JPWO2019069550A1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

As the first additive, an ultraviolet absorber, as the first component, a specific compound having a large positive dielectric anisotropy, as the second component, a specific compound having a high upper limit temperature or a small viscosity, as the third component It is a liquid crystal composition which may contain a specific compound which has a positive dielectric anisotropy, or a specific compound which has a large negative dielectric anisotropy as a fourth component.

Description

The present invention relates to a liquid crystal composition, a liquid crystal display device containing the composition, and the like. In particular, it relates to a liquid crystal composition having a positive dielectric anisotropy, and an AM (active matrix) device containing the composition and having a mode of TN, ECB, OCB, IPS, FFS, or FPA.

In liquid crystal display elements, classification based on the operation mode of liquid crystal molecules is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) and other modes. The classifications based on the driving method of the element are PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like. The classification of TFT is amorphous silicon (amorphous silicon) and polycrystalline silicon (polycrystal silicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source is a reflective type that uses natural light, a transmissive type that uses a backlight, and a semi-transmissive type that uses both natural light and a backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM element having good characteristics can be obtained. The relationships in these properties are summarized in Table 1 below. The properties of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time of even 1 millisecond is desirable. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred. The elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is more preferable.

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, 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 device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operating mode. For devices in modes such as TN, a suitable value is about 0.45 μm. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large permittivity anisotropy in the composition contributes to the low threshold voltage, low power consumption and large contrast ratio in the device. Therefore, large dielectric anisotropy is preferred. A large resistivity in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, a composition having a large resistivity at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long-term use, a composition having a large resistivity not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. The stability of the composition against UV and heat is related to the life of the liquid crystal display device. When these stability is high, the life of this device is long. Such characteristics are preferable for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, the composition to which a small amount of the polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of this device. The polymerizable compound polymerizes to form a network structure of the polymer in the composition. In this composition, since the orientation of the liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened and the screen burn-in is improved. Such effects of the polymer can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.

In the AM device having the TN mode, a composition having a positive dielectric anisotropy is used. In the AM device having the VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy is used. Compositions containing compound (1) are disclosed in Patent Documents 1 and 2.

Japanese Unexamined Patent Publication No. 2006-625734 JP-A-2007-320985

One object of the present invention is a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, appropriate optical anisotropy, a large dielectric anisotropy, a large specific resistance, high stability against ultraviolet rays, and heat. It is to provide a liquid crystal composition that satisfies at least one of the properties such as high stability against and a large elastic constant. Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long lifetime.

式（１）および式（２）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、または式（Ａ−１）で表される基であってもよく；Ｒ^２は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ａおよび環Ｂは独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^１およびＺ^２は独立して、単結合、エチレン、カルボニルオキシ、またはジフルオロメチレンオキシであり；Ｘ^１は、水素、フッ素、または塩素であり；Ｘ^２、Ｘ^３、Ｘ^４、およびＸ^５は独立して、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；ａは、０、１、２、３、または４であり；ｂおよびｃは独立して、０、１、２、または３であり、ｂおよびｃの和は、２または３であり；

式（Ａ−１）において、Ｒ^ａは、フッ素、塩素、炭素数１から１２のアルキル、炭素数２から１２のアルケニル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく；Ｚ^ａは、炭素数１から２０の分岐してもよいアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく；ｓは、０または１であり；ｔは、０、１、２、３、４、または５である。The present invention contains at least one compound selected from the compound represented by the formula (1) as the first additive and at least one compound selected from the compound represented by the formula (2) as the first component. The present invention relates to a liquid crystal composition having a positive dielectric anisotropy, and a liquid crystal display element containing the composition.

In formulas (1) and (2), R ¹ is an alkyl having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, and an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. In these groups, at least one -CH _2- may be replaced by -O-, -COO-, or -OCO-, or is a group represented by the formula (A-1). at best; ^{R 2} is alkyl of 1 to 12 carbons, alkenyl alkoxy of 1 to 12 carbons, or 2 to 12 carbons; ring a and ring B are independently 1,4-cyclohexylene Silen, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ and Z ² are independently single-bonded, ethylene, carbonyloxy, or difluoromethyleneoxy; X ¹ is hydrogen, fluorine, or chlorine; X ² , X ³ , X ⁴ , and X ⁵ are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen is fluorine or From an alkyl with 1 to 12 carbons replaced with chlorine, an alkoxy with 1 to 12 carbons with at least one hydrogen replaced with fluorine or chlorine, or from 2 carbons with at least one hydrogen replaced with fluorine or chlorine. Twelve alkenyloxys; a is 0, 1, 2, 3, or 4; b and c are independently 0, 1, 2, or 3, and the sum of b and c is 2. Or 3;

In formula (A-1), ^Ra is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. an alkyl, in these groups, at least one of _-CH 2 -, -O -, - COO-, or it may be replaced by -OCO-; ^{Z a} is branched from 1 to 20 carbon atoms in the It may be an alkylene, in which at least one −CH ₂ − may be replaced by −O−, −COO−, or −OCO−, and at least one −CH ₂ CH ₂₋ It may be replaced by −CH = CH−; s is 0 or 1; t is 0, 1, 2, 3, 4, or 5.

The advantages of the present invention are high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high resistance to heat. It is to provide a liquid crystal composition that satisfies at least one of the properties such as stability and large elastic constant. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide AM devices with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long lifetime.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase, but is composed for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric constant anisotropy of the nematic phase. It is a general term for compounds mixed in a product. This 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. Liquid crystal compounds with alkenyl are not polymerizable in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as needed. To. The proportion of the liquid crystal compound is expressed as a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive even when the additive is added. The ratio of the additive is expressed as a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound. Parts per million (ppm) may be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". "Large specific resistance" means that the composition has a large specific resistance at an initial stage and has a large specific resistance after a long period of use. "Large voltage retention" means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after long-term use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. It means having a retention rate. The properties of the composition or device may be examined by aging tests. The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.

Expressions such as "at least one -CH _2- may be replaced by -O-" are used herein. In this _case, -CH ₂ -CH ₂ -CH ₂ - it is, -CH ₂ nonadjacent - may be converted _-O-CH 2 -O- to by is replaced by -O-. However, the adjacent −CH ₂₋ is not replaced by −O−. This is because -O-O-CH _2- (peroxide) is produced by this replacement. That is, this expression includes both "one -CH _2- may be replaced by -O-" and "at least two non-adjacent -CH _2- may be replaced by -O-". means. This rule applies not only to the replacement with -O-, but also with the replacement with divalent groups such as -CH = CH- and -COO-.

In the chemical formulas of the component compounds, with symbols of terminal groups R ² to a plurality of compounds. In these compounds, two groups represented by any two R ² may be may be the same or different. For example, there are cases where R ^{2 of} compound (2-1) is ethyl and R ² of compound (2-2) is ethyl. In some cases, R ^{2 of} compound (2-1) is ethyl and R ² of compound (2-2) is propyl. This rule also applies to symbols such as other end groups. In equation (2), when the subscript'b'is 2, there are two rings A. In this compound, the two rings represented by the two rings A may be the same or different. This rule also applies to any two rings A when the subscript'b'is greater than 2. This rule also applies to symbols such as Z ¹ and ring B.

