CN111051473B

CN111051473B - Liquid crystal composition and liquid crystal display element

Info

Publication number: CN111051473B
Application number: CN201880052963.2A
Authority: CN
Inventors: 井上大辅; 斋藤将之; 奥村一雄; 泽田道子
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2017-10-02
Filing date: 2018-08-03
Publication date: 2023-08-01
Anticipated expiration: 2038-08-03
Also published as: JP7070582B2; TWI775916B; JPWO2019069549A1; WO2019069549A1; CN111051473A; TW201918545A

Abstract

The invention provides a compound, a liquid crystal composition and a liquid crystal display element. A liquid crystal composition contains a specific ultraviolet absorber as a first additive, and may contain a specific compound having a small viscosity or a high upper limit temperature as a first component, a specific compound having a large positive dielectric anisotropy as a second component, a specific compound having a large negative dielectric anisotropy as a third component, or a specific compound having a polymerizable group as a second additive.

Description

Liquid crystal composition and liquid crystal display element

Technical Field

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. And relates to a liquid crystal composition having positive or negative dielectric anisotropy, and an Active Matrix (AM) element containing the composition and having a mode of TN, OCB, IPS, VA, FFS, FPA or the like. And a polymer stabilized alignment type liquid crystal display element.

Background

In the liquid crystal display element, modes based on the operation mode of liquid crystal molecules are classified into Phase Change (PC), twisted Nematic (TN), super twisted nematic (super twisted nematic, STN), electrically controlled birefringence (electrically controlled birefringence, ECB), optically compensated bend (optically compensated bend, OCB), in-plane switching (IPS), vertical alignment (vertical alignment, VA), fringe field switching (fringe field switching, FFS), field-induced photo-reactive alignment (FPA), and the like. The driving modes based on the elements are classified into Passive Matrix (PM) and Active Matrix (AM). PM is classified into static type (static), multiplex type (multiplex) and the like, and AM is classified into thin film transistor (thin film transistor, TFT), metal-insulator-metal (metal insulator metal, MIM) and the like. TFTs are classified as amorphous silicon (amorphous silicon) and polysilicon (polycrystal silicon). The latter is classified into a high temperature type and a low temperature type according to the 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. The composition has suitable properties. By improving the characteristics of the composition, an AM element having good characteristics can be obtained. The correlation among these characteristics is summarized in table 1 below. The properties of the composition are further described based on commercially available AM elements. The temperature range of the nematic phase is associated with the temperature range in which the element can be used. The preferable upper limit temperature of the nematic phase is about 70 ℃ or higher, and the preferable lower limit temperature of the nematic phase is about-10 ℃ or lower. The viscosity of the composition is related to the response time of the element. In order to display a moving image (moving image) in an element, the response time is preferably short. Ideally less than 1 millisecond of response time. Therefore, the viscosity of the composition is preferably small. Further, the viscosity at low temperature is preferably small.

TABLE 1

TABLE 1 Properties of composition and AM element Properties

The optical anisotropy of the composition is related to the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. 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 ratio. The value of the appropriate product depends on the type of operation mode. In elements of TN-like mode, a suitable value is about 0.45. Mu.m. In this case, a composition having large optical anisotropy is preferable for an element having a small cell gap. The large dielectric anisotropy of the composition contributes to a low threshold voltage, small power consumption and large contrast ratio of the element. Therefore, a large dielectric anisotropy is preferable. In particular, in FFS mode, since some of the liquid crystal molecules are aligned not parallel to the panel substrate by the oblique electric field, it is preferable that the dielectric constant (ε Σ) in the short axis direction of the liquid crystal molecules is large in order to suppress upward tilt of the liquid crystal molecules. By suppressing upward tilting of the liquid crystal molecules, the transmittance of the element having FFS mode can be improved, thus contributing to a large contrast ratio. The large specific resistance of the composition contributes to a large voltage holding ratio to a large contrast ratio of the element. Therefore, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable. And is preferably a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition to ultraviolet light and heat is related to the lifetime of the liquid crystal display element. When these are of high stability, the elements have a long life. Such characteristics are preferable for AM devices used in liquid crystal monitors, liquid crystal televisions, and the like.

A composition having positive dielectric anisotropy is used in an AM element having a TN mode. A composition having negative dielectric anisotropy is used in an AM element having a VA mode. A composition having positive or negative dielectric anisotropy is used in an AM element having an IPS mode or FFS mode. In AM elements with polymer stabilized orientation (polymer sustained alignment, PSA), compositions with positive or negative dielectric anisotropy are used.

On the other hand, patent document 1 describes a compound for improving the stability of a thermosetting composition and a thermoplastic composition against heat, oxygen, or light.

Prior art literature

Patent literature

Patent document 1: international publication No. 2002/079173

Disclosure of Invention

Problems to be solved by the invention

An object of the present invention is to provide a liquid crystal composition having high stability against ultraviolet rays. Another object is to provide a liquid crystal composition which sufficiently satisfies at least one of characteristics such as high upper limit temperature of a nematic phase, low lower limit temperature of a nematic phase, low viscosity, proper optical anisotropy, high dielectric anisotropy, high specific resistance, high thermal stability, and suppression of display failure such as afterimage. It is a further object to provide a liquid crystal composition having an appropriate balance between at least two of these properties.

It is another object of the present invention to provide a compound which can be added to a liquid crystal composition to improve the stability of the liquid crystal composition against ultraviolet rays.

It is still another object to provide a liquid crystal display element which contains such a composition and has characteristics of short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

Technical means for solving the problems

The present invention relates to a liquid crystal composition containing at least one compound selected from the compounds represented by formula (1) (hereinafter, sometimes referred to as compound (1)) as a first additive and having a nematic phase, and a liquid crystal display element containing the composition.

In the formula (1), R ¹ Is hydrogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkenyloxy of 2 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; r is R ² Is C1-12 alkyl, C2-12 alkenyl, or C1-12 alkyl with at least one hydrogen substituted by fluorine or chlorine, at least one of these groups being-CH ₂ -may be substituted with-O-, -COO-, or-OCO-, or a group represented by formula (A-1); ring A is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 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, and at least one hydrogen in these rings may be fluorinated, Chlorine, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms with at least one hydrogen substituted with fluorine or chlorine; a is 1 or 2; b is 0, 1,2, 3, or 4;

in the formula (A-1), R ^a Is fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, at least one-CH ₂ -may be substituted by-O-, -COO-, or-OCO-; z is Z ^a An optionally branched alkylene group having 1 to 20 carbon atoms, at least one of the alkylene groups-CH ₂ -can be substituted by-O-, -COO-, or-OCO-, at least one-CH ₂ -CH ₂ -may be substituted with-ch=ch-; s is 0 or 1; t is 0, 1,2, 3, 4, or 5.

The present invention also relates to a compound represented by the following formula (1').

In the formula (1'), R ¹ Is hydrogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkenyloxy of 2 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; r is R ² Is C1-12 alkyl, C2-12 alkenyl, or C1-12 alkyl with at least one hydrogen substituted by fluorine or chlorine, at least one of these groups being-CH ₂ -may be substituted by-O-, -COO-, or-OCO-; ring A is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 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, and at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, or a cyclic ring having 1 to 12 carbon atoms Alkoxy, or at least one hydrogen substituted with fluoro or chloro alkyl of 1 to 12 carbon atoms; a is 1 or 2; b is 0, 1, 2, 3, or 4.

ADVANTAGEOUS EFFECTS OF INVENTION

An advantage of the present invention is to provide a liquid crystal composition having high stability to ultraviolet rays. Another advantage is to provide a liquid crystal composition which sufficiently satisfies at least one of characteristics such as high upper limit temperature of a nematic phase, low lower limit temperature of a nematic phase, low viscosity, proper optical anisotropy, high dielectric anisotropy, high specific resistance, high thermal stability, and suppression of display failure such as afterimage. Yet another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. In addition, it is another advantage to provide a compound that can be added to a liquid crystal composition to improve the stability of the liquid crystal composition against ultraviolet rays. Further, it is another advantage to provide a liquid crystal display element which contains such a composition and has characteristics of short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

Detailed Description

The method of using the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" are sometimes abbreviated as "composition" and "element", respectively. The term "liquid crystal display element" refers to a liquid crystal display panel and a liquid crystal display module. The "liquid crystalline compound" is a general term for a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a compound which is mixed in a composition for the purpose of adjusting characteristics such as a temperature range, viscosity, and dielectric anisotropy of the nematic phase, although not having the liquid crystal phase. The compound has a six-membered ring such as 1, 4-cyclohexylene 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 crystalline compound having an alkenyl group is not polymerizable in its meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystalline compounds. 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 to the liquid crystal composition as needed. Even when the additive is added, the ratio of the liquid crystalline compound is expressed by a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. The proportion of the additive is represented by mass percent (mass%) based on the mass of the liquid crystal composition without the additive. That is, the ratio of the liquid crystalline compound or the additive is calculated based on the total mass of the liquid crystalline compound. Sometimes parts per million (ppm) by mass is used. The proportion of the polymerization initiator and the polymerization inhibitor is expressed based on the mass of the polymerizable compound.

The "upper limit temperature of the nematic phase" is sometimes simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as "lower limit temperature". By "large specific resistance" is meant that the composition has a large specific resistance in the initial stage and also has a large specific resistance after long use. The "large voltage holding ratio" means that the element has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and also has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. The properties of the composition or element are sometimes studied by time-varying tests. The expression "improving dielectric anisotropy" means that the value thereof increases positively when the composition has positive dielectric anisotropy, and that the value thereof increases negatively when the composition has negative dielectric anisotropy.

In the present specification "at least one-CH" is used ₂ -may be expressed via-O-substitution "or the like. In the case of, -CH ₂ -CH ₂ -CH ₂ By non-contiguous-CH ₂ -conversion to-O-CH by-O-substitution ₂ -O-. However, adjacent-CH ₂ -not being-O-substituted. This is because of the formation of-O-CH in the substitution ₂ - (peroxides). That is, the expression means "one-CH ₂ -optionally substituted by-O-with "at least two non-adjacent-CH ₂ -accessible via-O-extractionGeneration "both. The rule applies not only to the case of substitution with-O-, the substitution with divalent radicals such as-CH=CH-or-COO-is also applicable.

