JP7131048B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal composition containing a piperidine derivative, a liquid crystal display device containing this composition, and the like. In particular, it relates to a liquid crystal composition having a positive dielectric anisotropy, and an AM (active matrix) element containing this 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 the like. Classification based on the drive system of the element is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), and the like. TFT classifications are amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type depending on the manufacturing process. Classifications based on light source are reflective, which uses natural light, transmissive, which uses backlight, and transflective, which uses both natural light and backlight.

A liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM device with good properties can be obtained. The relationships between these properties are summarized in Table 1 below. The properties of the composition are further described based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. 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 desirable for displaying moving images on the device. A shorter response time, even 1 millisecond, is desirable. Therefore, low viscosity in the composition is preferred. A low viscosity at low temperatures is even more desirable. The elastic constant of the composition is related to the contrast of the device. A large elastic constant in the composition is more preferable in order to increase the contrast in the device.

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, ie a suitable 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. Appropriate values for the product depend on the type of operating mode. For TN-like mode devices, a suitable value is about 0.45 μm. In this case, a composition having a large optical anisotropy is preferable for an element with a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferred. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a high resistivity in the initial stage not only at room temperature but also at temperatures close to the upper temperature limit of the nematic phase is preferred. Compositions that have a high resistivity after extended use not only at room temperature but also at temperatures close to the upper temperature limit of the nematic phase are preferred. The stability of the composition against ultraviolet light and heat is related to the life of the liquid crystal display device. When their stability is high, the lifetime of the device is long. Such characteristics are preferable for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

A composition having a positive dielectric anisotropy is used in an AM device having a TN mode. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. A composition having positive or negative dielectric anisotropy is used in an AM device having an IPS mode or FFS mode. Compositions having positive or negative dielectric anisotropy are used in polymer sustained alignment (PSA) type AM devices. Compositions containing compounds similar to compound (1) of the present invention are disclosed in US Pat.

WO2015/079797 WO2015/076077

An object of the present invention is to select a compound that has high solubility in a liquid crystal composition and has an effect of suppressing display defects of a liquid crystal display element. Another issue is the high upper limit temperature of the nematic phase, the lower lower limit temperature of the nematic phase, the small viscosity, the appropriate optical anisotropy, the large positive dielectric anisotropy, the large resistivity, the high stability to light, and the heat resistance. An object of the present invention is to provide a liquid crystal composition which satisfies at least one of characteristics such as high stability and large elastic constant. Another challenge is to provide liquid crystal compositions that have 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 challenge is to provide an AM device with properties such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, few display defects and long lifetime.

式（１）および式（２）において、Ｒ^１およびＲ^３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、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；Ｒ^２は、水素、ヒドロキシ、オキシラジカル、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、これらの基において、炭素に結合した少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；環Ａ、環Ｂ、および環Ｃは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、３，４－ジヒドロ－２Ｈ－ピラン－２，５－ジイル、３，４－ジヒドロ－２Ｈ－ピラン－３，６－ジイル、３，６－ジヒドロ－２Ｈ－ピラン－２，５－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、１，４－フェニレン、ピリジン－２，５－ジイル、デカヒドロナフタレン－２，６－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、またはナフタレン－２，７－ジイルであり、これらの環において、環上の少なくとも１つの水素は、フッ素、塩素、シアノ、炭素数１から５のアルキル、炭素数１から５のアルコキシ、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５のアルキル、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５のアルコキシで置き換えられてもよく；環Ｄおよび環Ｅは、１，４－シクロヘキシレン、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、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、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ₂－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－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｚ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ₂－は、－Ｏ－、－ＮＨ－、－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－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｚ^４およびＺ^５は、単結合、エチレン、ビニレン、メチレンオキシ、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およびＸ^２は、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およびｂは、０または１であり；ｃは、１、２、３、または４であり；ｄは、０、１、２、または３であり、そしてｃおよびｄの和は４以下である。 The present invention uses at least one compound selected from the compounds represented by the formula (1) as the first additive and at least one compound selected from the compounds represented by the formula (2) as the first component. and having a positive dielectric anisotropy.

In formulas (1) and (2), R ¹ and R ³ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine; R ² is hydrogen, hydroxy, oxy radical, alkyl of 1 to 12 carbons, alkoxy of 1 to 12 carbons, or alkenyl of 2 to 12 carbons and in these groups, at least one carbon-bonded hydrogen may be replaced by fluorine or chlorine; Ring A, Ring B, and Ring C are 1,4-cyclohexylene, 1,4- Cyclohexenylene, 3,4-dihydro-2H-pyran-2,5-diyl, 3,4-dihydro-2H-pyran-3,6-diyl, 3,6-dihydro-2H-pyran-2,5- diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, decahydronaphthalene-2,6-diyl, naphthalene-1 ,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3 -diyl, naphthalene-2,6-diyl, or naphthalene-2,7-diyl, wherein at least one hydrogen on the ring is fluorine, chlorine, cyano, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or alkoxy having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, pyrimidine-2,5-diyl , 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ and Z ² are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least One -CH ₂ - may be replaced with -O-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ - is -CH=CH- or -C≡C- may be substituted, and in these groups at least and one hydrogen may be replaced by fluorine or chlorine; Z ³ is a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, -NH-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C-; at least one hydrogen in the group may be replaced by fluorine or chlorine; Z ⁴ and Z ⁵ are a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X ¹ and X ² is hydrogen or fluorine; Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, carbon in which at least one hydrogen is replaced by fluorine or chlorine alkoxy of number 1 to 12, or alkenyloxy of 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; a and b are 0 or 1; c is 1, 2, 3 , or 4; d is 0, 1, 2, or 3, and the sum of c and d is 4 or less.

An advantage of the present invention is to select a compound that has high solubility in a liquid crystal composition and has an effect of suppressing display defects of a liquid crystal display element. Another advantage is the high upper temperature limit of the nematic phase, the lower lower temperature limit of the nematic phase, small viscosity, suitable optical anisotropy, large positive dielectric anisotropy, large resistivity, high stability to light and heat. An object of the present invention is to provide a liquid crystal composition which satisfies at least one of characteristics such as high stability and large elastic constant. Another advantage is to provide a liquid crystal composition that has a proper 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 an AM device with properties such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, few display defects and long lifetime.

Terms used in this specification are 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 liquid crystal display panels and liquid crystal display modules. "Liquid crystal compound" means a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase, but for the purpose of adjusting the properties of the nematic phase such as temperature range, viscosity, dielectric It is a general term for compounds mixed in the composition. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecules (liquid crystal molecules) are rod-like. A "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. A liquid crystalline compound having alkenyl is not classified as a polymerizable compound in that sense.

A 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 quencher, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are optionally added to the liquid crystal composition. is added. The ratio of the liquid crystalline compound, even when the additive is added, is represented by mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. The proportion of the additive is represented by mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystalline compound and the additive is calculated based on the total mass of the liquid crystalline compound. Mass parts per million (ppm) are sometimes used. Proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed on the basis of the weight of the polymerizable compound.

"The upper limit temperature of the nematic phase" may be abbreviated as "the upper limit temperature". "Lower limit temperature of nematic phase" may be abbreviated as "lower limit temperature". The expression "increase the dielectric anisotropy" means that the value increases positively in the case of a composition with a positive dielectric anisotropy, and in a composition with a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "High resistivity" means that the composition has a high resistivity in the initial stage and a high resistivity after extended use. "Large voltage holding ratio" means that the element has a large voltage holding ratio at the initial stage not only at room temperature but also at temperatures close to the upper limit temperature, and after long-term use, the voltage is large not only at room temperature but also at temperatures close to the upper limit temperature. It means having a retention rate. Properties of compositions and devices may be examined by aging tests.

上記の化合物（１ｚ）を例にして説明する。式（１ｚ）において、六角形で囲んだαおよびβの記号はそれぞれ環αおよび環βに対応し、六員環、縮合環のような環を表す。添え字‘ｘ’が２のとき、２つの環αが存在する。２つの環αが表す２つの基は、同一であってもよく、または異なってもよい。このルールは、添え字‘ｘ’が２より大きいとき、任意の２つの環αに適用される。このルールは、結合基Ｚのような、他の記号にも適用される。環βの一辺を横切る斜線は、環β上の任意の水素が置換基（－Ｓｐ－Ｐ）で置き換えられてもよいことを表す。添え字‘ｙ’は置き換えられた置換基の数を示す。添え字‘ｙ’が０のとき、そのような置き換えはない。添え字‘ｙ’が２以上のとき、環β上には複数の置換基（－Ｓｐ－Ｐ）が存在する。この場合にも、「同一であってもよく、または異なってもよい」のルールが適用される。なお、このルールは、Ｒａの記号を複数の化合物に用いた場合にも適用される。

The above compound (1z) will be described as an example. In formula (1z), the symbols α and β surrounded by hexagons correspond to ring α and ring β, respectively, and represent rings such as six-membered rings and condensed rings. When the index 'x' is 2, there are two rings α. Two groups represented by two rings α may be the same or different. This rule applies to any two rings α when the index 'x' is greater than two. This rule also applies to other symbols, such as the bonding group Z. A slash across one side of ring β indicates that any hydrogen on ring β may be replaced with a substituent (-Sp-P). The subscript 'y' indicates the number of substituents replaced. When the index 'y' is 0, there is no such replacement. When the subscript 'y' is 2 or more, there are multiple substituents (-Sp-P) on the ring β. In this case as well, the "can be the same or can be different" rule applies. This rule also applies when the symbol Ra is used for a plurality of compounds.

