JP7348598B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

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

In liquid crystal display elements, the classification based on the operating mode of liquid crystal molecules is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving method 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), etc. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter are classified into high-temperature type and low-temperature type depending on the manufacturing process. The classification based on the light source is reflective type that uses natural light, transmissive type that uses backlight, and transflective type that 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 element with good properties can be obtained. The relationships among these properties are summarized in Table 1 below. The properties of the composition will be further explained based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. The preferable upper limit temperature of the nematic phase is about 70°C or higher, and the preferable lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying moving images on the device. A shorter response time, even 1 millisecond, is desirable. Therefore, a low viscosity in the composition is preferred. Small viscosities at low temperatures are even more preferred. The elastic constant of the composition is related to the contrast ratio of the device. A large elastic constant in the composition is preferred to increase the contrast ratio in the device.

The optical anisotropy of a composition is related to the contrast ratio of the device. Depending on the mode of the device, large optical anisotropy or small optical anisotropy, ie, appropriate optical anisotropy, is required. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. For a mode device such as TN, it is approximately 0.45 μm. In this case, a composition having large optical anisotropy is preferable for an element with a small cell gap. The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, a large dielectric constant anisotropy is preferred. A large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, compositions that have a large specific resistance in the initial stage are preferred. Compositions that have a high resistivity after long-term use are preferred. The stability of the composition against ultraviolet light and heat is related to the lifetime of the liquid crystal display element. When these 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 positive dielectric constant anisotropy is used in an AM element having a TN mode. A composition having negative dielectric anisotropy is used in an AM element having VA mode. A composition having positive or negative dielectric constant anisotropy is used in an AM element having an IPS mode or an FFS mode. A composition having positive or negative dielectric anisotropy is used in a polymer sustained alignment (PSA) type AM element.

Japanese Patent Application Laid-Open No. 58-194822 International Publication No. 2012-043387 Japanese Patent Application Publication No. 8-302353

The objects of the present invention are a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, a positively large dielectric anisotropy, a large resistivity, a high stability against light, and a It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of the following properties, such as high stability against and a 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 element containing such a composition. Another challenge is to provide AM devices with characteristics such as short response time, high voltage holding ratio, low threshold voltage, high contrast ratio, and long lifetime.

式（１）および式（２）において、Ｒ^１およびＲ^２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、炭素数２から１２のアルケニルオキシ、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１から１２のアルキルであり；Ｒ^３は、炭素数１から３のアルキルまたは炭素数２から５のアルケニルであり；Ｚ^１、Ｚ^２、およびＺ^３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る。The present invention contains at least one compound selected from compounds represented by formula (1) as component A, at least one compound selected from compounds represented by formula (2) as component B, and The present invention relates to a liquid crystal composition having positive dielectric anisotropy and a liquid crystal display element containing this composition.

In formula (1) and formula (2), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and alkenyl having 2 to 12 carbon atoms. alkenyloxy, or C1-C12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine; R ³ is C1-C3 alkyl or C2-5 alkenyl; Z ¹ , Z ² , and Z ³ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy.

The advantages of the present invention are a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, a positively large dielectric anisotropy, a large resistivity, a high stability against light, and a thermal It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of the following properties, such as high stability against and a large elastic constant. Another advantage is to provide liquid crystal compositions that have a suitable balance between at least two of these properties. Another advantage is to provide liquid crystal display elements containing such compositions. Another advantage is to provide an AM device with characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

The 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" refers to a compound that has a liquid crystal phase such as a nematic phase or a smectic phase, and a compound that does not have a liquid crystal phase but is used for the purpose of adjusting the properties of the nematic phase such as temperature range, viscosity, and dielectric anisotropy. A general term for compounds mixed into a 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 producing a polymer in a composition. Liquid crystalline compounds having alkenyl are not classified as polymerizable compounds in that sense.

A liquid crystal composition is prepared by mixing multiple liquid crystal compounds. Additives such as optically active compounds and polymerizable compounds are added to this liquid crystal composition as necessary. Even when additives are added, the proportion of the liquid crystal compound is expressed as a mass percentage (mass %) based on the mass of the liquid crystal composition that does not contain additives. The proportion of the additive is expressed as a mass percentage (% by mass) based on the mass of the liquid crystal composition that does not contain the additive. That is, the proportions of the liquid crystal compound and additives are calculated based on the total mass of the liquid crystal compound. The proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the weight of the polymerizable compound.

"Upper limit temperature of nematic phase" may be abbreviated as "upper limit temperature." The "lower limit temperature of nematic phase" may be abbreviated as "lower limit temperature." The expression "increase the dielectric anisotropy" means that for a composition with a positive dielectric anisotropy, the value increases positively, and for a composition with a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "High voltage holding rate" means that the device has a large voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature in the initial stage, and after long-term use, it has a large voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature. It means having a retention rate. Characteristics of compositions and devices are sometimes investigated through 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。

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

At least one compound selected from the 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 the 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's is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A's is one, the position of 'A' is arbitrary, and the number of 'A's is two. If there are more than one, their positions can be selected without restriction. The expression "at least one -CH ₂ - may be replaced by -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, an adjacent -CH ₂ - is never replaced with -O-. This is because -OO-CH ₂ - (peroxide) is produced in this substitution.

テトラヒドロピラン－２，５－ジイルのような二価基においても同様である。カルボニルオキシのような結合基（－ＣＯＯ－または－ＯＣＯ－）も同様である。The alkyl of the liquid crystalline compound is linear or branched and does not contain a cyclic alkyl. Straight chain alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis in order to increase the upper limit temperature. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are left-handed (L) and right-handed (R) orientations.

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to bonding groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

式（１）および式（２）において、Ｒ^１およびＲ^２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、炭素数２から１２のアルケニルオキシ、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１から１２のアルキルであり；Ｒ^３は、炭素数１から３のアルキルまたは炭素数２から５のアルケニルであり；Ｚ^１、Ｚ^２、およびＺ^３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る。Item 1. Contains at least one compound selected from the compounds represented by formula (1) as component A, at least one compound selected from the compounds represented by formula (2) as component B, and has a positive dielectric constant A liquid crystal composition with anisotropy.

