JP7268312B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal composition, 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 to light and heat is related to the life of liquid crystal display elements. 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.

Furthermore, these liquid crystal display elements are required to have excellent display quality in which display defects such as burn-in and display unevenness are eliminated or suppressed. In order to achieve this, attempts have been made to improve the reliability of the entire LCD panel by adding various additives to the liquid crystal composition.

JP 2017-105762 A

An object of the present invention is to provide a liquid crystal composition containing a compound having an effect of suppressing display defects such as line afterimages and an antistatic effect. 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 object of the present invention is to provide a liquid crystal display element with excellent display quality in which display defects such as burn-in and display unevenness are eliminated or suppressed by using 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 and long lifetime.

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－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_２－ＣＨ_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、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。 The present inventors have studied various liquid crystal compounds and various chemical substances, and have found that the above problems can be solved by using specific compounds, and have completed the present invention. That is, the present invention contains at least one compound selected from compounds having a monovalent group represented by formula (S) as a first additive, and has a nematic phase and positive dielectric anisotropy. A composition is provided, and a liquid crystal display device using the composition is provided.

In formula (S), R ^a is hydrogen, O., OH, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms. and in these groups, at least one —CH ₂ — may be replaced with —O—, —NH—, —CO—, —COO—, or —OCO—, and at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, in which at least one hydrogen is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, , halogen, OH, NHR ^1b , or NR ^1c R ^1d ; R ^1b , R ^1c , and R ^1d are alkyl having 1 to 10 carbon atoms.

An advantage of the present invention is to provide a liquid crystal composition containing a compound having an effect of suppressing display defects such as line afterimages and an antistatic effect. 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 that satisfies at least one of properties such as high stability. 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 a liquid crystal display element with excellent display quality in which display defects such as burn-in and display unevenness are eliminated or suppressed. An object of the present invention is to provide an AM element having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio and long life.

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 optically active compounds and polymerizable compounds are added to the liquid crystal composition as required. 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.

"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. "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 substituted substituents. 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, expressions such as "Ra and Rb are alkyl, alkoxy, or alkenyl" mean that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. means Here, the group represented by Ra and the group represented by Rb may be the same or different. This rule also applies when the Ra symbol is used for multiple compounds. This rule also applies when multiple Ra's are used in one compound.

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.

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。なお、好ましいテトラヒドロピラン－２，５－ジイルは、上限温度を上げるために右向き（Ｒ）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。 Alkyl in the liquid crystalline compound 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. 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. A preferred tetrahydropyran-2,5-diyl is rightward (R) in order to increase the maximum temperature. The same is true for linking groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－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_２－ＣＨ_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、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。 Section 1. A liquid crystal composition containing, as a first additive, at least one compound selected from compounds having a monovalent group represented by formula (S), and having a nematic phase and positive dielectric anisotropy.

In formula (S), R ^a is hydrogen, O., OH, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms. and in these groups, at least one —CH ₂ — may be replaced with —O—, —NH—, —CO—, —COO—, or —OCO—, and at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, in which at least one hydrogen is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, , halogen, OH, NHR ^1b , or NR ^1c R ^1d ; R ^1b , R ^1c , and R ^1d are alkyl having 1 to 10 carbon atoms.

式（１）において、Ｒ^ｂは、水素、フッ素、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－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_２－ＣＨ_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、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルであり；Ｍは、単結合、炭素数１から２０の四価の脂肪族炭化水素基、または炭素数６から２０の四価の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－または－Ｓ－で置き換えられてもよく、１つまたは２つの－ＣＨ＝ＣＨ－は－ＣＨ＝Ｎ－で置き換えられてもよく、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^ａおよびＺ^ｂは、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、炭素数１から２０のアルキレン、または炭素数２から２０のアルケニレンであり、これらの基において、少なくとも１つの水素は、フッ素、塩素、ＯＨで置き換えられてもよく；Ｑ^ａは、式（Ｓ）で表される一価基であり；ｎは、１、２、３、または４であり；ｍは、４－ｎであり；ただし、Ｍが単結合の場合、ｎおよびｍは１であり；

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－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_２－ＣＨ_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、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。 Section 2. Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from the compounds represented by formula (1) as the first additive.

In formula (1), R ^b is hydrogen, fluorine, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms, In these groups, at least one -CH ₂ - may be replaced with -O-, -NH-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH- or -C≡C-, wherein at least one hydrogen is alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, halogen, OH, NHR ^lb , or NR ^lc R ^ld ; R ^lb , R ^lc , and R ^ld are alkyl having 1 to 10 carbon atoms; M is a single bond, a tetravalent aliphatic hydrocarbon group or a tetravalent aromatic hydrocarbon group having 6 to 20 carbon atoms, in which at least one —CH ₂ — is replaced with —O— or —S— one or two -CH=CH- may be replaced by -CH=N- and at least one hydrogen may be replaced by fluorine or chlorine; Z ^a and Z ^b are , a single bond, —O—, —COO—, —OCO—, alkylene having 1 to 20 carbon atoms, or alkenylene having 2 to 20 carbon atoms, wherein at least one hydrogen in these groups is fluorine, chlorine, optionally replaced by OH; Q ^a is a monovalent group represented by formula (S); n is 1, 2, 3, or 4; m is 4-n; , where M is a single bond, n and m are 1;

In formula (S), R ^a is hydrogen, O., OH, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms. and in these groups, at least one —CH ₂ — may be replaced with —O—, —NH—, —CO—, —COO—, or —OCO—, and at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, in which at least one hydrogen is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, , halogen, OH, NHR ^1b , or NR ^1c R ^1d ; R ^1b , R ^1c , and R ^1d are alkyl having 1 to 10 carbon atoms.