In formula (1z), for example, the expression "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. do. That is, the group represented by Ra and the group represented by Rb may be the same or different.

At least one compound selected from compounds represented by formula (1z) may be abbreviated as "compound (1z)". "Compound (1z)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1z). The same applies to compounds represented by other formulas. The expression "at least one compound selected from compounds represented by formula (1z) and formula (2z)" means at least one compound selected from the group of compound (1z) and compound (2z) .

The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' may be replaced with 'B'" means that when the number of 'A' is 1, the position of 'A' is arbitrary, and the number of 'A' is 2 When there are more than one, their positions can be chosen without restriction. The expression "at least one -CH ₂ - may be replaced with -O-" is sometimes used. In this case, -CH ₂ -CH ₂ -CH ₂ - may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ - with -O-. However, adjacent -CH ₂ - is not replaced by -O-. This is because —O—O—CH ₂ — (peroxide) is produced by this replacement.

For example, in Ra and Rb of formula (1z), alkyl is linear or branched and does not include cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl.

テトラヒドロピラン－２，５－ジイルのような二価基においても同様である。カルボニルオキシのような結合基（－ＣＯＯ－または－ＯＣＯ－）も同様である。 The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there is a leftward (L) and a rightward (R).

The same is true for divalent groups such as tetrahydropyran-2,5-diyl. The same is true for linking groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

式（１）および式（２）において、Ｒ^１およびＲ^３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、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；Ｒ^２は、水素、ヒドロキシ、オキシラジカル、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、これらの基において、炭素に結合した少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；環Ａ、環Ｂ、および環Ｃは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、３，４－ジヒドロ－２Ｈ－ピラン－２，５－ジイル、３，４－ジヒドロ－２Ｈ－ピラン－３，６－ジイル、３，６－ジヒドロ－２Ｈ－ピラン－２，５－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、１，４－フェニレン、ピリジン－２，５－ジイル、デカヒドロナフタレン－２，６－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、またはナフタレン－２，７－ジイルであり、これらの環において、環上の少なくとも１つの水素は、フッ素、塩素、シアノ、炭素数１から５のアルキル、炭素数１から５のアルコキシ、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５のアルキル、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５のアルコキシで置き換えられてもよく；環Ｄおよび環Ｅは、１，４－シクロヘキシレン、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、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、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ₂－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－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｚ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ₂－は、－Ｏ－、－ＮＨ－、－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－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｚ^４およびＺ^５は、単結合、エチレン、ビニレン、メチレンオキシ、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およびＸ^２は、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およびｂは、０または１であり；ｃは、１、２、３、または４であり；ｄは、０、１、２、または３であり、そしてｃおよびｄの和は４以下である。 Section 1. containing at least one compound selected from the compounds represented by the formula (1) as the first additive and at least one compound selected from the compounds represented by the formula (2) as the first component, A liquid crystal composition having a dielectric anisotropy of

In formulas (1) and (2), R ¹ and R ³ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine; R ² is hydrogen, hydroxy, oxy radical, alkyl of 1 to 12 carbons, alkoxy of 1 to 12 carbons, or alkenyl of 2 to 12 carbons and in these groups, at least one carbon-bonded hydrogen may be replaced by fluorine or chlorine; Ring A, Ring B, and Ring C are 1,4-cyclohexylene, 1,4- Cyclohexenylene, 3,4-dihydro-2H-pyran-2,5-diyl, 3,4-dihydro-2H-pyran-3,6-diyl, 3,6-dihydro-2H-pyran-2,5- diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, decahydronaphthalene-2,6-diyl, naphthalene-1 ,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3 -diyl, naphthalene-2,6-diyl, or naphthalene-2,7-diyl, wherein at least one hydrogen on the ring is fluorine, chlorine, cyano, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or alkoxy having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, pyrimidine-2,5-diyl , 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ and Z ² are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least One -CH ₂ - may be replaced with -O-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ - is -CH=CH- or -C≡C- may be substituted, and in these groups at least and one hydrogen may be replaced by fluorine or chlorine; Z ³ is a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, -NH-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C-; at least one hydrogen in the group may be replaced by fluorine or chlorine; Z ⁴ and Z ⁵ are a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X ¹ and X ² is hydrogen or fluorine; Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, carbon in which at least one hydrogen is replaced by fluorine or chlorine alkoxy of number 1 to 12, or alkenyloxy of 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; a and b are 0 or 1; c is 1, 2, 3 , or 4; d is 0, 1, 2, or 3, and the sum of c and d is 4 or less.

式（１－１）から式（１－１４）において、Ｒ^１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、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；Ｒ^２は、水素、ヒドロキシ、オキシラジカル、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、これらの基において、炭素に結合した少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｘ¹、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、およびＸ⁶は、水素またはフッ素である。 Section 2. Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from the compounds represented by formulas (1-1) to (1-14) as the first additive.

In formulas (1-1) to (1-14), R ¹ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms, and in these groups , at least one hydrogen may be replaced by fluorine or chlorine; R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl in which at least one carbon-bonded hydrogen may be replaced by fluorine or chlorine; X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are hydrogen or fluorine.

式（２－１）から式（２－１４）において、Ｒ^３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；Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３、およびＸ^１４は、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る。 Item 3. Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from the compounds represented by formulas (2-1) to (2-14) as the first component.

In formulas (2-1) to (2-14), R ³ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms; X ¹ , X ² , X3 ^{, X4} , ^X5 , ^X6 , ^X7 , ^X8 , ^X9 , ^X10 , ^X11 , ^X12 , ^X13 , and ^X14 are hydrogen or fluorine; ^Y1 is fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, 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 alkenyloxy having 2 to 12 carbon atoms substituted with fluorine or chlorine;

Section 4. 4. Any one of items 1 to 3, wherein the proportion of the first additive is in the range of 0.005% by mass to 1% by mass, and the proportion of the first component is in the range of 5% by mass to 55% by mass. liquid crystal composition.

式（３）において、Ｒ^４および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、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Ｆおよび環Ｇ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、または２，５－ジフルオロ－１，４－フェニレンであり；Ｚ^５は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｅは、１、２、または３である。 Item 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, containing at least one compound selected from the compounds represented by formula (3) as the second component.

In formula (3), R ⁴ and R ⁵ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine. alkenyl having 2 to 12 carbon atoms; ring F and ring G are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -phenylene; Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; e is 1, 2, or 3.

式（３－１）から式（３－１３）において、Ｒ^４および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、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 6. Item 6. The liquid crystal composition according to any one of items 1 to 5, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-13) as the second component.

In formulas (3-1) to (3-13), R ⁴ and R ⁵ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or at least one It is alkenyl having 2 to 12 carbon atoms in which hydrogen is replaced with fluorine or chlorine.

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

式（４）において、Ｒ^６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Ｉは、１，４－シクロヘキシレン、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、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^７は、単結合、エチレン、ビニレン、またはカルボニルオキシであり；Ｘ^１５およびＸ^１６は、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；ｆは、１、２、３、または４である。 Item 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from the compounds represented by formula (4) as the third component.

In formula (4), R ⁶ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms; ring I is 1,4-cyclohexylene, 1,4 -phenylene, 1,4-phenylene with at least one hydrogen replaced by fluorine or chlorine, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl Z ⁷ is a single bond, ethylene, vinylene, or carbonyloxy; X ¹⁵ and X ¹⁶ are hydrogen or fluorine; Y ² is fluorine, chlorine, at least one hydrogen is fluorine or chlorine substituted alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or alkoxy of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine is alkenyloxy; f is 1, 2, 3, or 4;

式（４－１）から式（４－１６）において、Ｒ^６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 9. 9. The liquid crystal composition according to any one of items 1 to 8, containing at least one compound selected from compounds represented by formulas (4-1) to (4-16) as a third component.

In formulas (4-1) to (4-16), R ⁶ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms.

Item 10. Item 10. The liquid crystal composition according to item 8 or 9, wherein the proportion of the third component is in the range of 5% by mass to 50% by mass.

式（５）において、Ｒ^７およびＲ^８は、水素、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Ｊおよび環Ｌは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、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、ナフタレン－２，６－ジイル、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ナフタレン－２，６－ジイル、クロマン－２，６－ジイル、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クロマン－２，６－ジイルであり；環Ｋ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、７，８－ジフルオロクロマン－２，６－ジイル、３，４，５，６－テトラフルオロフルオレン－２，７－ジイル、４，６－ジフルオロジベンゾフラン－３，７－ジイル、４，６－ジフルオロジベンゾチオフェン－３，７－ジイル、または１，１，６，７－テトラフルオロインダン－２，５－ジイルであり；Ｚ^８およびＺ^９は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｇは、０、１、２、または３であり、ｈは、０または１であり、そしてｇとｈとの和は３以下である。 Item 11. Item 11. The liquid crystal composition according to any one of items 1 to 10, containing at least one compound selected from the compounds represented by formula (5) as the fourth component.

In formula (5), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms. ring J and ring L are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen replaced by fluorine or chlorine; 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen in which fluorine or chroman-2,6-diyl substituted with chlorine; ring K 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, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro fluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2, 5-diyl; Z ⁸ and Z ⁹ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; g is 0, 1, 2, or 3; h is 0 or 1; and the sum of g and h is 3 or less.