In the chemical formula of the component compound, the terminal group R ³ The notations of (2) are for a variety of compounds. Of these compounds, any two R ³ The two groups represented may be the same or may be different. For example, there is R of the compound (2-1) ³ Is ethyl, and R of the compound (2-2) ³ In the case of ethyl. Also R of the compound (2-1) ³ Is ethyl, R of the compound (2-2) ³ In the case of propyl. The rules also apply to other end group or like indicia. In formula (1), when the subscript 'a' is 2, there are two rings a. In the compounds, the two rings represented by the two rings a may be the same or may be different. When the subscript 'a' is greater than 2, the rule applies to any two rings a as well. The rule also applies to Z ¹ Ring B, etc. The rules also apply for two-Sp in Compounds (5-27) ² -P ⁵ And the like.

The symbols A, B, C, D enclosed 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 the compounds (1) and (5), the diagonal lines crossing one side of the hexagon represent any hydrogen on the ring and may pass through R ² 、-Sp ¹ -P ¹ And the like. The subscripts of 'b' and the like denote the number of substituted groups. When subscript 'b' is 0 (zero), no such substitution is present. When subscript ' b ' is 2 or more, there are a plurality of R's on the ring ² . From R ² The multiple groups represented may be the same or may be different. In the expression "ring a and ring B are independently X, Y or Z", the expression "independently" is used because the subject is plural. When the subject is "ring a", the subject is singular, and thus "independent" is not used.

2-fluoro-1, 4-phenylene refers to the following two divalent radicals. In the chemical formula, fluorine can be left (L) or right (R). The rules also apply to laterally asymmetric divalent radicals such as tetrahydropyran-2, 5-diyl which are generated by removal of two hydrogens from the ring. The rules also apply to divalent bonding groups such as carbonyloxy (-COO-or-OCO-).

The alkyl group of the liquid crystalline compound is linear or branched and does not contain a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. These are also the same for terminal groups such as alkoxy and alkenyl. In order to raise the upper temperature, the steric configuration associated with 1, 4-cyclohexylene is that of trans configuration over cis configuration.

The present invention is the following items.

The liquid crystal composition according to item 1 contains at least one compound selected from the compounds represented by formula (1) as a first additive and has a nematic phase.

In the formula (1), R ¹ Is hydrogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkenyloxy of 2 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; r is R ² Is C1-12 alkyl, C2-12 alkenyl, or C1-12 alkyl with at least one hydrogen substituted by fluorine or chlorine, at least one of these groups being-CH ₂ -may be substituted with-O-, -COO-, or-OCO-, or a group represented by formula (A-1); ring a is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 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, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted with fluorine or chlorine; a is 1 or 2; b is 0, 1,2, 3, or 4;

In the formula (A-1), R ^a Is fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, at least one-CH ₂ -may be substituted by-O-, -COO-, or-OCO-; z is Z ^a An optionally branched alkylene group having 1 to 20 carbon atoms, at least one of the alkylene groups-CH ₂ -can be substituted by-O-, -COO-, or-OCO-, at least one-CH ₂ -CH ₂ -may be substituted with-ch=ch-; s is 0 or 1; t is 0, 1, 2, 3, 4, or 5.

Item 2. The liquid crystal composition according to item 1, wherein R in the compound represented by formula (1) ² Methyl, tert-butyl, tert-amyl, tert-octyl, or alpha-amyl, b is 1, 2, 3, or 4.

Item 3. The liquid crystal composition according to item 1 or item 2 contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-4) as a first additive.

In the formulae (1-1) to (1-4), R ² Methyl, tert-butyl, tert-amyl, tert-octyl, or alpha-amyl.

The liquid crystal composition according to any one of items 1 to 3, wherein the proportion of the first additive is in the range of 0.005 to 2 mass%.

The liquid crystal composition according to any one of items 1 to 4, which contains at least one compound selected from the compounds represented by the formula (2) as a first component.

In the formula (2), R ³ R is R ⁴ Independently isAn 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 at least one alkenyl group having 2 to 12 carbon atoms, hydrogen being substituted with fluorine or chlorine; ring B and ring C are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, or 2, 5-difluoro-1, 4-phenylene; z is Z ¹ Is a single bond, ethylene, carbonyloxy, or methyleneoxy; c is 1, 2, or 3.

The liquid crystal composition according to any one of items 1 to 5, which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-13) as a first component.

In the formulae (2-1) to (2-13), R ³ R is R ⁴ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Item 7. The liquid crystal composition according to item 5 or item 6, wherein the proportion of the first component is in the range of 10 to 85 mass%.

The liquid crystal composition according to any one of items 1 to 7, which has at least one compound selected from the compounds represented by formula (3) as a second component.

In the formula (3), R ⁵ Is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; ring D is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl; z is Z ² Is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; x is X ¹ X is X ² Independently hydrogen or fluorine; y is Y ¹ Is fluorine, chlorine, at least one hydrogen having 1 to 1 carbon number substituted by fluorine or chlorine12, at least one alkoxy group having 1 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine, or at least one alkenyloxy group having 2 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine; d is 1, 2, 3, or 4.

The liquid crystal composition according to any one of items 1 to 8, which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-35) as a second component.

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In the formulae (3-1) to (3-35), R ⁵ Is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.

Item 10. The liquid crystal composition according to item 8 or item 9, wherein the proportion of the second component is in the range of 10 to 85 mass%.

The liquid crystal composition according to any one of items 1 to 10, which contains at least one compound selected from the compounds represented by the formula (4) as a third component.

In the formula (4), R ⁶ R is R ⁷ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyloxy group of 2 to 12 carbon atoms; ring E and ring G are independently 1, 4-cyclohexylene Hexyl, 1, 4-cyclohexenylene, 1, 4-phenylene with at least one hydrogen substituted with fluorine or chlorine, or tetrahydropyran-2, 5-diyl; ring F 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-difluorochromane-2, 6-diyl; z is Z ³ Z is as follows ⁴ Independently a single bond, ethylene, carbonyloxy, or methyleneoxy; e is 1, 2, or 3, f is 0 or 1; the sum of e and f is 3 or less.

The liquid crystal composition according to any one of items 1 to 11, which contains at least one compound selected from the group of compounds represented by the formulas (4-1) to (4-27) as a third component.

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In the formulae (4-1) to (4-27), R ⁶ R is R ⁷ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyloxy group of 2 to 12 carbon atoms.

Item 13. The liquid crystal composition according to item 11 or item 12, wherein the proportion of the third component is in the range of 5 to 80 mass%.

The liquid crystal composition according to any one of items 1 to 13, which contains at least one compound selected from the polymerizable compounds represented by the formula (5) as a second additive.

In formula (5), ring I and ring K are independently cyclohexylA group, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which rings at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkyl group of 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring J is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 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, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted with fluorine or chlorine; z is Z ⁵ Z is as follows ⁶ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, or-OCO-, at least one-CH ₂ -CH ₂ Can be modified by-ch=ch-, -C (CH ₃ )＝CH-、-CH＝C(CH ₃ ) -, or-C (CH) ₃ )＝C(CH ₃ ) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine; p (P) ¹ 、P ² P and P ³ Independently a polymerizable group; sp (Sp) ¹ 、Sp ² And Sp ³ Independently a single bond, or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-, or-OCOO-, at least one-CH ₂ -CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine; g is 0, 1, or 2; h. i, and j are independently 0, 1, 2, 3, or 4; and the sum of h, i, and j is 1 or more.

Item 15. The liquid crystal composition according to item 14, wherein in formula (5), P ¹ 、P ² P and P ³ Independently a group selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5).

In the formulae (P-1) to (P-5), M ¹ 、M ² And M ³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

The liquid crystal composition according to any one of items 1 to 15, which contains at least one compound selected from the group of polymerizable compounds represented by formulas (5-1) to (5-29) as a second additive.

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In the formulae (5-1) to (5-29), P ⁴ 、P ⁵ P and P ⁶ Independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-3), M ¹ 、M ² And M ³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

Sp ¹ 、Sp ² and Sp ³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-, or-OCOO-, at least one-CH ₂ -CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

The liquid crystal composition according to any one of items 14 to 16, wherein the proportion of the second additive is in the range of 0.03 to 10 mass%.

A liquid crystal display element comprising the liquid crystal composition according to any one of items 1 to 17.

Item 19. The liquid crystal display element according to item 18, wherein the operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving mode of the liquid crystal display element is an active matrix mode.

Item 20. A liquid crystal display element having a polymer stabilized alignment type, comprising the liquid crystal composition according to any one of items 14 to 17, wherein a polymerizable compound in the liquid crystal composition is polymerized.

The use of the liquid crystal composition according to any one of items 1 to 17 in a liquid crystal display element.

The use of the liquid crystal composition according to any one of items 14 to 17 in a liquid crystal display element of polymer-stabilized alignment type.

The compound of item 23, which is represented by formula (1').

In the formula (1'), R ¹ Is hydrogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkenyloxy of 2 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; r is R ² Is C1-12 alkyl, C2-12 alkenyl, or C1-12 alkyl with at least one hydrogen substituted by fluorine or chlorine, at least one of these groups being-CH ₂ -may be substituted by-O-, -COO-, or-OCO-; ring A is 1, 4-cyclohexylene, 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-diylA group, 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, wherein at least one hydrogen in these rings is substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, at least one hydrogen being substituted by fluorine or chlorine; a is 1 or 2; b is 0, 1,2, 3, or 4.

Item 24. The compound of item 23, wherein R ² Methyl, tert-butyl, tert-amyl, or tert-octyl, b is 1, 2, 3, or 4.

The compound according to item 24, which is represented by formula (1 '-1), formula (1' -2), formula (1 '-3), or formula (1' -4).

In the formulae (1 '-1) to (1' -4), R ² Methyl, tert-butyl, tert-amyl, or tert-octyl.

The present invention also includes the following items. (a) The composition contains one compound, two compounds or more than three compounds selected from the group of optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors and other additives. (b) an AM element comprising said composition. (c) The composition, and a polymer-stabilized-oriented (PSA) -type AM element containing the composition, wherein the composition further contains a polymerizable compound. (d) An AM element of polymer stabilized orientation (PSA) comprising the composition, and a polymerizable compound in the composition is polymerized. (e) A component comprising the composition and having a pattern of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (f) a permeation type element comprising 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 said composition.