In formula (1) and formula (2), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and alkenyl having 2 to 12 carbon atoms. alkenyloxy, or C1-C12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine; R ³ is C1-C3 alkyl or C2-5 alkenyl; Z ¹ , Z ² , and Z ³ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy.

Item 2. Item 2. The liquid crystal composition according to item 1, wherein the proportion of component A is in the range of 3% by mass to 30% by mass, and the proportion of component B is in the range of 10% by mass to 70% by mass.

式（３）において、Ｒ^４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^４は、単結合、エチレン、ビニレン、メチレンオキシ、カルボニルオキシ、またはジフルオロメチレンオキシであり；Ｘ^１およびＸ^２は、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；ａは、１、２、３、または４である。Item 3. Item 3. The liquid crystal composition according to item 1 or 2, which contains as component C at least one compound selected from the group of compounds represented by formula (3).

In formula (3), R ⁴ 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- is dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ⁴ is a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X ¹ and X ² are , hydrogen or fluorine; Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, or 1 carbon in which at least one hydrogen is replaced with fluorine or chlorine; alkoxy of 12 to 12, or alkenyloxy of 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; a is 1, 2, 3, or 4;

式（３－１）から式（３－３５）において、Ｒ^４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 4. The liquid crystal composition according to any one of Items 1 to 3, containing as component C at least one compound selected from the group of compounds represented by formulas (3-1) to (3-35). .

In formulas (3-1) to (3-35), R ⁴ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms.

Item 5. Item 5. The liquid crystal composition according to item 3 or 4, wherein the proportion of component C is in the range of 10% by mass to 80% by mass.

式（４）において、Ｒ^５およびＲ^６は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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^５は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｂは、１または２であり；ｂが１であるとき、環Ｃは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－フェニレンである。Item 6. 6. The liquid crystal composition according to any one of Items 1 to 5, which contains as component D at least one compound selected from compounds represented by formula (4).

In formula (4), R ⁵ and R ⁶ 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 has been replaced with fluorine or chlorine. It is 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 ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; b is 1 or 2; when b is 1, ring C is 1,4-phenylene; 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene.

式（４－１）から式（４－８）において、Ｒ^５およびＲ^６は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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。Section 7. Item 7. The liquid crystal composition according to any one of items 1 to 6, which contains as component D at least one compound selected from compounds represented by formulas (4-1) to (4-8).

In formulas (4-1) to (4-8), R ⁵ and R ⁶ 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 an alkenyl having 2 to 12 carbon atoms in which hydrogen is replaced with fluorine or chlorine.

Section 8. Item 8. The liquid crystal composition according to item 6 or 7, wherein the proportion of component D is in the range of 5% by mass to 60% by mass.

式（５）において、Ｒ^７およびＲ^８は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシであり；環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^６およびＺ^７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およびｄの和は、３以下である。Item 9. 9. The liquid crystal composition according to any one of Items 1 to 8, containing as component E at least one compound selected from compounds represented by formula (5).

In formula (5), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms. ; Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced with fluorine or chlorine; 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen replaced with 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, 5-diyl; Z ⁶ and Z ⁷ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3; d is 0 or 1; Yes, and the sum of c and d is 3 or less.

式（５－１）から式（５－３５）において、Ｒ^７およびＲ^８は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシである。Item 10. 10. The liquid crystal composition according to any one of Items 1 to 9, which contains as component E at least one compound selected from compounds represented by formulas (5-1) to (5-35).

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

Item 11. Item 11. The liquid crystal composition according to item 9 or 10, wherein the proportion of component E is in the range of 3% by mass to 45% by mass.

Item 12. The upper limit temperature of the nematic phase is 100°C or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25°C) is 0.09 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25°C) is 2. The liquid crystal composition according to any one of Items 1 to 11, which is the above.

Item 13. Item 13. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 12.

Section 14. 14. The liquid crystal display element according to item 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 an active matrix method. .

Item 15. Use of the liquid crystal composition according to any one of Items 1 to 12 in a liquid crystal display element.

The present invention also includes the following sections. (a) one compound selected from additives such as optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds; , two compounds, or three or more compounds. (b) An AM element containing the above composition. (c) The above composition further containing a polymerizable compound, and a polymer supported alignment (PSA) type AM element containing this composition. (d) A polymer supported alignment (PSA) type AM element containing the above composition and in which a 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 element containing the above composition. (g) Use of the above compositions as compositions 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 explained in the following order. First, the structure of the composition will be explained. Second, the main properties of the component compounds and the main effects that these compounds have on the compositions and devices will be explained. Third, the combinations of component compounds in the composition, their preferred ratios, and their basis will be explained. Fourth, preferred forms of the component compounds will be explained. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be explained. Seventh, the method of synthesizing the component compounds will be explained. Finally, the uses of the composition will be explained.

First, the structure of the composition will be explained. This composition contains multiple liquid crystal compounds. The composition may also 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 crystal compound. Composition A contains, in addition to a liquid crystal compound selected from compound (1), compound (2), compound (3), compound (4), and compound (5), other liquid crystal compounds, additives, etc. It may further contain. "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (2), compound (3), compound (4), and compound (5). Such compounds are mixed into the composition for the purpose of further adjusting its properties.

Composition B consists essentially only of liquid crystalline compounds selected from compound (1), compound (2), compound (3), compound (4), and compound (5). "Substantially" means that Composition B may contain additives but does not contain other liquid crystal compounds. Composition B has fewer components than Composition A. Composition B is preferable to composition A from the viewpoint of lowering costs. Composition A is more preferable than composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

Second, the main properties of the component compounds and the main effects that these compounds have on the compositions and devices will be explained. The main properties of the component compounds are summarized in Table 2. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, and S are classifications based on qualitative comparisons between component compounds, and the symbol 0 (zero) means less than S.

The main effects of the component compounds are as follows. Compound (1) increases the upper limit temperature. Compound (2) lowers the viscosity. Compound (3) increases dielectric anisotropy. Compound (4) lowers the minimum temperature or increases optical anisotropy. Compound (5) increases the dielectric constant in the minor axis direction of liquid crystal molecules.