In compound (1), diagonal lines across one side of the benzene ring indicate that any hydrogen on the ring may be replaced by -R ¹ . The subscript of'a'indicates the number of replaced groups. When the subscript'a'is 0 (zero), there is no such replacement. When the subscript'a'is 2 or more, there are a plurality of -R ¹ 's. A plurality of groups -R ¹ represents may be the same or different.

2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent binding groups such as carbonyloxy (-COO- or -OCO-).

The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit.

The present invention includes the following items.

式（１）および式（２）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、または式（Ａ−１）で表される基であってもよく；Ｒ^２は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ａおよび環Ｂは独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^１およびＺ^２は独立して、単結合、エチレン、カルボニルオキシ、またはジフルオロメチレンオキシであり；Ｘ^１は、水素、フッ素、または塩素であり；Ｘ^２、Ｘ^３、Ｘ^４、およびＸ^５は独立して、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；ａは、０、１、２、３、または４であり；ｂおよびｃは独立して、０、１、２、または３であり、ｂおよびｃの和は、２または３であり；

式（Ａ−１）において、Ｒ^ａは、フッ素、塩素、炭素数１から１２のアルキル、炭素数２から１２のアルケニル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく；Ｚ^ａは、炭素数１から２０の分岐してもよいアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく；ｓは、０または１であり；ｔは、０、１、２、３、４、または５である。Item 1. It contains at least one compound selected from the compound represented by the formula (1) as the first additive and at least one compound selected from the compound represented by the formula (2) as the first component, and is positive. A liquid crystal composition having dielectric anisotropy.

In formulas (1) and (2), R ¹ is an alkyl having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, and an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. In these groups, at least one -CH _2- may be replaced by -O-, -COO-, or -OCO-, or is a group represented by the formula (A-1). at best; ^{R 2} is alkyl of 1 to 12 carbons, alkenyl alkoxy of 1 to 12 carbons, or 2 to 12 carbons; ring a and ring B are independently 1,4-cyclohexylene Silen, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ and Z ² are independently single-bonded, ethylene, carbonyloxy, or difluoromethyleneoxy; X ¹ is hydrogen, fluorine, or chlorine; X ² , X ³ , X ⁴ , and X ⁵ are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen is fluorine or From an alkyl with 1 to 12 carbons replaced with chlorine, an alkoxy with 1 to 12 carbons with at least one hydrogen replaced with fluorine or chlorine, or from 2 carbons with at least one hydrogen replaced with fluorine or chlorine. Twelve alkenyloxys; a is 0, 1, 2, 3, or 4; b and c are independently 0, 1, 2, or 3, and the sum of b and c is 2. Or 3;

In formula (A-1), ^Ra is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. an alkyl, in these groups, at least one of _-CH 2 -, -O -, - COO-, or it may be replaced by -OCO-; ^{Z a} is branched from 1 to 20 carbon atoms in the It may be an alkylene, in which at least one −CH ₂ − may be replaced by −O−, −COO−, or −OCO−, and at least one −CH ₂ CH ₂₋ It may be replaced by −CH = CH−; s is 0 or 1; t is 0, 1, 2, 3, 4, or 5.

Item 2. Item 2. The liquid crystal composition according to Item 1, which contains at least one compound selected from the group of compounds represented by the formulas (1-1) to (1-8) as the first additive.

式（２−１）から式（２−１１）において、Ｒ^２は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルである。Item 3. Item 2. The liquid crystal composition according to Item 1 or 2, which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-11) as a first component.

In formulas (2-1) to (2-11), R ² is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms.

Item 4. Item 6. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first additive is in the range of 0.005% by mass to 2% by mass.

Item 5. Item 8. The liquid crystal composition according to any one of Items 1 to 4, wherein the proportion of the first component is in the range of 5% by mass to 40% by mass.

式（３）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｃおよび環Ｄは独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、または２，５−ジフルオロ−１，４−フェニレンであり；Ｚ^３は、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ｄは、１、２、または３である。Item 6. Item 6. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from the compounds represented by the formula (3) as the second component.

In formula (3), R ³ and R ⁴ are independently an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or at least one hydrogen being fluorine or chlorine. It is an alkenyl having 2 to 12 carbon atoms replaced; rings C and D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5. -Difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, carbonyloxy, or methyleneoxy; d is 1, 2, or 3.

式（３−１）から式（３−１３）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。Item 7. Item 6. The liquid crystal composition according to any one of Items 1 to 6, which contains at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-13) as the second component. object.

In formulas (3-1) to (3-13), R ³ and R ⁴ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or An alkoxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

Item 8. Item 6. The liquid crystal composition according to Item 6 or 7, wherein the proportion of the second component is in the range of 10% by mass to 80% by mass.

式（４）において、Ｒ^５は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ｅは、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^４は、単結合、エチレン、カルボニルオキシ、またはジフルオロメチレンオキシであり；Ｘ^６およびＸ^７は独立して、水素またはフッ素であり；Ｙ^２は、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；ｅは、１、２、３、または４である。ここで、ｅが３または４であるとき、Ｚ^４は、単結合、エチレン、またはカルボニルオキシである。Item 9. Item 8. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the compounds represented by the formula (4) as the third component.

In formula (4), R ⁵ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms; ring E is 1,4-cyclohexylene, 1, 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 ⁴ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; X ⁶ and X ⁷ are independently hydrogen. Or fluorine; Y ² is fluorine, chlorine, an alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, and 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Aalkoxy, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; e is 1, 2, 3, or 4. Here, when e is 3 or 4, Z ⁴ is a single bond, ethylene, or carbonyloxy.

式（４−１）から式（４−２４）において、Ｒ^５は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルである。Item 10. Item 2. The liquid crystal composition according to any one of Items 1 to 9, which contains at least one compound selected from the group of compounds represented by the formulas (4-1) to (4-24) as the third component. object.

In the formula (4-24) from equation (4-1), ^{R 5} is an alkenyl alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons.

Item 11. Item 9. The liquid crystal composition according to Item 9 or 10, wherein the proportion of the third component is in the range of 10% by mass to 80% by mass.

式（５）において、Ｒ^６およびＲ^７は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシであり；環Ｆおよび環Ｉは独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、またはテトラヒドロピラン−２，５−ジイルであり；環Ｇは、２，３−ジフルオロ−１，４−フェニレン、２−クロロ−３−フルオロ−１，４−フェニレン、２，３−ジフルオロ−５−メチル−１，４−フェニレン、３，４，５−トリフルオロナフタレン−２，６−ジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり；Ｚ^５およびＺ^６は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ｆは、１、２、または３であり、ｇは、０または１であり；ｆとｇとの和は３以下である。Item 12. Item 8. The liquid crystal composition according to any one of Items 1 to 11, which contains at least one compound selected from the compounds represented by the formula (5) as the fourth component.