式（１－１）から式（１－５）において、Ｚ^ｃは、単結合、炭素数１から５のアルキレンまたは炭素数２から５のアルケニレンであり、これらの基において、少なくとも１つの水素は、ＯＨで置き換えられてもよく；Ｒ^ｃは、水素、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－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_２－ＣＨ_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、ＯＨ、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、または炭素数６から２０の芳香族炭化水素基で置き換えられてもよく；ｓは、１から２０の整数であり；Ｑ^ｂは、式（Ｓ－１）で表される一価基であり；

式（Ｓ－１）において、Ｒ^ｄは、水素、Ｏ・、ＯＨ、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、または炭素数１から１０のアルコキシであり、これらの基において、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。 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 (1-1) to (1-5) as the first additive.

In formulas (1-1) to (1-5), Z ^c is a single bond, alkylene having 1 to 5 carbon atoms or alkenylene having 2 to 5 carbon atoms, and in these groups, at least one hydrogen is , OH; R ^c is hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms; , in these groups, at least one -CH ₂ - may be replaced with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - is may be substituted with -CH=CH- or -C≡C-, in which at least one hydrogen is OH, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or may be substituted with 6 to 20 aromatic hydrocarbon groups; s is an integer of 1 to 20; Q ^b is a monovalent group represented by formula (S-1);

In formula (S-1), R ^d is hydrogen, O., OH, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, and in these groups , at least one hydrogen may be replaced by a halogen.

Section 4. 4. The liquid crystal composition according to any one of items 1 to 3, wherein the proportion of the first additive is in the range of 0.001% by mass to 2% by mass.

式（２）において、Ｒ^２ａは、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ａは、１，４－シクロヘキシレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、２，３－ジフルオロ－１，４－フェニレン、２，６－ジフルオロ－１，４－フェニレン、ピリミジン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、またはテトラヒドロピラン－２，５－ジイルであり；Ｚ^２ａは、単結合、エチレン、ビニレン、カルボニルオキシ、またはジフルオロメチレンオキシであり；Ｘ^２ａおよびＸ^２ｂは、水素またはフッ素であり；Ｙ^２ａは、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；ａは、１、２、３、または４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 (2) as the first component.

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

式（２－１）から式（２－３５）において、Ｒ^２ａ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 6. Item 6. The liquid crystal composition according to any one of items 1 to 5, containing at least one compound selected from compounds represented by formulas (2-1) to (2-35) as the first component.

In formulas (2-1) to (2-35), R ^2a is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms.

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

式（３）において、Ｒ^３ａおよびＲ^３ｂ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Ｂおよび環Ｃ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^３ａ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；ｂは、１、２、または３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 (3) as the second component.

In formula (3), R ^3a and R ^3b 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 with fluorine or chlorine. alkenyl having 2 to 12 carbon atoms; ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -phenylene; Z ^3a is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; b is 1, 2, or 3;

式（３－１）から式（３－１３）において、Ｒ^３ａおよびＲ^３ｂ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 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 (3-1) to (3-13) as the second component.

In formulas (3-1) to (3-13), R ^3a and R ^3b 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 10. Item 10. The liquid crystal composition according to item 8 or 9, wherein the ratio of the second component is in the range of 10% by mass to 85% by mass.

式（４）において、Ｒ^４ａおよびＲ^４ｂ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Ｄおよび環Ｆ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Ｅ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^４ａおよびＺ^４ｂ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；ｃは０、１、２、または３であり、ｄは０または１であり；そしてｃとｄ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 (4) as the third component.

In formula (4), R ^4a and R ^4b 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 D and ring F 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 E 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, is 5-diyl; Z ^4a and Z ^4b are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3 and d is 0 or 1; And the sum of c and d is 3 or less.

式（４－１）から式（４－３５）において、Ｒ^４ａおよびＲ^４ｂ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 (4-1) to (4-35) as a third component.

In formulas (4-1) to (4-35), R ^4a and R ^4b 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. Item 13. The liquid crystal composition according to Item 11 or 12, wherein the proportion of the third 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. 15. A liquid crystal display device comprising 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; A composition as described above containing a compound, 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 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. Composition A may further contain other liquid crystalline compounds, additives, etc., in addition to the liquid crystalline compound selected from compound (2), compound (3), and compound (4). "Other liquid crystalline compounds" are liquid crystalline compounds different from compound (2), compound (3), and compound (4). 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) and compound (4). "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, and the symbol 0 (zero) means less than S.

The main effects of the component compounds are as follows. The first additive acts as a display defect inhibitor such as burn-in and display unevenness. Since compound (1) is added in a small amount, it does not affect properties such as maximum temperature, optical anisotropy, and dielectric anisotropy in many cases. Compound (2) raises the dielectric anisotropy and lowers the minimum temperature. Compound (3) lowers the viscosity or raises the maximum temperature. Compound (4) increases the dielectric constant in the minor axis direction.