Third, the combinations of component compounds in the composition, their preferred ratios, and their basis will be explained. Preferred combinations of component compounds in the composition are compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (3) + compound (4), and compound (1) + Compound (2) + compound (3) + compound (5), or compound (1) + compound (2) + compound (3) + compound (4) + compound (5).

A preferable proportion of compound (1) is about 3% by mass or more to increase the upper limit temperature, and about 30% by mass or less to lower the lower limit temperature. More preferred proportions range from about 5% to about 20% by weight. Particularly preferred proportions range from about 5% to about 15% by weight.

A preferred proportion of compound (2) is about 10% by mass or more in order to lower the viscosity, and about 70% by mass or less in order to lower the minimum temperature. More preferred proportions range from about 15% to about 65% by weight. Particularly preferred proportions range from about 20% to about 60% by weight.

A preferred proportion of compound (3) is about 10% by mass or more to increase dielectric anisotropy, and about 80% by mass or less to decrease viscosity. More preferred proportions range from about 15% to about 75% by weight. Particularly preferred proportions range from about 20% to about 70% by weight.

A preferable proportion of compound (4) is about 5% by mass or more in order to lower the minimum temperature or increase optical anisotropy, and about 60% by mass or less in order to increase dielectric anisotropy. More preferred proportions range from about 10% to about 55% by weight. Particularly preferred proportions range from about 10% to about 50% by weight.

A preferable proportion of compound (5) is about 3% by mass or more in order to increase the dielectric constant in the minor axis direction of the liquid crystal molecules, and about 45% by mass or less in order to lower the minimum temperature. More preferred proportions range from about 10% to about 40% by weight. Particularly preferred proportions range from about 15% to about 35% by weight.

Fourth, preferred forms of the component compounds will be explained. In formula (1), formula (2), formula (3), formula (4), and formula (5), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, and hydrogen having 1 to 12 carbon atoms. Alkoxy, alkenyl having 2 to 12 carbon atoms, alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Preferred R ¹ or R ² is alkenyl having 2 to 12 carbon atoms to reduce viscosity, and alkyl having 1 to 12 carbon atoms to increase stability. R ³ is alkyl having 1 to 3 carbon atoms or alkenyl having 2 to 5 carbon atoms. Preferred R ³ is propyl, vinyl, or 1-propenyl. R ⁴ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms. Preferred R ⁴ is alkyl having 1 to 12 carbon atoms in order to increase stability. R ⁵ and R ⁶ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or a group having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. It is alkenyl. Preferred R ⁵ or R ⁶ is alkenyl having 2 to 12 carbon atoms to reduce viscosity, and alkyl having 1 to 12 carbon atoms to increase stability. R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Preferred R ⁷ or R ⁸ is alkyl having 1 to 12 carbon atoms to increase stability, and alkoxy having 1 to 12 carbon atoms to increase the dielectric constant in the minor axis direction of the liquid crystal molecule.

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 is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More preferred alkoxy to reduce viscosity is methoxy or ethoxy.

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 preferable for alkenyl 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 alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy to reduce 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 in order 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-cyclohexylene to increase the upper limit temperature, 1,4-phenylene to increase optical anisotropy, and 2,6-difluoro to increase dielectric anisotropy. -1,4-phenylene. Tetrahydropyran-2,5-diyl is

or

and preferably

It is.

Ring B and Ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene, and b is 1 When ring C is 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 the viscosity or increasing the upper temperature limit, and 1,4-phenylene for lowering the lower temperature limit. Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 in which at least one hydrogen is replaced with fluorine or chlorine. ,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen with fluorine or chlorine chroman-2,6-diyl substituted 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. An example of naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine is 3,4,5-trifluoronaphthalene-2,6-diyl. An example of chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine is 7,8-difluorochroman-2,6-diyl. Preferred ring D or ring F is 1,4-cyclohexylene to lower the viscosity, tetrahydropyran-2,5-diyl to increase the dielectric anisotropy, and preferred ring D or ring F to increase the optical anisotropy. It is 1,4-phenylene.

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 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-tetrafluoroindan-2,5-diyl (InF4) It is.

Preferred ring E is 2,3-difluoro-1,4-phenylene to lower the viscosity, 2-chloro-3-fluoro-1,4-phenylene to lower the optical anisotropy, and the dielectric constant 7,8-difluorochroman-2,6-diyl is used to increase anisotropy.

Z ¹ , Z ² , and Z ³ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferably Z ¹ , Z ² or Z ³ is a single bond in order to lower the viscosity. Z ⁴ is a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy. Preferably Z ⁴ is a single bond in order to lower the viscosity, and is preferably difluoromethyleneoxy in order to increase the dielectric anisotropy. Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ⁵ is a single bond to reduce viscosity. Z ⁶ and Z ⁷ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferably Z ⁶ or Z ⁷ is a single bond to reduce viscosity.

Divalent groups such as methyleneoxy are asymmetric. In methyleneoxy, -CH ₂ O- is more preferred than -OCH ₂ -. In carbonyloxy, -COO- is more preferred than -OCO-. In difluoromethyleneoxy, -CF ₂ O- is more preferred than -OCF ₂ -.

X ¹ and X ² are hydrogen or fluorine. Preferably X ¹ or X ² is fluorine in order to increase the dielectric anisotropy.

Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, alkoxy having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or at least It is alkenyloxy having 2 to 12 carbon atoms in which one hydrogen is replaced with fluorine or chlorine. Preferred Y ¹ 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 alkenyloxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluorovinyloxy.

a is 1, 2, 3, or 4. Preferably a is 2 or 3 in order to increase the dielectric anisotropy. b is 1 or 2. Preferably b is 1 in order to lower the viscosity, and preferably 2 in order to increase the upper limit 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 in order to lower the viscosity, and 2 or 3 in order to increase the upper limit temperature. Preferably d is 0 in order to lower the viscosity, and 1 in order to lower the lower limit temperature.