In formula (5), R ⁶ and R ⁷ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Rings F and I are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Or tetrahydropyran-2,5-diyl; ring G 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-trifluoro-2,6-diyl or 7,8-be difluorochroman-2,6-diyl; ^{Z 5} and ^{Z 6} are each independently , Single bond, ethylene, carbonyloxy, or methyleneoxy; f is 1, 2, or 3, g is 0 or 1; the sum of f and g is 3 or less.

式（５−１）から式（５−２７）において、Ｒ^６およびＲ^７は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシである。Item 13. Item 2. The liquid crystal composition according to any one of Items 1 to 12, which contains at least one compound selected from the group of compounds represented by the formulas (5-1) to (5-27) as the fourth component. object.

In formulas (5-1) to (5-27), R ⁶ and R ⁷ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkoxyoxy having 2 to 12 carbon atoms.

Item 14. Item 12. The liquid crystal composition according to Item 12 or 13, wherein the proportion of the fourth component is in the range of 5% by mass to 40% by mass.

Item 15. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2. Item 2. The liquid crystal composition according to any one of Items 1 to 14.

Item 16. A liquid crystal display device containing the liquid crystal composition according to any one of Items 1 to 15.

Item 17. Item 16. The liquid crystal display element according to Item 16, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, FFS mode, or FPA mode, and the drive method of the liquid crystal display element is the active matrix method. ..

Item 18. Use of the liquid crystal composition according to any one of Items 1 to 15 in a liquid crystal display element.

The present invention also includes the following items. (A) As the second additive, additives such as an optically active compound, an antioxidant, an ultraviolet absorber other than the compound (1), a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor. The above composition comprising one compound selected from the group, two compounds, or three or more compounds. (B) AM device containing the above composition. (C) A polymer-supported orientation (PSA) type AM device containing the above composition further containing a polymerizable compound. (D) A polymer-supported orientation (PSA) type AM device containing the above composition and in which the polymerizable compound in the composition is polymerized. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the above composition.

The composition of the present invention will be described in the following order. First, the composition of the constituent compounds in the composition will be described. Secondly, the main properties of the constituent compounds and the main effects of this compound on the composition will be described. Thirdly, the combination of components in the composition, the preferable ratio of the components, and the rationale thereof will be described. Fourth, preferred forms of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing a component compound will be described. Finally, the use of the composition will be described.

First, the composition of the constituent compounds in the composition will be described. The compositions of the present invention are classified into composition A and composition B. The composition A further contains other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (2), the compound (3), the compound (4) and the compound (5). May be good. The "other liquid crystal compound" is a liquid crystal compound different from the compound (2), the compound (3), the compound (4), and the compound (5). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors and the like. Quenching agents are also classified as additives.

The composition B is substantially composed of only a liquid crystal compound selected from the compound (2), the compound (3), the compound (4), and the compound (5). "Substantially" means that the composition may contain additives but does not contain other liquid crystal compounds. An example of the composition B is a composition containing the compound (2), the compound (3), the compound (4), and the compound (5) as essential components. The composition B has a smaller number of components than the composition A. The composition B is preferable to the composition A from the viewpoint of reducing the cost. Composition A is preferable to composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

Secondly, the main properties of the component compound and the main effects of this compound on the composition and the device will be described. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M and S are classifications based on qualitative comparisons between the constituent compounds, with 0 (zero) meaning extremely small.

The main effects of the component compounds are as follows. Compound (1) acts as an ultraviolet absorber and contributes to high stability against heat or ultraviolet rays. Since the amount of compound (1) added is extremely small, it often does not affect properties such as upper temperature, optical anisotropy, and dielectric anisotropy. Compound (2) increases the dielectric anisotropy. Compound (3) lowers the viscosity or raises the upper temperature limit. Compound (4) lowers the lower limit temperature and raises the dielectric anisotropy. Compound (5) increases the dielectric constant in the minor axis direction.

When added to the liquid crystal composition, the ultraviolet absorber absorbs ultraviolet rays instead of the liquid crystal molecules. The absorption of light energy causes the UV absorber to transition from the ground state to the excited state. Excited state The molecule undergoes a structural change due to the intramolecular proton transfer process, which releases heat and returns to the ground state. As another mechanism, it returns to the ground state by radiating as light with lower energy than absorbed light. By adding the ultraviolet absorber to the liquid crystal composition, it is possible to suppress the deterioration of the liquid crystal molecules due to the absorption of ultraviolet rays.

Thirdly, the combination of the components in the composition, the preferable ratio of the component compounds, and the rationale thereof will be described. Preferred combinations of components in the composition are compound (1) + compound (2), 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 (3) + compound (4) + compound (5). A more preferred combination is compound (1) + compound (2) + compound (3) or compound (1) + compound (2) + compound (3) + compound (4).

The preferred proportion of compound (1) is about 0.005% by mass or more to increase stability against ultraviolet rays or heat, and about 2% by mass or less to lower the lower limit temperature. A more preferable ratio is in the range of about 0.05% by mass to about 1.5% by mass. A particularly preferable ratio is in the range of about 0.8% by mass to about 1.3% by mass.

The preferable ratio of the compound (2) is about 5% by mass or more in order to increase the dielectric anisotropy, and about 40% by mass or less in order to lower the lower limit temperature. A more preferable ratio is in the range of about 5% by mass to about 35% by mass. A particularly preferable ratio is in the range of about 10% by mass to about 35% by mass.

The preferable ratio of the compound (3) is about 10% by mass or more in order to raise the upper limit temperature or lower the viscosity, and about 80% by mass or less in order to raise the dielectric anisotropy. A more preferable ratio is in the range of about 20% by mass to about 75% by mass. A particularly preferable ratio is in the range of about 25% by mass to about 70% by mass.

The preferable ratio of the compound (4) is about 5% by mass or more in order to increase the dielectric anisotropy, and about 50% by mass or less in order to lower the lower limit temperature. A more preferable ratio is in the range of about 5% by mass to about 45% by mass. A particularly preferable ratio is in the range of about 5% by mass to about 35% by mass.

The preferable ratio of the compound (5) is about 5% by mass or more in order to increase the dielectric constant in the minor axis direction, and about 40% by mass or less in order to lower the lower limit temperature. A more preferable ratio is in the range of about 5% by mass to about 35% by mass. A particularly preferable ratio is in the range of about 5% by mass to about 30% by mass.