The composition of the present invention is described in the following order. First, the constitution of the constituent compounds in the composition will be described. Second, the main characteristics of the constituent compounds and the main effects of the compounds on the composition will be described. Third, the combination of components in the composition, preferred proportions of the components, and their basis will be described. Fourth, preferred forms 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 constitution of the composition will be described. The composition contains a plurality of liquid crystalline compounds. The composition may also contain additives. The additives include optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. From the viewpoint of the liquid crystalline compound, the compositions are classified into a composition a and a composition B. The composition a may further contain other liquid crystalline compounds, additives, and the like, in addition to the liquid crystalline compound selected from the group consisting of the compound (2), the compound (3), and the compound (4). The "other liquid crystalline compound" is a liquid crystalline compound different from the compound (2), the compound (3), and the compound (4). Such compounds are mixed in the composition for the purpose of further adjusting the properties.

The composition B contains substantially only the liquid crystalline compound selected from the group consisting of the compound (2), the compound (3), and the compound (4). "substantially" means that the composition B may contain additives but does not contain other liquid crystalline compounds. The amount of the components of composition B is small compared to composition a. From the viewpoint of cost reduction, composition B is superior to composition a. Composition a is superior to composition B in that the properties can be further adjusted by mixing other liquid crystalline compounds.

Second, the main characteristics of the constituent compounds and the main effects of the compounds on the composition or element will be described. Based on the effects of the present invention, the main characteristics of the constituent compounds are summarized in table 2. In the notation of table 2, L means large or high, M means medium, and S means small or low. The notation L, M, S is a classification based on qualitative comparisons between constituent compounds, with 0 (zero) indicating extremely small.

TABLE 2

TABLE 2 Properties of liquid Crystal Compounds

Characteristics of	Compound (2)	Compound (3)	Compound (4)
				Upper limit temperature	S～L	S～L	S～L
Viscosity of the mixture	S～M	M～L	M～L
				Optical anisotropy	S～L	M～L	M～L
Dielectric anisotropy	0	M～L	M～L ¹⁾
				Specific resistance	L	L	L

1) The dielectric anisotropy is negative, and the sign indicates the magnitude of the absolute value.

The main effects of the component compounds are as follows. The compound (1) functions as an ultraviolet absorber, contributing to high stability against heat or ultraviolet rays. Since the amount of the compound (1) to be added is very small, the properties such as the upper limit temperature, optical anisotropy, and dielectric anisotropy are not affected in many cases. Compound (2) decreases the viscosity, or increases the upper temperature. The compound (3) increases positive dielectric anisotropy and decreases the lower limit temperature. The compound (4) increases the negative dielectric anisotropy and decreases the lower limit temperature. Since the compound (5) is polymerizable, a polymer is provided by polymerization. The polymer stabilizes the alignment of liquid crystal molecules, thereby shortening the response time of the element and improving the afterimage of the screen.

The ultraviolet absorber absorbs ultraviolet rays by being added to the liquid crystal composition in place of liquid crystal molecules. The ultraviolet absorber transitions from a ground state to an excited state by absorption of light energy. The excited state molecules undergo structural changes due to intramolecular proton transfer processes, which release heat to return to the ground state. As another mechanism, light having a lower energy than the absorbed light is irradiated to return to the ground state. By adding an ultraviolet absorber to the liquid crystal composition, deterioration of liquid crystal molecules due to ultraviolet absorption can be suppressed.

The ultraviolet absorber preferably has an absorption wavelength range that widely covers the absorption wavelength of the liquid crystal composition or the wavelength of the exposed ultraviolet light. The ultraviolet absorber absorbs a wavelength range and efficiency differently depending on its structure. From this viewpoint, the compound (1) is a useful ultraviolet absorber.

Third, the combination of the components in the composition, the preferable ratio of the component compounds, and the basis thereof will be described. Preferred combinations of the components in the composition are compound (1) +compound (2), compound (1) +compound (3), compound (1) +compound (4), compound (1) +compound (2) +compound (3), compound (1) +compound (2) +compound (4), compound (1) +compound (2) +compound (3) +compound (4), or compound (1) +compound (2) +compound (4) +compound (5). Particularly preferred combinations are compound (1) +compound (2) +compound (3).

The preferable proportion of the compound (1) is about 0.005 mass% or more for improving the stability against heat or ultraviolet rays, and about 2 mass% or less for lowering the lower limit temperature. Further, the preferable ratio is in the range of about 0.01 to about 1 mass%. Particularly preferred proportions are in the range of about 0.03 mass% to about 0.5 mass%.

The preferable proportion of the compound (2) is about 10 mass% or more for increasing the upper limit temperature or for reducing the viscosity, and about 85 mass% or less for increasing the dielectric anisotropy. Further, the preferable ratio is in the range of about 20 to about 80 mass%. Particularly preferred proportions are in the range of about 30 to about 70 mass%.

The preferable proportion of the compound (3) is about 10 mass% or more for improving the positive dielectric anisotropy, and about 85 mass% or less for lowering the lower limit temperature. Further, the preferable ratio is in the range of about 20 to about 80 mass%. Particularly preferred proportions are in the range of about 30 to about 70 mass%.

The preferable proportion of the compound (4) is about 5 mass% or more for improving the negative dielectric anisotropy, and about 80 mass% or less for lowering the lower limit temperature. Further, the preferable ratio is in the range of about 5 to about 75 mass%. Particularly preferred proportions are in the range of about 10 to about 70 mass%.

The compound (5) may be added to the composition for the purpose of adapting the element for polymer stabilization orientation. The preferable proportion of the compound (5) is about 0.03 mass% or more for aligning the liquid crystal molecules, and about 10 mass% or less for preventing defective display of the element. Further, the preferable ratio is in the range of about 0.1% by mass to about 2% by mass. Particularly preferred proportions are in the range of about 0.2% to about 1.0% by mass.

Fourth, preferred forms of the component compounds will be described. In the formula (1), the formula (2), the formula (3) and the formula (4), R ¹ Is hydrogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkenyloxy of 2 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred R ¹ Is hydrogen or alkyl of 1 to 12 carbon atoms. R is R ² Is C1-12 alkyl, C2-12 alkenyl, or C1-12 alkyl with at least one hydrogen substituted by fluorine or chlorine, at least one of these groups being-CH ₂ -may be substituted with-O-, -COO-, or-OCO-, or a group represented by formula (A-1). In order to enhance the effect of contributing to the stability of the liquid crystal, R is preferably ² Methyl, tert-butyl, tert-amyl, tert-octyl, or alpha-amyl. R is R ³ R is R ⁴ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. In order to reduce the viscosity, R is preferably ³ Or R is ⁴ Alkenyl of 2 to 12 carbon atoms, R is preferable for improving stability ³ Or R is ⁴ Is an alkyl group having 1 to 12 carbon atoms. R is R ⁵ Is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. For improved stability, R is preferably ⁵ Is an alkyl group having 1 to 12 carbon atoms. R is R ⁶ R is R ⁷ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyloxy group of 2 to 12 carbon atoms. For improved stability, R is preferably ⁶ Or R is ⁷ Is an alkyl group having 1 to 12 carbon atoms, R is preferably selected for improving dielectric anisotropy ⁶ Or R is ⁷ Alkoxy groups having 1 to 12 carbon atoms.

In the formula (A-1), R ^a Is fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, or at least one hydrogen substituted with fluorine or chlorine1 to 12, of which at least one-CH ₂ -may be substituted by-O-, -COO-, or-OCO-. Preferred R ^a Is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Z is Z ^a An optionally branched alkylene group having 1 to 20 carbon atoms, at least one of the alkylene groups-CH ₂ -may be substituted by-O-, -COO-, or-OCO-. In addition, at least one of the alkylene groups-CH ₂ -CH ₂ -may be substituted with-ch=ch-. Preferred Z ^a Is an alkylene group having 1 to 3 carbon atoms which may be branched. Particularly preferred Z ^a Is methylene or dimethylmethylene. s is 0 or 1. Preferably s is 1.t is 0, 1, 2, 3, 4, or 5.

Preferably t is 0 or 1.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, t-butyl, pentyl, t-pentyl, hexyl, heptyl, octyl, or t-octyl. Further preferred alkyl groups are methyl, ethyl, propyl, butyl, or pentyl groups for viscosity reduction.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, or heptoxy. Further preferred alkoxy groups are methoxy or ethoxy groups for reducing the viscosity.

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. Further preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for viscosity reduction. The preferred stereochemistry of-ch=ch-in these alkenyl groups depends on the position of the double bond. Among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl, the trans configuration is preferable for the purpose of reducing viscosity and the like. Among alkenyl groups such as 2-butenyl, 2-pentenyl and 2-hexenyl, the cis configuration is preferable.

Preferred alkenyloxy groups are ethyleneoxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to reduce the viscosity, further preferred alkenyloxy groups are allyloxy or 3-butenyloxy.

Preferred examples of the at least one hydrogen fluorine-or chlorine-substituted alkyl group are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl, or 8-fluorooctyl. Further preferable examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl for improving dielectric anisotropy.

Preferred examples of the at least one hydrogen fluorine or chlorine substituted alkenyl group are 2, 2-difluorovinyl, 3-difluoro-2-propenyl, 4-difluoro-3-butenyl, 5-difluoro-4-pentenyl, or 6, 6-difluoro-5-hexenyl. Further preferred examples are 2, 2-difluorovinyl or 4, 4-difluoro-3-butenyl for viscosity reduction.

Ring a is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 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, and in these rings, at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted by fluorine or chlorine. Preferred ring A is 1, 4-phenylene or naphthalene-2, 6-diyl.

Ring B and ring C are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, or 2, 5-difluoro-1, 4-phenylene. In order to reduce the viscosity, or in order to raise the upper temperature, the preferred ring B or ring C is 1, 4-cyclohexylene, and in order to lower the lower temperature, the preferred ring B or ring C is 1, 4-phenylene.

Ring D is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl. In order to raise the upper limit temperature, the preferred ring D is 1, 4-cyclohexylene, in order to raise the optical anisotropy, the preferred ring D is 1, 4-phenylene, and in order to raise the dielectric anisotropy, the preferred ring D is 2, 6-difluoro-1, 4-phenylene. Tetrahydropyran-2, 5-diyl as

Or (b)

Preferably, it is

Ring E and ring G are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene with at least one hydrogen substituted with fluorine or chlorine, or tetrahydropyran-2, 5-diyl. Preferred examples of "1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine" are 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene or 2-chloro-3-fluoro-1, 4-phenylene. In order to reduce the viscosity, the preferred ring E or ring G is a 1, 4-cyclohexylene group, in order to improve the dielectric anisotropy, the preferred ring E or ring G is a tetrahydropyran-2, 5-diyl group, and in order to improve the optical anisotropy, the preferred ring E or ring G is a 1, 4-phenylene group.