式（５－１）から式（５－３５）において、Ｒ^７およびＲ^８は、水素、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 12. 12. The liquid crystal composition according to any one of items 1 to 11, containing at least one compound selected from compounds represented by formulas (5-1) to (5-35) as the fourth component.

In formulas (5-1) to (5-35), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or carbon alkenyloxy of numbers 2 to 12;

Item 13. 13. The liquid crystal composition according to Item 11 or 12, wherein the proportion of the fourth component is in the range of 3% by mass to 45% by mass.

Item 14. The nematic phase has an upper limit temperature of 70°C or higher, an optical anisotropy at a wavelength of 589 nm (measured at 25°C) of 0.07 or higher, and a dielectric anisotropy at a frequency of 1 kHz (measured at 25°C) of 2. 14. The liquid crystal composition according to any one of Items 1 to 13, which is the above.

Item 15. Item 15. A liquid crystal display device containing the liquid crystal composition according to any one of Items 1 to 14.

Item 16. Item 16. The liquid crystal display element according to item 15, 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 driving method of the liquid crystal display element is an active matrix method. .

Item 17. Item 15. Use of the liquid crystal composition according to any one of Items 1 to 14 in a liquid crystal display device.

The present invention also includes the following items. (a) one compound selected from additives such as optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds; , two compounds, or three or more compounds. (b) an AM device containing the above composition; (c) The above composition further containing a polymerizable compound, and a polymer support alignment (PSA) type AM device containing this composition. (d) A polymer-supported alignment (PSA) type AM device containing the above composition, wherein 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 transmission type device containing the above composition. (g) Use of the above composition as a composition having a nematic phase. (h) Use of an optically active composition obtained by adding an optically active compound to the above composition.

The composition of the present invention contains compound (1). This compound has 2,2,6,6-tetramethyl-4-piperidinyl and has high solubility in liquid crystal compositions. This is probably because the molecular structure was designed to be rod-shaped. This compound is classified as a polar compound because it has a >N- partial structure. This compound was found to be effective in suppressing display defects of the device as shown in Comparative Examples and Examples. However, the cause of display failure is complicated and has not been fully elucidated. Furthermore, the effect of this compound on display defects is also unclear at this stage. This situation can be explained as described in the next paragraph.

When the device is used for a long time, the brightness may partially decrease. One example is line persistence, which is a phenomenon in which the brightness between two adjacent electrodes is reduced in a streaky manner due to the repeated application of different voltages to two adjacent electrodes. This phenomenon is caused by accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrodes. Therefore, in order to suppress the line afterimage, it is effective to prevent the ionic impurities from being localized on the alignment film. For this purpose, the surface of the alignment film is coated with an additive, such as a polar compound, to which the ionic impurities are adsorbed. As a result, display defects are suppressed.

A liquid crystal composition is injected into the element through an injection port under reduced pressure. Typically, the composition fills the device without changing the proportions of its components. However, additives such as polar compounds may be adsorbed on the alignment film. When the adsorption speed is high, the additive may not reach the inner part of the element. The additive is left behind because the rate of adsorption is greater than the rate of injection. In order to prevent this phenomenon, it is preferable to use an additive having an appropriate adsorptivity to the alignment film. Therefore, it is also important to select additives with appropriate polarity. Compound (1) is suitable for this purpose.

In the liquid crystal dropping method, a liquid crystal composition is dropped onto an alignment film arranged on a substrate. At this time, a display defect called a drip mark occurs. This phenomenon generally occurs because the alignment film does not have a sufficient ability to vertically align the liquid crystal composition. It is considered that this is because it does not have a sufficient mobility (see JP-A-2012-113132, paragraph 0020). Compound (1) is also effective in preventing such drip marks.

The composition of the present invention will be described in the following order. First, the composition of the component compounds in the composition will be described. Second, the main properties of the component compound and the main effect of this compound on the composition are described. Third, the combination of ingredients in the composition, the preferred proportions of the ingredients and the rationale thereof are described. Fourth, preferred forms of component compounds are described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition are described. Seventh, the method for synthesizing the component compounds will be explained. Finally, the use of the composition will be explained.

First, the constitution of the composition will be explained. This composition contains a plurality of liquid crystalline compounds. This composition may contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. This composition is classified into composition A and composition B from the viewpoint of the liquid crystalline compound. In addition to the liquid crystalline compound selected from compound (2), compound (3), compound (4), and compound (5), composition A further contains other liquid crystalline compounds, additives, and the like. good too. "Other liquid crystalline compounds" are liquid crystalline compounds different from compound (2), compound (3), compound (4), and compound (5). Such compounds are incorporated into the composition for the purpose of further adjusting its properties.

Composition B consists essentially of a liquid crystalline compound selected from compound (2), compound (3), compound (4) and compound (5). "Substantially" means that composition B may contain additives, but does not contain other liquid crystalline compounds. Composition B has fewer components than Composition A. Composition B is preferable to composition A from the viewpoint of cost reduction. The composition A is preferable to the composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystalline compounds.

Second, the main properties of the component compound and the main effect of this compound on the composition or device are 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 medium, and S small or low. The symbols L, M, S are classifications based on qualitative comparisons between component compounds, with 0 (zero) meaning less than S.

The main effects of the component compounds are as follows. Compound (1) contributes to suppression of display defects such as afterimages and drip marks. Since compound (1) is added in a very small amount, it does not affect properties such as maximum temperature, optical anisotropy, and dielectric anisotropy in many cases. Compound (2) increases dielectric anisotropy. Compound (3) lowers the viscosity or raises the maximum temperature. Compound (4) raises the dielectric anisotropy and lowers the minimum temperature. Compound (5) increases the dielectric constant in the minor axis direction.

Compound (1) is characterized by having a piperidine ring. This compound is useful as a hindered amine light stabilizer. The piperidine ring of compound (1) is suitable for trapping decomposition products produced by photoreaction of liquid crystalline compounds. This compound can be added to a mixture of liquid crystalline compounds, ie, a liquid crystal composition. This is because this compound has a high solubility in the liquid crystal composition.

When the liquid crystal display element is used for a long time, the liquid crystal compound tends to be decomposed by light to produce decomposition products. Since this product is an impurity, it is not preferable for the device. This is because these impurities cause phenomena such as a decrease in contrast ratio, occurrence of display unevenness, and image burn-in. This phenomenon is easily discernible by eye and is very noticeable even if it is slight. Therefore, it is preferable to use a light stabilizer that can reduce the amount of impurities generated even by 1% compared to conventional light stabilizers. Compound (1) is such a light stabilizer.

Thirdly, the combination of component compounds in the composition, the preferred proportions, and the basis thereof are explained. Preferred combinations of the component compounds 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 (5), Compound (1) + Compound (2) + Compound (3) + Compound (4), Compound (1) + Compound (2) + Compound (3) + Compound (5), 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).

A preferable proportion of compound (1) is approximately 0.005% by mass or more for suppressing display defects of the device, and approximately 1% by mass or less for lowering the minimum temperature. A more preferred proportion ranges from about 0.01% to about 0.5% by weight. A particularly preferred proportion ranges from about 0.05% to about 0.3% by weight.

A preferable proportion of compound (2) is about 5% by mass or more for increasing dielectric anisotropy, and about 55% by mass or less for decreasing viscosity. A more preferred proportion ranges from about 10% to about 50% by weight. A particularly preferred proportion ranges from about 10% to about 45% by weight.

A preferable proportion of compound (3) is about 10% by mass or more for increasing the maximum temperature or decreasing viscosity, and about 85% by mass or less for increasing dielectric anisotropy. A more preferred proportion ranges from about 20% to about 80% by weight. A particularly preferred percentage is in the range of about 30% to about 70% by weight.

A preferable ratio of compound (4) is about 5% by mass or more for increasing the dielectric anisotropy, and about 50% by mass or less for lowering the minimum temperature. A more preferred proportion ranges from about 10% to about 40% by weight. A particularly preferred proportion ranges from about 10% to about 35% by weight.

A preferable ratio of compound (5) is about 3% by mass or more to increase the dielectric constant in the minor axis direction, and about 45% by mass or less to lower the minimum temperature. A more preferred proportion ranges from about 5% to about 40% by weight. A particularly preferred proportion ranges from about 5% to about 35% by weight.

Fourth, preferred forms of component compounds are described. The first additive (piperidine derivative) and the liquid crystalline compound will be collectively described.

In formula (1), formula (2), formula (3), formula (4), and formula (5), R ¹ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or 2 to 12 alkenyl, in which at least one hydrogen may be replaced by fluorine or chlorine. Preferred R ¹ is alkyl having 1 to 12 carbon atoms in order to increase stability against ultraviolet rays and heat. R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine. Hydroxy is -OH and oxyradical is oxygen free radical (>N-O.) attached to nitrogen. Preferred R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 3 carbon atoms, or alkoxy having 1 to 3 carbon atoms. More preferred ^R2 is hydrogen, hydroxy, oxy radical, methyl, ethyl, propyl, isopropyl, methoxy or ethoxy. Particularly preferred R ² is hydrogen, hydroxy, oxy radical, methyl or methoxy.

R ³ and R ⁶ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Preferred R ³ or R ⁶ is alkyl having 1 to 12 carbon atoms to increase stability. R ⁴ and R ⁵ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. It is alkenyl. Preferred R ⁴ or R ⁵ is alkenyl having 2 to 12 carbon atoms to reduce viscosity and alkyl having 1 to 12 carbon atoms to increase stability. R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Preferred R ⁷ or R ⁸ is alkyl having 1 to 12 carbon atoms to increase stability, and alkoxy having 1 to 12 carbon atoms to increase dielectric constant in the minor axis direction.