Fourth, preferred forms of the component compounds will be described. In formula (1), formula (2), formula (3), formula (4), and formula (5), R ¹ is an alkyl having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, and at least one of them. Hydrogen is an alkyl having 1 to 12 carbon atoms with fluorine or chlorine replaced, and in these groups at least one -CH ₂ − may be replaced with -O-, -COO-, or -OCO-. It may be a group represented by the formula (A-1). Preferred R ¹ is an alkyl having 1 to 12 carbon atoms, an alkyl having 1 to 12 carbon atoms in which at least one -CH _2- has been replaced with -COO-, or -OCO-, or represented by the formula (A-1). Is the basis for being done. Particularly preferred R ¹ is methyl, t-butyl, t-pentyl, t-octyl, or α-cumyl. R ² is alkenyl alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons. Preferred R ² is an alkyl having 1 to 12 carbon atoms to increase stability. R ³ and R ⁴ are independently alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or 2 carbons in which at least one hydrogen is replaced with fluorine or chlorine. To 12 alkenyl. Preferred R ³ or R ⁴ is an alkenyl having 2 to 12 carbons to reduce the viscosity and an alkyl having 1 to 12 carbons to increase stability. R ⁵ is alkenyl alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons. Preferred R ⁵ is alkyl from 1 to 12 carbons for increasing the stability. R ⁶ and R ⁷ are independently alkyls with 1 to 12 carbons, alkoxys with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or alkenyloxys with 2 to 12 carbons. Preferred R ⁶ or R ⁷ is an alkyl having 1 to 12 carbon atoms to increase stability and an alkoxy having 1 to 12 carbon atoms to increase dielectric anisotropy.

In formula (A-1), ^Ra is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. In these groups, at least one −CH ₂ − may be replaced by −O −, −COO−, or −OCO−. Preferred ^Ra is an alkyl having 1 to 12 carbon atoms or an alkoxy having 1 to 12 carbon atoms. Z ^a is a alkylene which may be branched from 1 to 20 carbon atoms of, in the alkylene, at least one of _-CH 2 -, -O -, - COO-, or -OCO- may be replaced by , At least one -CH ₂ CH _2- may be replaced by -CH = CH-. Preferred Z ^a is alkylene which may be branched 1 -C 3. Particularly preferred Z ^a is a methylene or dimethylmethylene. s is 0 or 1. The preferred s is 1. t is 0, 1, 2, 3, 4, or 5. Preferred t is 0 or 1. In formula (A-1), the wavy line indicates the site to be connected.

Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyls are methyl, ethyl, propyl, butyl, or pentyl to reduce viscosity.

Preferred alkoxys are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More preferred alkoxys are methoxy or ethoxy to reduce the viscosity.

Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to reduce the viscosity. The preferred configuration of -CH = CH- in these alkenyl depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl for the purpose of lowering the viscosity. Sith is preferred for alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl.

Preferred alkenyloxys are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy to reduce viscosity are allyloxy or 3-butenyloxy.

Preferred examples of alkyl in which at least one hydrogen is replaced with fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. , Or 8-fluorooctyl. More preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl to increase the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen is replaced with fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro. -4-pentenyl, or 6,6-difluoro-5-hexenyl. More preferred examples are 2,2-difluorovinyl, or 4,4-difluoro-3-butenyl to reduce the viscosity.

または

であり、好ましくは

である。Ring A and Ring B are independently 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. Preferred ring A or ring B is 1,4-cyclohexylene to increase the upper temperature limit, 1,4-phenylene to increase the optical anisotropy, and 2, to increase the dielectric anisotropy. 6-Difluoro-1,4-phenylene. Tetrahydropyran-2,5-diyl is

Or

And preferably

Is.

Rings C and D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring C or ring D is 1,4-cyclohexylene for lowering the viscosity or raising the upper temperature limit and 1,4-phenylene for lowering the lower limit temperature.

Ring E 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. Preferred ring E is 1,4-cyclohexylene to increase the upper temperature limit, 1,4-phenylene to increase the optical anisotropy, and 2,6-difluoro to increase the dielectric anisotropy. -1,4-Phenylene.

Rings F and I are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, or Tetrahydropyran-2,5-diyl. Preferred ring F or ring I is 1,4-cyclohexylene to reduce viscosity, tetrahydropyran-2,5-diyl to increase dielectric anisotropy, and to increase optical anisotropy. It is 1,4-phenylene. Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. The preferred ring G is 2,3-difluoro-1,4-phenylene to increase the dielectric anisotropy.

Z ¹ and Z ² are independently single bonds, ethylene, carbonyloxy, or difluoromethyleneoxy. Preferred Z ¹ or Z ² is a single bond to reduce viscosity. Z ³ is a single bond, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ³ is a single bond to reduce viscosity. Z ⁴ is single bond, ethylene, carbonyloxy, or difluoromethyleneoxy, and when e is 3 or 4, Z ⁴ is single bond, ethylene, or carbonyloxy. Preferred Z ⁴ is a single bond to reduce viscosity and difluoromethyleneoxy to increase dielectric anisotropy. Z ⁵ and Z ⁶ are independently single bonds, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ⁵ or Z ⁶ is a single bond to reduce the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the dielectric anisotropy.

X ¹ is hydrogen, fluorine, or chlorine. Preferred X ¹ is hydrogen or chlorine. ^{X 2, X 3, X 4} , and ^{X 5} are each independently hydrogen or fluorine. Preferred X ² , X ³ , X ⁴ or X ⁵ are fluorine to increase the dielectric anisotropy.

Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, an alkoxy having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or at least. One hydrogen is an alkenyloxy having 2 to 12 carbon atoms in which fluorine or chlorine is replaced. Preferred Y ¹ is fluorine to lower the lower limit temperature.

A preferred example of an alkyl in which at least one hydrogen has been replaced with fluorine or chlorine is trifluoromethyl. A preferred example of an alkoxy in which at least one hydrogen has been replaced with fluorine or chlorine is trifluoromethoxy. A preferred example of alkenyloxy in which at least one hydrogen has been replaced with fluorine or chlorine is trifluorovinyloxy.

a is 0, 1, 2, 3, or 4. Preferred a is 1 or 2. b and c are independently 0, 1, 2, or 3, and the sum of b and c is 2 or 3. Preferred b is 1 or 2 to raise the upper temperature limit. Preferred c is 0 or 1 to lower the lower limit temperature. d is 1, 2, or 3. The preferred d is 1 for lowering the viscosity and 2 or 3 for raising the upper temperature limit. e is 1, 2, 3, or 4. Preferred e is 2 or 3 to increase the dielectric anisotropy. f is 1, 2, or 3, g is 0 or 1, and the sum of f and g is 3 or less. The preferred f is 1 to reduce the viscosity and 2 or 3 to raise the upper temperature limit. The preferred g is 0 to lower the viscosity and 1 to lower the lower limit temperature.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to compounds (1-8) according to Item 2. Particularly preferred compound (1) is compound (1-1) or compound (1-2).

Preferred compounds (2) are compounds (2-1) to compounds (2-11) according to Item 3. In these compounds, at least one of the first components is compound (2-1), compound (2-2), compound (2-4), compound (2-6), or compound (2-8). Is preferable. At least two of the first components are compound (2-1) and compound (2-4), compound (2-1) and compound (2-6), compound (2-2) and compound (2-4), It is preferably a combination of compound (2-2) and compound (2-6), compound (2-4) and compound (2-6), or compound (2-4) and compound (2-8).