Ring F 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-difluorochromane-2, 6-diyl. For reducing the viscosity, the preferred ring F is 2, 3-difluoro-1, 4-phenylene, for reducing the optical anisotropy, the preferred ring F is 2-chloro-3-fluoro-1, 4-phenylene, and for improving the dielectric anisotropy, the preferred ring F is 7, 8-difluorochroman-2, 6-diyl.

Z ¹ Is a single bond, ethylene, carbonyloxy, or methyleneoxy. To reduce the viscosity, Z is preferably ¹ Is a single bond. Z is Z ² Is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. To reduce the viscosity, Z is preferably ² Is a single bond, for the purpose of carryingHigh dielectric anisotropy, preferably Z ² Is difluoromethyleneoxy. Z is Z ³ Z is as follows ⁴ Independently a single bond, ethylene, carbonyloxy, or methyleneoxy. To reduce the viscosity, Z is preferably ³ Or Z is ⁴ Is a single bond, Z is preferably selected in order to lower the lower limit temperature ³ Or Z is ⁴ Ethylene, Z is preferable for improving dielectric anisotropy ³ Or Z is ⁴ Is methyleneoxy.

X ¹ X is X ² Independently hydrogen or fluorine. In order to improve dielectric anisotropy, X is preferably selected ¹ Or X ² Is fluorine.

Y ¹ Is fluorine, chlorine, at least one alkyl group of 1 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine, at least one alkoxy group of 1 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine, or at least one alkenyloxy group of 2 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine. In order to improve dielectric anisotropy, preferably Y ¹ Is fluorine. A preferred example of at least one hydrogen fluorine or chlorine substituted alkyl group is trifluoromethyl. A preferred example of at least one hydrogen fluorine or chlorine substituted alkoxy group is trifluoromethoxy. A preferred example of at least one of the hydrogen fluorine or chlorine substituted alkenyloxy groups is trifluoroethenyloxy.

a is 1 or 2, b is 0, 1, 2, 3, or 4. Preferably a is 1 and preferably b is 1.c is 1, 2, or 3. In order to reduce the viscosity, c is preferably 1, and in order to raise the upper limit temperature, c is preferably 2 or 3.d is 1, 2, 3, or 4. In order to improve the dielectric anisotropy, d is preferably 2 or 3.e is 1, 2, or 3. In order to reduce the viscosity, e is preferably 1, and in order to raise the upper limit temperature, e is preferably 2 or 3.f is 0 or 1. In order to reduce the viscosity, f is preferably 0, and in order to reduce the lower limit temperature, f is preferably 1. The sum of e and f is 3 or less.

In the formula (5), P ¹ 、P ² P and P ³ Independently is a polymerizable group. Preferred P ¹ 、P ² Or P ³ Is a group selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5). Further preferably P ¹ 、P ² Or P ³ Is a group (P-1) or a group (P-2). Particularly preferred radicals (P-1) are-OCO-ch=ch ₂ or-OCO-C (CH) ₃ )＝CH ₂ . The wavy lines of the radicals (P-1) to (P-5) represent the bonded sites.

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Radicals (P-1) to (P-5), M ¹ 、M ² And M ³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. In order to increase the reactivity, M is preferably ¹ 、M ² Or M ³ Is hydrogen or methyl. Further preferably M ¹ Methyl group, and preferably M ² Or M ³ Is hydrogen.

In the formulae (5-1) to (5-29), P ⁴ 、P ⁵ P and P ⁶ Independently a group represented by the formula (P-1) to the formula (P-3). Preferred P ⁴ 、P ⁵ Or P ⁶ Is a group (P-1) or a group (P-2). Further preferred group (P-1) is-OCO-CH=CH ₂ or-OCO-C (CH) ₃ )＝CH ₂ . The wavy lines of the radicals (P-1) to (P-3) represent the bonded sites.

In formula (5), sp ¹ 、Sp ² And Sp ³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-, or-OCOO-, at least one-CH ₂ -CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine. Preferred 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-. Further preferred Sp ¹ 、Sp ² Or Sp ³ Is a single bond.

Ring I and ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl, at least one hydrogen of which may be substituted with fluorine or chlorine, an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or at least one hydrogen of which is substituted with a fluorine or chlorine substituted alkyl group of 1 to 12 carbon atoms. Preferred ring I or ring K is phenyl. The ring J is a 1, 4-cyclohexylene group, a 1, 4-cyclohexenylene group, a 1, 4-phenylene group, a naphthalene-1, 2-diyl group, a naphthalene-1, 3-diyl group, a naphthalene-1, 4-diyl group, a naphthalene-1, 5-diyl group, a naphthalene-1, 6-diyl group, a naphthalene-1, 7-diyl group, a naphthalene-1, 8-diyl group, a naphthalene-2, 3-diyl group, a naphthalene-2, 6-diyl group, a naphthalene-2, 7-diyl group, a tetrahydropyran-2, 5-diyl group, a 1, 3-dioxane-2, 5-diyl group, a pyrimidine-2, 5-diyl group, or a pyridine-2, 5-diyl group, and in these rings, at least one hydrogen may be substituted with fluorine or chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted with fluorine or chlorine. Preferred ring J is 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

Z ⁵ Z is as follows ⁶ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, or-OCO-, at least one-CH ₂ -CH ₂ Can be modified by-ch=ch-, -C (CH ₃ )＝CH-、-CH＝C(CH ₃ ) -, or-C (CH) ₃ )＝C(CH ₃ ) -substitution, in which at least one hydrogen may be substituted by fluorine or chlorine. Preferred Z ⁵ Or Z is ⁶ Is a single bond, -CH ₂ CH ₂ -、-CH ₂ O-、-OCH ₂ -, -COO-, or-OCO-. Further preferably Z ⁵ Or Z is ⁶ Is a single bond.

g is 0, 1, or 2. Preferably g is 0 or 1. h. i, and j are independently 0, 1, 2, 3, or 4, and the sum of h, i, and j is 1 or more. Preferably h, i, or j is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compounds (1) are the compounds (1-1) to (1-4) described in item 3, and more preferred compounds (1) are the compounds (1 '-1) to (1' -4) described in item 25.

Preferred compounds (2) are the compounds (2-1) to (2-13) as described in item 6. Of these compounds, at least one of the first component is preferably the compound (2-1)) Compound (2-3), compound (2-5), compound (2-6), or compound (2-8). Particularly preferred compounds (2) are R ³ R is R ⁴ At least one of the compounds (2-1) being an alkenyl group, 3-HH-V being particularly preferred. And preferably at least two of the first components are compound (2-1) and compound (2-3), compound (2-1) and compound (2-5), or a combination of compound (2-1) and compound (2-6).

Preferred compounds (3) are the compounds (3-1) to (3-35) as described in item 9. Of these compounds, at least one of the second components is preferably compound (3-4), compound (3-12), compound (3-14), compound (3-15), compound (3-18), compound (3-23), compound (3-24), compound (3-27), compound (3-29), or compound (3-30). And preferably at least two of the second components are compound (3-12) and compound (3-15), compound (3-14) and compound (3-27), compound (3-18) and compound (3-24), compound (3-18) and compound (3-29), compound (3-24) and compound (3-29), or a combination of compound (3-29) and compound (3-30).

Preferred compounds (4) are the compounds (4-1) to (4-27) as described in item 12. Of these compounds, at least one of the third component is preferably compound (4-1), compound (4-3), compound (4-6), compound (4-8), compound (4-10), or compound (4-14). And preferably at least two of the third components are compound (4-1) and compound (4-8), compound (4-3) and compound (4-14), compound (4-6) and compound (4-8), compound (4-6) and compound (4-10), or a combination of compound (4-8) and compound (4-14).

Preferred compounds (5) are the compounds (5-1) to (5-29) as described in item 16. Of these compounds, at least one of the second additives is preferably compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26), or compound (5-27). And preferably at least two of the second additives are compound (5-1) and compound (5-2), compound (5-1) and compound (5-18), compound (5-2) and compound (5-24), compound (5-2) and compound (5-25), compound (5-2) and compound (5-26), compound (5-25) and compound (5-26), or a combination of compound (5-18) and compound (5-24).

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. The optically active compound is added to the composition for the purpose of inducing a helical structure of the liquid crystal molecules to impart a twist angle (twist angle). Examples of such compounds are compounds (6-1) to (6-5). The preferable proportion of the optically active compound is about 5 mass% or less. Further, the preferable ratio is in the range of about 0.01 to about 2 mass%.

Antioxidants are added to the compositions 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 long-term use of the element.

Preferred examples of the antioxidant are compounds (7-1) to (7-3) and the like.

Since the compound (7-2) has low volatility, it is effective 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 period of time. In order to obtain the effect, the preferable proportion of the antioxidant is about 50ppm or more, and in order not to lower the upper limit temperature or in order not to raise the lower limit temperature, the preferable proportion of the antioxidant is about 600ppm or less. Further preferred ratios are in the range of about 100ppm to about 300 ppm.

The compound (1) is a benzotriazole derivative useful as an ultraviolet absorber. The benzotriazole derivatives may also be added to the composition along with other ultraviolet light absorbers. Preferable examples of such ultraviolet absorbers are benzophenone derivatives, benzoate derivatives, and the like. In addition, light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer are compounds (8-1) to (8-16) and the like. In order to obtain the effect, the preferable proportion of these absorbents or stabilizers is about 50ppm or more, and in order not to lower the upper limit temperature or in order not to raise the lower limit temperature, the preferable proportion of these absorbents or stabilizers is about 10000ppm or less. Further preferred ratios are in the range of about 100ppm to about 10000 ppm.

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The matting agent is a compound that prevents decomposition of the liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into heat energy. Preferred examples of the matting agent are compounds (9-1) to (9-7) and the like. In order to obtain the above-mentioned effect, the preferable proportion of these matting agents is about 50ppm or more, and in order not to raise the lower limit temperature, the preferable proportion of these matting agents is about 20000ppm or less. Further preferred ratios are in the range of about 100ppm to about 10000 ppm.

In order to be suitable for Guest Host (GH) mode elements, a dichroic dye (dichromatic dye) such as azo dye, anthraquinone dye, or the like is added to the composition. The preferable proportion of the coloring matter is in the range of about 0.01% by mass to about 10% by mass. To prevent foaming, defoamers such as dimethyl silicone oil, methyl phenyl silicone oil, and the like are added to the composition. In order to obtain the above effect, the preferable proportion of the antifoaming agent is about 1ppm or more, and in order to prevent the display failure, the preferable proportion of the antifoaming agent is about 1000ppm or less. Further preferred ratios are in the range of about 1ppm to about 500 ppm.