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 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More preferred alkoxy is methoxy or ethoxy for reducing 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, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyls are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to reduce viscosity. The preferred configuration of -CH=CH- in these alkenyls depends on the position of the double bond. Trans is preferred in alkenyls such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl in order to lower the viscosity. Cis is preferred in alkenyls such as 2-butenyl, 2-pentenyl, 2-hexenyl.

Preferred alkenyloxy are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. A more preferred alkenyloxy for reducing viscosity is allyloxy or 3-butenyloxy.

Preferred examples of alkyl in which at least one hydrogen is replaced by 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 by 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. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl to reduce viscosity.

Ring A, ring B, and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, 3,4-dihydro-2H-pyran-2,5-diyl, 3,4-dihydro-2H- pyran-3,6-diyl, 3,6-dihydro-2H-pyran-2,5-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene , pyridine-2,5-diyl, decahydronaphthalene-2,6-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl , naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, or naphthalene-2,7-diyl, in which ring at least one hydrogen above is fluorine, chlorine, cyano, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Alternatively, at least one hydrogen may be replaced by C1-C5 alkoxy in which fluorine or chlorine is substituted. Preferred ring A, ring B or ring C is 1,4-cyclohexylene or 1,4-phenylene.

または

であり、好ましくは

である。 Ring D, ring E, and ring I are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. Preferred ring D, ring E, or ring I is 1,4-cyclohexylene for increasing the maximum temperature, 1,4-phenylene for increasing optical anisotropy, and increasing dielectric anisotropy. Therefore, 2,6-difluoro-1,4-phenylene. Tetrahydropyran-2,5-diyl is

or

and preferably

is.

Ring F and ring G are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring F or ring G is 1,4-cyclohexylene for lowering the viscosity or raising the maximum temperature, and 1,4-phenylene for lowering the minimum temperature.

Ring J and ring L are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, and 1 in which at least one hydrogen is replaced by fluorine or chlorine. ,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine is chroman-2,6-diyl replaced with Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- 3-fluoro-1,4-phenylene. Preferred ring J or ring L is 1,4-cyclohexylene for lowering viscosity, tetrahydropyran-2,5-diyl for increasing dielectric anisotropy, and 1,4-phenylene.

好ましい環Ｋは、粘度を下げるために２，３－ジフルオロ－１，４－フェニレンであり、光学異方性を下げるために２－クロロ－３－フルオロ－１，４－フェニレンであり、誘電率異方性を上げるために７，８－ジフルオロクロマン－２，６－ジイルである。 Ring K 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, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) is.

Preferred ring K is 2,3-difluoro-1,4-phenylene for lowering viscosity, 2-chloro-3-fluoro-1,4-phenylene for lowering optical anisotropy, dielectric constant It is 7,8-difluorochroman-2,6-diyl to increase anisotropy.

Z ¹ and Z ² are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —NH—, —COO—, or —OCO— optionally, at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C- in which at least one hydrogen is fluorine or chlorine; may be replaced. Preferred Z ¹ or Z ² is a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -CH ₂ O- or -CH=CH-. Z ³ is a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is replaced with —O—, —NH—, —COO—, or —OCO— at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C- in which at least one hydrogen is replaced with fluorine or chlorine good too. Preferred Z ³ is a single bond, -CH ₂ CH ₂ -, -O-, -COO- or -OCO-. More preferred ^Z3 is a single bond. ^Z4 and ^Z5 are a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy. Preferred ^Z4 or ^Z5 is a single bond to reduce viscosity.

^Z6 is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred ^Z6 is a single bond to reduce viscosity. ^Z7 is a single bond, ethylene, vinylene, or carbonyloxy. Preferred ^Z7 is a single bond to reduce viscosity. ^Z8 and ^Z9 are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred ^Z8 or ^Z9 is a single bond for lowering the viscosity, ethylene for lowering the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.

X1, ^X2 , ^X3 , ^X4 , ^X5 , ^X6 , ^{X7 , X8} , ^X9 , ^X10 , ^X11 , ^X12 , ^X13 , ^X14 , ^X15 , and ^X16 are hydrogen or fluorine; Preferred X ¹ to X ¹⁵ or X ¹⁶ are fluorine in order to increase the dielectric anisotropy.

Y ¹ and Y ² are fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine or C2-C12 alkenyloxy in which at least one hydrogen is replaced by fluorine or chlorine. Preferred Y ¹ or Y ² is fluorine in order to lower the minimum temperature. A preferred example of alkyl in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl. A preferred example of alkoxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethoxy. A preferred example of alkenyloxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluorovinyloxy.

a and b are 0 or 1; c is 1, 2, 3, or 4, d is 0, 1, 2, or 3, and the sum of c and d is 4 or less. Desirable c is 2 or 3 in order to increase the dielectric anisotropy. Preferred d is 0 or 1 in order to lower the lower limit temperature. e is 1, 2, or 3; Desirable e is 1 for lowering the viscosity, and 2 or 3 for raising the maximum temperature. f is 1, 2, 3, or 4; Preferred f is 2 or 3 to increase the dielectric anisotropy. g is 0, 1, 2, or 3, h is 0 or 1, and the sum of g and h is 3 or less. Preferred g is 1 for lowering the viscosity, and 2 or 3 for raising the maximum temperature. Preferred h is 0 for lowering the viscosity and 1 for lowering the minimum temperature.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to (1-14) described in Item 2. More preferred compound (1) is compound (1-2), compound (1-3), compound (1-9) or compound (1-10).

Preferred compounds (2) are compounds (2-1) to (2-14) described in item 3. In these compounds, at least one of the first components is compound (2-3), compound (2-4), compound (2-7), compound (2-9), compound (2-10), or compound (2-12) is preferred. at least two of the first components are compound (2-3) and compound (2-4), compound (2-3) and compound (2-7), compound (2-3) and compound (2-10); A combination of compound (2-7) and compound (2-10) or compound (2-9) and compound (2-10) is preferred.

Preferred compounds (3) are compounds (3-1) to (3-13) described in Item 6. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8), or compound (3-9) is preferred. at least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound (3-6) is preferably a combination of

Preferred compounds (4) are compounds (4-1) to (4-16) described in Item 9. In these compounds, at least one of the third components is compound (4-4), compound (4-8), compound (4-9), compound (4-11), compound (4-12), compound ( 4-13), or compound (4-16). at least two of the third components are compound (4-9) and compound (4-12), compound (4-11) and compound (4-12), compound (4-12) and compound (4-13), Alternatively, it is preferably a combination of compound (4-12) and compound (4-16).

Preferred compounds (5) are compounds (5-1) to (5-35) described in Item 12. In these compounds, at least one of the fourth components is compound (5-1), compound (5-3), compound (5-4), compound (5-6), compound (5-8), or compound (5-10) is preferred. at least two of the fourth components are compound (5-1) and compound (5-6), compound (5-1) and compound (5-10), compound (5-3) and compound (5-6), A combination of compound (5-3) and compound (5-10), compound (5-4) and compound (5-6), or compound (5-4) and compound (5-8) is preferred.

Sixth, additives that may be added to the composition are described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, 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 compounds (6-1) to (6-5). A preferred proportion of the optically active compound is about 5 mass % or less. A more preferred proportion ranges from about 0.01% to about 2% by weight.

In order to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at temperatures close to the upper limit temperature after using the device for a long time, the compound (7-1 ) to compound (7-3) may further be added to the composition.

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

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

The quenching agent is a compound that receives light energy absorbed by the liquid crystal compound and converts it into heat energy, thereby preventing decomposition of the liquid crystal compound. Preferred examples of the quenching agent include compounds (9-1) to (9-7). A preferable proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less so as not to raise the lower limit temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition in order to match the GH (guest host) mode device. Preferred percentages of pigment range from about 0.01% to about 10% by weight. Antifoaming agents such as dimethylsilicone oil, methylphenylsilicone oil, etc. are added to the composition to prevent foaming. A preferable proportion of the antifoaming agent is about 1 ppm or more to obtain its effect, and about 1000 ppm or less to prevent display defects. More preferred percentages range from about 1 ppm to about 500 ppm.

Polymerizable compounds are used to accommodate polymer-supported alignment (PSA) type devices. Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl ketones. Further preferred examples are derivatives of acrylates or methacrylates. A preferred proportion is 10% by weight or more based on the total weight of the polymerizable compound. A more preferable ratio is 50% by mass or more. A particularly preferable ratio is 80% by mass or more. The most preferred proportion is 100% by mass.

A polymerization inhibitor may be added to prevent polymerization during storage of the polymerizable compound. 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.

A polar compound is an organic compound that has polarity. Compounds with ionic bonds are not included here. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity results from the uneven distribution of partial charges between different atoms in a compound. For example, a polar compound has at least one substructure such as —OH, —COOH, —SH, —NH ₂ , >NH, >N—.