Preferred compounds (3) are compounds (3-1) to compounds (3-13) according to Item 7. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), or compound (3-8). Is preferable. At least two of the second components are compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), compound (3-1) and compound (3-8), compound. It is preferably a combination of (3-3) and compound (3-5), compound (3-3) and compound (3-6), compound (3-3) and compound (3-8).

Preferred compounds (4) are compounds (4-1) to compounds (4-24) according to Item 10. In these compounds, at least one of the third components is compound (4-2), compound (4-4), compound (4-8), compound (4-12), compound (4-14), compound ( 4-15), compound (4-18), or compound (4-19) is preferred. At least two of the third components are compound (4-8) and compound (4-15), compound (4-8) and compound (4-18), compound (4-12) and compound (4-15), Compound (4-14) and compound (4-18), compound (4-15) and compound (4-18), compound (4-15) and compound (4-19), or compound (4-18) and It is preferably a combination of compound (4-19).

Preferred compounds (5) are compounds (5-1) to compounds (5-27) according to Item 13. In these compounds, at least one of the fourth components is compound (5-1), compound (5-3), compound (5-6), compound (5-8), compound (5-10), or compound. It is preferably (5-14). At least two of the fourth components are compound (5-1) and compound (5-8), compound (5-3) and compound (5-8), compound (5-3) and compound (5-14), It is preferably a combination of compound (5-6) and compound (5-8), compound (5-6) and compound (5-10), or compound (5-8) and compound (5-14).

Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, UV absorbers, light extinguishing agents, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (6-1) to compound (6-5). The preferred proportion of the optically active compound is about 5% by mass or less. A more preferable ratio is in the range of about 0.01% by mass to about 2% by mass.

An antioxidant is composed to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage retention not only at room temperature but also at temperatures close to the upper limit temperature after long-term use of the device. It is added to the thing. Preferred examples of antioxidants are compounds (7-1) to compounds (7-3).

Since the compound (7-2) has low volatility, it is effective in maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time. The preferable ratio of the antioxidant is about 50 ppm or more in order to obtain the effect, and is about 600 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer are compounds (8-1) to compounds (8-16) and the like. The preferable ratio of these absorbents and stabilizers is about 50 ppm or more in order to obtain the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

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

Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition to accommodate devices in GH (guest host) mode. The preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, a defoaming agent such as dimethyl silicone oil or methyl phenyl silicone oil is added to the composition. The preferable ratio of the defoaming agent is about 1 ppm or more in order to obtain the effect, and about 1000 ppm or less in order to prevent display defects. A more preferred ratio is in the range of about 1 ppm to about 500 ppm.

Polymerizable compounds are added to the composition to accommodate polymer-supported orientation (PSA) type devices. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxylane, oxetane), vinyl ketone and the like. A more preferred example is a derivative of acrylate or methacrylate. The preferable ratio of the polymerizable compound is about 0.05% by mass or more in order to obtain the effect, and about 10% by mass or less in order to prevent display defects. A more preferable ratio is in the range of about 0.1% by mass to about 2% by mass. The polymerizable compound is polymerized by irradiation with ultraviolet rays. Polymerization may be carried out in the presence of an initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those of skill in the art and are described in the literature. For example, the photopolymerization initiators Irgacure651®, Irgacure184® (registered trademark; BASF), or Darocur1173® are suitable for radical polymerization. The preferred proportion of photopolymerization initiator is in the range of about 0.1% by mass to about 5% by mass based on the mass of the polymerizable compound. A more preferable ratio is in the range of about 1% by mass to about 3% by mass.

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

Seventh, a method for synthesizing a component compound will be described. These compounds can be synthesized by known methods. An example of the synthesis method. Compound (1-1) and the like can be obtained from Tokyo Chemical Industry (TCI). Compound (2-4) is synthesized by the method described in JP-A-10-251186. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Compound (4-4) is synthesized by the method described in JP-A No. 10-204016. Compound (5-1) is synthesized by the method described in JP-A-2000-053602. Antioxidants are commercially available. Compound (7-1) is available from Sigma-Aldrich Corporation. Compound (7-2) is synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which the synthetic method was not described are Organic Syntheses, John Wiley & Sons, Inc, Organic Reactions, John Wiley & Sons, Inc, Comprehensive Organic. It can be synthesized by the methods described in books such as Synthesis, Pergamon Press) and New Experimental Chemistry Course (Maruzen). The composition is prepared from the compound thus obtained by a known method. For example, the constituent compounds are mixed and dissolved by heating.

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

This composition can be used for AM devices. It can also be used for PM elements. This composition can be used for AM and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA. Use on AM devices with TN, OCB, IPS or FFS modes is particularly preferred. In an AM device having an IPS mode or an FFS mode, the arrangement of liquid crystal molecules may be parallel to or perpendicular to the glass substrate when no voltage is applied. These elements may be reflective, transmissive or transflective. Use for transmissive devices is preferred. It can also be used for non-crystalline silicon-TFT devices or polycrystalline silicon-TFT devices. It can also be used for NCAP (nematic curvilinear aligned phase) type devices produced by microencapsulating this composition and PD (polymer dispersed) type devices in which a three-dimensional network polymer is formed in the composition.

The present invention will be described in more detail by way of examples. The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the compositions of the Examples. The synthesized compound was identified by a method such as NMR analysis. The properties of the compound, composition and device were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for the measurement. ^{1 In the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was carried out at room temperature under the conditions of 500 MHz and 16 times of integration. Tetramethylsilane was used as an internal standard. ^{19 In the} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, and br is broad.

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

Chloroform, hexane or the like may be used as the solvent for diluting the sample. The following capillary columns may be used to separate the constituent compounds. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 manufactured by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). A capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.

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

Measurement sample: When measuring the characteristics of the composition or device, the composition was used as it was as a sample. When measuring the properties of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). From the values obtained by the measurement, the characteristic values of the compound were calculated by the extrapolation method. (Extrapolated value) = {(Measured value of sample) −0.85 × (Measured value of mother liquid crystal)} /0.15. When the smectic phase (or crystal) is precipitated at 25 ° C. at this ratio, the ratio of the compound to the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, and 1% by mass: 99% by mass. changed. The values of upper temperature, optical anisotropy, viscosity, and permittivity anisotropy for the compound were determined by this extrapolation method.

The following mother liquid crystal was used. The ratio of the component compounds is shown in mass%.

Measurement method: The characteristics were measured by the following method. Many of these are methods described in the JEITA standard (JEITA ED-2521B), which is deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. Met. A thin film transistor (TFT) was not attached to the TN element used for the measurement.

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

(2) Minimum Temperature of a Nematic Phase _{(T C;} ° C.): A sample having a nematic phase was put in a glass bottle, 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ for 10 days in a freezer After storage, the liquid crystal phase was observed. For example, _TC was described as <-20 ° C. when the sample remained in the nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

(3) Viscosity (bulk viscosity; η; measured at 20 ° C.; mPa · s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s): The measurement was carried out according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. The sample was placed in a TN device having a twist angle of 0 ° and a distance (cell gap) between the two glass substrates of 5 μm. A stepwise application was applied to this device in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) described on page 40 in the paper by M. Imai et al. The value of the dielectric anisotropy required for this calculation was obtained by the method described below using the device whose rotational viscosity was measured.