Fifth, preferred component compounds are shown. A preferred compound (1) is a compound in which R ¹ is alkenyl having 2 to 12 carbon atoms and R ² is alkyl having 1 to 12 carbon atoms. A more preferred compound (1) is a compound in which R ¹ is alkenyl having 2 to 5 carbon atoms and R ² is alkyl having 1 to 5 carbon atoms. A particularly preferred compound (1) is a compound in which R ¹ is alkenyl having 2 or 3 carbon atoms and R ² is alkyl having 2 or 3 carbon atoms.

Preferred compounds (3) are compounds (3-1) to (3-35) described in item 4. In these compounds, at least one of component C is compound (3-4), compound (3-12), compound (3-14), compound (3-15), compound (3-17), compound (3 -18), compound (3-23), compound (3-24), compound (3-27), compound (3-29), or compound (3-30). At least two of component C are compound (3-15) and compound (3-18), compound (3-15) and compound (3-29), compound (3-18) and compound (3-24), compound A combination of (3-18) and compound (3-23), compound (3-24) and compound (3-29), or compound (3-29) and compound (3-30) is preferred.

Preferred compounds (4) are compounds (4-1) to (4-8) described in Item 7. In these compounds, at least one of component D is compound (4-1), compound (4-2), compound (4-4), compound (4-5), or compound (4-7). is preferred. At least two of the components D are compound (4-1) and compound (4-4), compound (4-4) and compound (4-5), or compound (4-4) and compound (4-7). A combination is preferred.

Preferred compounds (5) are compounds (5-1) to (5-35) described in Item 10. In these compounds, at least one component E is a compound (5-1), a compound (5-3), a compound (5-6), a compound (5-8), a compound (5-10), a compound (5-5). -14) or compound (5-34). At least two of component E are compound (5-1) and compound (5-8), compound (5-1) and compound (5-14), compound (5-3) and compound (5-8), compound (5-3) and compound (5-14), compound (5-3) and compound (5-34), compound (5-6) and compound (5-8), compound (5-6) and compound ( 5-10) or a combination of compound (5-6) and compound (5-14).

Sixth, additives that may be added to the composition will be explained. 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 and giving a twist angle. Examples of such compounds are compounds (6-1) to (6-5). The preferred proportion of optically active compound is about 5% by weight or less. More preferred proportions range from about 0.01% to about 2% by weight.

The compound (7-1 ) may further add an antioxidant such as compound (7-3) to the composition.

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

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer include compounds (8-1) to (8-16). The preferable proportion of these absorbers and stabilizers is about 50 ppm or more in order to obtain the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

A quencher is a compound that prevents decomposition of a liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferred examples of the quencher include compounds (9-1) to (9-7). The preferred proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20,000 ppm or less so as not to raise the lower limit temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition in order to make it compatible with a guest host (GH) mode device. Preferred proportions of dye range from about 0.01% to about 10% by weight. Antifoaming agents such as dimethyl silicone oil, methylphenyl silicone oil are added to the composition to prevent foaming. The preferred 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 proportions range from about 1 ppm to about 500 ppm.

Polymerizable compounds are used to make them compatible with polymer supported alignment (PSA) type devices. Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxirane, oxetane), and vinyl ketones. Further preferred examples are acrylate or methacrylate derivatives. A preferred proportion is about 10% by weight or more, based on the total weight of the polymerizable compound. A more preferred proportion is about 50% by weight or more. A particularly preferred proportion is about 80% by weight or more. The most preferred proportion is 100% by weight.

When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-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 partially positively charged. Polarity results from uneven distribution of partial charges between different atoms in a compound. For example, the polar compound has at least one of the following partial structures: -OH, -COOH, -SH, -NH ₂ , >NH, >N-.

Seventh, the method of synthesizing the component compounds will be explained. These compounds can be synthesized by known methods. The synthesis method will be illustrated. Compound (1) is synthesized by the method described in JP-A-58-194822. Compound (2) is synthesized by the method described in JP-A-59-176221. Compound (3-2) is synthesized by the method described in JP-A-2-233626. Compound (4-1) is synthesized by the method described in JP-A-56-68636. Compound (5-1) and compound (5-8) are synthesized by the method described in Japanese Patent Publication No. Hei 2-503441. Antioxidants are commercially available. Compound (7-1) is available from Aldrich (Sigma-Aldrich Corporation). Compound (7-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which the synthesis method was not described are provided by Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., Comprehensive Organic Syntheses, Organic Reactions, John Wiley & Sons, Inc. Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), and other books. Compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds may be mixed and dissolved together by heating.

Finally, the uses of the composition will be explained. This composition primarily 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. By trial and error, compositions having optical anisotropy ranging from about 0.10 to about 0.30 may be prepared. A device containing this composition has a high voltage holding ratio. This composition is suitable for AM devices. This composition is particularly suitable for transmission type AM elements. This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.

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

The present invention will be explained in more detail with reference to Examples. The invention is not limited by these examples. The invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present 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 the compounds, compositions, and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for measurement. In ^{the 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, and with 16 integrations. Tetramethylsilane was used as an internal standard. ¹⁹ F-NMR measurements were carried out using CFCl ₃ as an internal standard and with 24 integrations. In the description of nuclear magnetic resonance spectra, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sex means sextet, m means multiplet, and br means broad.

Gas chromatography analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL/min). The sample vaporization chamber was set at 280°C, and the detector (FID) was set 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 to separate the component compounds. This column was held at 200°C for 2 minutes and then raised to 280°C at a rate of 5°C/min. After preparing the sample as an acetone solution (0.1% by mass), 1 μL of the solution was injected into the sample vaporization chamber. The recorder was a C-R5A Chromatopac manufactured by Shimadzu Corporation or an equivalent product. The resulting gas chromatogram showed the retention times and peak areas of the peaks corresponding to the component compounds.

Chloroform, hexane, etc. 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). In order to prevent overlapping of compound peaks, a capillary column CBP1-M50-025 manufactured by Shimadzu Corporation (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) may be used.

The proportion of the liquid crystal 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 area ratio of the peaks in the gas chromatogram corresponds to the proportion of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the proportion (mass %) of the liquid crystal compound can be calculated from the area ratio of the peaks.