In order to be suitable for a polymer stabilized oriented (PSA) type element, a polymerizable compound is used. Compound (5) is suitable for the purpose. The compound (5) and a polymerizable compound different from the compound (5) may be added to the composition. Preferable examples of such polymerizable compounds are compounds such as acrylic acid esters, methacrylic acid esters, vinyl compounds, ethyleneoxy compounds, propenyl ethers, epoxy compounds (oxetanes ), vinyl ketones, and the like. Further preferred examples are derivatives of acrylic or methacrylic esters. The preferable proportion of the compound (5) is 10 mass% or more based on the total mass of the polymerizable compounds. Further, the ratio is preferably 50% by mass or more. The ratio is particularly preferably 80% by mass or more. The most preferred ratio is 100 mass%.

The polymerizable compound such as the compound (5) is polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Suitable conditions for carrying out the polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and are described in the literature. For example, brilliant best (Irgacure) 651 (registered trademark; BASF), brilliant best (Irgacure) 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) as a photopolymerization initiator is suitable for radical polymerization. The preferable proportion of the photopolymerization initiator is in the range of about 0.1% by mass to about 5% by mass based on the total mass of the polymerizable compound. Further, the preferable ratio is in the range of about 1 to about 3 mass%.

In the case of storing a polymerizable compound such as the compound (5), a polymerization inhibitor may be added for the purpose of preventing polymerization. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone derivatives such as hydroquinone, methyl hydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine, etc.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is exemplified. The synthesis of compound (1) is described in the examples. The compound (2-1) was synthesized by the method described in Japanese patent application laid-open No. 59-176221. Compound (3-4) is synthesized by the method described in Japanese patent laid-open No. 10-204016. The compound (4-1) was synthesized by the method described in Japanese patent application laid-open No. 2000-053602. The compound (5-18) was synthesized by the method described in Japanese patent application laid-open No. 7-101900. Antioxidants are commercially available. Compounds of formula (7) wherein n is 1 are available from Sigma Aldrich (Sigma-Aldrich Corporation). The compound (7) having n of 7 and the like are synthesized by the method described in the specification of U.S. Pat. No. 3660505.

The compounds not described in the synthesis method can be synthesized by the methods described in the following written description: organic Synthesis (Organic Syntheses) (John Wiley father and son publishing company (John Wiley & Sons, inc.)), organic reactions (Organic Reactions) (John Wiley father and son, inc.)), comprehensive organic Synthesis (Comprehensive Organic Synthesis) (Pegman publishing company (Pergamon Press))), new laboratory lectures (Paddy), and the like. The compositions are prepared from the compounds obtained in the manner described using known methods. For example, the constituent compounds are mixed and then dissolved in each other by heating.

Finally, the use of the composition will be described. Most of the compositions have a lower temperature of about-10 ℃ or less, an upper temperature of about 70 ℃ or more, and an optical anisotropy in the range of about 0.07 to about 0.20. The composition having optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the constituent compounds, or by mixing other liquid crystalline compounds. Furthermore, compositions having an optical anisotropy in the range of about 0.10 to about 0.30 may also be prepared by trial and error. The components containing the composition have a large voltage holding ratio. The composition is suitable for AM elements. The composition is particularly suitable for transmissive AM devices. The composition may be used as a composition having a nematic phase, or may be used as an optically active composition by adding an optically active compound.

The composition is useful in AM elements. Furthermore, the present invention can be applied to a PM element. The composition can be used for AM elements and PM elements with modes of PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and the like. Particularly preferred is an AM element for use in a VA mode, OCB mode, IPS mode or FFS mode. In an AM element having an IPS mode or FFS mode, when no voltage is applied, the liquid crystal molecules may be arranged parallel to the glass substrate or may be arranged perpendicular to the glass substrate. These elements may be reflective, transmissive or semi-transmissive. Preferably for a permeation type element. And can also be used for amorphous silicon-TFT elements or polysilicon-TFT elements. The present invention can also be used for a nematic curve alignment phase (nematic curvilinear aligned phase, NCAP) element produced by microencapsulating the composition or a polymer dispersion (polymer dispersed, PD) element produced by forming a three-dimensional network polymer in the composition.

Examples

The present invention will be further described in detail by way of examples. The present invention is not limited by these examples. The present invention comprises a mixture of the composition of example 1 and the composition of example 2. The present invention also includes a mixture of at least two of the compositions of the examples. The synthesized compound is identified by nuclear magnetic resonance (nuclear magnetic resonance, NMR) analysis or the like. The properties of the compounds, compositions and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker Biospin, inc. was used in the assay. ¹ In the measurement of H-NMR, a sample was dissolved in CDCl ₃ The measurement was performed under conditions of room temperature, 500MHz, and the number of times of accumulation in the isotonic deuterated medium 16 times. Tetramethylsilane was used as an internal standard. ¹⁹ In the determination by F-NMR, CFCl was used ₃ As an internal standard, this was performed 24 times in total. In the description of nuclear magnetic resonance spectroscopy, s denotes a single peak (single), d denotes a double peak (doublet), t denotes a triplet (triplet), q denotes a quartet (quatet), quin denotes a quintet (quintet), sex denotes a hexa peak (setet), and m denotes a multiple peak (multiplet) ) Br refers to the broad peak (broad).

Gas chromatography analysis: for the measurement, a GC-14B type gas chromatograph manufactured by Shimadzu corporation was used. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set at 280℃and the detector (flame ionization detector (flame ionization detector, FID)) was set at 300 ℃. For the separation of the component compounds, capillary column DB-1 (30 m in length, 0.32mm in inside diameter, 0.25 μm in thickness; dimethylpolysiloxane as the stationary liquid phase; nonpolar) manufactured by Agilent technologies Co., ltd. (Agilent Technologies Inc.) was used. After the column was held at 200℃for 2 minutes, the temperature was raised to 280℃at a rate of 5℃per minute. After preparing a sample into an acetone solution (0.1 mass%), 1. Mu.L of the acetone solution was injected into the sample vaporization chamber. The record was a C-R5A chromatograph component (Chromatopac) manufactured by Shimadzu corporation or an equivalent thereof. The obtained gas chromatogram shows the retention time of the peak value and the area of the peak value corresponding to the component compound.

As a solvent for diluting the sample, chloroform, hexane or the like can be used. In order to separate the constituent compounds, the following capillary column may be used. HP-1 (30 m in length, 0.32mm in inside diameter, 0.25 μm in film thickness) manufactured by Agilent technologies Inc. (Agilent Technologies Inc.), rtx-1 (30 m in length, 0.32mm in inside diameter, 0.25 μm in film thickness) manufactured by Ruis Tex Co., ltd., and BP-1 (30 m in length, 0.32mm in inside diameter, 0.25 μm in film thickness) manufactured by Australian SGE International Inc. (SGE International Pty.Ltd.). For the purpose of preventing the overlapping of the peaks of the compounds, capillary columns CBP1-M50-025 (length 50M, inner diameter 0.25mm, film thickness 0.25 μm) manufactured by Shimadzu corporation can be used.

The proportion of the liquid crystalline compound contained in the composition can be calculated by the following method. The mixture of liquid crystalline compounds was analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio (mass ratio) of the liquid crystalline compound. When the capillary column described above is used, the correction coefficient of each liquid crystalline compound can be regarded as 1. Therefore, the ratio (mass%) of the liquid crystalline compound can be calculated from the area ratio of the peak.

Absorbance: for the measurement, a U-2001 type double beam spectrophotometer manufactured by Hitachi High-Tech Science (Hitachi High-Tech Science) was used. The measurement cell was T-23-UV-10 using a Quartz glass cell manufactured by Tosoh Quartz, inc., and only cyclohexane for spectroscopic analysis manufactured by Wako pure chemical industries, which was placed in the reference cell, and a measurement solution prepared by using cyclohexane for spectroscopic analysis was placed in the sample cell so that the concentration of the sample became 2.00. Mu. Mol/g. The absorbance is a region in which the wavelength is scanned from 800nm to 200nm in a unit width of 1 nm.

Measuring a sample: the composition is used directly as a sample in determining the characteristics of the composition or element. In measuring the characteristics of the compound, a measurement sample was prepared by mixing the compound (15 mass%) with a mother liquor crystal (85 mass%). From the values obtained by the measurement, the characteristic values of the compounds were calculated by extrapolation. (extrapolated value) = { (measurement of sample) -0.85× (measurement of mother liquor crystal) }/0.15. When a smectic phase (or crystal) is precipitated at 25 ℃ at the ratio, the ratio of the compound to the mother liquid crystal is 10 mass%: 90 mass%, 5 mass%: 95 mass%, 1 mass%: 99 mass% sequence was changed. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound were determined by the extrapolation method.

The following mother liquid crystals were used. The ratio of the component compounds is expressed in mass%.

The measuring method comprises the following steps: the characteristics were measured by the following method. Most of these methods are those described in the JEITA standard (JEITA. ED-2521B) which has been examined and established by the Japanese society of electronic information technology and industry (Japan Electronics and Information Technology Industries Association; referred to as JEITA) or modified. In the TN cell used for measurement, a Thin Film Transistor (TFT) was not mounted.

The liquid crystal compositions having positive dielectric anisotropy were measured by the following methods (1) to (15).

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

(2) Lower limit temperature of nematic phase (T _C The method comprises the steps of carrying out a first treatment on the surface of the DEG C): the samples having nematic phase were placed in glass bottles, and after keeping them in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days, the liquid crystal phase was observed. For example, T is determined when the sample is in a nematic phase at-20deg.C and changes to a crystalline or smectic phase at-30deg.C _C Recorded as < -20 ℃. The lower limit temperature of the nematic phase is sometimes simply referred to as "lower limit temperature".

(3) Viscosity (bulk viscosity; eta; measured at 20 ℃ C.; mPa.s): for the measurement, an E-type rotary viscometer manufactured by Tokyo counter Co., ltd was used.