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

(6) Dielectric constant anisotropy (Δε; measured at 25 ° C.): The sample was placed in a TN element having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε ‖) of the liquid crystal molecule in the long axis direction was measured. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε⊥) of the liquid crystal molecule in the minor axis direction was measured. The value of permittivity anisotropy was calculated from the formula Δε ＝ ε‖−ε⊥.

(7) Threshold voltage (Vth; measured at 25 ° C.; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(8) Voltage retention rate (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This device was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 1 V) was applied to the TN element to charge it. The decaying voltage was measured with a high-speed voltmeter for 166.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

(9) Voltage retention rate (VHR-2; measured at 60 ° C.;%): The voltage retention rate was measured by the same procedure as above except that the voltage retention rate was measured at 60 ° C. instead of 25 ° C. The obtained value was represented by VHR-2.

(10) Voltage retention rate (VHR-3; measured at 60 ° C.;%): After irradiation with ultraviolet rays, the voltage retention rate was measured to evaluate the stability against ultraviolet rays. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this device and irradiated with ultraviolet rays of 5 mW / cm ² for 167 minutes. The light source was a black light manufactured by Eye Graphics Co., Ltd., F40T10 / BL (peak wavelength 369 nm), and the distance between the element and the light source was 5 mm. In the VHR-3 measurement, the decaying voltage was measured for 166.7 milliseconds. Compositions with large VHR-3 have great stability to UV light.

(11) Voltage retention rate (VHR-4; measured at 60 ° C.;%): After heating the TN element into which the sample was injected for 20 hours in a constant temperature bath at 120 ° C., the voltage retention rate was measured and stability against heat was measured. Was evaluated. In the measurement of VHR-4, the voltage decayed for 166.7 milliseconds was measured. Compositions with large VHR-4 have great stability to heat.

(12) Response time (τ; measured at 25 ° C.; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 5.0 μm and the twist angle was 80 degrees. A square wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was 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 for the transmittance to change from 10% to 90%. The response time was expressed as the sum of the rise time and the fall time obtained in this way.

(13) Elastic constant (K; measured at 25 ° C.; pN): An HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for the measurement. The sample was placed in a horizontally oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to this device, and the capacitance and applied voltage were measured. Fit the measured capacitance (C) and applied voltage (V) values using the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), formulas (2.98) and formula (2.11) on page 75. Then, 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 earlier in the formula (3.18) on page 171 of the same. The elastic constant was represented by the average value of K11, K22, and K33 obtained in this way.

(14) Specific resistance (ρ; measured at 25 ° C.; Ωcm): 1.0 mL of the sample was injected into a container equipped with an electrode. A DC voltage (10 V) was applied to this container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following formula. (Specific resistance) = {(voltage) x (electric capacity of container)} / {(DC current) x (vacuum permittivity)}.

(15) Spiral pitch (P; measured at room temperature; μm): The spiral pitch was measured by the wedge method. See "LCD Handbook", page 196 (published in 2000, Maruzen). The sample was injected into a wedge-shaped cell, allowed to stand at room temperature for 2 hours, and then the spacing of the dispersion lines (d2-d1) was observed with a polarizing microscope (Nikon Corporation, trade name MM40 / 60 series). The spiral pitch (P) was calculated from the following equation in which the angle of the wedge cell was expressed as θ. P = 2 × (d2-d1) × tan θ.

(16) Permittivity in the minor axis direction (ε⊥; measured at 25 ° C.): The sample was placed in a TN element having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. .. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε⊥) of the liquid crystal molecule in the minor axis direction was measured.

The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

ＮＩ＝７８．０℃；Ｔｃ＜−２０℃；Δｎ＝０．１０６；Δε＝８．５；η＝１１．６ｍＰａ・ｓ；γ１＝６０．０ｍＰａ・ｓ；ＶＨＲ−３＝８１．１％．[Comparative Example 1]
3-HBBXB (F, F) -F (2-1) 3%
3-BB (F) B (F, F) XB (F, F) -F (2-4) 2%
4-BB (F) B (F, F) XB (F, F) -F (2-4) 8%
5-BB (F) B (F, F) XB (F, F) -F (2-4) 7%
3-HH-V (3-1) 44%
V-HHB-1 (3-5) 6%
2-BB (F) B-3 (3-8) 2%
3-HHXB (F, F) -F (4-4) 6%
3-BB (F, F) XB (F, F) -F (4-18) 13%
3-HHBB (F, F) -F (4-19) 4%
4-HHBB (F, F) -F (4-19) 5%
NI = 79.8 ° C; Tc <-20 ° C; Δn = 0.106; Δε = 8.5; η = 11.6 mPa · s; γ1 = 60.0 mPa · s; VHR-3 = 35.5%.
[Example 1]
A composition obtained by adding compound (1-1) to the composition of Comparative Example 1 was designated as Example 1.
3-HBBXB (F, F) -F (2-1) 3%
3-BB (F) B (F, F) XB (F, F) -F (2-4) 2%
4-BB (F) B (F, F) XB (F, F) -F (2-4) 8%
5-BB (F) B (F, F) XB (F, F) -F (2-4) 7%
3-HH-V (3-1) 44%
V-HHB-1 (3-5) 6%
2-BB (F) B-3 (3-8) 2%
3-HHXB (F, F) -F (4-4) 6%
3-BB (F, F) XB (F, F) -F (4-18) 13%
3-HHBB (F, F) -F (4-19) 4%
4-HHBB (F, F) -F (4-19) 5%
Compound (1-1) was added to this composition in a proportion of 0.5% by mass.

NI = 78.0 ° C; Tc <-20 ° C; Δn = 0.106; Δε = 8.5; η = 11.6 mPa · s; γ1 = 60.0 mPa · s; VHR-3 = 81.1%.

ＮＩ＝１０２．０℃；Ｔｃ＜−２０℃；Δｎ＝０．１１３；Δε＝３．５；γ１＝６３．０ｍＰａ・ｓ；ＶＨＲ−３＝８８．７％．[Example 2]
3-HBBXB (F, F) -F (2-1) 3%
3-HBB (F, F) XB (F, F) -F (2-2) 7%
4-BB (F) B (F, F) XB (F, F) -F (2-4) 2%
5-BB (F) B (F, F) XB (F, F) -F (2-4) 6%
3-HH-V (3-1) 34%
3-HH-V1 (3-1) 5%
3-HH-VFF (3-1) 2%
V-HHB-1 (3-5) 12%
V2-HHB-1 (3-5) 11.5%
3-HHB-1 (3-5) 2%
1-BB (F) B-2V (3-8) 2%
2-BB (F) B-2V (3-8) 6%
3-BB (F) B-2V (3-8) 4%
3-HHXB (F, F) -F (4-4) 3.5%
Compound (1-2) was added to this composition in a proportion of 0.5% by mass.