Long-term use of the liquid crystal display element may significantly degrade the display quality. One of the factors that can be considered is that, due to long-time driving, a small amount of charged particles existing in the liquid crystal composition are gathered unevenly, or some kind of phenomenon occurs between the element member other than the liquid crystal composition and the liquid crystal composition. For some reason, the potential accumulates, causing display defects such as display burn-in and display unevenness.

The first additive of the present invention is at least one compound selected from compounds having a monovalent group represented by formula (S). By adding this compound, the resistance of the liquid crystal display element can be extremely lowered without greatly lowering the specific resistance value of the liquid crystal composition. The amino group site of this compound is attracted to the adsorption site of the peripheral material of the LCD panel (for example, the carbonyl group on the surface of the alignment film) to form an adsorption layer. This layer has a low resistance value, which suppresses uneven distribution of charged particles and accumulation of electric potential, thereby suppressing display defects such as burn-in and display unevenness. It works as a so-called local antistatic agent.

Thirdly, the combination of ingredients in the composition, the preferred proportions of the ingredient compounds and the basis thereof will be explained. Preferred combinations of ingredients in the composition are first additive + compound (2), first additive + compound (3), first additive + compound (2) + compound (4), first additive + compound (3) + compound (4), first additive + compound (2) + compound (3), first additive + compound (2) + compound (3) + compound (4). A more preferred combination is first additive+compound (2)+compound (3) or first additive+compound (2)+compound (3)+compound (4).

A preferred proportion of the first additive is about 0.001% by mass or more and about 2% by mass or less to lower the minimum temperature. A more preferred proportion ranges from about 0.010% to about 1.000% by weight. A particularly preferred proportion ranges from about 0.020% to about 0.150% by weight.

A preferable proportion of compound (2) is about 10% by mass or more for increasing dielectric anisotropy, and about 85% by mass or less for lowering the minimum temperature or viscosity. 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 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 proportion ranges from about 25% to about 70% by weight.

A preferable ratio of compound (4) is about 3% by mass or more for increasing the dielectric constant in the minor axis direction, and about 45% by mass or less for decreasing 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.

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－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_２－ＣＨ_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、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよい。Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。好ましいＲ^ａは、メチルである。好ましいＲ^１ｂ、Ｒ^１ｃ、またはＲ^１ｄは、炭素数１から５のアルキルである。 Fourth, preferred forms of component compounds are described. In formula (1), R ^b is hydrogen, fluorine, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms, In these groups, at least one -CH ₂ - may be replaced with -O-, -NH-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH- or -C≡C-, wherein at least one hydrogen is alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, halogen, OH, NHR ^1b , or NR ^1c R ^1d may be substituted. R ^1b , R ^1c and R ^1d are alkyls having 1 to 10 carbon atoms. Preferred ^Rb is hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 6 to 15 carbon atoms, or aromatic hydrocarbon group having 6 to 15 carbon atoms. Preferred R ^1b , R ^1c or R ^1d is alkyl having 1 to 5 carbon atoms. M is a single bond, a tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a tetravalent aromatic hydrocarbon group having 6 to 20 carbon atoms, in which at least one —CH ₂ - may be replaced by -O- or -S-, one or two -CH=CH- may be replaced by -CH=N-, and at least one hydrogen is fluorine or chlorine may be replaced. Preferred M is a tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Z ^a and Z ^b are a single bond, —O—, —COO—, —OCO—, alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms, and in these groups, at least one hydrogen may be replaced by fluorine, chlorine, OH. Preferred Z ^a or Z ^b is a single bond, —COO—, —OCO—, or alkyl having 1 to 5 carbon atoms. Q ^a is a monovalent group represented by formula (S). n is 1, 2, 3, or 4, and m is 4-n. Preferred n is 2 or 4.

In formula (S), R ^a is hydrogen, O., OH, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms. and in these groups, at least one —CH ₂ — may be replaced with —O—, —NH—, —CO—, —COO—, or —OCO—, and at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, in which at least one hydrogen is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, , halogen, OH, NHR ^1b , or NR ^1c R ^1d . R ^1b , R ^1c and R ^1d are alkyls having 1 to 10 carbon atoms. A preferred R ^a is methyl. Preferred R ^1b , R ^1c or R ^1d is alkyl having 1 to 5 carbon atoms.

ここで、Ｒ^ｄは、水素、Ｏ・、ＯＨ、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、または炭素数１から１０のアルコキシであり、これらの基において、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。好ましいＲ^ｄはメチルである。 In formulas (1-1) to (1-5), Z ^c is a single bond, alkylene having 1 to 5 carbon atoms, or alkenylene having 2 to 5 carbon atoms, and in these groups, at least one hydrogen may be replaced by OH. Preferred ^Zc is a single bond, methylene, or ethylene. R ^c is hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms, and in these groups, at least one -CH ₂ - may be replaced by -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - is -CH=CH- or -C≡ may be substituted with C—, in which at least one hydrogen is OH, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; may be replaced with Preferred R ^c is an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms in which at least one hydrogen is replaced with OH. s is an integer from 1 to 20; Preferred s is an integer from 1 to 8. Q ^b is a monovalent group represented by formula (S-1).

wherein R ^d is hydrogen, O., OH, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, and in these groups, at least one hydrogen may be replaced by halogen. Preferred ^Rd is methyl.