Measurement sample: When measuring the characteristics of a composition or an element, the composition was used as it was as a sample. When measuring the properties of a compound, a sample for measurement was prepared by mixing this compound (15% by mass) with a mother liquid crystal (85% by mass). Characteristic values of the compound were calculated by extrapolation from the values obtained by measurement. (Extrapolated value) = {(measured value of sample)-0.85×(measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystals) precipitates at 25°C with this ratio, the ratio of the compound to the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, and 1% by mass: 99% by mass. changed. By this extrapolation method, the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The following mother liquid crystal was used. The proportions of component compounds are expressed in mass %.

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

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

(2) Lower limit temperature of nematic phase (TC; ° _C ): Place a sample having a nematic phase in a glass bottle and place it 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, T _C was written 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 was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. A sample was placed in a TN device in which the twist angle was 0° and the distance between two glass substrates (cell gap) was 5 μm. A voltage was applied to this element in steps of 0.5 V in the range of 16 V to 19.5 V. After 0.2 seconds of no application, application was repeated under the conditions of only one square wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The rotational viscosity value was obtained from these measured values and the calculation formula (10) described on page 40 of the paper by M. Imai et al. The dielectric anisotropy value required for this calculation was determined by the method described below using the element that measured this rotational viscosity.

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

(6) Dielectric constant anisotropy (Δε; measured at 25° C.): A sample was placed in a TN element in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. A sine wave (10 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (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): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 0.45/Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased in steps of 0.02 V from 0 V to 10 V. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance is 100% when the amount of light is maximum and the transmittance is 0% when this amount of light is the 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 element used in the measurement had a polyimide alignment film, and the distance between the two glass substrates (cell gap) was 5 μm. . After the sample was placed in the device, it was sealed with an adhesive that cures under ultraviolet light. This TN element was charged by applying a pulse voltage (1 V for 60 microseconds). The attenuating voltage was measured for 166.7 milliseconds using a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when no attenuation occurred. The voltage holding rate was expressed as a percentage of area A to area B.

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

(10) Voltage holding rate (VHR-11; measured at 60°C; %): After irradiation with ultraviolet rays, voltage holding rate was measured to evaluate stability against ultraviolet rays. The TN device used in the measurements had a polyimide alignment film and a cell gap of 5 μm. A sample was injected into this element and irradiated with ultraviolet rays of 5 mW/cm ² for 167 minutes. The light source was a black light manufactured by Eye Graphics Co., Ltd., F40T10/BL (peak wavelength 369 nm), and the distance between the element and the light source was 5 mm. The VHR-11 measurement measured a voltage decay over a period of 166.7 milliseconds. Compositions with large VHR-11 have greater stability to ultraviolet light.

(11) Voltage holding rate (VHR-12; measured at 60°C; %): After heating the TN element injected with the sample in a thermostat at 120°C for 20 hours, the voltage holding rate was measured and the stability against heat was measured. was evaluated. The VHR-12 measurement measured a voltage that decayed over 166.7 milliseconds. Compositions with large VHR-12 have greater thermal stability.

(12) Voltage holding rate (VHR-13; measured at 60°C; %): After heating the TN element injected with the sample in a thermostat at 100°C for 3 weeks, the voltage holding rate was measured and the stability against heat was measured. was evaluated. The VHR-13 measurement measured a voltage that decayed over a period of 166.7 milliseconds. Compositions with large VHR-13 have greater thermal stability.

(13) Response time (τ; measured at 25°C; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz. A sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 3.4 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. Rise time (τr: milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: milliseconds) 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 manner.

(14) Elastic constant (K; measured at 25°C; pN): For measurement, an HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used. A sample was placed in a horizontal alignment element in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 to 20 volts was applied to this element, and the capacitance and applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) using equations (2.98) and (2.101) in "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), page 75. Then, the values of K11 and K33 were obtained from equation (2.99). Next, K22 was calculated using the equation (3.18) on page 171 using the values of K11 and K33 found earlier. The elastic constant was expressed as the average value of K11, K22, and K33 obtained in this way.

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

(16) Helical pitch (P; measured at room temperature; μm): The helical pitch was measured by the wedge method. See "Liquid Crystal Handbook", page 196 (published in 2000, Maruzen). The sample was injected into a wedge-shaped cell and allowed to stand for 2 hours at room temperature, and then the distance between disclination lines (d2-d1) was observed using a polarizing microscope (Nikon Corporation, trade name MM40/60 series). The helical pitch (P) was calculated from the following formula, where θ represents the angle of the wedge cell. P=2×(d2−d1)×tanθ.

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

(18) Response time (τ-2; measured at -20°C; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz. A sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 3.4 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. Rise time (τr: milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: milliseconds) 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 manner.

(19) Response time (τ-3; measured at -30°C; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz. A sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 3.4 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. Rise time (τr: milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: milliseconds) 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 manner.

Examples of compositions are shown below. Component compounds were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is the mass percentage (mass %) based on the mass of the liquid crystal composition not containing additives. Finally, the characteristic values of the composition were summarized.

[Example 1]
V-HHBB-2 (1) 10%
3-HH-V (2) 28.5%
1V-HH-V (2) 22%
3-GB(F)B(F)-F (3-11) 3%
3-BB(F)B(F,F)XB(F)-F (3-28) 2%
4-BB(F)B(F,F)XB(F)-F (3-28) 2%
3-BB(F)B(F,F)XB(F)-F (3-28) 10%
V-HHB-1 (4-4) 4%
V2-HHB-1 (4-4) 4%
V-HBB-2 (4-5) 5%
1-BB(F)B-2V (4-7) 2%
2-BB(F)B-2V (4-7) 5.5%
3-BB(F)B-2V (4-7) 2%
NI=105.1℃; Tc<-30℃;Δn=0.123;Δε=3.0;Vth=2.59V;η=12.3mPa・s;γ1=57.1mPa・s; τ-3 =185.7ms.