NI = 102.0 ° C; Tc <-20 ° C; Δn = 0.113; Δε = 3.5; γ1 = 63.0 mPa · s; VHR-3 = 88.7%.

ＮＩ＝７０．９℃；Ｔｃ＜−２０℃；Δｎ＝０．０８７；Δε＝１３．５；γ１＝６５．３ｍＰａ・ｓ；ＶＨＲ−３＝８２．８％．[Example 3]
3-HBBXB (F, F) -F (2-1) 3%
5-BB (F) B (F, F) XB (F, F) -F (2-4) 12%
4-GB (F) B (F, F) XB (F, F) -F (2-8) 5%
5-GB (F) B (F, F) XB (F, F) -F (2-8) 5%
3-HH-V (3-1) 36%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 9%
3-HHXB (F, F) -CF3 (4-5) 12%
3-GB (F, F) XB (F, F) -F (4-14) 8%
Compound (1-1) was added to this composition in a proportion of 0.4% by mass.

NI = 70.9 ° C; Tc <-20 ° C; Δn = 0.087; Δε = 13.5; γ1 = 65.3 mPa · s; VHR-3 = 82.8%.

ＮＩ＝７３．２℃；Ｔｃ＜−２０℃；Δｎ＝０．０９９；Δε＝１１．０；γ１＝６０．８ｍＰａ・ｓ；ＶＨＲ−３＝８２．４％．[Example 4]
4-BB (F) B (F, F) XB (F, F) -F (2-4) 10%
5-BB (F) B (F, F) XB (F, F) -F (2-4) 6%
3-HH-V (3-1) 41%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 3%
3-HHB (F, F) -F (4-2) 10%
3-HHXB (F, F) -F (4-4) 2%
3-GHB (F, F) -F (4-7) 4%
3-BB (F) B (F, F) -F (4-15) 7%
3-BB (F, F) XB (F, F) -F (4-18) 7%
Compound (1-1) was added to this composition in a proportion of 0.5% by mass.

NI = 73.2 ° C; Tc <-20 ° C; Δn = 0.099; Δε = 11.0; γ1 = 60.8 mPa · s; VHR-3 = 82.4%.

ＮＩ＝８２．５℃；Ｔｃ＜−２０℃；Δｎ＝０．１３０；Δε＝５．２；η＝１３．６ｍＰａ・ｓ；γ１＝５５．０ｍＰａ・ｓ；ＶＨＲ−３＝８３．２％．[Example 5]
3-HBB (F, F) XB (F, F) -F (2-2) 4%
3-BB (F) B (F, F) XB (F, F) -F (2-4) 3%
4-BB (F) B (F, F) XB (F, F) -F (2-4) 4%
3-BB (F, F) XB (F) B (F, F) -F (2-5) 3%
3-HH-V (3-1) 34%
3-HH-V1 (3-1) 5.5%
V-HHB-1 (3-5) 13%
V-HBB-2 (3-6) 5%
2-BB (F) B-3 (3-8) 4%
1-BB (F) B-2V (3-8) 4%
2-BB (F) B-2V (3-8) 5%
3-BB (F) B-2V (3-8) 4%
3-BB (F) B (F, F) -CF3 (4-16) 3%
3-BB (F, F) XB (F, F) -F (4-18) 8.5%
Compound (1-2) was added to this composition in a proportion of 0.5% by mass.

NI = 82.5 ° C; Tc <-20 ° C; Δn = 0.130; Δε = 5.2; η = 13.6 mPa · s; γ1 = 55.0 mPa · s; VHR-3 = 83.2%.

ＮＩ＝７５．５℃；Ｔｃ＜−２０℃；Δｎ＝０．０８４；Δε＝１０．４；γ１＝５３．８ｍＰａ・ｓ；ＶＨＲ−３＝８１．５％．[Example 6]
3-HBBXB (F, F) -F (2-1) 3%
5-BB (F) B (F, F) XB (F, F) -F (2-4) 4%
3-dhBB (F, F) XB (F, F) -F (2-6) 4%
5-GB (F) B (F, F) XB (F, F) -F (2-8) 5%
3-HH-V (3-1) 47%
3-HH-V1 (3-1) 10%
V2-HHB-1 (3-5) 8%
3-HHXB (F, F) -CF3 (4-5) 6%
3-GB (F, F) XB (F, F) -F (4-14) 8%
3-GBB (F) B (F, F) -F (4-22) 3%
4-GBB (F) B (F, F) -F (4-22) 2%
Compound (1-1) was added to this composition in a proportion of 0.5% by mass.

NI = 75.5 ° C.; Tc <-20 ° C.; Δn = 0.084; Δε = 10.4; γ1 = 53.8 mPa · s; VHR-3 = 81.5%.

ＮＩ＝７４．３℃；Ｔｃ＜−２０℃；Δｎ＝０．１０５；Δε＝６．８；η＝１５．２ｍＰａ・ｓ；γ１＝６５．８ｍＰａ・ｓ；ＶＨＲ−３＝７７．３％．[Example 7]
5-BB (F) B (F, F) XB (F, F) -F (2-4) 5%
3-dhBB (F, F) XB (F, F) -F (2-6) 4%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(2-11) 2%
3-HH-V (3-1) 22%
3-HH-V1 (3-1) 10%
5-HB-O2 (3-2) 5%
3-HHEH-3 (3-4) 3%
3-HBB-2 (3-6) 7%
5-B (F) BB-3 (3-7) 3%
5-HXB (F, F) -F (4-1) 3%
3-HHXB (F, F) -F (4-4) 6%
3-HGB (F, F) -F (4-6) 3%
3-HB (F) B (F, F) -F (4-9) 5%
3-BB (F, F) XB (F, F) -F (4-18) 6%
3-HHBB (F, F) -F (4-19) 6%
3-BB (2F, 3F) XB (F, F) -F (4-23) 4%
3-HB-CL (4) 3%
3-HHB-OCF3 (4) 3%
Compound (1-1) was added to this composition in a proportion of 0.5% by mass.

NI = 74.3 ° C.; Tc <-20 ° C.; Δn = 0.105; Δε = 6.8; η = 15.2 mPa · s; γ1 = 65.8 mPa · s; VHR-3 = 77.3%.

ＮＩ＝７６．２℃；Ｔｃ＜−２０℃；Δｎ＝０．０９１；Δε＝５．０；η＝１２．４ｍＰａ・ｓ；γ１＝６１．２ｍＰａ・ｓ；ＶＨＲ−３＝７９．８％．[Example 8]
5-BB (F) B (F, F) XB (F, F) -F (2-4) 5%
3-GB (F) B (F, F) XB (F, F) -F (2-8) 6%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 8%
3-HH-VFF (3-1) 8%
V2-BB-1 (3-3) 2%
5-HB (F) BH-3 (3-12) 5%
5-HBBH-3 (3) 5%
3-HHB (F, F) -F (4-2) 8%
3-GB (F) B (F, F) -F (4-12) 3%
3-BB (F, F) XB (F, F) -F (4-18) 10%
Compound (1-1) was added to this composition in a proportion of 0.5% by mass.