Specific representative examples of the first additive are shown below, but the present invention is not limited to these.

In Formula (2), Formula (3), and Formula (4), R ^2a is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Preferred R ^2a is alkyl having 1 to 12 carbon atoms in order to increase stability to light or heat. R ^3a and R ^3b 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 ^3a or R ^3b is alkenyl having 2 to 12 carbon atoms to reduce viscosity and alkyl having 1 to 12 carbon atoms to increase stability to light or heat. R ^4a and R ^4b 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 ^4a or R ^4b is alkyl having 1 to 12 carbon atoms for increasing stability to light or heat, and alkoxy having 1 to 12 carbon atoms for increasing dielectric anisotropy.

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 to reduce 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.

または

であり、好ましくは

である。 Ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene , pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. Preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing optical anisotropy. Tetrahydropyran-2,5-diyl is

or

and preferably

is.

好ましい環Ｅ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 B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring B or ring C is 1,4-cyclohexylene for lowering viscosity or 1,4-phenylene for increasing optical anisotropy. Ring D and ring F 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 D or ring F is 1,4-cyclohexylene for lowering viscosity, tetrahydropyran-2,5-diyl for increasing dielectric anisotropy, and 1,4-phenylene. Ring E 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 E 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 ^2a is a single bond, ethylene, vinylene, carbonyloxy, or difluoromethyleneoxy. Preferred Z ^2a is a single bond to reduce viscosity and difluoromethyleneoxy to increase dielectric anisotropy. Z ^3a is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ^3a is a single bond to reduce viscosity. Z ^4a and Z ^4b are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ^4a or Z ^4b is a single bond for lowering the viscosity, ethylene for lowering the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.

A divalent group such as methyleneoxy is asymmetric. In methyleneoxy, -CH ₂ O- is preferred to -OCH ₂ -. In carbonyloxy, -COO- is preferred to -OCO-. In difluoromethyleneoxy, -CF ₂ O- is preferred to -OCF ₂ -.

X ^2a and X ^2b are hydrogen or fluorine. Preferred X ^2a or X ^2b is fluorine in order to increase the dielectric anisotropy.

Y ^2a 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 C2-C12 alkenyloxy in which one hydrogen is replaced by fluorine or chlorine. A preferred Y ^2a 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 is 1, 2, 3, or 4; A is preferably 2 for lowering the lower limit temperature and 3 for increasing dielectric anisotropy. b is 1, 2, or 3; Preferred b is 1 for lowering the viscosity, and 2 or 3 for raising the maximum temperature. c is 0, 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less. Preferably, c is 1 for lowering the viscosity, and 2 or 3 for raising the maximum temperature. Desirable d 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 (1-5) described in item 3. Among these compounds, compound (1-1) or compound (1-2) is preferred.

Preferred compounds (2) are compounds (2-1) to (2-35) described in Item 6. In these compounds, at least one of the first components is compound (2-4), compound (2-12), compound (2-14), compound (2-15), compound (2-17), compound ( 2-18), compound (2-23), compound (2-24), compound (2-27), compound (2-29), or compound (2-30). at least two of the first components are compound (2-12) and compound (2-15), compound (2-14) and compound (2-27), compound (2-18) and compound (2-24); A combination of compound (2-18) and compound (2-29), compound (2-24) and compound (2-29), or compound (2-29) and compound (2-30) is preferred.

Preferred compounds (3) are compounds (3-1) to (3-13) described in Item 9. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), or compound (3-7) is preferred. at least two of the second components are compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), compound (3-1) and compound (3-7), compound Combinations of (3-3) and compound (3-5), compound (3-3) and compound (3-6), and compound (3-3) and compound (3-7) are preferred.

Preferred compounds (4) are compounds (4-1) to (4-35) described in Item 12. In these compounds, at least one of the third components is compound (4-1), compound (4-3), compound (4-6), compound (4-8), compound (4-10), compound ( 4-14), or compound (4-16). at least two of the third components are compound (4-1) and compound (4-8), compound (4-1) and compound (4-14), compound (4-3) and compound (4-8), compound (4-3) and compound (4-14), compound (4-3) and compound (4-16), compound (4-6) and compound (4-8), compound (4-6) and compound A combination of (4-10), compound (4-6) and compound (4-16), compound (4-10) and compound (4-16) 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 (5-1) to (5-5). 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 (6-1 ) to compound (6-3) may further be added to the composition.

Since compound (6-2) 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 (7-1) to (7-16). 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.

A quenching agent is a compound that receives light energy absorbed by a liquid crystalline compound and converts it into heat energy, thereby preventing decomposition of the liquid crystalline compound. Preferred examples of the quenching agent include compounds (8-1) to (8-7). A preferable proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less to lower the minimum 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 added to the composition to make it compatible with polymer support alignment (PSA) type devices. Preferred examples of polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes) and vinyl ketones. Further preferred examples are derivatives of acrylates or methacrylates. A preferable ratio of the polymerizable compound is about 0.05% by mass or more to obtain the effect, and about 10% by mass or less to prevent display failure. A more preferred percentage ranges from about 0.1% to about 2% by weight. The polymerizable compound is polymerized by UV irradiation. Polymerization may be carried out in the presence of an initiator such as a photoinitiator. Suitable conditions for polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and described in the literature. For example, the photoinitiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF) or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization. A preferred proportion of photoinitiator ranges from about 0.1% to about 5% by weight based on the weight of the polymerizable compound. A more preferred percentage is in the range of about 1% to about 3% by weight.