[Comparative example 1]
Compound (1) of Example 1 was not included, and the upper limit temperature of the nematic phase was adjusted to be the same.
3-HH-V (2) 28.5%
1V-HH-V (2) 10%
3-GB(F)B(F)-F (3-11) 3%
3-BB(F)B(F,F)XB(F)-F (3-28) 2%
4-BB(F)B(F,F)XB(F)-F (3-28) 2%
3-BB(F)B(F,F)XB(F)-F (3-28) 10%
3-HHB-1 (4-4) 2%
V-HHB-1 (4-4) 14%
V2-HHB-1 (4-4) 14%
V-HBB-2 (4-5) 5%
1-BB(F)B-2V (4-7) 2%
2-BB(F)B-2V (4-7) 5.5%
3-BB(F)B-2V (4-7) 2%
NI=105.0℃; Tc<-30℃;Δn=0.120;Δε=3.0;Vth=2.67V;η=12.8mPa・s;γ1=62.3mPa・s; τ-3 =235.8ms.

[Example 2]
V-HHBB-1 (1) 5%
V-HHBB-3 (1) 2%
3-HH-V (2) 20%
V-HH-V (2) 11%
1V-HH-V (2) 10%
3-HHB(F,F)-F (3-2) 5%
3-GB(F)B(F,F)-F (3-12) 5%
3-HHBB(F,F)-F (3-19) 3%
3-HHB(F)B(F,F)-F (3-20) 3%
3-GB(F)B(F,F)XB(F,F)-F(3-27) 5%
3-HHB-1 (4-4) 6%
3-HHB-O1 (4-4) 4%
3-HHB-3 (4-4) 6%
3-HBB-2 (4-5) 3%
2-BB(F)B-3 (4-7) 6%
2-BB(F)B-5 (4-7) 6%
NI=106.0°C; Tc<-20°C;Δn=0.110;Δε=3.3;Vth=2.53V; η=17.2 mPa·s; γ1=66.6 mPa·s.

[Example 3]
V-HHBB-1 (1) 5%
V-HHBB-2 (1) 5%
3-HH-V (2) 15%
1V-HH-V (2) 15%
3-GB(F)B(F,F)XB(F,F)-F(3-27) 3%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 5%
3-BB(F,F)XB(F)B(F,F)-F(3-30) 5%
3-HB-O2 (4-1) 4%
1-BB-3 (4-2) 5%
V-HHB-1 (4-4) 8%
V2-HHB-1 (4-4) 8%
1-BB(F)B-2V (4-7) 6%
2-BB(F)B-2V (4-7) 6%
2-HH-3 (-) 5%
3-HH-V1 (-) 5%
NI=104.4°C; Tc<-20°C;Δn=0.123;Δε=3.7;Vth=2.48V; η=14.3 mPa·s; γ1=62.1 mPa·s.

[Example 4]
V-HHBB-1 (1) 5%
V-HHBB-2 (1) 5%
3-HH-V (2) 35%
3-HHXB(F,F)-F (3-4) 6%
3-HHXB(F,F)-CF3 (3-5) 4%
3-HBB(F,F)-F (3-8) 5%
3-GB(F,F)XB(F)-F (3-13) 3%
3-GB(F,F)XB(F,F)-F (3-14) 3%
V2-BB-1 (4-2) 4%
3-HHEH-3 (4-3) 3%
3-HHB-O1 (4-4) 4%
3-HBB-2 (4-5) 3%
5-B(F)BB-3 (4-6) 7%
2-B2BB-3 (4-8) 7%
3-HBB(2F,3F)-O2 (5-14) 3%
5-HBB(F)B-2 (-) 3%
NI=101.5°C; Tc<-20°C;Δn=0.112;Δε=2.9;Vth=2.62V; η=16.6 mPa·s; γ1=64.4 mPa·s.

[Example 5]
V-HHBB-2 (1) 8%
V-HH-V (2) 12%
1V-HH-V (2) 27%
3-BB(F)B(F,F)-F (3-15) 10%
3-GB(F)B(F)B(F)-F (3-21) 3%
3-GBB(F)B(F,F)-F (3-22) 3%
3-HBBXB(F,F)-F (3-23) 5%
1V2-BB-1 (4-2) 4%
V-HHB-1 (4-4) 6%
V2-HHB-1 (4-4) 7%
2-BB(F)B-3 (4-7) 5%
3-BB(F)B-5 (4-7) 5%
1-BB(F)B-2V (4-7) 5%
NI=106.3°C; Tc<-20°C;Δn=0.139;Δε=3.4;Vth=2.51V; η=17.9 mPa·s; γ1=66.5 mPa·s.

[Example 6]
V-HHBB-2 (1) 7%
V-HHBB-3 (1) 7%
3-HH-V (2) 24%
1V-HH-V (2) 24%
3-GB(F)B(F)-F (3-11) 5%
3-BB(F,F)XB(F,F)-F (3-18) 5%
3-HBB(F,F)XB(F,F)-F (3-24) 4%
3-dhBB(F,F)XB(F,F)-F (3-25) 6%
3-HHB-1 (4-4) 6%
3-HHB-3 (4-4) 5%
1-BB(F)B-2V (4-7) 4%
3-HH-4 (-) 3%
NI=105.6°C; Tc<-20°C;Δn=0.106;Δε=3.2;Vth=2.53V; η=14.0 mPa·s; γ1=62.0 mPa·s.

[Example 7]
V-HHBB-1 (1) 4%
V-HHBB-2 (1) 4%
3-HH-V (2) 18%
1V-HH-V (2) 30%
3-HHXB(F,F)-CF3 (3-5) 3%
3-BB(F)B(F,F)-CF3 (3-16) 3%
3-GBB(F)B(F,F)-F (3-22) 3%
5-GB(F)B(F,F)XB(F,F)-F(3-27) 4%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 4%
3-BB(2F,3F)XB(F,F)-F (3-32) 3%
V-HHB-1 (4-4) 10%
V2-HHB-1 (4-4) 8%
2-BB(F)B-3 (4-7) 3%
5-HB(F)BH-3 (-) 3%
NI=106.8°C; Tc<-20°C;Δn=0.109;Δε=4.1;Vth=2.45V; η=17.2 mPa·s; γ1=65.5 mPa·s.