Seventh, the method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Exemplify synthetic methods. The method for synthesizing compound (1) is described in the Examples section. Compound (2-2) is synthesized by the method described in JP-A-10-204016. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Compound (4-8) is synthesized by the method described in JP-A-2-233626. Compound (5-1) and compound (5-8) are synthesized by the method described in Japanese Patent Application Publication No. 2-503441. Antioxidants are commercially available. Compound (7-1) is available from Aldrich (Sigma-Aldrich Corporation). Compound (7-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which the method of synthesis was not listed were classified as Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive Organic Synthesis (John Wiley & Sons, Inc). Synthesis, Pergamon Press) and Shin Jikken Kagaku Koza (Maruzen). Compositions are prepared by known methods from the compounds thus obtained. For example, the component compounds are mixed and dissolved together by heating.

Finally, the use of the composition will be explained. This composition mainly has a lower temperature limit of about -10°C or less, an upper temperature limit of about 70°C or more, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the component compounds or by mixing other liquid crystalline compounds. Compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. A 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, and can be used as an optically active composition by adding an optically active compound.

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

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

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for the measurement. In the ¹ H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl ₃ and the measurement was performed at room temperature at 500 MHz with 16 integration times. Tetramethylsilane was used as an internal standard. In the ¹⁹ F-NMR measurement, CFCl ₃ was used as an internal standard, and 24 integration times were performed. In the description of nuclear magnetic resonance spectra, s means singlet, d doublet, t triplet, q quartet, quin quintet, sex sextet, m multiplet, and br broad.

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

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

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

Measurement sample: When measuring the properties of the composition or device, the composition was used as a sample as it was. When measuring the properties of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with mother liquid crystals (85% by mass). The characteristic value of the compound was calculated by extrapolation from the value obtained by the measurement. (Extrapolated value)={(measured value of sample)−0.85×(measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystal) precipitates at 25°C in 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 in this order. changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The following mother liquid crystals were used. The proportions of the component compounds are shown in % by mass.

Measurement method: Properties were measured by the following methods. Many of these are methods described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or modified methods thereof. Met. A thin film transistor (TFT) was not attached to the TN device 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 apparatus equipped with a polarizing microscope and heated at a rate of 1 °C/min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature".

(2) Lower limit temperature of nematic phase ( _TC ; °C): A sample with a nematic phase was placed in a glass bottle and placed in a freezer at 0°C, -10°C, -20°C, -30°C, and -40°C for 10 days. After storage, the liquid crystal phase was observed. For example, when a sample remained in a nematic phase at -20°C and changed to a crystalline or smectic phase at -30°C, the T _C was described as < -20°C. The lower limit temperature of the nematic phase is sometimes 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 measurement.

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa s): Measurement is performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). obeyed. A sample was placed in a TN device with a twist angle of 0° and a gap (cell gap) between two glass substrates of 5 μm. A voltage of 16 V to 19.5 V was applied to the device in steps of 0.5 V. After 0.2 seconds of no application, application was repeated under the conditions of only one rectangular 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. Rotational viscosity values were obtained from these measurements and equation (10) on page 40 of M. Imai et al. The value of the dielectric anisotropy required for this calculation was obtained by the method described below using the device for which the rotational viscosity was measured.

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25° C.): Measurement was performed with an Abbe refractometer equipped with a polarizing plate attached to an eyepiece using light with 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∥ was measured when the direction of polarization was parallel to the rubbing direction. The refractive index n⊥ was measured when the polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy was calculated from the formula Δn=n∥−n⊥.

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

(7) Threshold voltage (Vth; measured at 25° C.; V): A luminance meter LCD5100 manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample was placed in a normally white mode TN device 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 increased stepwise from 0 V to 10 V by 0.02 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared 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 was expressed as the voltage when the transmittance reached 90%.

(8) Voltage holding ratio (VHR-9; measured at 25° C.; %): The TN device used for measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. . The device was sealed with a UV curable adhesive after the sample was placed. This TN device was charged by applying a pulse voltage (1 V for 60 microseconds). 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 was expressed as a percentage of area A with respect to area B.

(9) Voltage holding rate (VHR-10; measured at 60°C; %): The voltage holding rate was measured in the same procedure as above except that the measurement was made at 60°C instead of 25°C. The obtained value was expressed as VHR-10.

(10) Voltage holding ratio (VHR-11; measured at 60° C.; %): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate the stability against ultraviolet rays. The TN device used for measurement had a polyimide alignment film and a cell gap of 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 F40T10/BL (peak wavelength 369 nm) manufactured by Eye Graphics Co., Ltd., and the distance between the element and the light source was 5 mm. The VHR-11 measurement measured the decaying voltage over a period of 166.7 milliseconds. A composition with a large VHR-11 has a large UV stability.

(11) Voltage holding rate (VHR-12; measured at 60°C; %): After heating the TN element into which the sample was injected in a constant temperature chamber at 120°C for 20 hours, the voltage holding rate was measured and the stability against heat was measured. evaluated. The VHR-12 measurement measured a voltage decaying over 166.7 milliseconds. A composition with a large VHR-12 has a large thermal stability.

(12) Response time (τ; measured at 25°C; ms): A luminance meter LCD5100 manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A Low-pass filter was set at 5 kHz. A sample was placed in a normally white mode TN device in which the distance (cell gap) between the two glass substrates was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device 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. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: 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 fall time obtained in this way.

(13) Elastic constant (K; measured at 25° C.; pN): HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for measurement. A sample was placed in a horizontally aligned element in which the interval (cell gap) between 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. The values of the measured capacitance (C) and applied voltage (V) are fitted using equations (2.98) and (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun). and the values of K11 and K33 were obtained from equation (2.99). Next, K22 was calculated using the previously obtained values of K11 and K33 in formula (3.18) on page 171 of the same. The elastic constant was expressed as the average value of K11, K22, and K33 thus obtained.

(14) Specific resistance (.rho.; measured at 25.degree. C.; .OMEGA.cm): 1.0 mL of a sample was poured into a container equipped with electrodes. A DC voltage (10 V) was applied to this container, and the DC current was measured after 10 seconds. The specific resistance was calculated from the following formula. (Specific resistance)={(Voltage)×(Electric capacity of container)}/{(DC current)×(Vacuum permittivity)}.

(15) Spiral pitch (P; measured at room temperature; μm): Spiral pitch was measured by the wedge method. See "Liquid Crystal Handbook", page 196 (published in 2000, Maruzen). The sample was poured into a wedge-shaped cell and allowed to stand at room temperature for 2 hours, after which the disclination line interval (d2-d1) was observed with a polarizing microscope (Nikon Co., Ltd., trade name MM40/60 series). The helical pitch (P) was calculated from the following formula, where θ is the angle of the wedge cell. P=2×(d2−d1)×tan θ.

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

(17) Line Image Sticking Parameter (LISP; %): Line image sticking was generated by applying electrical stress to the liquid crystal display element. The brightness of the area with line afterimage and the brightness of the remaining area were measured. The ratio of reduction in luminance due to the line afterimage was calculated, and the magnitude of the line afterimage was expressed by this ratio.
17a) Measurement of luminance: An image of the device was taken using an imaging color luminance meter (manufactured by Radiant Zemax, PM-1433F-0). This image was analyzed using software (Prometric 9.1, manufactured by Radiant Imaging) to calculate the brightness of each region of the device. An LED backlight with an average luminance of 3500 cd/m ² was used as the light source.

17b) Setting of stress voltage: A sample is placed in an FFS element having a matrix structure with a cell gap of 3.5 μm (16 cells of 4 cells in length × 4 cells in width), and an adhesive that cures this element with ultraviolet light is used. and sealed. A polarizing plate was placed on each of the upper and lower surfaces of this element so that the polarizing axes were perpendicular to each other. The device was irradiated with light and a voltage (rectangular wave, 60 Hz) was applied. The voltage was increased in steps of 0.1 V from 0 V to 7.5 V, and the luminance of transmitted light was measured at each voltage. The voltage at which the brightness reaches the maximum is abbreviated as V255. The voltage when the luminance reaches 21.6% of V255 (that is, 127 gradations) is abbreviated as V127.

17c) Stress conditions: V255 (rectangular wave, 30 Hz) and 0.5 V (rectangular wave, 30 Hz) were applied to the device at 60°C for 23 hours to display a checker pattern. Next, V127 (rectangular wave, 0.25 Hz) was applied, and luminance was measured under the condition of an exposure time of 4000 milliseconds.

17d) Calculation of line afterimage: Of the 16 cells, the central 4 cells (vertical 2 cells x horizontal 2 cells) were used for calculation. These 4 cells were divided into 25 regions (5 cells vertically×5 cells horizontally). The average luminance of the four areas (2 cells vertically×2 cells horizontally) at the four corners is abbreviated as luminance A. FIG. The area excluding the four corner areas from the 25 areas was cross-shaped. The minimum value of brightness in the four regions excluding the cross region in the center is abbreviated as brightness B. FIG. The line afterimage was calculated from the following formula. (line afterimage)=(luminance A−luminance B)/luminance A×100.

(18) Spreadability: The spreadability of the additive was qualitatively evaluated by applying a voltage to the device and measuring the luminance. Luminance measurements were made as in Section 14a above. Setting the voltage (V127) was performed in the same manner as in item 14b above. However, a VA element was used instead of the FFS element. Luminance was measured as follows. First, a DC voltage (2 V) was applied to the device for 2 minutes. Next, V127 (rectangular wave, 0.05 Hz) was applied, and luminance was measured under the condition of an exposure time of 4000 milliseconds. Spreadability was evaluated from this result.

[Synthesis Example 1]
Compound (1-2-1) was synthesized by the method described below.