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. Compound (1-A) is available from Tokyo Chemical Industry (TCI). Compound (2-4) 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 (4-1) is synthesized by the method described in JP-A-2000-053602. Antioxidants are commercially available. Compounds of formula (6) where n is 1 are available from Sigma-Aldrich Corporation. Compound (6) where n is 7, etc. 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 for 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 16.67 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was obtained. 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 16.67 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 16.67 milliseconds. A composition with a large VHR-12 has a large thermal stability.

(12) Voltage holding ratio (VHR-13; measured at 60° C.; %): After irradiating with LED light, the voltage holding ratio was measured to evaluate the stability against LED light. The LED light used was light (visible light) emitted from a general 32-inch TV backlight unit using LEDs as light-emitting elements. The luminance measured values within the irradiated surface were 3500 to 3970 cd/m2. In the test, the TN devices into which the samples were injected were arranged on a backlight unit and irradiated for 4 weeks, and then the voltage holding ratio was measured to evaluate the stability against LED light. The VHR-13 measurement measured a voltage decaying over 16.67 milliseconds. Compositions with large VHR-13 have greater stability to LED light.

(13) 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.

(14) Elastic constant (K; measured at 25° C.; pN): HP4284A type 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.

(15) Specific resistance (ρ; measured at 25°C; Ωcm): 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)}.

(16) 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.

(17) 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.

(18) Resistance value of liquid crystal display device (ρ; measured at 60° C.; Ω): DC voltage applied to the TN device into which the sample was injected was increased stepwise from 0V to 10V by 0.1V. At this time, the current value flowing through the device was measured, and a voltage value-current value straight line was created. According to Ohm's law, the reciprocal of the slope was taken as the resistance value of the element.

(19) Line Image Sticking Parameter (LISP; %): A 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.

(19a) 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.

(19b) Setting of stress voltage: A sample was placed in a liquid crystal display element having a matrix structure (16 cells of 4 cells in length×4 cells in width), and this element was sealed with an ultraviolet curable adhesive. 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 was applied. 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.

(19c) Stress conditions: V255 and 0.5 V were applied to the device under conditions of 60° C. and 23 hours to display a checker pattern. Next, V127 was applied, the entire surface was illuminated, and the luminance was measured.

(19d) Calculation of line afterimage: Of the 16 cells, the central 4 cells (vertical 2 cells×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.

The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The numbers in parentheses after the symbols correspond to the compound numbers. 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(2-5) 12%
3-GB(F,F)XB(F,F)-F(2-14) 8%
3-GBB(F)B(F,F)-F(2-22) 3%
4-GBB(F)B(F,F)-F(2-22) 2%
3-HBBXB(F,F)-F(2-23) 3%
4-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-BB(F)B(F,F)XB(F,F)-F (2-29) 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%
NI = 89.0°C; Tc <-20°C; Δn = 0.101; Δε = 13.4; Vth = 1.34V;

[Example 1]
Example 1 was prepared by adding compound (1-A) to the composition of Comparative Example 1.
3-HHXB(F,F)-CF3(2-5) 12%
3-GB(F,F)XB(F,F)-F(2-14) 8%
3-GBB(F)B(F,F)-F(2-22) 3%
4-GBB(F)B(F,F)-F(2-22) 2%
3-HBBXB(F,F)-F(2-23) 3%
4-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-BB(F)B(F,F)XB(F,F)-F (2-29) 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%
Compound (1-A) was added to this composition at a rate of 0.100% by mass.
NI = 89.0°C; Tc <-20°C; Δn = 0.101; Δε = 13.4; Vth = 1.34V;

[Example 2]
Example 2 was prepared by adding compound (1-C) to the composition of Comparative Example 1.
3-HHXB(F,F)-CF3(2-5) 12%
3-GB(F,F)XB(F,F)-F(2-14) 8%
3-GBB(F)B(F,F)-F(2-22) 3%
4-GBB(F)B(F,F)-F(2-22) 2%
3-HBBXB(F,F)-F(2-23) 3%
4-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-BB(F)B(F,F)XB(F,F)-F (2-29) 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%
Compound (1-C) was added to this composition at a rate of 0.100% by mass.
NI = 89.0°C; Tc <-20°C; Δn = 0.101; Δε = 13.4; Vth = 1.34V;

In addition, line afterimages were observed in order to confirm the effect on burn-in, display unevenness, and the like. The liquid crystal compositions of Comparative Example 1, Example 1, and Example 2 were placed in a liquid crystal display element, and line afterimages were observed. The line afterimage was observed in the initial state before stress was applied and in the state after stress was applied (Table 4).

It can be seen that display defects such as burn-in and display unevenness do not occur in the initial state. After the application, in Comparative Example 1, a line afterimage was clearly observed between the electrodes, and a checker pattern burn-in was slightly observed. On the other hand, in Examples 1 and 2, no line afterimage was generated and there was no change from the initial state.