[Example 8]
V-HHBB-1 (1) 5%
V-HHBB-2 (1) 5%
V-HHBB-3 (1) 5%
3-HH-V (2) 23%
V-HH-V (2) 13%
1V-HH-V (2) 12%
3-HBB(F,F)-F (3-8) 5%
3-GB(F)B(F,F)-F (3-12) 5%
3-GB(F)B(F)B(F)-F (3-21) 3%
3-dhBB(F,F)XB(F,F)-F (3-25) 4%
3-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
V-HHB-1 (4-4) 7%
3-BB(F)B-2V (4-7) 7%
NI=104.7°C; Tc<-20°C;Δn=0.115;Δε=3.7;Vth=2.48V; η=16.9 mPa·s; γ1=64.9 mPa·s.

[Example 9]
V-HHBB-2 (1) 5%
3-HH-V (2) 34.5%
1V-HH-V (2) 7%
3-HHB-OCF3 (3) 4%
2-BB(F)B(F,F)-F (3-15) 2%
3-BB(F,F)XB(F,F)-F (3-18) 2%
3-HBBXB(F,F)-F (3-23) 3%
3-HBB(F,F)XB(F,F)-F (3-24) 3.5%
3-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 7%
V-HHB-1 (4-4) 12%
1-BB(F)B-2V (4-7) 3%
2-BB(F)B-2V (4-7) 5%
3-BB(F)B-2V (4-7) 4%
3-HH-V1 (-) 5%
NI=100.0°C; Tc<-20°C;Δn=0.120;Δε=3.7;Vth=2.47V; η=11.6 mPa·s; γ1=54.0 mPa·s.

[Example 10]
V-HHBB-2 (1) 5%
3-HH-V (2) 34.5%
1V-HH-V (2) 4.5%
3-HHB-OCF3 (3) 4%
2-BB(F)B(F,F)-F (3-15) 2%
3-BB(F,F)XB(F,F)-F (3-18) 4%
3-HBB(F,F)XB(F,F)-F (3-24) 3.5%
3-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 7%
V-HHB-1 (4-4) 12%
V2-HHB-1 (4-4) 3.5%
1-BB(F)B-2V (4-7) 3%
2-BB(F)B-2V (4-7) 5%
3-BB(F)B-2V (4-7) 4%
3-HH-V1 (-) 5%
NI=100.4°C; Tc<-40°C;Δn=0.120;Δε=3.7;Vth=2.41V; η=11.5 mPa·s; γ1=54.1 mPa·s.

[Example 11]
V-HHBB-2 (1) 5%
3-HH-V (2) 31.5%
3-HHB-OCF3 (3) 4%
3-BB(F,F)XB(F,F)-F (3-18) 2%
3-HBBXB(F,F)-F (3-23) 3%
3-HBB(F,F)XB(F,F)-F (3-24) 3.5%
3-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 7%
3-HB-O2 (4-1) 9%
V-HHB-1 (4-4) 12%
V2-HHB-1 (4-4) 3%
1-BB(F)B-2V (4-7) 3%
2-BB(F)B-2V (4-7) 5%
3-BB(F)B-2V (4-7) 4%
3-HH-V1 (-) 5%
NI=100.1°C; Tc<-40°C;Δn=0.120;Δε=3.7;Vth=2.46V; η=12.2 mPa·s; γ1=55.8 mPa·s.

[Example 12]
V-HHBB-2 (1) 5%
3-HH-V (2) 26.5%
1V-HH-V (2) 7%
3-HHB-OCF3 (3) 4%
2-BB(F)B(F,F)-F (3-15) 2%
3-BB(F,F)XB(F,F)-F (3-18) 2%
3-HBBXB(F,F)-F (3-23) 3%
3-HBB(F,F)XB(F,F)-F (3-24) 3.5%
3-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 7%
V-HHB-1 (4-4) 10%
1-BB(F)B-2V (4-7) 3%
2-BB(F)B-2V (4-7) 5%
3-BB(F)B-2V (4-7) 4%
3-HH-V1 (-) 5%
3-HH-VFF (-) 10%
NI=100.6°C; Tc<-20°C;Δn=0.119;Δε=3.7;Vth=2.44V; η=11.9 mPa·s; γ1=54.6 mPa·s.

[Example 13]
V-HHBB-2 (1) 5%
3-HH-V (2) 27.5%
1V-HH-V (2) 7%
3-HHB-OCF3 (3) 4%
3-BB(F,F)XB(F,F)-F (3-18) 2%
3-HBBXB(F,F)-F (3-23) 3%
3-HBB(F,F)XB(F,F)-F (3-24) 3.5%
3-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 7%
V2-BB-1 (4-2) 7%
V-HHB-1 (4-4) 12%
V2-HHB-1 (4-4) 7%
1-BB(F)B-2V (4-7) 3%
2-BB(F)B-2V (4-7) 4%
3-HH-V1 (-) 5%
NI=100.4°C; Tc<-20°C;Δn=0.120;Δε=3.6;Vth=2.48V; η=12.3 mPa·s; γ1=56.0 mPa·s.

[Example 14]
3-HHBB-2 (1) 3%
3-HH-V (2) 30%
1V-HH-V (2) 13%
3-BB(F)B(F,F)-F (3-15) 3%
3-HHBB(F,F)-F (3-19) 5%
3-GBB(F)B(F,F)-F (3-22) 2%
3-HBBXB(F,F)-F (3-23) 2%
3-HBB(F,F)XB(F,F)-F (3-24) 1%
3-GB(F)B(F,F)XB(F,F)-F(3-27) 2%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 4%
V-HHB-1 (4-4) 11%
V2-HHB-1 (4-4) 11%
2-BB(F)B-3 (4-7) 3%
2-BB(F)B-2V (4-7) 5%
3-BB(F)B-2V (4-7) 5%
NI=109.2°C; Tc<-20°C;Δn=0.120;Δε=3.1;Vth=2.72V; γ1=68.0 mPa·s.