NI = 76.2 ° C; Tc <-20 ° C; Δn = 0.091; Δε = 5.0; η = 12.4 mPa · s; γ1 = 61.2 mPa · s; VHR-3 = 79.8%.

ＮＩ＝７９．５℃；Ｔｃ＜−２０℃；Δｎ＝０．１０９；Δε＝４．８；η＝１３．３ｍＰａ・ｓ；γ１＝５７．４ｍＰａ・ｓ；ＶＨＲ−３＝７７．８％．[Example 9]
3-BB (F) B (F, F) XB (F, F) -F (2-4) 3%
4-BB (F) B (F, F) XB (F, F) -F (2-4) 5%
3-BB (F, F) XB (F) B (F, F) -F (2-5) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(2-11) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 28%
4-HH-V1 (3-1) 7%
5-HB-O2 (3-2) 2%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 8%
VFF-HHB-1 (3-5) 3%
3-HBB (F, F) -F (4-8) 5%
5-HBB (F, F) -F (4-8) 4%
3-BB (F) B (F, F) -F (4-15) 3%
3-HH2BB (F, F) -F (4) 3%
4-HH2BB (F, F) -F (4) 3%
3-HBB (2F, 3F) -O2 (5-14) 2%
2-BB (2F, 3F) B-3 (5-19) 4%
Compound (1-2) was added to this composition in a proportion of 0.3% by mass.

NI = 79.5 ° C; Tc <-20 ° C; Δn = 0.109; Δε = 4.8; η = 13.3 mPa · s; γ1 = 57.4 mPa · s; VHR-3 = 77.8%.

The voltage retention rate (VHR-3) of the composition of Comparative Example 1 after irradiation with ultraviolet rays was 35.5%. On the other hand, the VHR-3 of the composition of Example 1 was 81.1%. As described above, the composition of Example 1 had a large VHR-3 as compared with the composition of Comparative Example 1. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

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

Claims (18)

It contains at least one compound selected from the compound represented by the formula (1) as the first additive and at least one compound selected from the compound represented by the formula (2) as the first component, and is positive. A liquid crystal composition having dielectric anisotropy.

In formulas (1) and (2), R ¹ is an alkyl having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, and an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. In these groups, at least one -CH _2- may be replaced by -O-, -COO-, or -OCO-, or is a group represented by the formula (A-1). at best; ^{R 2} is alkyl of 1 to 12 carbons, alkenyl alkoxy of 1 to 12 carbons, or 2 to 12 carbons; ring a and ring B are independently 1,4-cyclohexylene Silen, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ and Z ² are independently single-bonded, ethylene, carbonyloxy, or difluoromethyleneoxy; X ¹ is hydrogen, fluorine, or chlorine; X ² , X ³ , X ⁴ , and X ⁵ are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen is fluorine or From an alkyl with 1 to 12 carbons replaced with chlorine, an alkoxy with 1 to 12 carbons with at least one hydrogen replaced with fluorine or chlorine, or from 2 carbons with at least one hydrogen replaced with fluorine or chlorine. Twelve alkenyloxys; a is 0, 1, 2, 3, or 4; b and c are independently 0, 1, 2, or 3, and the sum of b and c is 2. Or 3;

In formula (A-1), ^Ra is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. an alkyl, in these groups, at least one of _-CH 2 -, -O -, - COO-, or it may be replaced by -OCO-; ^{Z a} is branched from 1 to 20 carbon atoms in the It may be an alkylene, in which at least one −CH ₂ − may be replaced by −O−, −COO−, or −OCO−, and at least one −CH ₂ CH ₂₋ It may be replaced by −CH = CH−; s is 0 or 1; t is 0, 1, 2, 3, 4, or 5. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group of compounds represented by the formulas (1-1) to (1-8) as the first additive.

The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-11) as a first component.

In formulas (2-1) to (2-11), R ² is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms. The liquid crystal composition according to any one of claims 1 to 3, wherein the proportion of the first additive is in the range of 0.005% by mass to 2% by mass. The liquid crystal composition according to any one of claims 1 to 4, wherein the proportion of the first component is in the range of 5% by mass to 40% by mass. The liquid crystal composition according to any one of claims 1 to 5, which contains at least one compound selected from the compounds represented by the formula (3) as the second component.

In formula (3), R ³ and R ⁴ are independently an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or at least one hydrogen being fluorine or chlorine. It is an alkenyl having 2 to 12 carbon atoms replaced; rings C and D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5. -Difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, carbonyloxy, or methyleneoxy; d is 1, 2, or 3. The liquid crystal according to any one of claims 1 to 6, which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component. Composition.

In formulas (3-1) to (3-13), R ³ and R ⁴ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or An alkoxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 6 or 7, wherein the proportion of the second component is in the range of 10% by mass to 80% by mass. The liquid crystal composition according to any one of claims 1 to 8, which contains at least one compound selected from the compounds represented by the formula (4) as the third component.

In formula (4), R ⁵ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms; ring E is 1,4-cyclohexylene, 1, 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 ⁴ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; X ⁶ and X ⁷ are independently hydrogen. Or fluorine; Y ² is fluorine, chlorine, an alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, and 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Aalkoxy, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; e is 1, 2, 3, or 4. However, the compound represented by the formula (2) is excluded. The liquid crystal according to any one of claims 1 to 9, which contains at least one compound selected from the group of compounds represented by formulas (4-1) to (4-24) as a third component. Composition.

In the formula (4-24) from equation (4-1), ^{R 5} is an alkenyl alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons. The liquid crystal composition according to claim 9 or 10, wherein the proportion of the third component is in the range of 10% by mass to 80% by mass. The liquid crystal composition according to any one of claims 1 to 11, which contains at least one compound selected from the compounds represented by the formula (5) as the fourth component.

In formula (5), R ⁶ and R ⁷ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Rings F and I are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Or tetrahydropyran-2,5-diyl; ring G 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-trifluoro-2,6-diyl or 7,8-be difluorochroman-2,6-diyl; ^{Z 5} and ^{Z 6} are each independently , Single bond, ethylene, carbonyloxy, or methyleneoxy; f is 1, 2, or 3, g is 0 or 1; the sum of f and g is 3 or less. The liquid crystal according to any one of claims 1 to 12, which contains at least one compound selected from the group of compounds represented by the formulas (5-1) to (5-27) as the fourth component. Composition.

In formulas (5-1) to (5-27), R ⁶ and R ⁷ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkoxyoxy having 2 to 12 carbon atoms. The liquid crystal composition according to claim 12 or 13, wherein the proportion of the fourth component is in the range of 5% by mass to 40% by mass. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2. The liquid crystal composition according to any one of claims 1 to 14, which is the above. A liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 15. The liquid crystal display according to claim 16, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, FFS mode, or FPA mode, and the drive method of the liquid crystal display element is an active matrix method. element. Use of the liquid crystal composition according to any one of claims 1 to 15 in a liquid crystal display element.