Table 4. Afterimage observation result

[Example 3]
3-HHXB(F,F)-F(2-4) 6%
3-BB(F,F)XB(F,F)-F(2-18) 13%
3-HHBB(F,F)-F(2-19) 4%
4-HHBB(F,F)-F(2-19) 5%
3-HBBXB(F,F)-F(2-23) 3%
3-BB(F)B(F,F)XB(F)-F (2-28) 2%
4-BB(F)B(F,F)XB(F,F)-F (2-29) 8%
5-BB(F)B(F,F)XB(F,F)-F (2-29) 7%
3-HH-V (3-1) 44%
V-HHB-1 (3-5) 6%
2-BB(F)B-3 (3-8) 2%
Compound (1-B) was added to this composition at a rate of 0.050% by mass.
NI = 80.2°C; Tc <-30°C; Δn = 0.106; Δε = 8.1; Vth = 1.45V; η = 11.6 mPa s; .8%

[Example 4]
5-HXB(F,F)-F(2-1) 3%
3-HHXB(F,F)-F(2-4) 3%
3-HHXB(F,F)-CF3 (2-5) 3%
3-HGB(F,F)-F(2-6) 3%
5-HB(F)B(F,F)-F(2-9) 1%
3-BB(F,F)XB(F,F)-F(2-18) 6%
3-HHBB(F,F)-F(2-19) 6%
5-BB(F)B(F,F)XB(F)B(F,F)-F (2-31) 1%
3-BB (2F, 3F) XB (F, F)-F (2-32) 4%
V2-B (2F, 3F) BXB (F, F)-F (2-33) 1%
3-HHB(F,F)XB(F,F)-F (2) 1%
3-HB-CL (2) 3%
3-HHB-OCF3 (2) 3%
3-HH-V (3-1) 28%
3-HH-V1 (3-1) 14%
5-HB-O2 (3-2) 5%
3-HHEH-3 (3-4) 3%
3-HBB-2 (3-6) 9%
5-B(F)BB-3 (3-7) 3%
Compound (1-C) was added to this composition at a rate of 0.070% by mass.
NI = 74.2°C; Tc <-20°C; Δn = 0.091; Δε = 3.7; Vth = 2.87V; η = 5.8 mPa s; .1%

[Example 5]
5-HXB(F,F)-F(2-1) 6%
3-HHXB(F,F)-F(2-4) 6%
5-HB(F)B(F,F)-F(2-9) 5%
3-HHB(F)B(F,F)-F(2-20) 7%
2-BB(F)B(F,F)XB(F)-F (2-28) 3%
3-BB(F)B(F,F)XB(F)-F (2-28) 3%
4-BB(F)B(F,F)XB(F)-F (2-28) 4%
5-HB-CL (2) 5%
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%
1-BB(F)B-2V (3-8) 3%
1O1-HBBH-3 (-) 5%
Compound (1-C) was added to this composition at a rate of 0.080% by mass.
NI = 80.3°C; Tc <-20°C; Δn = 0.091; Δε = 4.2; Vth = 1.50V; η = 8.4 mPa s; .9%

[Example 6]
3-HHEB(F,F)-F(2-3) 5%
3-HHXB(F,F)-F(2-4) 7%
5-HBEB(F,F)-F(2-10) 5%
3-BB(F,F)XB(F,F)-F(2-18) 10%
2-HHB(F)B(F,F)-F(2-20) 3%
3-HB (2F, 3F) BXB (F, F) -F (2-34) 3%
3-BB (2F, 3F) BXB (F, F) -F (2-35) 2%
5-HHB(F,F)XB(F,F)-F (2) 6%
2-HH-3 (3-1) 8%
2-HH-5 (3-1) 20%
3-HH-V (3-1) 6%
4-HH-V (3-1) 6%
V-HH-V (3-1) 1%
5-HB-O2 (3-2) 5%
V2-B2BB-1 (3-9) 3%
3-HHEBH-3 (3-11) 5%
3-HHEBH-5 (3-11) 5%
Compound (1-B) was added to this composition at a rate of 0.075% by mass.
NI = 90.8°C; Tc <-20°C; Δn = 0.084; Δε = 5.4; Vth = 1.65V; η = 13.6 mPa s; .5%

[Example 7]
3-BBXB(F,F)-F(2-17) 1%
3-BB(F,F)XB(F,F)-F(2-18) 11%
3-HHBB(F,F)-F(2-19) 5%
4-HHBB(F,F)-F(2-19) 3%
5-HHBB(F,F)-F(2-19) 1%
3-HBBXB(F,F)-F(2-23) 2%
3-HBB(F,F)XB(F,F)-F(2-24) 1%
3-BB(F)B(F,F)XB(F)-F (2-28) 3%
3-BB(F)B(F,F)XB(F,F)-F (2-29) 3%
4-BB(F)B(F,F)XB(F,F)-F (2-29) 5%
5-BB(F)B(F,F)XB(F,F)-F (2-29) 4%
2-HH-3 (3-1) 6%
3-HH-5 (3-1) 6%
3-HH-V (3-1) 24%
3-HH-VFF (3-1) 6%
V-HH-V1 (3-1) 1%
3-HB-O2 (3-2) 2%
5-HB-O2 (3-2) 5%
V-HHB-1 (3-5) 6%
V-HBB-2 (3-6) 5%
Compound (1-B) was added to this composition at a rate of 0.090% by mass.
NI = 79.6°C; Tc <-20°C; Δn = 0.105; Δε = 6.8; Vth = 1.55V; η = 11.6 mPa s; .4%