[Example 15]
V-HHBB-2 (1) 4%
3-HH-V (2) 35%
1V-HH-V (2) 8%
3-HHB-OCF3 (3) 2%
3-HBB(F,F)-F (3-8) 4%
3-BB(F,F)XB(F,F)-F (3-18) 2%
3-HHBB(F,F)-F (3-19) 5%
3-HBBXB(F,F)-F (3-23) 1%
3-GB(F)B(F,F)XB(F,F)-F(3-27) 1%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 7%
V-HHB-1 (4-4) 10%
V2-HHB-1 (4-4) 10%
2-BB(F)B-2V (4-7) 5%
3-BB(F)B-2V (4-7) 4%
3-HH-V1 (-) 2%
NI=104.3°C; Tc<-20°C;Δn=0.110;Δε=3.1;Vth=2.56V; γ1=64.0 mPa·s.

[Example 16]
3-HHBB-2 (1) 4%
3-HH-V (2) 36%
1V-HH-V (2) 9%
3-HHB-OCF3 (3) 3%
3-BB(F,F)XB(F,F)-F (3-18) 2%
3-HBB(F,F)XB(F,F)-F (3-24) 1%
3-BB(F)B(F,F)XB(F,F)-F(3-29) 1%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 8%
V-HHB-1 (4-4) 7%
V2-HHB-1 (4-4) 10%
2-BB(F)B-3 (4-7) 5%
2-BB(F)B-2V (4-7) 5%
3-BB(F)B-2V (4-7) 6%
3-HB(2F)B(2F,3F)-O2 (5-18) 1%
NI=100.0°C; Tc<-20°C;Δn=0.119;Δε=2.7;Vth=2.71V; γ1=59.0 mPa·s.

[Example 17]
3-HHBB-2 (1) 4%
3-HH-V (2) 34%
1V-HH-V (2) 10%
3-HHXB(F,F)-CF3 (3-5) 3%
4-HHBB(F,F)-F (3-19) 2%
4-GBB(F)B(F,F)-F (3-22) 2%
3-HBBXB(F,F)-F (3-23) 2%
4-GB(F)B(F,F)XB(F)-F (3-27) 1%
4-BB(F)B(F,F)XB(F,F)-F(3-29) 5%
5-BB(F)B(F,F)XB(F,F)-F(3-29) 3%
3-HB-O2 (4-1) 2%
V-HHB-1 (4-4) 12%
V2-HHB-1 (4-4) 12%
2-BB(F)B-2V (4-7) 3%
3-BB(F)B-2V (4-7) 3%
3-HH-V1 (-) 2%
NI=104.3°C; Tc<-20°C;Δn=0.104;Δε=3.0;Vth=2.58V; γ1=64.8 mPa·s.

The rotational viscosity of the composition of Comparative Example 1 was 62.3 mPa·s, and the response time at -30°C was 235.8 ms. On the other hand, the rotational viscosity of the composition of Example 1 was 57.1 mPa·s, and the response time at -30°C was 185.7 ms. Thus, the Example compositions had lower rotational viscosities and shorter response times than the Comparative Example compositions. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

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

Claims (15)

Contains at least one compound selected from the compounds represented by formula (1) as component A, at least one compound selected from the compounds represented by formula (2) as component B, and has a positive dielectric constant A liquid crystal composition with anisotropy.

In formula (1) and formula (2), R ¹ is alkenyl having 2 to 12 carbon atoms; R ² is alkyl having 1 to 12 carbon atoms ; R ³ is alkyl having 1 to 3 carbon atoms. or alkenyl having 2 to 5 carbon atoms; Z ¹ , Z ² , and Z ³ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. The liquid crystal composition according to claim 1, wherein the proportion of component A is in the range of 3% by weight to 30% by weight, and the proportion of component B is in the range of 10% by weight to 70% by weight. The liquid crystal composition according to claim 1 or 2, containing as component C at least one compound selected from the group of compounds represented by formula (3).

In formula (3), R ⁴ 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- is dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ⁴ is a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X ¹ and X ² are , hydrogen or fluorine; Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, or 1 carbon in which at least one hydrogen is replaced with fluorine or chlorine; alkoxy of 12 to 12, or alkenyloxy of 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; a is 1, 2, 3, or 4; The liquid crystal composition according to any one of claims 1 to 3, containing as component C at least one compound selected from the group of compounds represented by formulas (3-1) to (3-35). thing.

In formulas (3-1) to (3-35), R ⁴ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms. The liquid crystal composition according to claim 3 or 4, wherein the proportion of component C is in the range of 10% by mass to 80% by mass. The liquid crystal composition according to any one of claims 1 to 5, containing as component D at least one compound selected from compounds represented by formula (4).

In formula (4), R ⁵ and R ⁶ 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 has been replaced with fluorine or chlorine. It is 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 ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; b is 1 or 2; when b is 1, ring C is 1,4-phenylene; 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. The liquid crystal composition according to any one of claims 1 to 6, containing as component D at least one compound selected from compounds represented by formulas (4-1) to (4-8).

In formulas (4-1) to (4-8), R ⁵ and R ⁶ 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 an alkenyl having 2 to 12 carbon atoms in which hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 6 or 7, wherein the proportion of component D is in the range of 5% by mass to 60% by mass. The liquid crystal composition according to any one of claims 1 to 8, containing as component E at least one compound selected from compounds represented by formula (5).

In formula (5), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms. ; Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced with fluorine or chlorine; 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen replaced with 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, 5-diyl; Z ⁶ and Z ⁷ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3; d is 0 or 1; Yes, and the sum of c and d is 3 or less. The liquid crystal composition according to any one of claims 1 to 9, containing as component E at least one compound selected from compounds represented by formulas (5-1) to (5-35).

In formulas (5-1) to (5-35), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or carbon It is alkenyloxy having numbers 2 to 12. The liquid crystal composition according to claim 9 or 10, wherein the proportion of component E is in the range of 3% by mass to 45% by mass. The upper limit temperature of the nematic phase is 100°C or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25°C) is 0.09 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25°C) is 2. The liquid crystal composition according to any one of claims 1 to 11, which is the above. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 12. 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 an active matrix method. element. Use of the liquid crystal composition according to any one of claims 1 to 12 in a liquid crystal display element.