First step:
2,2,6,6-tetramethylpiperidin-4-one (15.0 g, 96.6 mmol), benzyl bromide (BnBr) (19.83 g, 116.0 mmol), potassium carbonate ( 26.71 g, 193.3 mmol), potassium iodide (1.49 g, 8.99 mmol), and acetonitrile (120 ml) were added and stirred at 80°C to 85°C for 24 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted with toluene (100 ml) three times. The extract was washed with water until the pH reached 7, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Petroleum ether (24 ml) was added to the residue and recrystallized at −25° C. for 2 hours, followed by addition of ethanol (24 ml) and recrystallization at −25° C. for 1 hour to give compound (T-1) (10.8 g, yield 45.6%) was obtained.

Second step:
Magnesium (1.67 g, 72.7 mmol) and tetrahydrofuran (THF) (20 ml) were placed in a 200 ml three-necked flask, and compound (T-2) (18.6 g, 66.1 mmol) was added at 55°C to 65°C. and stirred for 1 hour. A solution of compound (T-1) (10.8 g, 44.1 mmol) in THF (30 ml) was added dropwise and stirred for 1 hour. Dilute hydrochloric acid was added dropwise to the reaction solution cooled in an ice bath to adjust the pH from 4 to 5. Next, saturated sodium bicarbonate water was added dropwise to adjust the pH from 8 to 9. This solution was extracted with toluene (50 ml) three times. The extract was washed with water until pH7. After drying over anhydrous magnesium sulfate, concentration under reduced pressure gave compound (T-3) (29.6 g, yield 100%).

Third step:
After dissolving compound (T-3) (29.6 g, 44.1 mmol) in toluene (150 ml), p-toluenesulfonic acid monohydrate (p-TsOH.H ₂ O) (2.96 g) was added. and stirred at 75° C. to 110° C. for 2 hours. After returning the reaction solution to room temperature, saturated aqueous sodium bicarbonate solution was added dropwise to adjust the pH from 8 to 9. The solution was washed with water until pH 7, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was recrystallized from a mixed solvent of toluene (15 ml) and heptane (30 ml) to obtain compound (T-4) (15.2 g, yield 80.2%).

Fourth step:
After dissolving the compound (T-4) (15.2 g, 35.4 mmol) in a mixed solvent of toluene (90 ml) and ethanol (30 ml), palladium on carbon (0.75 g, 0.05 wt%) was added to obtain hydrogen. The mixture was stirred at 55° C. to 60° C. for 24 hours under atmosphere. Insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate). Compound (1-2-1) (6.09 g, yield 50.4%) was obtained by recrystallization from a mixed solvent of ethanol (20 ml) and heptane (40 ml).

¹ H-NMR (ppm; CDCl ₃ ): δ 7.17-7.13 (m, 4H), 2.99 (tt, J = 10.1 Hz, J = 3.1 Hz, 1H), 2.44 (tt , J = 12.1 Hz, J = 3.1 Hz, 1 H), 1.90-1.83 (m, 4 H), 1.77 (dd, J = 13.3 Hz, J = 3.2 Hz, 2 H), 1.59 (brs, 1H) 1.48-1.18 (m, 16H) 1.14 (s, 6H), 0.90 (t, J=7.2Hz, 3H).

Examples of compositions are given below. Component compounds 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 symbolized compound represents the chemical formula to which the compound belongs. The symbol (-) means other liquid crystalline compounds. The ratio (percentage) of the liquid crystal compound is the mass percentage (mass %) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

[Comparative Example 1]
3-HHXB(F,F)-CF3(2-2) 12%
3-GB(F,F)XB(F,F)-F(2-3) 8%
3-HBBXB(F,F)-F(2-7) 3%
4-GB(F)B(F,F)XB(F,F)-F(2-9) 5%
5-GB(F)B(F,F)XB(F,F)-F(2-9) 5%
5-BB(F)B(F,F)XB(F,F)-F (2-10) 12%
3-HH-V (3-1) 23%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 9%
V2-HHB-1 (3-5) 8%
3-GB(F)B(F,F)-F(4-11) 3%
4-GB(F)B(F,F)-F(4-11) 2%
NI = 89.0°C; Tc <-20°C; Δn = 0.101; Δε = 13.4; Vth = 1.34 V; η = 15.9 mPa s; .4%.

[Comparative Example 2]
Comparative compound (A) was added to the composition of Comparative Example 1 at a rate of 0.15% by mass.
The lower temperature limit (Tc) was <0°C.

[Comparative Example 3]
Comparative compound (B) was added to the composition of Comparative Example 1 at a rate of 0.15% by mass.
The lower temperature limit (Tc) was <0°C.

[Example 1]
Compound (1-2-1) was added to the composition of Comparative Example 1 at a rate of 0.15% by mass.
NI = 89.0°C; Tc <-20°C; Δn = 0.101; Δε = 13.4; Vth = 1.34 V; η = 15.9 mPa s; .1%.

[Example 2]
Compound (1-3-1) was added to the composition of Comparative Example 1 at a rate of 0.15% by mass.
NI = 89.0°C; Tc <-20°C; Δn = 0.101; Δε = 13.4; Vth = 1.34 V; η = 15.9 mPa s; .9%.

[Example 3]
3-BB(F,F)XB(F,F)-F(2-4) 16%
3-HH-V (3-1) 13%
5-HB-O2 (3-2) 2%
V-HHB-1 (3-5) 10%
3-HHB-1 (3-5) 5%
3-HHB-O1 (3-5) 3.5%
2-BB(F)B-2V (3-8) 4%
3-BB(F)B-2V (3-8) 4%
2-HHB(F,F)-F(4-4) 10%
3-HHB(F,F)-F(4-4) 12%
3-HBB(F,F)-F(4-8) 8%
3-BB(F)B(F,F)-F(4-12) 8.5%
3-HHBB(F,F)-F(4-14) 4%
Compound (1-2-1) was added to this composition at a rate of 0.10% by mass.
NI = 83.8°C; Tc <-20°C; Δn = 0.120; Δε = 8.4; Vth = 1.54 V; η = 19.2 mPa s; .2%.

[Example 4]
3-HHXB(F,F)-CF3(2-2) 12%
3-HBBXB(F,F)-F(2-7) 4%
5-BB(F)B(F,F)XB(F,F)-F (2-10) 10%
3-HH-V (3-1) 16%
3-HH-V1 (3-1) 6%
1V2-HH-1 (3-1) 9%
1V2-HH-3 (3-1) 8%
V-HHB-1 (3-5) 12%
V2-HHB-1 (3-5) 13%
2-BB(F)B-2V (3-8) 4%
3-BB(F)B-2V (3-8) 2%
3-BB(F)B(F,F)-CF3 (4-13) 4%
Compound (1-2-1) was added to this composition at a rate of 0.07% by mass.
NI = 103.0°C; Tc <-20°C; Δn = 0.110; Δε = 4.86; Vth = 2.41 V; η = 14.8 mPa s; .5%.

[Example 5]
3-HBBXB(F,F)-F(2-7) 7%
3-BB(F)B(F,F)XB(F,F)-F (2-10) 5%
3-HH-V (3-1) 49%
V2-BB-1 (3-3) 8%
1-BB(F)B-2V (3-8) 8%
2-BB(F)B-2V (3-8) 10%
3-BB(F)B-2V (3-8) 7%
3-BB(F)B(F,F)-F(4-12) 6%
Compound (1-3-1) was added to this composition at a rate of 0.009% by mass.
NI = 75.3°C; Tc <-20°C; Δn = 0.135; Δε = 2.7; Vth = 2.80V; η = 13.4 mPa s; .1%.

[Example 6]
3-BB(F,F)XB(F,F)-F(2-4) 11%
3-HH-V (3-1) 40%
3-HH-4 (3-1) 3%
2-BB(F)B-3 (3-8) 4%
2-HBB-F (4) 5%
3-HBB-F (4) 5%
3-HHB(F,F)-F(4-4) 4%
3-HBB(F,F)-F(4-8) 15%
2-HHBB(F,F)-F(4-14) 5%
3-HHBB(F,F)-F(4-14) 4%
4-HHBB(F,F)-F(4-14) 4%
Compound (1-2-1) was added to this composition at a rate of 0.07% by mass.
NI = 75.0°C; Tc <-30°C; Δn = 0.100; Δε = 5.1; Vth = 1.70V; η = 15.6 mPa s; .0%.

[Example 7]
3-HHXB(F,F)-CF3(2-2) 5%
4-GB(F)B(F,F)XB(F,F)-F (2-9) 4%
5-GB(F)B(F,F)XB(F,F)-F(2-9) 4%
5-BB(F)B(F,F)XB(F,F)-F (2-10) 6%
3-HH-V (3-1) 18%
3-HH-V1 (3-1) 6%
1V2-HH-1 (3-1) 6%
1V2-HH-3 (3-1) 7%
3-HH-4 (3-1) 4%
3-HB-O2 (3-2) 6%
V-HHB-1 (3-5) 9%
V2-HHB-1 (3-5) 12%
2-BB(F)B-2V (3-8) 6%
3-BB(F)B-2V (3-8) 5%
4-GBB(F)B(F,F)-F(4-16) 2%
Compound (1-3-1) was added to this composition at a rate of 0.10% by mass.
NI = 96.8°C; Tc <-20°C; Δn = 0.111; Δε = 4.2; Vth = 2.35 V; η = 12.8 mPa s; .5%.