(4) Viscosity (rotational viscosity; gamma.1; measured at 25 ℃ C.; mPa.s): the measurement was performed according to the method described in M.Imai et al, molecular Crystal and liquid Crystal (Molecular Crystals and Liquid Crystals), 259, 37 (1995). Samples were placed in a TN cell having a torsion angle of 0℃and a gap (cell gap) between two glass substrates of 5. Mu.m. The voltage was applied to the element in a range of 16V to 19.5V in units of 0.5V stepwise. After the voltage was not applied for 0.2 seconds, the application was repeated with only one rectangular wave (rectangular pulse; 0.2 seconds) applied and no voltage (2 seconds) applied. The peak current (peak current) and the peak time (peak time) of the transient current (transient current) generated by the application are measured. The rotational viscosity value is obtained from these measurement values and the calculation formula (8) described on page 40 of the paper by m. The value of the dielectric anisotropy required for the calculation was obtained by using an element for measuring the rotational viscosity and using the method described below.

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ℃): the measurement was performed using an Abbe refractometer having a polarizing plate attached to an eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index n/is measured when the direction of polarization is parallel to the direction of rubbing. The refractive index n+.t is measured when the direction of polarization is perpendicular to the direction of rubbing. The value of the optical anisotropy is calculated from the equation of Δn=n-n ∈.

(6) Dielectric anisotropy (. DELTA.. Epsilon.; measured at 25 ℃ C.): samples were placed in a TN cell having a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. Cndot.) of the liquid crystal molecules was measured in the long axis direction after 2 seconds. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. DELTA.T.) of the liquid crystal molecules was measured in the short axis direction after 2 seconds. The value of dielectric anisotropy is calculated from the equation of Δε=ε - ε.

(7) Threshold voltage (Vth; measured at 25 ℃ C.; V): for the measurement, an LCD5100 type luminance meter manufactured by tsukamureluctant electronic corporation was used. The light source is a halogen lamp. Samples were placed in a TN cell in a normal white mode (normally white mode) in which the interval (cell gap) between two glass substrates was 0.45/. DELTA.n (. Mu.m) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to the element was increased stepwise from 0V to 10V in units of 0.02V. At this time, light is irradiated from the vertical direction to the element, and the amount of light transmitted through the element is measured. A voltage-transmittance curve was made in which the transmittance was 100% when the light amount reached the maximum, and the transmittance was 0% when the light amount was the minimum. The threshold voltage is represented by the voltage at which the transmittance reaches 90%.

(8) Voltage holding ratio (VHR-1; measured at 25 ℃;%) was: the TN element used in the measurement had a polyimide alignment film, and the interval (cell gap) between two glass substrates was 5. Mu.m. After the sample is placed, the element is sealed with an adhesive that is cured by ultraviolet light. The TN element was charged by applying a pulse voltage (1V, 60 μsec). The attenuated voltage was measured during 166.7 milliseconds by a high-speed voltmeter, and the area a between the voltage curve and the horizontal axis in the unit cycle was obtained. Area B is the area when unattenuated. The voltage holding ratio is expressed by the percentage of the area a to the area B.

(9) Voltage holding ratio (VHR-2; measured at 60 ℃;%) was: the voltage holding ratio was measured in the same manner as described above except that the measurement was performed at 60℃instead of 25 ℃. The obtained value is denoted by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 60 ℃;%) was: after irradiation with ultraviolet rays, the voltage holding ratio was measured, and stability to ultraviolet rays was evaluated. The TN element used in the measurement had a polyimide alignment film, and the cell gap was 5. Mu.m. The sample was injected into the cell and irradiated for 167 minutes at 5mW/cm ² Is a ultraviolet ray of (a). The light source was a black light (F40T 10/BL (peak wavelength 369 nm) manufactured by Ai Gufei (EYEGRAPHICS) Inc., and the element was spaced 5mm from the light source. In the determination of VHR-3, the attenuated voltage was determined during 166.7 milliseconds. Compositions with large VHR-3 have large stability to uv light.

(11) Voltage holding ratio (VHR-4; measured at 60 ℃;%) was: after the TN element filled with the sample was heated in a constant temperature bath at 120℃for 20 hours, the voltage holding ratio was measured and the stability to heat was evaluated. In the VHR-4 assay, the attenuated voltage was measured during 166.7 milliseconds. Compositions with large VHR-4 have a large stability to heat.

(12) Response time (τ; measured at 25 ℃ C.; ms): for the measurement, an LCD5100 type luminance meter manufactured by tsukamureluctant electronic corporation was used. The light source is a halogen lamp. The Low pass filter (Low pass filter) was set to 5kHz. A sample was placed in a TN cell in a normal white mode (normally white mode) in which the interval (cell gap) between two glass substrates was 5.0 μm and the twist angle was 80 degrees. Rectangular waves (60 Hz, 5V, 0.5 seconds) were applied to the element. At this time, light is irradiated from the vertical direction to the element, and the amount of light transmitted through the element is measured. The transmittance was regarded as 100% when the light amount reached the maximum, and as 0% when the light amount was the minimum. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) is the time required to change from 10% to 90% transmittance. The response time is represented by the sum of the rise time and the fall time obtained in the above manner.

(13) Elastic constant (K; measured at 25 ℃ C.; pN): for the measurement, an HP4284A type LCR tester manufactured by Hewlett-Packard Co., ltd was used. Samples were placed in a horizontally oriented element having a gap (cell gap) of 20 μm between two glass substrates. The device was charged with 0 to 20 volts, and the capacitance and applied voltage were measured. The measured capacitance (C) was fitted to the value of the applied voltage (V) using the formulas (2.98) and (2.101) on page 75 of the handbook of liquid crystal devices (journal of the industry and news corporation), and the values of K11 and K33 were obtained from the formula (2.99). Next, K22 was calculated using the values of K11 and K33 obtained previously in the formula (3.18) on page 171 of the handbook of liquid crystal devices (journal of industrial news). The elastic constant is represented by the average value of K11, K22, and K33 obtained in the above manner.

(14) Specific resistance (. Rho.; measured at 25 ℃ C.; Ω cm): 1.0mL of the sample was poured into a container equipped with an electrode. A DC voltage (10V) was applied to the container, and a DC current was measured after 10 seconds. The specific resistance is calculated according to the following equation. (specific resistance) = { (voltage) × (capacitance of container) }/{ (direct current) × (dielectric constant of vacuum) }.

(15) Dielectric constant in the short axis direction (. Epsilon.; measured at 25 ℃ C.): samples were placed in a TN cell having a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. DELTA.T.) of the liquid crystal molecules was measured in the short axis direction after 2 seconds.

The liquid crystal compositions having negative dielectric anisotropy were measured by the following methods (16) to (28).

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

(17) Lower limit temperature of nematic phase (T _C The method comprises the steps of carrying out a first treatment on the surface of the DEG C): the samples having nematic phase were placed in glass bottles, and after keeping them in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days, the liquid crystal phase was observed. For example, T is determined when the sample is in a nematic phase at-20deg.C and changes to a crystalline or smectic phase at-30deg.C _C Recorded as < -20 ℃. The lower limit temperature of the nematic phase is sometimes simply referred to as "lower limit temperature".

(18) Viscosity (bulk viscosity; eta; measured at 20 ℃ C.; mPa.s): for the measurement, an E-type rotary viscometer manufactured by Tokyo counter Co., ltd was used.

(19) Viscosity (rotational viscosity; gamma.1; measured at 25 ℃ C.; mPa.s): the measurement was performed according to the method described in M.Imai et al, molecular Crystal and liquid Crystal (Molecular Crystals and Liquid Crystals), 259, 37 (1995). Samples were placed in VA elements having a gap (cell gap) of 20 μm between two glass substrates. The elements are applied in steps of 1 volt in the range of 39 volts to 50 volts. After the voltage was not applied for 0.2 seconds, the application was repeated with only one rectangular wave (rectangular pulse; 0.2 seconds) applied and no voltage (2 seconds) applied. The peak current (peak current) and the peak time (peak time) of the transient current (transient current) generated by the application are measured. The value of the rotational viscosity is obtained from these measurement values and the calculation formula (8) on page 40 of the paper by m. The dielectric anisotropy required for the calculation was measured using item (6).

(20) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ℃): the measurement was performed using an Abbe refractometer having a polarizing plate attached to an eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index n/is measured when the direction of polarization is parallel to the direction of rubbing. The refractive index n+.t is measured when the direction of polarization is perpendicular to the direction of rubbing. The value of the optical anisotropy is calculated from the equation of Δn=n-n ∈.

(21) Dielectric anisotropy (. DELTA.. Epsilon.; measured at 25 ℃ C.): the value of dielectric anisotropy is calculated from the equation of Δε=ε - ε. The dielectric was determined as follows constant (ε. T.).

1) Determination of dielectric constant (ε): a well-cleaned glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). After the glass substrate was rotated by a rotator, the glass substrate was heated at 150℃for 1 hour. Samples were placed in VA elements having a gap (cell gap) of 4 μm between two glass substrates, and the elements were sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon./V) of the liquid crystal molecules was measured in the long axis direction after 2 seconds.

2) Determination of dielectric constant (ε+.T): a polyimide solution was coated on the sufficiently cleaned glass substrate. After the glass substrate is calcined, the obtained alignment film is subjected to a rubbing treatment. Samples were placed in a TN cell having a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. DELTA.T.) of the liquid crystal molecules was measured in the short axis direction after 2 seconds.

(22) Threshold voltage (Vth; measured at 25 ℃ C.; V): for the measurement, an LCD5100 type luminance meter manufactured by tsukamureluctant electronic corporation was used. The light source is a halogen lamp. A sample was placed in a VA element having a gap (cell gap) between two glass substrates of 4 μm and a normal blackening mode (normally black mode) having an anti-parallel rubbing direction, and the element was sealed with an adhesive cured by ultraviolet rays. The voltage (60 Hz, rectangular wave) applied to the element was increased stepwise from 0V to 20V in units of 0.02V. At this time, light is irradiated from the vertical direction to the element, and the amount of light transmitted through the element is measured. A voltage-transmittance curve was made in which the transmittance was 100% when the light amount reached the maximum, and the transmittance was 0% when the light amount was the minimum. The threshold voltage is represented by the voltage at which the transmittance reaches 10%.

(23) Voltage holding ratio (VHR-1; measured at 25 ℃;%) was: the TN element used in the measurement had a polyimide alignment film, and the interval (cell gap) between two glass substrates was 5. Mu.m. After the sample is placed, the element is sealed with an adhesive that is cured by ultraviolet light. The TN element was charged by applying a pulse voltage (1V, 60 μsec). The attenuated voltage was measured during 166.7 milliseconds by a high-speed voltmeter, and the area a between the voltage curve and the horizontal axis in the unit cycle was obtained. Area B is the area when unattenuated. The voltage holding ratio is expressed by the percentage of the area a to the area B.