[Example 8]
3-HGB(F,F)-F(2-6) 3%
5-GHB(F,F)-F(2-7) 4%
3-GB(F,F)XB(F,F)-F(2-14) 5%
3-BB(F)B(F,F)-CF3 (2-16) 2%
3-HHBB(F,F)-F(2-19) 4%
3-GBB(F)B(F,F)-F(2-22) 2%
2-dhBB(F,F)XB(F,F)-F(2-25) 4%
3-GB(F)B(F,F)XB(F,F)-F (2-27) 3%
3-HGB(F,F)XB(F,F)-F (2) 5%
7-HB(F,F)-F (2) 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%
1-BB-3 (3-3) 3%
2-BB(F)B-3 (3-8) 3%
3-HB(F)HH-2 (3-10) 4%
5-HBB(F)B-2 (3-13) 6%
Compound (1-C) was added to this composition at a rate of 0.080% by mass.
NI = 79.3°C; Tc <-20°C; Δn = 0.099; Δε = 5.2; Vth = 1.45V; η = 11.5 mPa s; .8%

[Example 9]
3-HBB(F,F)-F(2-8) 5%
5-HBB(F,F)-F(2-8) 4%
3-BB(F)B(F,F)-F(2-15) 3%
3-BB(F)B(F,F)XB(F,F)-F (2-29) 3%
4-BB(F)B(F,F)XB(F,F)-F (2-29) 5%
3-BB(F,F)XB(F)B(F,F)-F (2-30) 3%
5-BB(F)B(F,F)XB(F)B(F,F)-F (2-31) 1%
3-HH2BB(F,F)-F (2) 3%
4-HH2BB(F,F)-F (2) 3%
2-HH-5 (3-1) 9%
3-HH-V (3-1) 28%
3-HH-V1 (3-1) 10%
4-HH-V1 (3-1) 9%
5-HB-O2 (3-2) 5%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 1%
VFF-HHB-1 (3-5) 3%
Compound (1-C) was added to this composition at a rate of 0.075% by mass.
NI = 71.5°C; Tc <-20°C; Δn = 0.0894; Δε = 3.0; Vth = 2.62V; η = 10.0 mPa s; .1%

[Example 10]
3-HHB(F,F)-F(2-2) 8%
3-GB(F)B(F)-F(2-11) 1%
3-GB(F)B(F,F)-F(2-12) 2%
3-BB(F,F)XB(F,F)-F(2-18) 9%
3-GB(F)B(F,F)XB(F,F)-F (2-27) 6%
5-GB(F)B(F,F)XB(F,F)-F(2-27) 6%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 8%
3-HH-VFF (3-1) 8%
1-BB-3 (3-3) 2%
5-HB(F)BH-3 (3-12) 10%
Compound (1-B) was added to this composition at a rate of 0.070% by mass.
NI = 79.5°C; Tc <-20°C; Δn = 0.087; Δε = 6.5; Vth = 1.85V; η = 13.9 mPa s; .5%

[Example 11]
3-HHEB(F,F)-F(2-3) 4%
5-HHEB(F,F)-F(2-3) 3%
3-HBEB(F,F)-F(2-10) 3%
5-HBEB(F,F)-F(2-10) 3%
3-GB(F,F)XB(F)-F(2-13) 1%
3-BB(F)B(F,F)-F(2-15) 2%
3-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
4-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-HB-CL (2) 5%
3-HHB-OCF3 (2) 4%
3-HHB(F,F)XB(F,F)-F (2) 5%
5-HHB(F,F)XB(F,F)-F (2) 3%
3-HGB(F,F)XB(F,F)-F (2) 5%
2-HH-5 (3-1) 3%
3-HH-5 (3-1) 5%
3-HH-V (3-1) 24%
4-HH-V (3-1) 5%
1V2-HH-3 (3-1) 5%
3-HHEH-3 (3-4) 5%
5-B(F)BB-2 (3-7) 3%
5-B(F)BB-3 (3-7) 2%
Compound (1-C) was added to this composition at a rate of 0.060% by mass.
NI = 82.9°C; Tc <-20°C; Δn = 0.093; Δε = 6.9; Vth = 1.50V; η = 16.3 mPa s; .2%

[Example 12]
3-HHEB(F,F)-F(2-3) 4%
3-HBEB(F,F)-F(2-10) 3%
5-HBEB(F,F)-F(2-10) 3%
3-BB(F)B(F,F)-F(2-15) 3%
3-HBBXB(F,F)-F(2-23) 6%
4-GBB(F,F)XB(F,F)-F(2-26) 2%
5-GBB(F,F)XB(F,F)-F(2-26) 2%
3-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
4-GB(F)B(F,F)XB(F,F)-F (2-27) 5%
5-HHB(F,F)XB(F,F)-F (2) 3%
3-HGB(F,F)XB(F,F)-F (2) 3%
5-HB-CL (2) 2%
3-HHB-OCF3 (2) 4%
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%
3-HB(2F,3F)-O2 (4-1) 3%
3-BB(2F,3F)-O2 (4-6) 2%
3-HHB(2F,3F)-O2(4-8) 4%
F3-HH-V (-) 3%
Compound (1-C) was added to this composition at a rate of 0.080% by mass.
NI = 78.2°C; Tc <-20°C; Δn = 0.101; Δε = 6.7; Vth = 1.45V; η = 17.8 mPa s; .8%