[Example 8]
3-HHXB(F,F)-CF3(2-2) 6%
3-HBBXB(F,F)-F(2-7) 4%
4-GB(F)B(F,F)XB(F,F)-F (2-9) 2%
5-GB(F)B(F,F)XB(F,F)-F (2-9) 2%
4-BB(F)B(F,F)XB(F,F)-F (2-10) 4.5%
5-BB(F)B(F,F)XB(F,F)-F (2-10) 6%
3-HH-V (3-1) 18%
3-HH-V1 (3-1) 2%
1V2-HH-1 (3-1) 9%
1V2-HH-3 (3-1) 8%
3-HB-O2 (3-2) 8%
V-HHB-1 (3-5) 11%
V2-HHB-1 (3-5) 11.5%
2-BB(F)B-2V (3-8) 5%
3-BB(F)B-2V (3-8) 3%
Compound (1-3-1) was added to this composition at a rate of 0.07% by mass.
NI = 95.7°C; Tc <-20°C; Δn = 0.111; Δε = 4.2; Vth = 2.32V; η = 13.2 mPa s; .1%.

[Example 9]
4-BB(F)B(F,F)XB(F,F)-F (2-10) 4.5%
5-BB(F)B(F,F)XB(F,F)-F (2-10) 11%
2-HH-3 (3-1) 25%
3-HH-4 (3-1) 2.5%
3-HB-O2 (3-2) 5%
5-HB-O2 (3-2) 5%
1V2-HHB-1 (3-5) 2%
V-HHB-1 (3-5) 12%
V2-HHB-1 (3-5) 11%
3-HBB-F (4) 5%
5-HBB-F (4) 5%
2-HHBB(F,F)-F(4-14) 5%
3-HHBB(F,F)-F(4-14) 7%
Compound (1-2-1) was added to this composition at a rate of 0.10% by mass.
NI = 109.6°C; Tc <-20°C; Δn = 0.109; Δε = 5.4; Vth = 2.32V; η = 16.2 mPa s; .9%.

[Example 10]
3-HBBXB(F,F)-F(2-7) 3%
3-HBB(F,F)XB(F,F)-F(2-7) 5%
3-BB(F)B(F,F)XB(F,F)-F (2-10) 4%
4-BB(F)B(F,F)XB(F,F)-F (2-10) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 4%
V-HH-V1 (3-1) 7%
V-HHB-1 (3-5) 14%
V2-HHB-1 (3-5) 14%
1-BB(F)B-2V (3-8) 2%
2-BB(F)B-2V (3-8) 6%
3-BB(F)B-2V (3-8) 6%
Compound (1-2-1) was added to this composition at a rate of 0.005% by mass.
NI = 105.7°C; Tc <-30°C; Δn = 0.119; Δε = 3.0; Vth = 2.74V; η = 12.5 mPa s; %.

[Example 11]
3-BB(F,F)XB(F,F)-F(2-4) 2%
3-HBB(F,F)XB(F,F)-F(2-7) 7%
4-GB(F)B(F,F)XB(F,F)-F(2-9) 3%
5-GB(F)B(F,F)XB(F,F)-F(2-9) 3%
3-BB(F)B(F,F)XB(F,F)-F (2-10) 3%
4-BB(F)B(F,F)XB(F,F)-F (2-10) 5%
5-BB(F)B(F,F)XB(F,F)-F (2-10) 2.5%
3-HH-V (3-1) 22%
3-HH-V1 (3-1) 7%
1V2-HH-3 (3-1) 6%
1V2-HHB-1 (3-5) 9%
V2-HHB-1 (3-5) 12%
1-BB(F)B-2V (3-8) 3%
2-BB(F)B-2V (3-8) 7%
3-BB(F)B(F,F)-CF3 (4-13) 5%
3-HHBB(F,F)-F(4-14) 3.5%
Compound (1-2-1) was added to this composition at a rate of 0.15% by mass.
NI = 111.2°C; Tc <-30°C; Δn = 0.131; Δε = 7.94; Vth = 2.10 V; η = 20.3 mPa s; .6%.

[Example 12]
5-HXB(F,F)-F(2-1) 3%
3-HHXB(F,F)-F(2-2) 6%
3-BB(F,F)XB(F,F)-F(2-4) 6%
3-BB (2F, 3F) XB (F, F) -F (2-4) 4%
3-HHB(F,F)XB(F,F)-F(2-5) 4%
3-HBB (2F, 3F) XB (F, F) -F (2-7) 5%
5-BB(F)B(F,F)XB(F)B(F,F)-F (2-14) 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%
3-HB-CL (4-1) 3%
3-HHB-OCF3 (4-3) 3%
3-HGB(F,F)-F(4-6) 3%
3-HB(F)B(F,F)-F(4-9) 5%
3-HHBB(F,F)-F(4-14) 6%
Compound (1-3-1) was added to this composition at a rate of 0.15% by mass.
NI = 77.2°C; Tc <-20°C; Δn = 0.101; Δε = 5.8; Vth = 1.88 V; η = 13.7 mPa s; .2%.

[Example 13]
5-HXB(F,F)-F(2-1) 6%
3-HHXB(F,F)-F(2-2) 6%
2-BB(F)B(F,F)XB(F)-F (2-10) 3%
3-BB(F)B(F,F)XB(F)-F (2-10) 3%
4-BB(F)B(F,F)XB(F)-F (2-10) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 10%
3-HH-V1 (3-1) 7%
4-HH-V (3-1) 10%
4-HH-V1 (3-1) 8%
5-HB-O2 (3-2) 7%
4-HHEH-3 (3-4) 3%
V2-BB(F)B-1 (3-8) 3%
5-HB-CL (4-1) 5%
V-HB(F)B(F,F)-F(4-9) 5%
3-HHB(F)B(F,F)-F(4-15) 7%
1O1-HBBH-3 (-) 5%
Compound (1-2-1) was added to this composition at a rate of 0.10% by mass.
NI = 78.5°C; Tc <-20°C; Δn = 0.095; Δε = 3.4; Vth = 1.50 V; η = 8.4 mPa s; .9%.

[Example 14]
3-HHXB(F,F)-F(2-2) 7%
3-BB(F,F)XB(F,F)-F(2-4) 10%
5-HHB(F,F)XB(F,F)-F(2-5) 6%
3-HBB (2F, 3F) XB (F, F) -F (2-7) 5%
2-HH-3 (3-1) 8%
3-HH-V (3-1) 20%
3-HH-V1 (3-1) 7%
4-HH-V (3-1) 6%
5-HB-O2 (3-2) 5%
V2-B2BB-1 (3-9) 3%
3-HHEBH-3 (3-11) 5%
3-HHEBH-5 (3-11) 5%
3-HHEB(F,F)-F(4-5) 5%
5-HBEB(F,F)-F(4-10) 5%
2-HHB(F)B(F,F)-F(4-15) 3%
Compound (1-3-1) was added to this composition at a rate of 0.01% by mass.
NI = 90.3°C; Tc <-20°C; Δn = 0.088; Δε = 5.4; Vth = 1.69 V; η = 13.7 mPa s; .0%.

[Example 15]
3-GB(F,F)XB(F,F)-F(2-3) 5%
3-HGB(F,F)XB(F,F)-F(2-6) 5%
2-dhBB (F, F) XB (F, F) -F (2-8) 4%
3-dhB (F, F) B (F, F) XB (F) B (F, F) - F (2-13) 3%
3-BB (2F, 5F) B-3 (3) 3%
2-HH-3 (3-1) 14%
2-HH-5 (3-1) 4%
3-HH-V (3-1) 26%
1V2-HH-3 (3-1) 5%
1V2-BB-1 (3-3) 3%
3-HB(F)HH-2 (3-10) 4%
5-HBB(F)B-2 (3-13) 6%
7-HB(F,F)-F(4-2) 3%
3-HGB(F,F)-F(4-6) 3%
5-GHB(F,F)-F(4-7) 4%
3-BB(F)B(F,F)-CF3 (4-13) 2%
3-HHBB(F,F)-F(4-14) 4%
3-GBB(F)B(F,F)-F(4-16) 2%
Compound (1-2-1) was added to this composition at a rate of 0.03% by mass.
NI = 78.3°C; Tc <-20°C; Δn = 0.094; Δε = 5.9; Vth = 1.25 V; η = 12.8 mPa s; .2%.

[Example 16]
3-BB(F,F)XB(F,F)-F(2-4) 10%
3-GB(F)B(F,F)XB(F,F)-F(2-9) 6%
5-GB(F,F)XB(F)B(F,F)-F(2-11) 5%
5-HBBH-3 (3) 5%
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%
3-HHB(F,F)-F(4-4) 8%
3-GB(F)B(F,F)-F(4-11) 3%
Compound (1-2-1) was added to this composition at a rate of 0.01% by mass.
NI = 76.6°C; Tc <-20°C; Δn = 0.088; Δε = 5.5; Vth = 1.81 V; η = 12.1 mPa s; .1%.

[Example 17]
3-BB(F,F)XB(F,F)-F(2-4) 14%
3-dhB (F, F) B (F, F) XB (F) B (F, F) - F (2-13) 7%
3-BB (2F, 5F) B-3 (3) 3%
2-HH-5 (3-1) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 3%
3-HH-VFF (3-1) 10%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 3%
3-HHEBH-3 (3-11) 3%
3-HHEBH-4 (3-11) 4%
3-HHEBH-5 (3-11) 3%
7-HB(F,F)-F(4-2) 6%
Compound (1-3-1) was added to this composition at a rate of 0.03% by mass.
NI = 82.7°C; Tc <-20°C; Δn = 0.085; Δε = 5.1; Vth = 1.70V; η = 8.0 mPa s; .0%.