(24) Voltage holding ratio (VHR-2; measured at 60 ℃;%) was: the voltage holding ratio was measured in the same manner as described above except that the measurement was performed at 60℃instead of 25 ℃. The obtained value is denoted by VHR-2.

(25) Voltage holding ratio (VHR-3; measured at 60 ℃;%) was: after irradiation with ultraviolet rays, the voltage holding ratio was measured, and stability to ultraviolet rays was evaluated. The TN element used in the measurement had a polyimide alignment film, and the cell gap was 5. Mu.m. The sample was injected into the cell and irradiated for 167 minutes at 5mW/cm ² Is a ultraviolet ray of (a). The light source was a black light (F40T 10/BL (peak wavelength 369 nm) manufactured by Ai Gufei (EYEGRAPHICS) Inc., and the element was spaced 5mm from the light source. In the determination of VHR-3, the attenuated voltage was determined during 166.7 milliseconds. Compositions with large VHR-3 have large stability to uv light.

(26) Voltage holding ratio (VHR-4; measured at 25 ℃;%) was: after the TN element filled with the sample was heated in a constant temperature bath at 80℃for 500 hours, the voltage holding ratio was measured and the stability to heat was evaluated. In the VHR-4 assay, the attenuated voltage was measured during 166.7 milliseconds. Compositions with large VHR-4 have a large stability to heat.

(27) Response time (τ; measured at 25 ℃ C.; ms): for the measurement, an LCD5100 type luminance meter manufactured by tsukamureluctant electronic corporation was used. The light source is a halogen lamp. The Low pass filter (Low pass filter) was set to 5kHz. Samples were placed in a VA element having a normal black display mode (normally black mode) in which the interval (cell gap) between the two glass substrates was 4 μm and the rubbing direction was antiparallel. The element is sealed with an adhesive that is cured with ultraviolet light. Rectangular waves (60 Hz, 10V, 0.5 seconds) were applied to the element. At this time, light is irradiated from the vertical direction to the element, and the amount of light transmitted through the element is measured. The transmittance was regarded as 100% when the light amount reached the maximum, and as 0% when the light amount was the minimum. The response time is represented by the sum of the time (rise time; millisecond) required for the transmittance to change from 10% to 90% and the time (fall time; millisecond) required for the transmittance to change from 90% to 10%.

(28) Specific resistance (. Rho.; measured at 25 ℃ C.; Ω cm): 1.0mL of the sample was poured into a container equipped with an electrode. A DC voltage (10V) was applied to the container, and a DC current was measured after 10 seconds. The specific resistance is calculated according to the following equation. (specific resistance) = { (voltage) × (capacitance of container) }/{ (direct current) × (dielectric constant of vacuum) }.

Synthesis example 1

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

Into a 1000ml three-necked flask, 2- (tert-butyl) -6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol (40.0 g, 0.126 mol), phenylboronic acid (15.598 g, 0.127 mol), pdCl were placed ₂ (Amphos) ₂ (Pd-132, 0.179g, 0.250 mmol), potassium carbonate (35.010 g, 0.253 mol), tetrabutylammonium bromide (12.520 g, 38.000 mmol), toluene (200 ml), isopropyl alcohol (200 ml), water (20 ml) and heat refluxing. After 3 hours, the aqueous layer was separated from the organic layer by pouring into water (200 ml), and then the aqueous layer was further extracted with toluene (200 ml). The organic layer was washed with saturated brine (100 ml. Times.2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent, whereby compound (1-1) (26.1 g, 0.073mol, yield 58%) was obtained.

¹ H-NMR(ppm；CDCl ₃ )：δ11.73(s,1H),8.09(dd,J＝16.5Hz,J＝1.3Hz,2H),7.98(d,J＝8.8Hz,1H),7.74(dd,J＝8.8Hz,J＝1.3Hz,1H),7.69(dd,J＝16.5Hz,J＝1.3Hz,2H),7.52-7.49(m,2H),7.44-7.41(m,1H),7.19(d,J＝1.9Hz,1H),2.41(s,3H),1.51(s,9H).

Absorbance (arbitrary unit): 0.216 (369 nm).

Synthesis example 2

The compound (1-2) was synthesized by the following route.

Into a 500ml three-necked flask, 2- (tert-butyl) -6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol (50.0 g, 0.158 mol), 4-propylphenylboronic acid (26.277 g, 0.160 mol), pdCl were placed ₂ (Amphos) ₂ (Pd-132, 0.224g, 0.320 mmol), potassium carbonate (43.762 g, 0.317 mol), tetrabutylammonium bromide (15.312 g, 47.50 mmol), isopropyl alcohol (250 ml) and refluxing with heat. After 3 hours, the aqueous layer was separated from the organic layer by pouring into water (200 ml), and then the aqueous layer was further extracted with toluene (200 ml). The organic layer was washed with saturated brine (100 ml. Times.2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent, whereby compound (1-2) (39.3 g, 0.0984mol, yield 62%) was obtained.

¹ H-NMR(ppm；CDCl ₃ )：δ11.73(s,1H),8.09(d,J＝1.3Hz,1H),6.04(dd,J＝1.3Hz,J＝1.0Hz,1H),7.94(d,J＝8.8Hz,1H),7.72(dd,J＝8.8Hz,J＝1.3Hz,1H),7.58(d,J＝8.1Hz,2H),7.30(d,J＝8.1Hz,2H),7.18(d,J＝1.9Hz,1H),2.65(t,J＝7.5Hz,2H),2.39(s,3H),1.70(sext,J＝7.5Hz,2H),1.51(s,9H),0.99(t,J＝7.4Hz,3H).

Absorbance (arbitrary unit): 0.216 (369 nm).

Synthesis example 3

The compounds (1-3) were synthesized by the following routes.

In a 200ml three-necked flask, 2- (tert-butyl) -6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol (5.00 g, 0.0158 mol), 4' -propyl-4-biphenylboronic acid (3.840 g, 0.0160 mol), pdCl were placed ₂ (Amphos) ₂ (Pd-132, 0.0224g, 0.0320 mmol), potassium carbonate (4.3762 g, 0.0317 mol), tetrabutylammonium bromide (1.5312 g, 4.750 mmol), toluene (25 ml), isopropyl alcohol (25 ml), water (2.5 ml) and refluxing with heat. After 3 hours, the aqueous layer was separated from the organic layer by pouring into water (20 ml), and then the aqueous layer was further extracted with toluene (20 ml). The organic layer was washed with saturated brine (10 ml. Times.2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent, whereby compound (1-3) (3.30 g, 6.94mmol, yield 44%) was obtained.

¹ H-NMR(ppm；CDCl ₃ )：δ11.74(s,1H),8.12-8.11(m,2H),8.03(dd,J＝8.9Hz,J＝0.75Hz,1H),7.80(dd,J＝8.9Hz,J＝1.3Hz,1H),7.77-7.72(m,4H),7.59(d,J＝8.1Hz,2H),7.29(d,J＝8.1Hz,2H),7.19(d,J＝1.9Hz,1H),2.65(t,J＝7.5Hz,2H),2.40(s,3H),1.70(sext,J＝7.5Hz,2H),1.51(s,9H),0.99(t,J＝7.4Hz,3H).

Absorbance (arbitrary unit): 0.294 (369 nm).

Synthesis example 4

The compounds (1-4) were synthesized by the following routes.

In a 200ml three-necked flask, 2- (tert-butyl) -6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol (5.00 g, 0.0158 mol), 2-naphthaleneboronic acid (2.750 g, 0.0160 mol) and PdCl were placed ₂ (Amphos) ₂ (Pd-132, 0.0224g, 0.0320 mmol), potassium carbonate (4.3762 g, 0.0317 mol), tetrabutylammonium bromide (1.5312 g, 4.750 mmol), toluene (25 ml), isopropyl alcohol (25 ml), water (2.5 ml) and refluxing with heat. After 3 hours pouring into water (20 ml) the aqueous layer was separated from the organic layer,the aqueous layer was then extracted with toluene (20 ml). The organic layer was washed with saturated brine (10 ml. Times.2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent, whereby compound (1-4) (0.52 g, 1.28mmol, yield 8.1%) was obtained.

¹ H-NMR(ppm；CDCl ₃ )：δ11.74(s,1H),8.20(s,1H),8.13(d,J＝6.6,J＝1.3Hz,2H),8.02(d,J＝8.9Hz,1H),7.98(d,J＝8.6Hz,1H),7.94(d,J＝7.4Hz,1H),7.89(ddd,J＝8.4Hz,J＝8.0Hz,J＝1.2Hz,2H),7.82(dd,J＝8.4Hz,J＝1.7Hz,1H),7.56-7.51(m,2H),7.12(d,J＝1.9Hz,1H),2.41(s,3H),1.52(s,9H).

Absorbance (arbitrary unit): 0.176 (369 nm).

Examples of the composition are shown below. The constituent compounds are represented by symbols based on the definition of table 3 below. In Table 3, the steric configuration associated with 1, 4-cyclohexylene was the trans configuration. The numbers located in brackets after the labeled compounds represent the chemical formulas to which the compounds belong. The symbol of (-) refers to other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition are summarized.

TABLE 3

TABLE 3 expression method of chemical table object using the marks

R-(A ₁ )-Z ₁ -·····-Z _n -(A _n )-R′

Comparative example 1

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NI＝79.8℃；Tc＜-20℃；Δn＝0.106；Δε＝8.5；Vth＝2.18V；η＝11.6mPa·s；γ1＝60.0mPa·s；VHR-3＝35.5％.

Example 1

The composition obtained by adding the compound (1-1) to the composition of comparative example 1 was set as example 1.

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝78.8℃；Tc＜-20℃；Δn＝0.106；Δε＝8.5；Vth＝2.18V；η＝11.6mPa·s；γ1＝60.0mPa·s；VHR-3＝87.8％.

Comparative example 2

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NI＝74.5℃；Tc＜-20℃；Δn＝0.106；Δε＝-3.0；Vth＝2.21V；η＝14.7mPa·s；VHR-3＝40.9％.

Example 2

The composition obtained by adding the compound (1-1) to the composition of comparative example 2 was set as example 2.

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝73.5℃；Tc＜-20℃；Δn＝0.106；Δε＝-3.0；Vth＝2.21V；η＝14.7mPa·s；VHR-3＝78.1％.

