrogen may be replaced by fluorine or chlorine, - COO - -,; a is 0, 1, or 3. The compound according to item 1 of the scope of patent application, which is represented by any one of formula (1-1) to formula (1-9), In formulas (1-1) to (1-9), R ² is an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons; Z ⁴ is an alkylene group having 1 to 15 carbons; Z ⁵ and Z ^{6 are} independently an alkylene group having 1 to 5 carbon atoms; Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 20 carbon atoms, and at least one of the alkylene groups is -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, in which at least one hydrogen may be substituted with fluorine or chlorine; X ¹ is hydrogen or fluorine. A liquid crystal composition containing at least one compound as described in any one of claims 1 to 4 of the scope of patent application as a first additive, and having negative dielectric anisotropy. The liquid crystal composition according to item 5 of the scope of patent application, wherein the proportion of the first additive is in the range of 0.005% by weight to 1% by weight. The liquid crystal composition according to item 5 or item 6 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (2) as a first component, In formula (2), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an olefin having 2 to 12 carbons Oxygen; ring B and ring D are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least 1,4-phenylene substituted with fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, chromogen-2,6 -Diyl, or chromogen-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; ring C is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro -1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8 -Difluorochroman-2,6-diyl; Z ⁹ and Z ^{10 are} independently a single bond, ethylene, carbonyloxy, or methyleneoxy; b is 1, 2, or 3, and c is 0 or 1, and the sum of b and c is 3 or less. The liquid crystal composition according to item 5 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-22) as a first component, In the formulae (2-1) to (2-22), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyloxy group having 2 to 12 carbon atoms. The liquid crystal composition according to item 7 of the scope of patent application, wherein the ratio of the first component is in a range of 10% by weight to 90% by weight. The liquid crystal composition according to item 5 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (3) as a second component, In formula (3), R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least one hydrogen is substituted with fluorine or chlorine Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring E and ring F are independently 1,4-cyclohexyl, 1,4-cyclohexyl Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ¹¹ is a single bond, ethylene, carbonyloxy, or methyleneoxy ; D is 1, 2, or 3. The liquid crystal composition according to item 5 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as a second component, In the formulae (3-1) to (3-13), R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , At least one hydrogen having 1 to 12 carbons substituted with fluorine or chlorine, or at least one hydrogen having 2 to 12 carbons substituted with fluorine or chlorine. The liquid crystal composition according to item 10 of the scope of patent application, wherein the proportion of the second component is in a range of 10% by weight to 90% by weight. The liquid crystal composition according to item 5 of the scope of patent application, which contains at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive, In formula (4), ring G and ring J are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Or at least one hydrogen substituted with fluorine or chlorine and 1 to 12 carbon alkyl groups; ring I is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be passed through fluorine, chlorine , An alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Z ¹² and Z ^{13 are} independently a single bond Or an alkylene group having 1 to 10 carbon atoms, at least one -CH ₂ -of which may be substituted with -O-, -CO-, -COO-, or -OCO- -CH ₂ CH ₂ -may be replaced by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, Among these groups, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ^{3 are} independently polymerizable groups; Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or a carbon number of 1 to 10 alkylene groups, at least one -CH ₂ -of which may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be- CH = CH- or -C≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; e is 0, 1, or 2; f, g, and h are independently 0, 1, 2 , 3, or 4, and the sum of f, g, and h is 1 or more. The liquid crystal composition according to item 13 of the scope of patent application, wherein in formula (4), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of formulas (P-1) to (P-5) Radicals in the group of polymerizable radicals, In the formulae (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkyl having 1 to 5 carbons. The liquid crystal composition according to item 13 of the scope of patent application, which contains at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27) as a second additive. , In Formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ^{6 are} independently selected from the group consisting of polymerizable groups represented by Formulas (P-1) to (P-3) Base in group, Here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the alkylene groups, at least one of -CH ₂ -may pass through -O-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine. The liquid crystal composition according to item 13 of the scope of patent application, wherein the ratio of the second additive is in a range of 0.03% by weight to 10% by weight. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 5 to 16 of the scope of patent application. The liquid crystal display element according to item 17 of the scope of the patent application, wherein the operation mode of the liquid crystal display element is an in-plane switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced light reaction alignment mode, and a driving mode of the liquid crystal display element. Active matrix method. A polymer-stable alignment type liquid crystal display element includes the liquid crystal composition according to any one of claims 13 to 16 of the scope of application for a patent, and a second additive contained in the liquid crystal composition is subjected to polymerization. A use of a liquid crystal composition, which is the liquid crystal composition according to any one of items 5 to 16 of the scope of application for a patent, which is used in a liquid crystal display element. A use of a liquid crystal composition, which is the liquid crystal composition according to any one of items 5 to 16 of the scope of application for a patent, which is used in a polymer-stabilized alignment type liquid crystal display element.