[Example 18]
3-BB(F)B(F,F)XB(F,F)-F (2-10) 3%
4-BB(F)B(F,F)XB(F,F)-F (2-10) 5%
3-BB(F,F)XB(F)B(F,F)-F (2-12) 3%
5-BB(F)B(F,F)XB(F)B(F,F)-F (2-14) 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-HH2BB(F,F)-F (4) 3%
4-HH2BB(F,F)-F (4) 3%
3-HBB(F,F)-F(4-8) 5%
5-HBB(F,F)-F(4-8) 4%
3-BB(F)B(F,F)-F(4-12) 3%
3-HBB(2F,3F)-O2(5-14) 2%
2-BB (2F, 3F) B-3 (5-19) 4%
Compound (1-3-1) was added to this composition at a rate of 0.05% by mass.
NI = 81.9°C; Tc <-20°C; Δn = 0.109; Δε = 4.8; Vth = 1.75 V; η = 13.3 mPa s; .1%.

[Example 19]
5-HHB(F,F)XB(F,F)-F(2-5) 3%
3-HGB(F,F)XB(F,F)-F(2-6) 4%
3-HBBXB(F,F)-F(2-7) 6%
3-GB(F)B(F,F)XB(F,F)-F(2-9) 5%
4-GB(F)B(F,F)XB(F,F)-F(2-9) 5%
3-HH-5 (3-1) 4%
3-HH-V (3-1) 21%
3-HH-V1 (3-1) 3%
4-HH-V (3-1) 4%
1V2-HH-3 (3-1) 6%
5-B(F)BB-2 (3-7) 3%
5-B(F)BB-3 (3-7) 2%
5-HEB(F,F)-F (4) 3%
5-HB-CL (4-1) 2%
3-HHB-OCF3 (4-3) 4%
3-HHEB(F,F)-F(4-5) 4%
3-HBEB(F,F)-F(4-10) 3%
5-HBEB(F,F)-F(4-10) 3%
3-BB(F)B(F,F)-F(4-12) 3%
3-HB(2F,3F)-O2 (5-1) 3%
3-BB(2F,3F)-O2 (5-6) 2%
3-HHB(2F,3F)-O2(5-8) 4%
F3-HH-V (-) 3%
Compound (1-2-1) was added to this composition at a rate of 0.05% by mass.
NI = 78.1°C; Tc <-20°C; Δn = 0.100; Δε = 6.6; Vth = 1.50V; η = 16.2 mPa s; .5%.

[Example 20]
3-BB(F,F)XB(F,F)-F(2-4) 4%
3-BB(F)B(F,F)XB(F,F)-F (2-10) 5%
4-BB(F)B(F,F)XB(F,F)-F (2-10) 5%
V-HH-V (3-1) 10%
V-HH-2V (3-1) 20%
1V-HH-V (3-1) 10%
3-HH-V (3-1) 15%
V2-BB-1 (3-3) 4%
1-BB(F)B-2V (3-8) 7%
2-BB(F)B-2V (3-8) 8%
3-HHEB(F,F)-F(4-5) 3%
3-HBEB(F,F)-F(4-10) 3%
3-HHB(F)B(F,F)-F(4-15) 3%
1O1-HBBH-5 (-) 3%
Compound (1-3-1) was added to this composition at a rate of 0.10% by mass.
NI = 74.3°C; Tc <-20°C; Δn = 0.111; Δε = 3.0; Vth = 2.39V; η = 11.0 mPa s; .2%.

The line retention (LISP) of the composition of Comparative Example 1 was 4.4%. On the other hand, the line retention of the compositions of Examples 1-20 ranged from 1.1% to 2.2%. Therefore, it can be said that the first additive has the effect of suppressing the line afterimage.

Table 4 summarizes the results of the lower limit temperatures of Examples 1 and 2 and Comparative Examples 2 and 3. From Table 4, it can be said that the first additive is superior to similar comparative compounds in terms of lower temperature limit, ie low temperature solubility. Therefore, it is concluded that the 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 (14)

At least one compound selected from compounds represented by formula (1) as a first additive, at least one compound selected from compounds represented by formula (2) as a first component , and as a second component It contains at least one compound selected from the compounds represented by formula (3), the ratio of the first additive is in the range of 0.005% by mass to 1% by mass, and the ratio of the first component is 5% by mass. % to 55% by mass, the ratio of the second component is in the range of 10% to 85% by mass, and the liquid crystal composition has positive dielectric anisotropy.

In formula (1) and formula (2), R ¹ and R ³ are alkyl having 1 to 12 carbon atoms ; R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 3 carbon atoms, or 1 to 3 alkoxy ; ring A, ring B and ring C are 1,4-cyclohexylene or 1,4-phenylene ; ring D and ring E are 1,4-cyclohexylene , 1, 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ¹ and Z ² is a single bond , -CH ₂ CH ₂ - , -COO-, -OCO-, -CH ₂ O-, or -CH=CH- ; Z ³ is a single bond , -COO-, or -OCO Z ⁴ and Z ⁵ are a single bond, ethylene , vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy ; X ¹ and X ² are hydrogen or fluorine; Y ¹ is fluorine, chlorine, alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is replaced by fluorine or a and b are 0 or 1; c is 1, 2, 3, or 4; d is 0, 1, 2, or 3, and the sum of c and d is 4 or less ;
In formula (3), R ⁴ and R ⁵ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine. alkenyl having 2 to 12 carbon atoms; ring F and ring G are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -phenylene; Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; e is 1, 2, or 3. 2. The liquid crystal composition according to claim 1, containing at least one compound selected from compounds represented by formulas (1-1) to (1-1 1 ) as the first additive.

In formulas (1-1) to (1-1 1 ), R ¹ is alkyl having 1 to 12 carbon atoms ; R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 3 carbon atoms, or alkoxy having 1 to 3 carbon atoms ; X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are hydrogen ; 3. The liquid crystal composition according to claim 1, comprising at least one compound selected from compounds represented by formulas (2-1) to (2-14) as the first component.

In formulas (2-1) to (2-14), R ³ is alkyl having 1 to 12 carbon atoms; X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , and X ¹⁴ are hydrogen or fluorine; Y ¹ is fluorine, chlorine, carbon with at least one hydrogen replaced with fluorine or chlorine alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine . 4. The liquid crystal composition according to any one of claims 1 to 3 , containing at least one compound selected from the compounds represented by formulas (3-1) to (3-13) as the second component. .

In formulas (3-1) to (3-13), R ⁴ and R ⁵ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or at least one It is alkenyl having 2 to 12 carbon atoms in which hydrogen is replaced with fluorine or chlorine. 5. The liquid crystal composition according to any one of claims 1 to 4 , containing at least one compound selected from the compounds represented by formula (4) as the third component.

In formula (4), R ⁶ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms; ring I is 1,4-cyclohexylene, 1,4 -phenylene, 1,4-phenylene with at least one hydrogen replaced by fluorine or chlorine, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl Z ⁷ is a single bond, ethylene, vinylene, or carbonyloxy; X ¹⁵ and X ¹⁶ are hydrogen or fluorine; Y ² is fluorine, chlorine, at least one hydrogen is fluorine or chlorine substituted alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or alkoxy of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine is alkenyloxy; f is 1, 2, 3, or 4; 6. The liquid crystal composition according to any one of claims 1 to 5 , containing at least one compound selected from compounds represented by formulas (4-1) to (4-16) as a third component. .

In formulas (4-1) to (4-16), R ⁶ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms. 7. A liquid crystal composition according to claim 5 or 6 , wherein the proportion of the third component is in the range of 5 wt% to 50 wt%. 8. The liquid crystal composition according to any one of claims 1 to 7 , containing at least one compound selected from compounds represented by formula (5) as the fourth component.

In formula (5), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms. ring J and ring L are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen replaced by fluorine or chlorine; 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen in which fluorine or chroman-2,6-diyl substituted with chlorine; ring K 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, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro fluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2, 5-diyl; Z ⁸ and Z ⁹ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; g is 0, 1, 2, or 3; h is 0 or 1; and the sum of g and h is 3 or less. 9. The liquid crystal composition according to any one of claims 1 to 8 , containing at least one compound selected from compounds represented by formulas (5-1) to (5-35) as a fourth component. .

In formulas (5-1) to (5-35), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or carbon alkenyloxy of numbers 2 to 12; 10. A liquid crystal composition according to claim 8 or 9 , wherein the proportion of the fourth component is in the range of 3% to 45% by weight. The nematic phase has an upper limit temperature of 70°C or higher, an optical anisotropy at a wavelength of 589 nm (measured at 25°C) of 0.07 or higher, and a dielectric anisotropy at a frequency of 1 kHz (measured at 25°C) of 2. 11. The liquid crystal composition according to any one of claims 1 to 10 , wherein: A liquid crystal display device comprising the liquid crystal composition according to claim 1 . 13. The liquid crystal display according to claim 12 , 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 driving method of the liquid crystal display element is the active matrix method. element. Use of the liquid crystal composition according to any one of claims 1 to 11 in a liquid crystal display device.