Example 3

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝87.8℃；Tc＜-20℃；Δn＝0.101；Δε＝13.4；Vth＝1.34V；η＝20.6mPa·s；γ1＝123.7mPa·s；VHR-3＝84.8％.

Example 4

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝77.2℃；Tc＜-20℃；Δn＝0.108；Δε＝10.4；Vth＝1.35V；η＝17.8mPa·s；γ1＝79.9mPa·s；VHR-3＝82.4％.

Example 5

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Compound (1-2) was added to the composition in a proportion of 0.5 mass%.

NI＝77.1℃；Tc＜-20℃；Δn＝0.108；Δε＝10.4；Vth＝1.35V；η＝17.8mPa·s；γ1＝79.9mPa·s；VHR-3＝81.5％.

Example 6

Compound (1-3) was added to the composition in a proportion of 0.5 mass%.

NI＝79.3℃；Tc＜-20℃；Δn＝0.106；Δε＝8.5；Vth＝1.45V；η＝11.6mPa·s；γ1＝60.0mPa·s；VHR-3＝80.2％.

Example 7

The compounds (1-4) were added to the composition in a proportion of 0.5 mass%.

NI＝78.0℃；Tc＜-20℃；Δn＝0.095；Δε＝3.4；Vth＝1.50V；η＝8.4mPa·s；γ1＝54.2mPa·s；VHR-3＝78.3％.

Example 8

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Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝78.8℃；Tc＜-20℃；Δn＝0.101；Δε＝4.6；Vth＝1.71V；η＝11.0mPa·s；γ1＝47.2mPa·s；VHR-3＝80.1％.

Example 9

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝80.7℃；Tc＜-20℃；Δn＝0.109；Δε＝4.8；Vth＝3.01V；η＝13.3mPa·s；γ1＝57.4mPa·s；VHR-3＝79.8％.

Example 10

Compound (1-1) was added to the composition in a proportion of 0.3 mass%.

Tc＜-20℃；Δn＝0.161；Δε＝4.1；Vth＝2.15V；η＝13.6mPa·s；γ1＝44.0mPa·s；VHR-3＝72.1％.

Example 11

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝83.0℃；Tc＜-20℃；Δn＝0.120；Δε＝8.4；Vth＝1.54V；VHR-3＝70.2％.

Example 12

Compound (1-1) was added to the composition in a proportion of 0.4 mass%.

NI＝103.5℃；Tc＜-20℃；Δn＝0.113；Δε＝3.5；Vth＝2.52V；γ1＝63.0mPa·s；VHR-3＝91.7％.

Example 13

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Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝80.7℃；Tc＜-20℃；Δn＝0.102；Δε＝6.5；Vth＝1.59V；η＝14.2mPa·s；γ1＝60.0mPa·s；VHR-3＝70.0％.

Example 14

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝89.4℃；Tc＜-20℃；Δn＝0.105；Δε＝4.9；Vth＝1.91V；η＝13.7mPa·s；γ1＝63.0mPa·s；VHR-3＝70.4％.

Example 15

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝84.8℃；Tc＜-20℃；Δn＝0.119；Δε＝5.3；Vth＝1.93V；η＝12.1mPa·s；γ1＝49.0mPa·s；VHR-3＝70.4％.

Example 16

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Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝84.9℃；Tc＜-20℃；Δn＝0.130；Δε＝5.2；Vth＝2.06V；η＝13.6mPa·s；γ1＝55.0mPa·s；VHR-3＝85.2％.

Example 17

Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

Tc＜-20℃；Δn＝0.130；Δε＝3.6；Vth＝2.15V；η＝12.0mPa·s；γ1＝33.0mPa·s；VHR-3＝70.5％.

Example 18

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Compound (1-1) was added to the composition in a proportion of 0.5 mass%.

NI＝73.8℃；Tc＜-20℃；Δn＝0.103；Δε＝-2.9；Vth＝2.26V；η＝16.7mPa·s；γ1＝94.0mPa·s；VHR-3＝76.8％.

The voltage holding ratios (VHR-3) of the compositions of comparative examples 1 and 2 after irradiation with ultraviolet light were 35.5% and 40.9%. On the other hand, the compositions of example 1 and example 2 exhibited VHR-3 of 87.8% and 78.1%. Thus, the compositions of the examples have a greater VHR-3 than the compositions of the comparative examples. Therefore, it was concluded that the liquid crystal composition of the present invention has excellent characteristics.

Industrial applicability

The liquid crystal composition of the present invention can be used in liquid crystal monitors, liquid crystal televisions, and the like.

Claims

1. A liquid crystal composition comprising at least one compound selected from the compounds represented by the formula (1) as a first additive and having a nematic phase,

in the formula (1), R ¹ Is hydrogen, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, or alkenyloxy of 2 to 12 carbon atoms; r is R ² Is C1-12 alkyl, C2-12 alkenyl, or C1-12 alkyl with at least one hydrogen substituted by fluorine or chlorine, at least one of these groups being-CH ₂ -may be substituted by-O-, -COO-, or-OCO-; ring A is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 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, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms1 to 12, or at least one hydrogen substituted by fluorine or chlorine substituted alkyl of 1 to 12 carbon atoms; a is 1 or 2; b is 0, 1,2, 3, or 4.

2. The liquid crystal composition according to claim 1, wherein R in the compound represented by formula (1) ² Methyl, tert-butyl, tert-amyl, or tert-octyl, b is 1, 2, 3, or 4.

3. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group of compounds represented by the formulas (1-1) to (1-4) as a first additive,

in the formulae (1-1) to (1-4), R ² Methyl, tert-butyl, tert-amyl, or tert-octyl.

4. The liquid crystal composition according to claim 1, wherein the proportion of the first additive is in the range of 0.005 to 2 mass%.

5. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group consisting of compounds represented by formula (2) as a first component,

in the formula (2), R ³ R is R ⁴ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring B and ring C are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, or 2, 5-difluoro-1, 4-phenylene; z is Z ¹ Is a single bond, ethylene, carbonyloxy, or methyleneoxy; c is 1, 2, or 3.

6. The liquid crystal composition according to claim 5, comprising at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-13) as a first component,

7. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group consisting of compounds represented by formula (3) as a second component,

in the formula (3), R ⁵ Is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; ring D is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl; z is Z ² Is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; x is X ¹ X is X ² Independently hydrogen or fluorine; y is Y ¹ Is fluorine, chlorine, at least one alkyl group of 1 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine, at least one alkoxy group of 1 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine, or at least one alkenyloxy group of 2 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine; d is 1, 2,3, or 4.

8. The liquid crystal composition according to claim 7, comprising at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-35) as a second component,

9. The liquid crystal composition according to claim 5, comprising at least one compound selected from the group consisting of compounds represented by the formula (3) as a second component,

in the formula (3), R ⁵ Is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; ring D is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl; z is Z ² Is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; x is X ¹ X is X ² Independently hydrogen or fluorine; y is Y ¹ Is fluorine, chlorine, at least one alkyl group of 1 to 12 carbon atoms with hydrogen substituted by fluorine or chlorine, at least one alkoxy group of 1 to 12 carbon atoms with hydrogen substituted by fluorine or chlorine, or at least oneAn alkenyloxy group having 2 to 12 carbon atoms in which each hydrogen is substituted with fluorine or chlorine; d is 1, 2,3, or 4.

10. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group consisting of compounds represented by formula (4) as a third component,

in the formula (4), R ⁶ R is R ⁷ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyloxy group of 2 to 12 carbon atoms; ring E and ring G are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene with at least one hydrogen substituted with fluorine or chlorine, or tetrahydropyran-2, 5-diyl; ring F 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-difluorochromane-2, 6-diyl; z is Z ³ Z is as follows ⁴ Independently a single bond, ethylene, carbonyloxy, or methyleneoxy; e is 1, 2, or 3, f is 0 or 1; the sum of e and f is 3 or less.

11. The liquid crystal composition according to claim 10, comprising at least one compound selected from the group of compounds represented by the formulas (4-1) to (4-27) as a third component,

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12. The liquid crystal composition according to claim 5, comprising at least one compound selected from the group consisting of compounds represented by the formula (4) as a third component,

in the formula (4), R ⁶ R is R ⁷ Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an alkenyloxy group of 2 to 12 carbon atoms; ring E and ring G are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene with at least one hydrogen substituted with fluorine or chlorine, or tetrahydropyran-2, 5-diyl; ring F 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-difluorochromane-2, 6-diyl; z is Z ³ Z is as follows ⁴ Independently a single bond, ethylene, carbonyloxy, or methyleneoxy; e is 1,2, or 3, f is 0 or 1; the sum of e and f is 3 or less.

13. The liquid crystal composition according to claim 1, comprising at least one compound selected from the polymerizable compounds represented by the formula (5) as a second additive,

in formula (5), ring I and ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl, at least one of which may be substituted with fluorine, chlorine, C1-12 alkyl, C1-12 alkoxy, orAt least one hydrogen is substituted with a fluorine or chlorine substituted alkyl group of 1 to 12 carbon atoms; ring J is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 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, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted with fluorine or chlorine; z is Z ⁵ Z is as follows ⁶ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, or-OCO-, at least one-CH ₂ -CH ₂ Can be modified by-ch=ch-, -C (CH ₃ )＝CH-、-CH＝C(CH ₃ ) -, or-C (CH) ₃ )＝C(CH ₃ ) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine; p (P) ¹ 、P ² P and P ³ Independently a polymerizable group; sp (Sp) ¹ 、Sp ² And Sp ³ Independently a single bond, or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-, or-OCOO-, at least one-CH ₂ -CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine; g is 0, 1, or 2; h. i, and j are independently 0, 1, 2, 3, or 4; and the sum of h, i, and j is 1 or more.

14. The liquid crystal composition according to claim 13, comprising at least one compound selected from the group of polymerizable compounds represented by the formulas (5-1) to (5-29) as a second additive,

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15. The liquid crystal composition according to claim 13, wherein the proportion of the second additive is in the range of 0.03 to 10 mass%.

16. A liquid crystal display element comprising the liquid crystal composition according to claim 1.

17. The liquid crystal display element of claim 16, wherein the operating mode of the liquid crystal display element is a twisted nematic mode, an electrically controlled birefringence mode, an optically compensated bend mode, a co-planar switching mode, a homeotropic alignment mode, a fringe field switching mode, or an electric field induced photoreaction alignment mode, and the liquid crystal display element is driven in an active matrix mode.