[Example 13]
3-HHXB(F,F)-F(2-4) 9%
3-BB(F)B(F,F)-F(2-15) 14%
3-HH-V (3-1) 39%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 6%
V-HHB-1 (3-5) 3%
V2-HHB-1 (3-5) 3%
2-HBB(2F,3F)-O2(4-14) 3%
3-HBB(2F,3F)-O2(4-14) 7%
4-HBB(2F,3F)-O2(4-14) 3%
3-dhBB(2F,3F)-O2(4-16) 2%
2-BB (2F, 3F) B-3 (4-19) 1%
Compound (1-C) was added to this composition at a rate of 0.070% by mass.
NI = 82.2°C; Tc <-20°C; Δn = 0.099; Δε = 2.0; Vth = 2.94V; η = 9.9 mPa s; .1%

The LISP of the composition of Comparative Example 1 was 9.5%. On the other hand, the LISP of the compositions of Examples 1-13 ranged from 1.5% to 2.5%. Further, from the observation results of line afterimages, line afterimages and image sticking were observed in the element containing the composition of Comparative Example 1, whereas in the elements containing the compositions of Examples 1 and 2, No line afterimage or burn-in was observed. Therefore, it is concluded that the liquid crystal composition of the present invention has superior properties, and that a liquid crystal display element having excellent display quality can be obtained by using the liquid crystal composition of the present invention.

The specific resistance of the liquid crystal compositions of Comparative Example 1, Example 1, and Example 2 was measured. Further, these liquid crystal compositions were placed in a liquid crystal display element, and the resistance value of the liquid crystal display element was measured. The results are summarized in Table 5. The specific resistance values of Examples 1 and 2 are slightly lower than those of Comparative Example 1, but the resistance values of the liquid crystal display elements of Examples 1 and 2 are significantly lower than those of Comparative Example 1. I understand. Therefore, it can be concluded that the use of the liquid crystal composition of the present invention provides a liquid crystal display device in which electrification is further suppressed.

Table 5. Comparison of composition resistivity and element resistance

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

Claims (15)

A liquid crystal composition containing at least one compound selected from compounds represented by formulas (1-1) to (1-5) as a first additive and having a nematic phase and positive dielectric anisotropy .

In formulas (1-1) to (1-5), Z ^c is a single bond, alkylene having 1 to 5 carbon atoms or alkenylene having 2 to 5 carbon atoms, and in these groups, at least one hydrogen is , OH; R ^c is hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic hydrocarbon group having 6 to 20 carbon atoms; , in these groups, at least one -CH ₂ - may be replaced with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - is may be substituted with -CH=CH- or -C≡C-, in which at least one hydrogen is OH, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or may be substituted with 6 to 20 aromatic hydrocarbon groups; s is an integer of 1 to 20; Q ^b is a monovalent group represented by formula (S-1);

In formula (S-1), R ^d is hydrogen, O., OH, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, and in these groups , at least one hydrogen may be replaced by a halogen. 2. The liquid crystal composition according to claim 1 , wherein the proportion of the first additive is in the range of 0.001 wt% to 2 wt%. 3. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formula (2) as the first component.

In formula (2), R ^2a is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms; ring A is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3- dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ^2a is a single bond, ethylene, vinylene, carbonyloxy, or difluoromethyleneoxy; X ^2a and X ^2b are hydrogen or is fluorine; Y ^2a is fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine alkoxy, or alkenyloxy of 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 compounds represented by formulas (2-1) to (2-35) as a first component. .

In formulas (2-1) to (2-35), R ^2a is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms. 5. A liquid crystal composition according to claim 3 or 4 , wherein the proportion of the first component ranges from 10% to 85% by weight. 6. The liquid crystal composition according to any one of claims 1 to 5 , containing at least one compound selected from the compounds represented by formula (3) as the second component.

In formula (3), R ^3a and R ^3b 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 with fluorine or chlorine. alkenyl having 2 to 12 carbon atoms; ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -phenylene; Z ^3a is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; b is 1, 2, or 3; 7. The liquid crystal composition according to any one of claims 1 to 6 , 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 ^3a and R ^3b 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. 8. A liquid crystal composition according to claim 6 or 7 , wherein the proportion of the second component ranges from 10% by weight to 85% by weight. 9. The liquid crystal composition according to any one of claims 1 to 8 , containing at least one compound selected from compounds represented by formula (4) as a third component.

In formula (4), R ^4a and R ^4b 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 D and ring F 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 E 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, is 5-diyl; Z ^4a and Z ^4b are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3 and d is 0 or 1; And the sum of c and d is 3 or less. 10. The liquid crystal composition according to any one of claims 1 to 9 , which contains at least one compound selected from compounds represented by formulas (4-1) to (4-35) as a third component. .

In formulas (4-1) to (4-35), R ^4a and R ^4b 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; 11. The liquid crystal composition according to claim 9 or 10 , wherein the proportion of the third 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. 12. The liquid crystal composition according to any one of claims 1 to 11 , wherein: A liquid crystal display device comprising the liquid crystal composition according to claim 1 . 14. The liquid crystal display according to claim 13 , 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 12 in a liquid crystal display device.